WO2020121708A1

WO2020121708A1 - Laminate, method for producing same, circular polarizer, display device, and touch panel

Info

Publication number: WO2020121708A1
Application number: PCT/JP2019/044248
Authority: WO
Inventors: 幹文柏木
Original assignee: 日本ゼオン株式会社
Priority date: 2018-12-10
Filing date: 2019-11-12
Publication date: 2020-06-18
Also published as: CN112996657A; JP7355036B2; JPWO2020121708A1; KR20210102228A; TWI829817B; TW202031495A

Abstract

Provided are: a laminate comprising a thermoplastic resin layer, an electorconductive layer, and a substrate in the stated order, the thermoplastic resin layer having a moisture permeability of 5 g/m2⋅24 h or less and having a storage elastic modulus at 25°C of 1300 MPa or less, and the electroconductive layer including at least one element selected from among Sn, Pb, Ag, Cu, and Au; and a circular polarizer, a display device, and a touch panel that include the laminate. Also provided is a method for producing the laminate. The thermoplastic resin layer preferably includes a polymer having a silyl group. The polymer having a silyl group is preferably a silyl-group-modified substance of a block copolymer.

Description

Laminated body and manufacturing method thereof, circularly polarizing plate, display device and touch panel

The present invention relates to a laminated body and a manufacturing method thereof, a circularly polarizing plate, a display device, and a touch panel.

Conventionally, conductive glass in which an indium oxide thin film is formed on a glass plate is known as a conductive member. However, the conductive glass is inferior in flexibility because the base material is glass and is difficult to apply depending on the application. Therefore, as a conductive member having excellent flexibility, a conductive member using resin has been proposed (Patent Document 1).

JP, 2017-65217, A

Patent Document 1 describes a conductive member including a flexible base material, a conductive layer formed on the flexible base material, and an adhesive layer formed on the conductive layer. There is. Such a conductive member may be used for a touch panel or the like. In such a case, depending on the environment of use, a phenomenon called migration may occur in which the metal material contained in the conductive layer is ionized and moved to be regenerated as a metal. When the migration occurs, the touch panel does not operate normally, so improvement is required.

The present invention was devised in view of the above problems, and has a laminated body having excellent flexibility and an excellent migration preventing effect, and a method for producing the same; circularly polarized light provided with the laminated body. It is an object to provide a display device including a plate and a touch panel; and the circularly polarizing plate.

The present inventor, as a result of intensive studies to solve the above problems, the laminate is a thermoplastic resin layer having a predetermined moisture permeability and a predetermined storage elastic modulus, a conductive layer, and a substrate, It has been found that, by providing in this order, the laminate can be made excellent in flexibility and migration prevention effect, and the present invention has been completed.
That is, the present invention includes the following.

[1] A thermoplastic resin layer, a conductive layer, and a base material are provided in this order,
The thermoplastic resin layer has a moisture permeability of 5 g/m ² ·24 h or less and a storage elastic modulus at 25° C. of 1300 MPa or less,
The said conductive layer is a laminated body containing the element of at least 1 type of Sn, Pb, Ag, Cu, and Au.
[2] The laminate according to [1], wherein the thermoplastic resin layer contains a polymer having a silyl group.
[3] The laminate according to [2], wherein the polymer having a silyl group is a silyl group-modified product of a block copolymer.
[4] The laminate according to [2] or [3], wherein the polymer having a silyl group is a silyl group-modified product of a copolymer of an aromatic vinyl monomer and a conjugated diene monomer.
[5] The hydrogenation rate of the unit based on the aromatic vinyl monomer is 90% or more, and the hydrogenation rate of the unit based on the conjugated diene monomer is 90% or more, [4] Stack of.
[6] The ratio (E ₂ /E ₁ ) of the storage elastic modulus E ₂ at 100° C. of the thermoplastic resin layer to the storage elastic modulus E ₁ at −40° C. of the thermoplastic resin layer is 15 or less. The laminate according to any one of [1] to [5].
[7] The laminate according to any one of [1] to [6], wherein the water vapor permeability of the base material is 3 g/m ² ·24 h or less.
[8] The laminate according to any one of [1] to [7], wherein the substrate is a polymer film containing a polymer.
[9] The laminate according to any one of [1] to [8], wherein the base material contains an alicyclic structure-containing polymer.
[10] The laminate according to any one of [1] to [9], wherein the base material is a long film and has a slow axis in a direction oblique to the width direction of the film.
[11] The laminate according to any one of [1] to [10], wherein the substrate has a storage elastic modulus at 25° C. of 2000 to 3000 MPa.
[12] The laminate according to any one of [1] to [11], wherein the thermoplastic resin layer has a retardation in the in-plane direction of 10 nm or less.
[13] The laminate according to any one of [1] to [12], wherein the total light transmittance of at least one of the thermoplastic resin layer and the substrate is 80% or more.
[14] A circularly polarizing plate comprising the laminate according to any one of [1] to [13] and a polarizing plate.
[15] A display device including the circularly polarizing plate according to [14].
[16] The display device according to [15], wherein the display device is an organic electroluminescence device.
[17] A touch panel comprising the laminate according to any one of [1] to [13].
[18] The touch panel according to [17], including a polarizing plate provided in contact with the thermoplastic resin layer of the laminate.
[19] comprises the laminate and a polarizing plate,
Comprising the laminate and a polarizing plate,
The touch panel according to [17] or [18], wherein an angle formed by an absorption axis of the polarizing plate with respect to a slow axis of the base material of the laminate is 45°.
[20] The method for producing a laminate according to any one of [1] to [13],
Step 1 of forming the conductive layer on the substrate,
A step 2 of forming the thermoplastic resin layer on the conductive layer,
The said process 2 is a manufacturing method of a laminated body including thermocompression-bonding the said thermoplastic resin layer, or applying the solution containing a thermoplastic resin.

According to the present invention, a laminate having excellent flexibility and an excellent effect of preventing migration, and a method for producing the same; a circularly polarizing plate and a touch panel including the laminate, and the circularly polarizing plate are provided. A display device provided with the display device can be provided.

FIG. 1 is a sectional view schematically showing a laminated body according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail by showing embodiments and exemplifications. However, the present invention is not limited to the embodiments and exemplifications shown below, and may be implemented by being arbitrarily modified within the scope of the claims of the present invention and the scope of equivalents thereof.

In the present application, the “long film” means a film having a length of 5 times or more, preferably 10 times or more, specifically, a width of the film. It has a length that allows it to be rolled up and stored or transported. The upper limit of the ratio of the length to the width of the film is not particularly limited, but may be 100,000 times or less, for example.

In the present application, the retardation Re in the in-plane direction of the film is calculated according to the formula Re=(nx−ny)×d. Here, nx is the refractive index in the in-plane slow axis direction of the film (maximum in-plane refractive index), and ny is the refractive index in the direction perpendicular to the in-plane slow axis of the film, d is the thickness (nm) of the film. Unless otherwise specified, the measurement wavelength is 590 nm which is a typical wavelength in the visible light region.

[1. Overview of laminate]
FIG. 1 is a sectional view schematically showing a laminated body 10 according to an embodiment of the present invention.
As shown in FIG. 1, a laminate 10 according to an embodiment of the present invention includes a thermoplastic resin layer 110, a conductive layer 120, and a base material 130 in this order in the thickness direction. In the present invention, the thermoplastic resin layer has a predetermined moisture permeability and a predetermined storage elastic modulus, and the conductive layer contains a predetermined element.

[2. Thermoplastic resin layer]
The thermoplastic resin layer is a layer formed of a thermoplastic resin. The thermoplastic resin layer is a layer having a moisture permeability of 5 g/m ² ·24 h or less and a storage elastic modulus at 25° C. of 1300 MPa or less. The moisture permeability of the thermoplastic resin layer in the above range, and by setting the storage elastic modulus in the above range, by increasing the adhesion between the thermoplastic resin layer and the conductive layer, while improving the migration prevention effect, the laminate Flexibility can be improved.

The water vapor permeability of the thermoplastic resin layer is 5 g/m ² ·24 h or less, preferably 4 g/m ² ·24 h or less, more preferably 3 g/m ² ·24 h or less. The lower limit of the moisture permeability of the thermoplastic resin is not particularly limited, but is preferably 1 g/m ² ·24 h or more, more preferably 2 g/m ² ·24 h or more. By setting the water vapor permeability to the upper limit or less, the degree of adhesion between the thermoplastic resin layer and the conductive layer can be increased, and the migration preventing effect can be improved.

The water vapor transmission rate of the thermoplastic resin layer can be measured by the Lissi method (measuring instrument L80-5000 type (manufactured by Systec Illinois), temperature condition 40°C, humidity 90%).

The storage elastic modulus at 25° C. of the thermoplastic resin layer is 1300 MPa or less, preferably 1100 MPa or less, and preferably 100 MPa or more. By setting the storage elastic modulus at 25° C. of the thermoplastic resin layer to the upper limit value or less, the flexibility of the thermoplastic resin layer can be made excellent.

The ratio (E ₂ /E ₁ ) of the storage elastic modulus E ₂ of the thermoplastic resin layer at 100° C. to the storage elastic modulus E ₁ of −40° C. is preferably 15 or less, and more preferably It is 12 or less. The lower limit of E ₂ /E ₁ is not particularly limited, but is preferably 5 or more, more preferably 8 or more. By setting E ₂ /E ₁ to be equal to or less than the above upper limit, the flexibility of the laminate can be made excellent in an environment with a temperature difference.

Each storage elastic modulus of the thermoplastic resin layer can be measured using a dynamic viscoelasticity measuring device under the condition of a frequency of 1 Hz. As specific measurement conditions, the conditions of Examples described later can be adopted.

The retardation Re in the in-plane direction of the thermoplastic resin layer is preferably 10 nm or less, more preferably 5 nm or less. The lower limit of Re can be 0 nm.

[2.1. Thermoplastic resin]
As the thermoplastic resin forming the thermoplastic resin layer, a thermoplastic resin that contains a polymer (hereinafter, also referred to as “polymer X”) and may further contain any component as necessary can be used. As the polymer X, one type may be used alone, or two or more types may be used in combination at an arbitrary ratio.

As the polymer X contained in the thermoplastic resin, a polymer having a silyl group is preferable. A thermoplastic resin layer formed from a thermoplastic resin containing a polymer having a silyl group exhibits high adhesion to other materials. Therefore, since the thermoplastic resin layer formed of a resin containing a polymer having a silyl group has excellent adhesion to the conductive layer, it is possible to prevent entry of water and the like and effectively prevent migration, and thus the laminate Overall, the mechanical strength can be improved.

As the polymer having a silyl group, a block copolymer modified with a silyl group is preferable. Examples of silyl group-modified products of block copolymers include block copolymers and hydrogenated products thereof in which a silyl group is introduced. Further, the silyl group-containing polymer is preferably a silyl group-modified product of a copolymer of an aromatic vinyl monomer and a conjugated diene monomer. The silyl group-modified product of the copolymer of an aromatic vinyl monomer and a conjugated diene monomer includes a copolymer of an aromatic vinyl monomer and a conjugated diene monomer or a hydride thereof with a silyl group. The thing which introduced is mentioned. However, the polymer and the constituent elements of the polymer used in the present invention are not limited by the production method thereof.

The polymer having a silyl group is a block copolymer containing a polymer block [A] containing an aromatic vinyl monomer unit and a polymer block [B] containing a conjugated diene monomer unit. A hydride having a silyl group introduced, and a polymer block [A] containing an aromatic vinyl monomer unit, and a polymer block containing an aromatic vinyl monomer unit and a conjugated diene monomer unit It is more preferable to introduce a silyl group into a hydride of a block copolymer containing [C].

Hereinafter, a hydride of a block copolymer containing a polymer block [A] and a polymer block [B] or a polymer block [C], which is suitable as a polymer having a silyl group, having a silyl group introduced therein. However, the present invention is not limited to this. In the following description, the block copolymer containing the polymer block [A] and the polymer block [B] or the polymer block [C] may be referred to as a block copolymer [1]. Moreover, the hydride of the block copolymer [1] may be called a hydride [2].

The block copolymer [1] includes two or more polymer blocks [A] per molecule of the block copolymer [1] and one or more polymer blocks [1] per molecule of the block copolymer [1]. B] or the polymer block [C] is particularly preferable.

The polymer block [A] is a polymer block containing an aromatic vinyl monomer unit. Here, the aromatic vinyl monomer unit refers to a structural unit having a structure formed by polymerizing an aromatic vinyl compound, and is also referred to as an aromatic vinyl compound unit.

Examples of the aromatic vinyl compound corresponding to the aromatic vinyl monomer unit contained in the polymer block [A] include styrene; α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2 Styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent, such as 4,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-t-butylstyrene, and 5-t-butyl-2-methylstyrene; 4 -Styrenes having a halogen atom as a substituent, such as chlorostyrene, dichlorostyrene, 4-monofluorostyrene; Styrenes having an alkoxy group having 1 to 6 carbon atoms as a substituent, such as 4-methoxystyrene; 4- Examples thereof include styrenes having an aryl group as a substituent such as phenylstyrene; vinylnaphthalenes such as 1-vinylnaphthalene and 2-vinylnaphthalene. These may be used individually by 1 type and may be used in combination of 2 or more types in arbitrary ratios. Of these, aromatic vinyl compounds containing no polar group, such as styrene and styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent, are preferable because of their low hygroscopicity, and they are industrially easily available. Therefore, styrene is particularly preferable.

The content of the aromatic vinyl monomer unit in the polymer block [A] is preferably 90% by weight or more, more preferably 95% by weight or more, and particularly preferably 99% by weight or more. When the amount of the aromatic vinyl monomer unit is large in the polymer block [A] as described above, the hardness and heat resistance of the thermoplastic resin layer can be increased.

The polymer block [A] may contain any structural unit in addition to the aromatic vinyl monomer unit. The polymer block [A] may contain one type of any structural unit alone or may contain two or more types in combination at any ratio.

Examples of the optional structural unit that can be contained in the polymer block [A] include a conjugated diene monomer unit. Here, the conjugated diene monomer unit refers to a structural unit having a structure formed by polymerizing a conjugated diene compound, and is also referred to as a conjugated diene compound unit. Examples of the conjugated diene compound corresponding to the conjugated diene monomer unit include the same examples as the examples of the conjugated diene compound corresponding to the conjugated diene monomer unit included in the polymer block [B].

Further, as the arbitrary structural unit that can be contained in the polymer block [A], for example, a structural unit having a structure formed by polymerizing any unsaturated compound other than the aromatic vinyl compound and the chain conjugated diene compound can be mentioned. Can be mentioned. Examples of the optional unsaturated compound include vinyl compounds such as chain vinyl compounds and cyclic vinyl compounds; unsaturated cyclic acid anhydrides; unsaturated imide compounds; and the like. These compounds may have a substituent such as a nitrile group, an alkoxycarbonyl group, a hydroxycarbonyl group, or a halogen group. Among these, from the viewpoint of hygroscopicity, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-eicosene, Chain olefins having 2 to 20 carbon atoms per molecule such as 4-methyl-1-pentene and 4,6-dimethyl-1-heptene; cyclic olefins having 5 to 20 carbon atoms per molecule such as vinylcyclohexane; A vinyl compound having no polar group is preferable, a chain olefin having 2 to 20 carbon atoms per molecule is more preferable, and ethylene and propylene are particularly preferable.

The content of any structural unit in the polymer block [A] is preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably 1% by weight or less.

The number of polymer blocks [A] in one molecule of block copolymer [1] is preferably 2 or more, preferably 5 or less, more preferably 4 or less, and particularly preferably 3 or less. The plural polymer blocks [A] in one molecule may be the same or different from each other.

The polymer block [B] is a polymer block containing a conjugated diene monomer unit. As described above, the conjugated diene monomer unit means, for example, a structural unit having a structure formed by polymerizing a conjugated diene compound and is also called a conjugated diene compound unit.

Examples of the conjugated diene compound corresponding to the conjugated diene monomer unit contained in the polymer block [B] include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and 1,3- Examples thereof include chain conjugated diene compounds such as pentadiene. These may be used individually by 1 type and may be used in combination of 2 or more types in arbitrary ratios. Among them, a chain conjugated diene compound containing no polar group is preferable, and 1,3-butadiene and isoprene are particularly preferable, because they can reduce hygroscopicity.

The content of the conjugated diene monomer unit in the polymer block [B] is preferably 90% by weight or more, more preferably 95% by weight or more, and particularly preferably 99% by weight or more. When the content of the conjugated diene monomer unit in the polymer block [B] is within the above range, the flexibility of the thermoplastic resin layer can be improved.

The polymer block [B] may contain an arbitrary structural unit in addition to the conjugated diene monomer unit. The polymer block [B] may contain one kind of any structural unit alone or may contain two or more kinds of structural units in combination at any ratio.

The arbitrary structural unit that can be contained in the polymer block [B] is formed, for example, by polymerizing an aromatic vinyl compound unit and any unsaturated compound other than the aromatic vinyl compound and the chain conjugated diene compound. The structural unit which has a structure is mentioned. The aromatic vinyl compound unit and the structural unit having a structure formed by polymerizing any unsaturated compound are exemplified as those which may be contained in the polymer block [A]. And the same example.

The content of any structural unit in the polymer block [B] is preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably 1% by weight or less. When the content of the optional structural unit in the polymer block [B] is within the above range, the flexibility of the thermoplastic resin layer can be improved.

The number of polymer blocks [B] in one molecule of the block copolymer [1] is usually 1 or more, but may be 2 or more. When the number of polymer blocks [B] in the block copolymer [1] is 2 or more, those polymer blocks [B] may be the same as or different from each other.

The polymer block [C] is a polymer block containing an aromatic vinyl monomer unit and a conjugated diene monomer unit. As described above, the conjugated diene monomer unit means, for example, a structural unit having a structure formed by polymerizing a conjugated diene compound and is also called a conjugated diene compound unit. The aromatic vinyl monomer unit refers to a structural unit having a structure formed by polymerizing an aromatic vinyl monomer unit, for example, and is also called an aromatic vinyl compound unit.

The aromatic vinyl compound corresponding to the aromatic vinyl monomer unit contained in the polymer block [C] is exemplified as the aromatic vinyl compound corresponding to the aromatic vinyl monomer unit contained in the polymer block [A]. There are things. Examples of the conjugated diene compound corresponding to the conjugated diene monomer unit contained in the polymer block [C] include those exemplified as the conjugated diene compound corresponding to the conjugated diene monomer unit contained in the polymer block [B]. ..

The content of the aromatic vinyl monomer unit in the polymer block [C] is preferably 30% by weight or more, more preferably 40% by weight or more, preferably 76% by weight or less, more preferably 60% by weight. It is particularly preferably 55% by weight or less. When the content of the aromatic vinyl monomer unit in the polymer block [C] is within the above range, the hardness and heat resistance of the thermoplastic resin layer can be increased.

The content of the conjugated diene monomer unit in the polymer block [C] is preferably 24% by weight or more, more preferably 40% by weight or more, particularly preferably 45% by weight or more, preferably 70% by weight or less, It is more preferably 60% by weight or less. When the content of the conjugated diene monomer unit in the polymer block [C] is within the above range, the flexibility of the thermoplastic resin layer can be improved.

The polymer block [C] may contain any structural unit in addition to the aromatic vinyl monomer unit and the conjugated diene monomer unit. The polymer block [C] may contain one kind of any structural unit alone or may contain two or more kinds of structural units in combination at any ratio.

As an arbitrary structural unit that can be contained in the polymer block [C], for example, a structural unit having a structure formed by polymerizing any unsaturated compound other than the aromatic vinyl compound and the chain conjugated diene compound can be mentioned. .. Examples of the structural unit having a structure formed by polymerizing an arbitrary unsaturated compound include the same examples as those exemplified as those which may be contained in the polymer block [A].

The content of any structural unit in the polymer block [C] is preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably 1% by weight or less. When the content of the optional structural unit in the polymer block [C] is within the above range, the flexibility of the thermoplastic resin layer can be improved.

The number of polymer blocks [C] in one molecule of the block copolymer [1] is usually 1 or more, but may be 2 or more. When the number of polymer blocks [C] in the block copolymer [1] is 2 or more, those polymer blocks [C] may be the same as or different from each other.

The block form of the block copolymer [1] may be a chain type block or a radial type block. Among them, a chain block is preferable because it has excellent mechanical strength. When the block copolymer [1] has the form of a chain type block, the both ends of the molecular chain of the block copolymer [1] are polymer blocks [A], and thus the stickiness of the thermoplastic resin layer is desired. Can be suppressed to a low value.

A particularly preferred block morphology of the block copolymer [1] is a polymer block [B] as represented by [A]-[B]-[A] and [A]-[C]-[A]. ] Or [C], a triblock copolymer having polymer blocks [A] bonded to both ends; [A]-[B]-[A]-[B]-[A] and [A]-[C] As represented by -[A]-[C]-[A], the polymer block [B] or [C] is bonded to both ends of the polymer block [A], and further both polymer blocks [B] ] Or [C] is a pentablock copolymer in which the polymer block [A] is bonded to the other end, respectively. In particular, a triblock copolymer of [A]-[B]-[A] and [A]-[C]-[A] facilitates production and facilitates physical properties within a desired range. It is particularly preferable because it can be stored.

In the block copolymer [1], the weight fraction wA of the polymer block [A] in the whole block copolymer [1] and the polymer block [B] in the whole block copolymer [1] The ratio (wA/wB) to the weight fraction wB of is preferably within a specific range. Specifically, the ratio (wA/wB) is preferably 30/70 or more, more preferably 40/60 or more, particularly preferably 45/55 or more, preferably 85/15 or less, and further preferably 70/30 or less, particularly preferably 55/45 or less. When the ratio wA/wB is not less than the lower limit value of the above range, the rigidity and heat resistance of the thermoplastic resin layer can be improved and the birefringence can be reduced. Further, when the ratio wA/wB is equal to or less than the upper limit value of the above range, the flexibility of the thermoplastic resin layer can be improved. Here, the weight fraction wA of the polymer block [A] indicates the weight fraction of the whole polymer block [A], and the weight fraction wB of the polymer block [B] is the whole polymer block [B]. The weight fraction of is shown.

In the block copolymer [1], the weight fraction wA of the polymer block [A] in the whole block copolymer [1] and the polymer block [C] in the whole block copolymer [1] The ratio (wA/wC) to the weight fraction wC of is preferably within a specific range. Specifically, the ratio (wA/wC) is preferably 30/70 or more, more preferably 40/60 or more, particularly preferably 45/55 or more, preferably 85/15 or less, and further preferably 70/30 or less, particularly preferably 55/45 or less. When the ratio wA/wC is equal to or more than the lower limit value of the above range, the rigidity and heat resistance of the thermoplastic resin layer can be improved and the birefringence can be reduced. Further, when the ratio wA/wC is equal to or less than the upper limit value of the above range, the flexibility of the thermoplastic resin layer can be improved. Here, the weight fraction wA of the polymer block [A] indicates the weight fraction of the whole polymer block [A], and the weight fraction wC of the polymer block [C] is the whole polymer block [C]. The weight fraction of is shown.

The weight average molecular weight (Mw) of the block copolymer [1] is preferably 30,000 or more, more preferably 40,000 or more, particularly preferably 50,000 or more, preferably 200,000 or less, It is more preferably 150,000 or less, and particularly preferably 100,000 or less.
The molecular weight distribution (Mw/Mn) of the block copolymer [1] is preferably 3 or less, more preferably 2 or less, particularly preferably 1.5 or less, and preferably 1.0 or more.
The weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the block copolymer [1] are as polystyrene-converted values by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent. It can be measured.

As a method for producing the block copolymer [1], for example, the methods described in International Publication No. 2015/0909079 and JP-A-2016-204217 can be adopted.

Hydride [2] is a polymer obtained by hydrogenating the unsaturated bond of block copolymer [1]. Here, the unsaturated bond of the block copolymer [1] to be hydrogenated includes aromatic and non-aromatic carbon-carbon unsaturated of the main chain and side chain of the block copolymer [1]. Both include bonds.

The hydrogenation rate of the hydride [2] is preferably 90% or more, more preferably 97% or more, and particularly preferably 99% or more. In the hydride [2], it is preferable that the aromatic vinyl monomer unit has a hydrogenation rate of 90% or more, and the conjugated diene monomer unit has a hydrogenation rate of 90% or more. Unless otherwise specified, the hydrogenation rate of the hydride [2] is the same as that of the aromatic and non-aromatic carbon-carbon unsaturated bonds in the main chain and side chains of the block copolymer [1]. It is the rate of hydrogenated bonds. The higher the hydrogenation rate, the better the transparency, heat resistance, and weather resistance of the thermoplastic resin layer, and the more easily the birefringence of the thermoplastic resin layer can be reduced. Here, the hydrogenation rate of the hydride [2] can be determined by measurement by ¹ H-NMR. The upper limit of the hydrogenation rate may be 100%.

Particularly, the hydrogenation rate of the non-aromatic carbon-carbon unsaturated bond is preferably 95% or more, more preferably 99% or more. By increasing the hydrogenation rate of the non-aromatic carbon-carbon unsaturated bond, the light resistance and oxidation resistance of the thermoplastic resin layer can be further increased.

The hydrogenation rate of the aromatic carbon-carbon unsaturated bond is preferably 90% or more, more preferably 93% or more, and particularly preferably 95% or more. By increasing the hydrogenation rate of the aromatic carbon-carbon unsaturated bond, the glass transition temperature of the polymer block obtained by hydrogenating the polymer block [A] becomes high, so that the heat resistance of the thermoplastic resin layer is improved. Can be effectively increased. Furthermore, the photoelastic coefficient of the thermoplastic resin can be lowered.

The weight average molecular weight (Mw) of the hydride [2] is preferably 30,000 or more, more preferably 40,000 or more, still more preferably 45,000 or more, preferably 200,000 or less, more preferably It is 150,000 or less, and more preferably 100,000 or less. When the weight average molecular weight (Mw) of the hydride [2] is within the above range, the mechanical strength and heat resistance of the thermoplastic resin layer can be improved, and further the birefringence of the thermoplastic resin layer can be reduced. easy.

The molecular weight distribution (Mw/Mn) of the hydride [2] is preferably 3 or less, more preferably 2 or less, particularly preferably 1.8 or less, and preferably 1.0 or more. When the molecular weight distribution (Mw/Mn) of the hydride [2] is within the above range, the mechanical strength and heat resistance of the thermoplastic resin layer can be improved, and the birefringence of the thermoplastic resin layer can be reduced. Easy to do.

The weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the hydride [2] can be measured in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.

The above-mentioned hydride [2] can be produced by hydrogenating the block copolymer [1]. As a hydrogenation method, a hydrogenation method that can increase the hydrogenation rate and that causes less chain cleavage reaction of the block copolymer [1] is preferable. Examples of such a hydrogenation method include the methods described in International Publication No. 2015/0999079 and JP-A-2016-204217.

The hydride [2] is preferably one having a silyl group introduced. Among the hydrides [2], those into which a silyl group is introduced may be appropriately referred to as "silyl group-modified product [3]" hereinafter. Due to the introduction of the silyl group, the silyl group-modified product [3] exhibits high adhesion to other materials. Therefore, since the thermoplastic resin layer formed of the thermoplastic resin containing the silyl group-modified product [3] has excellent adhesion to the conductive layer, the mechanical strength of the laminate as a whole can be improved.

The silyl modified product (silyl group modified product [3]) of the block copolymer is a polymer obtained by introducing a silyl group into the hydride (hydride [2]) of the block copolymer described above. Examples of the silyl group introduced into the block copolymer include an alkoxysilyl group. The silyl group introduced into the block copolymer may be directly bonded to the above-mentioned hydride [2], or may be indirectly bonded through a divalent organic group such as an alkylene group. ..

The amount of the silyl group introduced in the modified silyl group [3] is preferably 0.1 part by weight or more, more preferably 0.2 part by weight, based on 100 parts by weight of the hydride [2] before the introduction of the silyl group. The amount is particularly preferably 0.3 part by weight or more, preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and particularly preferably 3 parts by weight or less. When the introduced amount of the silyl group is within the above range, it is possible to prevent the degree of crosslinking between the silyl groups decomposed by water or the like from becoming excessively high, so that the adhesiveness of the thermoplastic resin layer can be maintained high.
The amount of silyl group introduced can be measured by ¹ H-NMR spectrum. Further, when measuring the introduction amount of the silyl group, if the introduction amount is small, it is possible to increase the number of times of integration and perform the measurement.

The weight average molecular weight (Mw) of the silyl group-modified product [3] is usually smaller than the weight average molecular weight (Mw) of the hydride [2] before the silyl group is introduced, because the amount of the introduced silyl group is small. Does not change significantly. However, when the silyl group is introduced, the hydride [2] is usually subjected to a modification reaction in the presence of a peroxide, so that the crosslinking reaction and the cleavage reaction of the hydride [2] proceed and the molecular weight distribution is It tends to change greatly. The weight average molecular weight (Mw) of the silyl group-modified product [3] is preferably 30,000 or more, more preferably 40,000 or more, still more preferably 45,000 or more, and preferably 200,000 or less, It is preferably 150,000 or less, and more preferably 100,000 or less. The molecular weight distribution (Mw/Mn) of the modified silyl group [3] is preferably 3.5 or less, more preferably 2.5 or less, particularly preferably 2.0 or less, and preferably 1.0 or more. Is. When the weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) of the silyl group-modified product [3] are in this range, good mechanical strength and tensile elongation of the thermoplastic resin layer can be maintained.
The weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the silyl group-modified product [3] can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.

The modified silyl group [3] can be produced by introducing an alkoxysilyl group into the hydride [2] of the block copolymer [1] described above. Examples of the method of introducing an alkoxysilyl group into the hydride [2] include the methods described in International Publication No. 2015/099079 and JP-A-2016-204217.

The proportion of the polymer X such as hydride [2] (including silyl group modified product [3]) in the thermoplastic resin is preferably 80% by weight to 100% by weight, more preferably 90% by weight to 100% by weight. , Particularly preferably 95 to 100% by weight. When the ratio of the polymer in the resin B is within the above range, the storage elastic modulus of the resin B is easily within the above range.

The thermoplastic resin layer may contain an arbitrary component in combination with the polymer X described above. Examples of optional components include inorganic fine particles; stabilizers such as antioxidants, heat stabilizers, ultraviolet absorbers and near infrared absorbers; resin modifiers such as lubricants and plasticizers; coloring agents such as dyes and pigments. And antistatic agents. As these optional components, one type may be used alone, or two or more types may be used in combination at any ratio. From the viewpoint of remarkably exerting the effect of the present invention, it is preferable that the content ratio of any component is small.

The thermoplastic resin layer usually has high transparency. The specific total light transmittance of the thermoplastic resin layer is preferably 80% or more, more preferably 85% or more, still more preferably 90% or more. The total light transmittance can be measured in the wavelength range of 400 nm to 700 nm using an ultraviolet/visible spectrometer. The upper limit of the total light transmittance is preferably 100%, but may be a value less than 100%.

The thickness of the thermoplastic resin layer is preferably 10 μm or more, more preferably 20 μm or more, particularly preferably 30 μm or more, preferably 100 μm or less, more preferably 80 μm or less, particularly preferably 60 μm or less. When the thickness of the thermoplastic resin layer is equal to or more than the lower limit value of the above range, the thermoplastic resin layer can prevent water from entering the conductive layer and effectively prevent migration. On the other hand, when the thickness of the thermoplastic resin layer is not more than the upper limit value of the above range, flexibility can be effectively enhanced.

There is no limitation on the manufacturing method of the thermoplastic resin layer. Examples of the method for producing the thermoplastic resin layer include a melt molding method and a solution casting method. Among them, the melt molding method is preferable because it is possible to suppress the volatile components such as the solvent from remaining in the thermoplastic resin layer. Furthermore, in order to obtain a thermoplastic resin layer having excellent mechanical strength and surface accuracy, among the melt molding methods, the extrusion molding method, the inflation molding method and the press molding method are preferable, and the thermoplastic resin layer can be produced efficiently and easily. The extrusion molding method is particularly preferable from the viewpoint that it can be formed.

[3. Conductive layer]
In the present invention, the conductive layer contains at least one element selected from Sn (tin), Pb (lead), Ag (silver), Cu (copper), and Au (gold). The element is a material that can cause migration, but in the present invention, the occurrence of migration can be prevented by providing a thermoplastic resin layer having a predetermined moisture permeability and a predetermined storage elastic modulus.

Among the above elements, Ag, Cu and Au are preferable, and Ag is more preferable. These metals may be used alone or in combination of two or more at an arbitrary ratio. When the conductive layer is formed of these metals, a transparent conductive layer can be obtained by forming the conductive layer into a thin linear shape. For example, a transparent conductive layer can be obtained by forming the conductive layer as a metal mesh layer formed in a grid pattern.

The conductive layer is formed of a material containing the above element (hereinafter also referred to as “conductive material”). Examples of such a conductive material include a metal material. Unlike the so-called metal oxide, the metal material here is a material formed by metal bonding of metal atoms. Examples of such a metal material include metal particles and metal nanowires. As the conductive material, one type may be used alone, or two or more types may be used in combination at an arbitrary ratio.

The conductive layer can be formed by, for example, a forming method including applying a conductive layer forming composition containing metal particles. At this time, by printing the conductive layer forming composition in a predetermined lattice pattern, a conductive layer as a metal mesh layer can be obtained. Furthermore, for example, by applying a composition for forming a conductive layer containing metal particles such as silver salt and silver nanoparticles, and forming a thin metal wire into a predetermined lattice pattern by an exposure treatment and a development treatment, the conductive layer is formed into a metal mesh. It can be formed as a layer. For details of such a conductive layer and a method for forming the conductive layer, reference can be made to JP-A-2012-18634 and JP-A-2003-331654.

ㆍMetallic nanowire refers to a conductive substance with a needle-like or thread-like shape and a diameter of nanometer. The metal nanowire may be linear or curved. Such metal nanowires can form a good electrical conduction path even with a small amount of metal nanowires by forming a gap between the metal nanowires and forming a mesh-like shape, and thus a conductive material with low electrical resistance can be formed. Layers can be realized. Further, since the metal wire has a mesh shape, an opening is formed in a gap between meshes, so that a conductive layer having high light transmittance can be obtained.

The ratio of the thickness d to the length L of metal nanowires (aspect ratio: L/d) is preferably 10 to 100,000, more preferably 50 to 100,000, and particularly preferably 100 to 10 1,000. By using the metal nanowires having a large aspect ratio as described above, the metal nanowires can be crossed well and high conductivity can be exhibited by a small amount of the metal nanowires. As a result, a laminate having excellent transparency can be obtained. Here, the "thickness of the metal nanowire" means the diameter when the cross section of the metal nanowire is circular, the short diameter when the cross section is elliptical, and the most when it is polygonal. Means a long diagonal. The thickness and length of the metal nanowire can be measured by a scanning electron microscope or a transmission electron microscope.

The thickness of the metal nanowire is preferably less than 500 nm, more preferably less than 200 nm, still more preferably 10 nm to 100 nm, and particularly preferably 10 nm to 50 nm. Thereby, the transparency of the conductive layer can be increased.

The length of the metal nanowire is preferably 2.5 μm to 1000 μm, more preferably 10 μm to 500 μm, and particularly preferably 20 μm to 100 μm. Thereby, the conductivity of the conductive layer can be increased.

The metal contained in the metal nanowire is preferably a metal having high conductivity. Examples of suitable metals include gold, silver and copper, more preferably silver. Alternatively, a material obtained by plating the above metal (for example, gold plating) may be used. Furthermore, one kind of the above materials may be used alone, or two or more kinds thereof may be used in combination at an arbitrary ratio.

Any appropriate method can be adopted as the method for producing the metal nanowire. For example, a method of reducing silver nitrate in a solution; a method of applying an applied voltage or current to the precursor surface from the tip of the probe, extracting the metal nanowire at the tip of the probe, and continuously forming the metal nanowire; Can be mentioned. In the method of reducing silver nitrate in a solution, a silver nanowire can be synthesized by liquid-phase reduction of a silver salt such as silver nitrate in the presence of a polyol such as ethylene glycol and polyvinylpyrrolidone. Uniformly sized silver nanowires are described, for example, in Xia, Y. et al. , Chem. Mater. (2002), 14, 4736-4745, Xia, Y. et al. Mass production is possible according to the method described in Nano letters (2003) 3(7), 955-960.

The conductive layer containing metal nanowires can be formed by, for example, a forming method including applying and drying a metal nanowire dispersion liquid obtained by dispersing metal nanowires in a solvent.

As the solvent contained in the metal nanowire dispersion liquid, for example, water, alcohol solvents, ketone solvents, ether solvents, hydrocarbon solvents, aromatic solvents, and the like, among them, from the viewpoint of environmental load reduction, It is preferable to use water. Further, the solvent may be used alone or in combination of two or more kinds at an arbitrary ratio.

The concentration of the metal nanowires in the metal nanowire dispersion liquid is preferably 0.1% by weight to 1% by weight. This makes it possible to form a conductive layer having excellent conductivity and transparency.

The metal nanowire dispersion liquid may contain an optional component in combination with the metal nanowire and the solvent. Examples of the optional component include a corrosion inhibitor that suppresses corrosion of the metal nanowires, a surfactant that suppresses aggregation of the conductive nanowires, and a binder polymer for holding the conductive nanowires in the conductive layer. In addition, one type of optional component may be used alone, or two or more types may be used in combination at an arbitrary ratio.

Examples of the coating method of the metal nanowire dispersion liquid include a spray coating method, a bar coating method, a roll coating method, a die coating method, an inkjet coating method, a screen coating method, a dip coating method, a slot die coating method, a relief printing method, an intaglio printing method. , A gravure printing method and the like. Any appropriate drying method (for example, natural drying, blast drying, heat drying) can be adopted as the drying method. For example, in the case of heat drying, the drying temperature may be 100°C to 200°C and the drying time may be 1 minute to 10 minutes.

The proportion of metal nanowires in the conductive layer is preferably 80% by weight to 100% by weight, more preferably 85% by weight to 99% by weight, based on the total weight of the conductive layer. This makes it possible to obtain a conductive layer having excellent conductivity and light transmittance.

The conductive layer may include any conductive material other than the above in addition to the above conductive material. Examples of the optional conductive material include carbon nanotubes and conductive polymers.

As the carbon nanotubes, for example, so-called multi-walled carbon nanotubes, double-walled carbon nanotubes, single-walled carbon nanotubes having a diameter of 0.3 nm to 100 nm and a length of 0.1 μm to 20 μm are used. Among them, single-walled or double-walled carbon nanotubes having a diameter of 10 nm or less and a length of 1 μm to 10 μm are preferable from the viewpoint of high conductivity. Further, it is preferable that the aggregate of carbon nanotubes does not contain impurities such as amorphous carbon and catalytic metal. Any appropriate method can be adopted as a method for producing carbon nanotubes. Carbon nanotubes produced by the arc discharge method are preferably used. Carbon nanotubes produced by the arc discharge method are preferable because they have excellent crystallinity.

As the conductive polymer, for example, polythiophene-based polymer, polyacetylene-based polymer, polyparaphenylene-based polymer, polyaniline-based polymer, polyparaphenylenevinylene-based polymer, polypyrrole-based polymer, polyphenylene-based polymer, polyester-based modified with acrylic polymer Examples thereof include polymers. Among them, polythiophene-based polymers, polyacetylene-based polymers, polyparaphenylene-based polymers, polyaniline-based polymers, polyparaphenylenevinylene-based polymers and polypyrrole-based polymers are preferable.

Among them, polythiophene-based polymers are particularly preferable. By using a polythiophene-based polymer, a conductive layer having excellent transparency and chemical stability can be obtained. Specific examples of the polythiophene-based polymer include polythiophene; poly(3-C _1-8 alkyl-thiophene) such as poly(3-hexylthiophene); poly(3,4-ethylenedioxythiophene), poly(3,4 -Propylenedioxythiophene), poly[3,4-(1,2-cyclohexylene)dioxythiophene] and other poly(3,4-(cyclo)alkylenedioxythiophenes); polythienylenevinylene, etc. .. Here, “C _1-8 alkyl” refers to an alkyl group having 1 to 8 carbon atoms. Moreover, the said electroconductive polymer may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.

The conductive polymer is preferably polymerized in the presence of an anionic polymer. For example, the polythiophene-based polymer is preferably oxidatively polymerized in the presence of an anionic polymer. Examples of the anionic polymer include a polymer having a carboxyl group, a sulfonic acid group, or a salt thereof. Preferably, an anionic polymer having a sulfonic acid group such as polystyrene sulfonic acid is used.

Since the conductive layer is formed of the conductive material as described above, it has conductivity. The conductivity of the conductive layer can be represented by, for example, a surface resistance value. The specific surface resistance value of the conductive layer can be set according to the application of the laminate. In one embodiment, the surface resistance value of the conductive layer is preferably 1000 Ω/sq. Or less, more preferably 900 Ω/sq. The following is particularly preferable 800 Ω/sq. It is below. Although the lower limit of the surface resistance value of the conductive layer is not particularly limited, it is preferably 1 Ω/sq. Or more, more preferably 2.5Ω/sq. Above, especially preferably 5Ω/sq. That is all.

The conductive layer may be formed entirely or partially between the thermoplastic resin layer and the base material. For example, the conductive layer may be patterned and formed into a pattern having a predetermined planar shape. Here, the planar shape means a shape when viewed from the thickness direction of the layer. The planar shape of the pattern of the conductive layer can be set according to the application of the laminate. For example, when the laminate is used as a circuit board, the planar shape of the conductive layer may be formed in a pattern corresponding to the wiring shape of the circuit. Further, for example, when the laminated body is used as a sensor film for a touch panel, the planar shape of the conductive layer is preferably a pattern that works well as a touch panel (for example, a capacitive touch panel). The patterns described in JP-A-2011-511357, JP-A-2010-164938, JP-A-2008-310550, JP-A-2003-511799 and JP-A-2010-541109 can be mentioned.

The conductive layer usually has high transparency. Therefore, visible light can usually pass through this conductive layer. The specific transparency of the conductive layer can be adjusted according to the application of the laminate. The specific total light transmittance of the conductive layer is preferably 80% or more, more preferably 90% or more, still more preferably 95% or more.

The thickness of each conductive layer is preferably 0.01 μm to 10 μm, more preferably 0.05 μm to 3 μm, and particularly preferably 0.1 μm to 1 μm.

[4. Base material]
As the substrate, a polymer film containing a polymer (hereinafter, also referred to as “polymer Y”) can be used. As the polymer film, it is possible to use a film formed of a resin containing the polymer Y and further containing any component as required. As the polymer Y, one type may be used alone, or two or more types may be used in combination at an arbitrary ratio.

The polymer Y is preferably a polymer containing an alicyclic structure. Hereinafter, a polymer containing an alicyclic structure may be appropriately referred to as a “polymer containing an alicyclic structure”.

The alicyclic structure-containing polymer has excellent mechanical strength. Further, the alicyclic structure-containing polymer is usually excellent in transparency, low water absorption, moisture resistance, dimensional stability and light weight.

Alicyclic structure-containing polymer is a polymer containing an alicyclic structure in the repeating unit, for example, a polymer or a hydride thereof obtained by a polymerization reaction using a cyclic olefin as a monomer. Can be mentioned. As the alicyclic structure-containing polymer, both a polymer having an alicyclic structure in its main chain and a polymer having an alicyclic structure in its side chain can be used. Among them, the alicyclic structure-containing polymer preferably has an alicyclic structure in the main chain. Examples of the alicyclic structure include a cycloalkane structure and a cycloalkene structure, and the cycloalkane structure is preferable from the viewpoint of thermal stability and the like.

The number of carbon atoms contained in one alicyclic structure is preferably 4 or more, more preferably 5 or more, more preferably 6 or more, preferably 30 or less, more preferably 20 or less, Particularly preferably, it is 15 or less. When the number of carbon atoms contained in one alicyclic structure is within the above range, mechanical strength, heat resistance, and moldability are highly balanced.

The proportion of repeating units having an alicyclic structure in the alicyclic structure-containing polymer is preferably 30% by weight or more, more preferably 50% by weight or more, further preferably 70% by weight or more, particularly preferably 90% by weight. That is all. By increasing the proportion of repeating units having an alicyclic structure as described above, heat resistance can be improved.
Further, in the alicyclic structure-containing polymer, the balance other than the repeating unit having an alicyclic structure is not particularly limited and may be appropriately selected according to the purpose of use.

As the alicyclic structure-containing polymer, either a polymer having crystallinity or a polymer having no crystallinity may be used, or both may be used in combination. Here, the crystalline polymer means a polymer having a melting point Mp. Further, the polymer having the melting point Mp means a polymer whose melting point Mp can be observed by a differential scanning calorimeter (DSC). Since the alicyclic structure-containing polymer having crystallinity is solvent resistant, by using it as a material of the base material, a thermoplastic resin layer can be formed by applying a thermoplastic resin dissolved in a solvent. it can. Further, by using a crystalline alicyclic structure-containing polymer as the material of the base material, the mechanical strength of the laminate can be effectively increased. When an alicyclic structure-containing polymer having no crystallinity is used as the material of the base material, the production cost of the laminate can be reduced.

Examples of the alicyclic structure-containing polymer having crystallinity include the following polymers (α) to (δ). Among these, the polymer (β) is preferable as the crystalline alicyclic structure-containing polymer because a laminated body having excellent heat resistance can be easily obtained.
Polymer (α): A ring-opening polymer of a cyclic olefin monomer, which has crystallinity.
Polymer (β): A hydride of the polymer (α) having crystallinity.
Polymer (γ): Addition polymer of cyclic olefin monomer, which has crystallinity.
Polymer (δ): A hydride or the like of the polymer (γ) having crystallinity.

Specifically, the alicyclic structure-containing polymer having crystallinity is a ring-opening polymer of dicyclopentadiene having crystallinity, and a hydride of the ring-opening polymer of dicyclopentadiene. Of these, those having crystallinity are more preferable, and hydrides of ring-opening polymers of dicyclopentadiene which have crystallinity are particularly preferable. Here, the ring-opening polymer of dicyclopentadiene, the ratio of structural units derived from dicyclopentadiene to all structural units is usually 50 wt% or more, preferably 70 wt% or more, more preferably 90 wt% or more, More preferably, it means 100% by weight of the polymer.

The alicyclic structure-containing polymer having crystallinity may not be crystallized before producing the laminated body. However, after the laminated body is produced, the crystalline alicyclic structure-containing polymer contained in the laminated body can usually have high crystallinity because it is crystallized. The specific range of the crystallinity can be appropriately selected according to the desired performance, but it is preferably 10% or more, more preferably 15% or more. By setting the crystallinity of the alicyclic structure-containing polymer contained in the laminate to be at least the lower limit value of the above range, it is possible to impart high heat resistance and chemical resistance to the laminate. The crystallinity can be measured by an X-ray diffraction method.

The melting point Mp of the crystalline alicyclic structure-containing polymer is preferably 200° C. or higher, more preferably 230° C. or higher, and preferably 290° C. or lower. By using a crystalline alicyclic structure-containing polymer having such a melting point Mp, it is possible to obtain a laminate having a better balance between moldability and heat resistance.

The alicyclic structure-containing polymer having crystallinity as described above can be produced, for example, by the method described in International Publication No. 2016/067893.

On the other hand, the alicyclic structure-containing polymer having no crystallinity is, for example, (1) norbornene-based polymer, (2) monocyclic cycloolefin polymer, (3) cyclic conjugated diene polymer, (4) Examples thereof include vinyl alicyclic hydrocarbon polymers and their hydrides. Among these, the norbornene-based polymer and its hydride are more preferable from the viewpoint of transparency and moldability.

Examples of the norbornene-based polymer include ring-opening polymers of norbornene-based monomers, ring-opening copolymers of norbornene-based monomers with other monomers capable of ring-opening copolymerization, and hydrides thereof; Examples thereof include addition polymers and addition copolymers with other monomers that are copolymerizable with norbornene-based monomers. Among these, hydrides of ring-opening polymers of norbornene-based monomers are particularly preferable from the viewpoint of transparency.
The alicyclic structure-containing polymer is selected, for example, from the polymers disclosed in JP-A-2002-321302.

As various resins are commercially available as a resin containing an alicyclic structure-containing polymer having no crystallinity, it is possible to appropriately select and use a resin having desired properties among them. Examples of such commercially available products include trade names "ZEONOR" (manufactured by Zeon Corporation), "Arton" (manufactured by JSR Corporation), "Apel" (manufactured by Mitsui Chemicals, Inc.), "TOPAS" (Polyplastics Co., Ltd.). Products).

The weight average molecular weight (Mw) of the polymer Y contained in the base material is preferably 10,000 or more, more preferably 15,000 or more, particularly preferably 20,000 or more, and preferably 100,000 or less. It is preferably 80,000 or less, particularly preferably 50,000 or less. The polymer Y having such a weight average molecular weight has an excellent balance of mechanical strength, moldability and heat resistance.

The molecular weight distribution (Mw/Mn) of the polymer Y contained in the base material is preferably 1.2 or more, more preferably 1.5 or more, particularly preferably 1.8 or more, preferably 3.5 or less, It is more preferably 3.4 or less, and particularly preferably 3.3 or less. When the molecular weight distribution is at least the lower limit value of the above range, the productivity of the polymer Y can be increased and the production cost can be suppressed. Further, when it is at most the upper limit value, the amount of the low-molecular component becomes small, so that the relaxation upon exposure to high temperature can be suppressed and the stability of the laminate can be enhanced.

The weight average molecular weight Mw and the number average molecular weight Mn of the polymer Y are determined by gel permeation chromatography (hereinafter, abbreviated as “GPC”) using cyclohexane (toluene when the resin does not dissolve) as a solvent. The value can be measured in terms of polyisoprene (in terms of polystyrene when the solvent is toluene).

The proportion of the polymer Y in the substrate is preferably 80% by weight to 100% by weight, more preferably 90% by weight to 100% by weight, from the viewpoint of obtaining a laminate having particularly excellent heat resistance and bending bending resistance. It is preferably 95% to 100% by weight, particularly preferably 98% to 100% by weight.

The base material may contain an optional component in combination with the above-mentioned polymer Y. Examples of the optional component include the same examples as those exemplified as the optional component that may be contained in the thermoplastic resin layer. As the optional component, one type may be used alone, or two or more types may be used in combination at any ratio.

The glass transition temperature Tg of the resin containing the polymer Y (also referred to as “resin Y”) is preferably 130° C. or higher. Since the resin Y has the high glass transition temperature Tg as described above, the heat resistance of the resin Y can be enhanced, so that the dimensional change of the base material in a high temperature environment can be suppressed. Since the base material has excellent heat resistance as described above, the conductive layer can be appropriately formed. In particular, the substrate having excellent heat resistance is useful when it is desired to form a conductive layer having a fine pattern shape. The upper limit of the glass transition temperature of the resin Y is preferably 200° C. or lower, more preferably 190° C. or lower, and particularly preferably 180° C. or lower from the viewpoint of easy availability of the resin Y. The glass transition temperature can be measured by the method described in Examples below.

The base material usually has high transparency. The specific total light transmittance of the substrate is preferably 80% or more, more preferably 85% or more, still more preferably 90% or more. In the present invention, the total light transmittance of at least one of the thermoplastic resin layer and the base material layer is preferably 80% or more, and more preferably the total light transmittance of both is 80% or more. When the total light transmittance of at least one layer is 80% or more, the laminate has high transparency, which is suitable for use in a display device or the like.

The water vapor permeability of the base material is preferably 3 g/m ² ·24 h or less, more preferably 2 g/m ² ·24 h or less. The lower limit of the water vapor transmission rate of the base material is not particularly limited, but is preferably 0 g/m ² ·24 h or more. By setting the water vapor permeability of the base material to be not more than the upper limit value, the degree of adhesion between the base material and the conductive layer can be increased, and the migration prevention effect can be improved. The moisture permeability of the base material can be measured by the Lissie method (measuring instrument L80-5000 type (manufactured by Systec Illinois Co., Ltd., temperature condition 40°C, humidity 90%).

The storage elastic modulus at 25° C. of the base material is preferably 2000 MPa or more, more preferably 2500 MPa or more, and preferably 3000 MPa or less. By setting the storage elastic modulus of the base material to the upper limit or less, the flexibility of the laminate can be made excellent. The storage elastic modulus of the base material can be measured using a dynamic viscoelasticity measuring device under the condition of a frequency of 1 Hz.

The thickness of the base material is preferably 1 μm or more, more preferably 10 μm or more, particularly preferably 15 μm or more, preferably 100 μm or less, more preferably 80 μm or less, particularly preferably 60 μm or less. When the thickness of the base material is equal to or more than the lower limit value of the above range, it is possible to suppress infiltration of water into the conductive layer by the base material. Therefore, the occurrence of migration can be effectively suppressed. On the other hand, when the thickness of the base material is not more than the upper limit value of the above range, the flexibility of the laminate can be effectively enhanced.

The retardation Re in the in-plane direction of the base material can be arbitrarily set according to the application of the laminate. In particular, when used as a circularly polarizing plate in combination with a linearly polarizing plate, it is desirable to have a retardation Re in the in-plane direction that can function as a quarter-wave plate. In that case, the retardation Re in the in-plane direction is preferably 100 nm or more, more preferably 110 nm or more, preferably 180 nm or less, more preferably 170 nm or less. For other uses, it is not particularly limited, but is preferably 10 nm or less, more preferably 5 nm or less.

There is no limit to the method of manufacturing the base material. Examples of the method for producing the base material include a melt molding method and a solution casting method. Among them, the melt molding method is preferable because it is possible to suppress the volatile components such as the solvent from remaining on the substrate. More specifically, the melt molding method can be classified into an extrusion molding method, a press molding method, an inflation molding method, an injection molding method, a blow molding method, a stretch molding method and the like. Among these methods, an extrusion molding method, an inflation molding method and a press molding method are preferable in order to obtain a base material excellent in mechanical strength and surface accuracy, and an extrusion molding method is preferable from the viewpoint of easily and efficiently manufacturing the base material. Is particularly preferable.

The shape of the substrate is not particularly limited, but a long film is preferable. Further, the substrate is preferably a long film having a slow axis in a direction oblique to the width direction. The oblique direction is an in-plane direction of the film and is a direction that is not parallel to both the longitudinal direction of the film and the width direction of the film. The film having the slow axis in the oblique direction can be obtained by stretching a long film in the oblique direction with respect to the width direction. In the obliquely stretched film, the direction of the optical axis is a direction inclined with respect to the width direction of the film. Therefore, when a film having a slow axis in the oblique direction (obliquely stretched film) is used as the substrate, the laminate of the present invention is obtained. The body is preferable because it can be easily manufactured roll-to-roll.

The diagonal stretching method and the stretching machine used for the diagonal stretching are not particularly limited, and a conventionally known tenter type stretching machine can be used. Further, the tenter type stretching machine includes a horizontal uniaxial stretching machine, a simultaneous biaxial stretching machine, etc., but is not particularly limited as long as it can continuously stretch a long film obliquely, and various types of stretching Machine can be used.

[5. Any layer]
The laminate may include any layer in addition to the thermoplastic resin layer, the conductive layer and the base material. For example, the laminated body may be provided with an arbitrary layer at a position such as a side of the thermoplastic resin layer opposite to the conductive layer or a side of the base material opposite to the conductive layer. Examples of the optional layer include a support layer, a hard coat layer, an index matching layer, an adhesive layer, a retardation layer, a polarizer layer, and an optical compensation layer.

In the laminated body, it is preferable that the base material and the conductive layer are in direct contact with each other. Further, it is preferable that the conductive layer and the thermoplastic resin layer are in direct contact with each other. Here, the term "directly" in which two layers are in contact with each other means that there is no other layer between the two layers. Furthermore, it is particularly preferable that the laminate is a film having a three-layer structure including only a base material, a conductive layer and a thermoplastic resin layer.

[6. Physical properties and thickness of laminate]
The total light transmittance of the laminate is preferably 70% or more, more preferably 80% or more, still more preferably 90% or more. When the total light transmittance of the laminate is at least the lower limit value, it is suitable for use as an optical member.
Further, the haze of the laminate is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less from the viewpoint of enhancing the image clarity of the image display device incorporating the laminate, and ideally Is 0%.

The thickness of the laminate is preferably 2 μm or more, more preferably 5 μm or more, even more preferably 7.5 μm or more, particularly preferably 10 μm or more, preferably 200 μm or less, more preferably 175 μm or less, particularly preferably 150 μm or less. is there. When the thickness of the laminate is not less than the lower limit of the above range, the mechanical strength of the laminate can be increased and wrinkles can be prevented when forming the conductive layer. Further, when the thickness of the laminated body is not more than the upper limit value of the above range, the flexibility of the laminated body can be improved, and the laminated body can be thinned.

[7. Actions and effects of the present invention]
In the present invention, the thermoplastic resin layer has a moisture permeability of 5 g/m ² ·24 h or less and a storage elastic modulus at 25°C of 1300 MPa or less. That is, in the present invention, since the thermoplastic resin layer has a moisture permeability in an appropriate range, it is possible to enhance the adhesiveness with the conductive layer and thereby enhance the migration prevention effect. Further, in the present invention, since the thermoplastic resin film has a storage elastic modulus in an appropriate range, it is possible to make the laminate excellent in flexibility. As a result, according to the present invention, it is possible to provide a laminate having excellent flexibility and an excellent effect of preventing migration.

Further, in the present invention, since the laminate has a flexible base material and a thermoplastic resin layer as a layer for supporting the conductive layer, the laminate usually has impact resistance and processing property higher than that of the conductive glass. Excellent in performance. Furthermore, the laminate is usually lighter than the conductive glass.

[8. Manufacturing method of laminated body]
The method for producing the laminate is not limited, but the above-mentioned laminate includes, for example, Step 1 of forming a conductive layer on a base material and Step 2 of forming a thermoplastic resin layer on the conductive layer. It can be manufactured by a method. According to such a manufacturing method, since the thermoplastic resin layer can be easily formed, the manufacturing method can be simplified.

(Process 1)
Step 1 is a step of forming a conductive layer on the base material.
The base material used in the step 1 can be formed from the resin Y by the above-described base material manufacturing method, for example. When an obliquely stretched film is used as the base material, the stretching step is performed before performing step 1.

In step 1, for example, the conductive layer is formed on the base material by the above-described conductive layer forming method. The conductive layer may be indirectly formed on the base material via any layer. However, the conductive layer is preferably formed directly on the substrate.

(Process 2)
Step 2 is a step of forming a thermoplastic resin layer on the conductive layer.
In step 2, a thermoplastic resin layer is formed on the conductive layer formed on the base material. The thermoplastic resin layer may be indirectly formed on the conductive layer via any layer. For example, the thermoplastic resin layer manufactured by the above-described method for manufacturing a thermoplastic resin layer may be formed by adhering it to the conductive layer via a pressure-sensitive adhesive or an adhesive. However, it is preferable that the thermoplastic resin layer is formed directly on the conductive layer.

Step 2 preferably includes thermocompression-bonding the thermoplastic resin layer or applying a solution containing the thermoplastic resin. According to this method, the manufacturing method can be simplified.

The method of thermocompression-bonding the thermoplastic resin layer is a method of pressure-bonding the thermoplastic resin layer produced by the above-mentioned method for producing a thermoplastic resin layer to the surface of the conductive layer while heating as necessary.
The method of applying a solution containing a thermoplastic resin is a method of forming a thermoplastic resin layer directly on the conductive layer by applying a solution containing a thermoplastic resin on the conductive layer and drying it if necessary. is there. When the material of the base material is solvent resistant, the thermoplastic resin layer can be easily formed by adopting this method. The solution containing the thermoplastic resin can be obtained by dissolving or dispersing the thermoplastic resin in a solvent.

The method for manufacturing a laminated body may further include an optional step in combination with the above-mentioned steps.

[9. Applications of laminate]
Since the laminate of the present invention has excellent flexibility and an excellent effect of preventing migration, it can be suitably used for optical applications such as circularly polarizing plates and touch panels, and applications such as circuit boards. ..

[10. Circular polarizer]
A circularly polarizing plate of the present invention includes the above-mentioned laminated body of the present invention and a polarizing plate. The circularly polarizing plate can be obtained, for example, by laminating the polarizing plate in a laminate so that the angle θ1 formed by the slow axis of the base material and the absorption axis of the polarizing plate is 45°. The angle θ1 formed by the slow axis of the substrate and the absorption axis of the polarizing plate may include an error within a range of ±5°, ±3°, ±2° or ±1°. With such a configuration, when a circularly polarizing plate is used in a display device, for example, it is possible to prevent the display contents from being difficult to be visually recognized due to reflected light of incident external light. When the polarizing plate is a long film having an absorption axis in the lengthwise direction or the width direction, it is easy to set the direction of the slow axis of the substrate and the direction of the absorption axis of the polarizing plate at an appropriate angle, and the circularly polarized light It is preferable because the plate can be easily manufactured.

When a long polarizing film is used as the polarizing plate, the polarizing film may be produced, for example, by adsorbing iodine or a dichroic dye on a polyvinyl alcohol film and then uniaxially stretching it in a boric acid bath. .. Alternatively, for example, it may be produced by adsorbing iodine or a dichroic dye on a polyvinyl alcohol film, stretching it, and further modifying a part of the polyvinyl alcohol unit in the molecular chain into a polyvinylene unit. Furthermore, for example, a polarizing film having a function of separating polarized light into reflected light and transmitted light, such as a grid polarizing plate or a multilayer polarizing plate, may be used. Among these, a polarizing film containing polyvinyl alcohol is preferable. The polarization degree of the polarizing film is preferably 98% or more, more preferably 99% or more.

When laminating the polarizing plate and the laminated body, an adhesive may be used. The adhesive is not particularly limited as long as it is optically transparent, and examples thereof include a water-based adhesive, a solvent-based adhesive, a two-component curable adhesive, an ultraviolet curable adhesive, and a pressure-sensitive adhesive. Among these, a water-based adhesive is preferable, and a polyvinyl alcohol-based water-based adhesive is particularly preferable. The adhesive may be used alone or in combination of two or more at an arbitrary ratio.

The average thickness of the layer formed by the adhesive (adhesive layer) is preferably 0.05 μm or more, more preferably 0.1 μm or more, preferably 5 μm or less, more preferably 1 μm or less.

There is no limitation on the method of laminating the laminated body on the polarizing plate, but a method of applying an adhesive on one surface of the polarizing plate and then bonding the polarizing plate and the laminated body using a roll laminator and drying is preferable. Prior to bonding, the surface of the laminate may be subjected to surface treatment such as corona discharge treatment and plasma treatment. The drying time and the drying temperature are appropriately selected according to the type of adhesive.

The obtained circularly polarizing plate can be cut into an appropriate size if necessary and used as an antireflection film of an organic electroluminescence display element (hereinafter, also referred to as an “organic EL display element” as appropriate).

[11. Display device]
The display device of the present invention includes the circularly polarizing plate of the present invention. As the display device of the present invention, an organic electroluminescence display device (hereinafter, also referred to as “organic EL display device” as appropriate) is preferable. In such an organic EL display device, the circularly polarizing plate of the present invention can be used as an antireflection film.

When the circularly polarizing plate of the present invention is used as an antireflection film, the circularly polarizing plate described above is provided on the surface of the organic EL display device so that the surface on the polarizing plate side faces the viewing side, so that the light is incident from the outside of the device. Light can be suppressed from being reflected inside the device and emitted to the outside of the device, and as a result, an undesired phenomenon such as glare on the display surface of the organic EL display device can be suppressed.

[12. Touch panel]
The touch panel of the present invention includes the laminate of the present invention.
In the touch panel, the arrangement direction of the laminate is not limited, but it is preferable that the laminate is provided so that the thermoplastic resin layer, the conductive layer, and the base material are sequentially discharged from the viewing side.

The touch panel of the present invention may include a laminate and a polarizing plate provided in contact with the thermoplastic resin layer of the laminate. In this case, it is preferable to provide the polarizing plate so that the angle θ2 formed by the absorption axis of the polarizing plate with respect to the slow axis of the base material of the laminate is 45°. With such a mode, it becomes possible to prevent the display contents from becoming difficult to be visually recognized due to the reflected light of the incident external light. The angle θ2 of the absorption axis of the polarizing plate with respect to the slow axis of the base material of the laminate may include an error within the range of ±5°, ±3°, ±2° or ±1°.

A touch panel usually has an image display element in combination with a laminated body. Examples of the image display element include a liquid crystal display element and an organic electroluminescence display element (hereinafter, also referred to as “organic EL display element” as appropriate). Usually, the laminate is provided on the viewing side of the image display device.

In order to obtain a flexible touch panel, it is preferable to employ a flexible image display element (flexible display element) as the image display element. Examples of such flexible image display elements include organic EL display elements.

An organic EL display device usually includes a first electrode layer, a light emitting layer and a second electrode layer on a substrate in this order, and the light emitting layer emits light when a voltage is applied from the first electrode layer and the second electrode layer. Can occur. Examples of the material forming the organic light emitting layer include polyparaphenylene vinylene-based materials, polyfluorene-based materials, and polyvinylcarbazole-based materials. Further, the light emitting layer may have a laminated body of a plurality of layers having different emission colors or a mixed layer in which a certain dye layer is doped with different dyes. Furthermore, the organic EL display element may include functional layers such as a barrier layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, an equipotential surface forming layer, and a charge generation layer.

The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the examples described below, and may be implemented by being arbitrarily modified within the scope of the claims and equivalents thereof.

In the following description, "%" and "parts" representing amounts are by weight unless otherwise specified. In addition, the operations described below were performed under the conditions of normal temperature and normal pressure unless otherwise specified.

[Evaluation method]
[Measurement method of molecular weight]
The weight average molecular weight and number average molecular weight of the polymer were measured at 38° C. as a standard polystyrene conversion value by gel permeation chromatography using tetrahydrofuran as an eluent. As a measuring device, HLC8320GPC manufactured by Tosoh Corporation was used.

[Method of measuring hydrogenation rate]
The hydrogenation rate of the polymer was measured by ¹ H-NMR measurement.

[Measuring method of glass transition temperature Tg]
Using a differential scanning calorimeter (DSC), the glass transition temperature Tg of the sample was determined by raising the temperature at 10°C/min.

[Measurement method of in-plane retardation Re]
Re of the base material and the thermoplastic resin layer used in Examples and Comparative Examples (hereinafter also referred to as “each example”) was measured at a wavelength of 590 nm by using a phase difference measuring device (product name “Axoscan” manufactured by Axometric). ..

[Measurement of total light transmittance]
The total light transmittances of the thermoplastic resin layer and the substrate were measured using an ultraviolet/visible spectrometer in the wavelength range of 400 nm to 700 nm.

[Method of measuring storage modulus]
The storage elastic moduli of the thermoplastic resin layer and the substrate used in each example were measured under the conditions of 25° C. and a frequency of 1 Hz using a dynamic viscoelastic device (“DMS6100” manufactured by SII). For the thermoplastic resin layer, the storage elastic modulus at −40° C. and 100° C. was measured in addition to the storage elastic modulus at 25° C. Using these measurement results, the ratio (E ₂ /E ₁ ) of the storage elastic modulus E ₂ at 100° C. to the storage elastic modulus E _{1 at} −40° C. was calculated.

[Measurement method of moisture permeability]
The moisture vapor transmission rates of the thermoplastic resin layer and the substrate used in each example were measured by the Lissi method (measuring instrument L80-5000 type (manufactured by Systec Illinois, Inc., temperature condition 40° C., humidity 90%).

[Adhesion evaluation test (cross-cut peel test)]
The thermoplastic resin layer side of the laminate produced in each example was scribed to form 100 1 mm×1 mm sections in a grid pattern. Cellophane tape (manufactured by Nichiban Co., Ltd., width: 24 mm) was adhered onto 100 compartments and peeled off within 1 second, and the number of compartments of the peeled base material was counted and evaluated according to the following evaluation criteria.
<Evaluation criteria>
A: The number of peels is 3 or less in a 100 cross-cut test (JIS standard).
B: 100 pieces of cross-cut test (JIS standard), the number of peeling is 4 or more and 10 or less.
C: The number of peels was 11 or more in the 100 cross-cut test (JIS standard).

[Evaluation of migration prevention effect]
<Production of Evaluation Substrates of Examples 1 to 6 and Comparative Examples 2 to 6>
A laminate having a comb-shaped conductive layer was manufactured and used as an evaluation substrate. Specifically, a silver ink (“Silver Nanoparticle Ink” manufactured by Sigma-Aldrich Japan) was applied on the substrate used in each example using a bar coater, and dried at 120° C. for 60 seconds. As a result, a layer containing silver particles having a thickness of 0.7 μm was formed on the base material. A positive photoresist (“ZPP1700” manufactured by Nippon Zeon Co., Ltd.) was applied on this, followed by coating, drying, exposing and developing to form a resist pattern. After that, etching treatment was performed with an acidic etching solution to form a comb-shaped electrode pattern to obtain a conductive layer. The line width of each electrode was 400 μm, and the gap between the electrodes was 100 μm. Next, according to the material and forming method of the thermoplastic resin layer used in each example, the thermoplastic resin layer was formed on the base material on which the conductive layer was formed to manufacture the evaluation substrate.

<Production of Evaluation Board of Comparative Example 1>
A substrate for evaluation was formed by comb-forming the ITO layer during the production of the laminate of Comparative Example 1.

<Evaluation method>
The evaluation substrate of each example was allowed to stand under conditions of 85° C. and 90% RH in heat and humidity, and a voltage of 50 V was applied between the electrodes in this state to perform a migration test. The resistance value of the comb-shaped electrode was measured, and the time (hour) until the resistance value suddenly dropped was measured. Here, "the resistance value sharply decreases" means that the resistance value decreases by 4 digits or more (energizes). The longer the time, the higher the effect of preventing migration.

[Evaluation of surface change by folding test]
A folding back test was conducted on the laminated body manufactured in each example. In this folding back test, a bending tester (“TCDM111LH” manufactured by Yuasa System Equipment Co., Ltd.) was used to perform folding back operation with a radius of curvature of 5 mm on the laminated body, which caused disconnection of the conductive layer and peeling phenomenon of each layer. The number of folds was measured when at least one occurred. The greater the number of folds, the higher the fold resistance.

[Production Example 1. Production of Thermoplastic Resin Layer A]
(A-1. Production of hydride of block copolymer)
With reference to the method described in International Publication No. 2014/077267, a mixture of 25 parts of styrene, 26 parts of styrene and 24 parts of isoprene, and 25 parts of styrene are polymerized in this order to give a triblock copolymer hydride (ia1). ) (Weight average molecular weight Mw=81,000; molecular weight distribution Mw/Mn=1.11; hydrogenation rate of carbon-carbon unsaturated bond of main chain and side chain, and carbon-carbon unsaturated bond of aromatic ring ≈ 100%).

(A-2. Production of modified silyl group)
Further, referring to the method described in International Publication No. 2014/077267, 1.8 parts of vinyltrimethoxysilane is bonded to 100 parts of the hydride of the triblock copolymer (ia1) to form a triblock product. Pellets of the alkoxysilyl modified product (ia1-s) of the hydride of the copolymer were produced.

(A-3. Production of thermoplastic resin layer)
Using a twin-screw extruder equipped with a side feeder and a T-die with a width of 400 mm (“TEM-37B” manufactured by Toshiba Machine Co., Ltd.), and a sheet take-up machine equipped with a cast roll and a release film supply device, the following method Then, a thermoplastic resin layer A was manufactured.

The alkoxysilyl modified product (ia1-s) was supplied to a twin-screw extruder to be in a molten state. This alkoxysilyl modified product (ia1-s) (molten resin) in a molten state was extruded from a T die onto a cast roll to form a film. This extrusion was performed under the molding conditions of a molten resin temperature of 180° C., a T die temperature of 180° C., and a cast roll temperature of 40° C. The extruded molten resin was cooled by a cast roll to obtain a thermoplastic resin layer having a thickness of 50 μm.
A polyethylene terephthalate (PET) film (thickness: 50 μm) for release is supplied to one surface of the thermoplastic resin layer extruded on the cast roll, and the thermoplastic resin layer and the PET film are overlapped and wound into a roll shape. , Recovered. In this way, a film roll of a multilayer film including the thermoplastic resin layer and the PET film was obtained.
The multilayer film was pulled out from the film roll of the multilayer film and the PET film was peeled off to obtain a thermoplastic resin layer A. The moisture permeability of this thermoplastic resin layer A was 2 g/m ² ·24 h, the storage elastic modulus at 25°C was 1000 MPa, and E ₂ /E ₁ was 10. The thermoplastic resin layer A had a total light transmittance of 92% and an in-plane retardation Re of 10 nm.

[Production Example 2. Production of Thermoplastic Resin Layer B]
(B-1. Production of hydride of block copolymer)
With reference to the method described in WO 2014/077267, 25 parts of styrene, 50 parts of isoprene and 25 parts of styrene are polymerized in this order to give a triblock copolymer hydride (ib1) (weight average molecular weight Mw =48,200; molecular weight distribution Mw/Mn=1.04; hydrogenation rates of carbon-carbon unsaturated bonds in the main chain and side chains, and carbon-carbon unsaturated bonds in aromatic rings ≈100%) were produced. ..

(B-2. Production of modified silyl group)
Further, referring to the method described in International Publication No. 2014/077267, 1.8 parts of vinyltrimethoxysilane was bonded to 100 parts of the hydride (ib1) of the triblock copolymer to give a triblock product. Pellets of the alkoxysilyl modified product (ib1-s) of the hydride of the copolymer were produced.

(B-3. Production of thermoplastic resin layer)
Using the sheet take-off machine used in (A-3) of Production Example 1, a thermoplastic resin layer B was produced by the following method.

The alkoxysilyl modified product (ib1-s) was fed to a twin-screw extruder. Hydrogenated polybutene was continuously supplied from the side feeder so that the ratio of the hydrogenated polybutene (“pearlream (registered trademark) 24” manufactured by NOF CORPORATION) 20 parts to 100 parts of the alkoxysilyl modified product (ib1-s). Was continuously supplied to obtain a molten resin containing the alkoxysilyl modified product (ib1-s) and hydrogenated polybutene. Then, this molten resin was extruded from a T-die onto a cast roll to form a film. This extrusion was performed under the molding conditions of a molten resin temperature of 180° C., a T die temperature of 180° C., and a cast roll temperature of 40° C. The extruded molten resin was cooled by a cast roll to obtain a thermoplastic resin layer having a thickness of 50 μm.
A polyethylene terephthalate (PET) film (thickness: 50 μm) for release is supplied to one surface of the thermoplastic resin layer extruded on the cast roll, and the thermoplastic resin layer and the PET film are overlapped and wound into a roll shape. , Recovered. In this way, a film roll of a multilayer film including the thermoplastic resin layer and the PET film was obtained.
The multilayer film was pulled out from the film roll of the multilayer film and the PET film was peeled off to obtain a thermoplastic resin layer B. The moisture permeability of the thermoplastic resin layer B was 5 g/m ² ·24 h, the storage elastic modulus at 25°C was 128 MPa, and E ₂ /E ₁ was 10. The total light transmittance of the thermoplastic resin layer B was 92%.
The thermoplastic resin layer B was manufactured by the following method.
A thermoplastic resin layer B was obtained by pulling out the multilayer film from the film roll of the multilayer film including the thermoplastic resin layer and the PET film obtained by the above method and peeling the PET film. The water vapor permeability of the thermoplastic resin layer B was 5 g/m ² ·24 h, the storage elastic modulus at 25°C was 12.8 MPa, and E ₂ /E ₁ was 10. The thermoplastic resin layer B had a total light transmittance of 90% and an in-plane retardation Re of 10 nm.

[Production Example 3. Production of Thermoplastic Resin Layer C]
Using the triblock copolymer hydride (ib1) (polymer before silylation) obtained in Production Example 2 (B-1), a thermoplastic resin layer C was produced by the following method.

(C-3) Production of Thermoplastic Resin Layer C A thermoplastic resin layer C was produced using the sheet take-off machine used in (A-3) of Production Example 1.
Instead of the alkoxysilyl modified product (ia1-s) in Preparation Example 1 (A-3), the triblock copolymer hydride (ib1) was supplied to the twin-screw extruder. The same operation as in (A-3) was performed to obtain a thermoplastic resin layer having a thickness of 50 μm.
On one surface of the thermoplastic resin layer extruded on the cast roll, a polyethylene terephthalate (PET) film for release (thickness 50 μm) was supplied, the thermoplastic resin layer and the PET film were overlapped and rolled up into a roll, Recovered. In this way, a film roll of a multilayer film including the thermoplastic resin layer and the PET film was obtained.
The multilayer film was pulled out from the film roll of the multilayer film and the PET film was peeled off to obtain a thermoplastic resin layer C. The water vapor permeability of the thermoplastic resin layer C was 10 g/m ² ·24 h, the storage elastic modulus at 25°C was 128 MPa, and E ₂ /E ₁ was 10. The thermoplastic resin layer C had a total light transmittance of 92% and an in-plane retardation Re of 10 nm.

[Production Example 4. Production of Thermoplastic Resin Layer D]
Using the triblock copolymer hydride (ib1) (polymer before silylation) obtained in (B-1) of Production Example 2 and a silane coupling agent, a thermoplastic resin layer is prepared by the following method. D was produced.

(D-3) Production of Thermoplastic Resin Layer D A thermoplastic resin layer D was produced using the sheet take-off machine used in (A-3) of Production Example 1.
In Production Example 1 (A-3), in place of the alkoxysilyl modified product (ia1-s), 5 parts of triblock copolymer hydride (ib1) and 5 parts of 100 parts of triblock copolymer hydride were used. A silane coupling agent (3-aminopropyltrieoxysilane (KE903, manufactured by Shin-Etsu Chemical Co., Ltd.)) was supplied to the twin-screw extruder, the same operation as in (A-3) of Production Example 1 was performed, and the thickness was 50 μm. To obtain a thermoplastic resin layer.
On one surface of the thermoplastic resin layer extruded on the cast roll, a polyethylene terephthalate (PET) film for release (thickness 50 μm) was supplied, the thermoplastic resin layer and the PET film were overlapped and rolled up into a roll, Recovered. In this way, a film roll of a multilayer film including the thermoplastic resin layer and the PET film was obtained.
The multilayer film was pulled out from the film roll of the multilayer film, and the PET film was peeled off to obtain a thermoplastic resin layer D. The water vapor permeability of the thermoplastic resin layer D was 10 g/m ² ·24 h, the storage elastic modulus at 25°C was 128 MPa, and E ₂ /E ₁ was 10. The thermoplastic resin layer D had a total light transmittance of 90% and an in-plane retardation Re of 10 nm.

[Example 1]
(1-1) Preparation of Base Material A As a base material, a resin film formed of a norbornene-based polymer as an alicyclic structure-containing polymer having no crystallinity (manufactured by Nippon Zeon Co., Ltd., “Zeonoa Film”) ZF16”; thickness 50 μm; glass transition temperature of resin 160° C., hereinafter also referred to as “base material A”). The storage elastic modulus of the substrate A at 25° C. was 2300 MPa. The water vapor permeability of the base material A was 2 g/m ² ·24 h, and the in-plane retardation Re was 5 nm. The total light transmittance of the base material A was 90%.

The surface of the base material A was plasma-treated. While flowing nitrogen and dry air at a nitrogen flow rate of 0.5 NL/min and a dry air flow rate of 0.1 NL/min, the substrate A was irradiated with plasma at a moving frequency of 5 cm/min at a resonance frequency of 25 kHz. The distance between the plasma generation source and the film was 5 mm.

(1-2) Formation of Conductive Layer A silver ink (“Silver Nanoparticle Ink” manufactured by Sigma-Aldrich Japan) as a composition for forming a conductive layer containing silver nanoparticles as metal particles was prepared.
The above-mentioned silver ink was applied onto the plasma-treated base material A using a bar coater and dried at 120° C. for 60 seconds. As a result, a layer containing silver particles having a thickness of 0.7 μm was formed on the base material A. A positive photoresist (Zeon Corporation, "ZPP1700" manufactured by Nippon Zeon Co., Ltd.) is applied on this, dried, exposed, and developed to form a pattern, which is then subjected to etching treatment with an acidic etching solution to form a base material A. A conductive layer was formed on. This obtained the base material A provided with a conductive layer.

(1-3) Production of Laminate A laminate was produced using the thermoplastic resin layer A produced in Production Example 1 as the thermoplastic resin layer.
After heating the base material A provided with the conductive layer to about 100° C. on a hot plate, the thermoplastic resin layer A was placed on the conductive layer and subjected to thermocompression bonding at a pressure of 0.3 MPa. In this way, a laminate was obtained in which the thermoplastic resin layer was thermocompression bonded onto the conductive layer. A folding test was conducted on the obtained laminate, and the results are shown in Table 1.

[Example 2]
In this example, a step of forming a thermoplastic resin layer on the conductive layer using a crystalline resin film (base material B) produced by the following method in place of the base material A is performed using a solution containing a thermoplastic resin. The coating method was used to obtain a laminate. The method for manufacturing the laminate of this example will be described below.

(2-1) Preparation of Base Material B (2-1-1) Crystalline Resin: Production of Crystalline COP Resin (y1) Containing Hydride of Ring-Opening Polymer of Dicyclopentadiene A metal pressure resistant reactor is used. After sufficiently drying, the atmosphere was replaced with nitrogen. In this pressure resistant reactor, 154.5 parts of cyclohexane, 42.8 parts of a 70% cyclohexane solution of dicyclopentadiene (end content 99% or more) (30 parts as the amount of dicyclopentadiene), and 1-hexene 1.9 parts was added and heated to 53°C.

A solution was prepared by dissolving 0.014 part of a tetrachlorotungsten phenylimide (tetrahydrofuran) complex in 0.70 part of toluene. To this solution, 0.061 part of a diethylaluminum ethoxide/n-hexane solution having a concentration of 19% was added and stirred for 10 minutes to prepare a catalyst solution.
This catalyst solution was added to the pressure resistant reactor to start the ring-opening polymerization reaction. Then, the reaction was carried out for 4 hours while maintaining 53° C. to obtain a solution of a ring-opening polymer of dicyclopentadiene. The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the obtained ring-opening polymer of dicyclopentadiene were 8,750 and 28,100, respectively, and the molecular weight distribution (Mw/Mn) obtained from them was obtained. Was 3.21.

To 200 parts of the obtained solution of the ring-opening polymer of dicyclopentadiene, 0.037 parts of 1,2-ethanediol was added as a terminating agent, and the mixture was heated to 60° C. and stirred for 1 hour to stop the polymerization reaction. Let To this, 1 part of a hydrotalcite-like compound (“Kyoward (registered trademark) 2000” manufactured by Kyowa Chemical Industry Co., Ltd.) was added, heated to 60° C., and stirred for 1 hour. Thereafter, 0.4 parts of a filter aid (“Radiolite (registered trademark) #1500” manufactured by Showa Chemical Industry Co., Ltd.) was added, and a PP pleated cartridge filter (“TCP-HX” manufactured by ADVANTEC Toyo Corp.) was used as an adsorbent. The solution was filtered off.

To 200 parts of a solution of a ring-opening polymer of dicyclopentadiene after filtration (100 parts of polymer), 100 parts of cyclohexane was added, and 0.0043 parts of chlorohydridocarbonyltris(triphenylphosphine)ruthenium was added to obtain hydrogen. The hydrogenation reaction was carried out at a pressure of 6 MPa and 180° C. for 4 hours. As a result, a reaction solution containing a hydride of a ring-opening polymer of dicyclopentadiene was obtained. The reaction solution was a slurry solution in which hydride was deposited.

27. The hydride and the solution contained in the reaction solution were separated using a centrifuge and dried under reduced pressure at 60° C. for 24 hours to give a hydride of a crystalline ring-opening polymer of dicyclopentadiene 28. 5 parts were obtained. The hydride had a hydrogenation ratio of 99% or more, a glass transition temperature Tg of 93° C., a melting point Mp of 262° C., and a racemo dyad ratio of 89%.
An antioxidant (tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane was added to 100 parts of the hydride of the obtained ring-opening polymer of dicyclopentadiene. After mixing 1.1 parts of "IRGANOX (registered trademark) 1010" manufactured by BASF Japan Ltd., a twin-screw extruder ("TEM-37B" manufactured by Toshiba Machine Co., Ltd.) equipped with four die holes having an inner diameter of 3 mmΦ was mixed. I put it in. A resin is formed into a strand-shaped molded product by hot melt extrusion molding using a twin-screw extruder, and then shredded with a strand cutter to obtain a resin containing a crystalline alicyclic structure-containing polymer (crystalline COP Resin (y1) pellets were obtained. The crystalline COP resin (y1) is a resin containing a hydride of a ring-opening polymer of dicyclopentadiene as a crystalline alicyclic structure-containing polymer.
The operating conditions of the twin-screw extruder were as follows.
・Barrel setting temperature = 270°C-280°C.
-Die setting temperature = 250°C.
-Screw rotation speed = 145 rpm.
-Feeder rotation speed = 50 rpm.

(2-1-2) Production of crystalline resin film 2.1.1. The crystalline COP resin (y1) obtained in (1) was supplied to a T die at an extrusion screw temperature of 280° C., discharged from the T die at a die extrusion temperature of 280° C., and cast on a cooling roll whose temperature was adjusted to 60° C., A film having a thickness of 15 μm and made of a crystalline COP resin was produced. The film was annealed in an oven at 170° C. for 30 seconds to obtain a crystalline resin film (base material B).
The storage elastic modulus at 25° C. of the base material B was 2500 MPa, the moisture permeability was 2 g/m ² ·24 h, and the in-plane retardation Re was 5 nm. The total light transmittance of the base material B was 90%.

(2-1-3) Plasma Treatment of Substrate B Plasma treatment was performed on the substrate B by performing the same operation as the plasma treatment of the substrate A of (1-1) of Example 1.

(2-2) Formation of Conductive Layer A conductive layer is formed on the base material B by performing the same operation as (2-1) of Example 1 except that the base material B is used instead of the base material A. did. This obtained the base material B provided with a conductive layer.

(2-3) Production of Laminated Body The thermoplastic resin layer A produced in Production Example 1 was dissolved in cyclohexane to prepare a solution containing 20% by weight of the thermoplastic resin (resin solution). This resin solution was slit-coated on a base material B having a conductive layer and then heated on a hot plate at 90° C. for 60 seconds to obtain a laminate having a thermoplastic resin layer A having a thickness of 35 μm. A folding test was conducted on the obtained laminate, and the results are shown in Table 1.

[Example 3]
A laminate was obtained by performing the same operation as in Example 1 except that a polyethylene terephthalate (PET) film (PET film, "Substrate C" manufactured by Teijin Ltd.) was used in place of the substrate A. A folding test was conducted on the obtained laminate, and the results are shown in Table 1.
The storage elastic modulus at 25° C. of the substrate C was 2300 MPa, the moisture permeability was 10 g/m ² ·24 h, and the in-plane retardation Re was 150 nm. The total light transmittance of the base material C was 88%.

[Example 4]
A laminated body was obtained by performing the same operation as in Example 1 except that the thermoplastic resin layer B produced in Production Example 2 was used instead of the thermoplastic resin layer A. A folding test was conducted on the obtained laminate, and the results are shown in Table 1.

[Example 5]
The same operation as in Example 1 was performed except that the thermoplastic resin layer B produced in Production Example 2 was used instead of the thermoplastic resin layer A, and the base material B was used instead of the base material A. A laminated body was obtained. A folding test was conducted on the obtained laminate, and the results are shown in Table 1.

[Example 6]
Instead of the thermoplastic resin layer A, the thermoplastic resin layer B produced in Production Example 2 was used, and instead of the base material A, crystallinity having a slow axis in the direction of 45° with respect to the longitudinal direction was used. A laminate was obtained by performing the same operation as in Example 1 except that a film containing an alicyclic structure-containing polymer (Zeonor film ZD series, thickness 80 μm, “Substrate D”) was used. A folding test was conducted on the obtained laminate, and the results are shown in Table 1. The storage elastic modulus at 25° C. of the substrate D was 2000 MPa, the moisture permeability was 2 g/m ² ·24 h, and the in-plane retardation Re was 140 nm. The total light transmittance of the substrate D was 92%.

[Comparative Example 1]
The same operation as in Example 1 was repeated except that a film of a resin containing an ethylene-vinyl acetate copolymer (UBE Maruzen Polyethylene Co., Ltd., UBE polyethylene V115, EVA film, thickness 100 μm) was used instead of the thermoplastic resin layer A. Then, a laminated body was obtained. A folding test was conducted on the obtained laminate, and the results are shown in Table 2.
The EVA film had a water vapor transmission rate of 50 g/m ² ·24 h, a storage elastic modulus at 25°C of 15 MPa, and an E ₂ /E ₁ of 250. The EVA film had a total light transmittance of 89% and an in-plane retardation Re of 10 nm.

[Comparative example 2]
A laminate was obtained by performing the same operations as in Example 1 except that an EVA film was used instead of the thermoplastic resin layer A and a base material C was used instead of the base material A. A folding test was conducted on the obtained laminate, and the results are shown in Table 2. The EVA film used was the same as that used in Comparative Example 1.

[Comparative Example 3]
Example 1 was repeated except that the thermoplastic resin layer A was replaced with the thermoplastic resin layer C (thermoplastic resin layer containing triblock copolymer hydride before silylation) produced in Production Example 3. The same operation was performed to obtain a laminated body. A folding test was conducted on the obtained laminate, and the results are shown in Table 2.

[Comparative Example 4]
Other than using the thermoplastic resin layer D (thermoplastic resin layer containing a triblock copolymer hydride before silylation and a silane coupling agent) produced in Production Example 4 instead of the thermoplastic resin layer A The same operation as in Example 1 was performed to obtain a laminate. A folding test was conducted on the obtained laminate, and the results are shown in Table 2.

[Comparative Example 5]
The same operation as in Example 1 was performed except that a resin film containing a copolymer of tetrafluoroethylene and ethylene (“Fluon” manufactured by AGC Co., ETFE film, thickness 100 μm) was used instead of the thermoplastic resin layer A. Then, a laminated body was obtained. A folding test was conducted on the obtained laminate, and the results are shown in Table 2.
The ETFE film had a water vapor permeability of 3 g/m ² ·24 h, a storage elastic modulus at 25°C of 2400 MPa, and an E ₂ /E ₁ of 30. The ETFE film had a total light transmittance of 90% and an in-plane retardation Re of 100 nm.

[Example 7]
The circularly polarizing plate of the commercially available display device (organic EL display element) having the circularly polarizing plate disposed on the outermost surface was peeled off, and the laminated body of Example 6 was mounted so that the thermoplastic resin layer was on the outermost surface. A display device including the laminated body was obtained. The reflectance before and after mounting the laminated body on the display surface of the display device was measured by a reflectance measuring spectroscope MCP-9800 manufactured by Otsuka Electronics Co., Ltd., and the reflectance from the external light of the display device was suppressed by 95%. We were able to.

The physical properties and the results of the evaluation tests of Examples 1 to 6 and Comparative Examples 1 to 5 are shown in Tables 1 and 2 below. In the table below, the abbreviations have the following meanings.
"HSIS silyl modified product": block copolymer hydride silyl modified product.
“Ag-NW”: silver nanowire.
"EVA": EVA film.
"HSIS": block copolymer hydride.
"ETFE": ETFE film.
"HSIS silyl modified product": block copolymer hydride silyl modified product.
“1000<”: more than 1000 times.
"100000<": over 100,000 hours.

[result]
As shown in Table 1 and Table 2, the laminates of Examples satisfying the requirements of the invention were excellent in the migration prevention effect and the bending resistance. As a result, it was found that the laminates of Examples satisfying the requirements of the invention were excellent in migration prevention effect and flexibility.

10... Laminated body 110... Thermoplastic resin layer 120... Conductive layer 130... Base material

Claims

A thermoplastic resin layer, a conductive layer and a substrate are provided in this order,
The thermoplastic resin layer has a moisture permeability of 5 g/m 2 ·24 h or less and a storage elastic modulus at 25° C. of 1300 MPa or less,
The said conductive layer is a laminated body containing the element of at least 1 type of Sn, Pb, Ag, Cu, and Au.
The laminate according to claim 1, wherein the thermoplastic resin layer contains a polymer having a silyl group.
The laminate according to claim 2, wherein the polymer having a silyl group is a silyl group-modified product of a block copolymer.
The laminate according to claim 2 or 3, wherein the polymer having a silyl group is a silyl group-modified product of a copolymer of an aromatic vinyl monomer and a conjugated diene monomer.
The laminate according to claim 4, wherein the hydrogenation rate of the unit based on the aromatic vinyl monomer is 90% or more, and the hydrogenation rate of the unit based on the conjugated diene monomer is 90% or more. ..
The ratio (E 2 /E 1 ) of the storage elastic modulus E 2 of the thermoplastic resin layer at 100° C. to the storage elastic modulus E 1 of −40° C. of the thermoplastic resin layer is 15 or less. The laminated body according to any one of 5 above.
The laminate according to any one of claims 1 to 6, wherein the water vapor permeability of the base material is 3 g/m 2 ·24 h or less.
The laminate according to any one of claims 1 to 7, wherein the base material is a polymer film containing a polymer.
The laminate according to any one of claims 1 to 8, wherein the base material contains an alicyclic structure-containing polymer.
The laminate according to any one of claims 1 to 9, wherein the base material is a long film and has a slow axis in a direction oblique to the width direction of the film.
The laminate according to any one of claims 1 to 10, wherein the base material has a storage elastic modulus at 25°C of 2000 to 3000 MPa.
The laminate according to any one of claims 1 to 11, wherein the thermoplastic resin layer has an in-plane retardation of 10 nm or less.
The laminate according to any one of claims 1 to 12, wherein the total light transmittance of at least one of the thermoplastic resin layer and the base material is 80% or more.
A circularly polarizing plate comprising the laminate according to any one of claims 1 to 13 and a polarizing plate.
A display device comprising the circularly polarizing plate according to claim 14.
The display device according to claim 15, wherein the display device is an organic electroluminescence device.
A touch panel comprising the laminate according to any one of claims 1 to 13.
The touch panel according to claim 17, further comprising a polarizing plate provided in contact with the thermoplastic resin layer of the laminate.
Comprising the laminate and a polarizing plate,
19. The touch panel according to claim 17, wherein an angle formed by an absorption axis of the polarizing plate with respect to a slow axis of the base material of the laminate is 45°.
The method for manufacturing a laminate according to any one of claims 1 to 13,
Step 1 of forming the conductive layer on the substrate,
A step 2 of forming the thermoplastic resin layer on the conductive layer,
The said process 2 is a manufacturing method of a laminated body including thermocompression-bonding the said thermoplastic resin layer, or applying the solution containing a thermoplastic resin.