CN112996657A

CN112996657A - Laminate, method for producing same, circularly polarizing plate, display device, and touch panel

Info

Publication number: CN112996657A
Application number: CN201980073702.3A
Authority: CN
Inventors: 柏木干文
Original assignee: Zeon Corp
Current assignee: Zeon Corp
Priority date: 2018-12-10
Filing date: 2019-11-12
Publication date: 2021-06-18
Also published as: WO2020121708A1; JP7355036B2; JPWO2020121708A1; KR20210102228A; TWI829817B; TW202031495A

Abstract

The invention provides a laminate comprising a thermoplastic resin layer, a conductive layer and a substrate in this order, wherein the moisture permeability of the thermoplastic resin layer is 5g/m²A storage modulus at 25 ℃ of 1300MPa or less for 24h or less, and the conductive layer contains at least one element selected from Sn, Pb, Ag, Cu, and Au. The present invention also provides a method for producing the laminate. The thermoplastic resin layer preferably contains a polymer having a silyl group. The silyl group functionalized polymer is preferably a silyl group modified product of a block copolymer.

Description

Laminate, method for producing same, circularly polarizing plate, display device, and touch panel

Technical Field

The invention relates to a laminate, a method for manufacturing the laminate, a circularly polarizing plate, a display device, and a touch panel.

Background

Conventionally, as a conductive member, a conductive glass in which an indium oxide thin film is formed on a glass plate has been known. However, since the base material of the conductive glass is glass, the flexibility is poor, and the application thereof is difficult depending on the application. Therefore, as a conductive member having excellent flexibility, a conductive member using a resin has been proposed (patent document 1).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2017-65217.

Disclosure of Invention

Problems to be solved by the invention

Patent document 1 describes a conductive member having a flexible base material, a conductive layer formed on the flexible base material, and a pressure-sensitive adhesive layer formed on the conductive layer. Such a conductive member is sometimes used for a touch panel or the like. In this case, depending on the use environment, a phenomenon may occur in which the metal material contained in the conductive layer is ionized and moved to be regenerated into metal. When the migration occurs, the touch panel becomes unable to be driven normally, so it is required to improve this.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a laminate having excellent flexibility and an excellent migration prevention effect, and a method for producing the same; a circularly polarizing plate and a touch panel each having the laminate; and a display device having the above circularly polarizing plate.

Means for solving the problems

As a result of intensive studies to solve the above problems, the present inventors have found that a laminate comprising a thermoplastic resin layer having a predetermined moisture permeability and a predetermined storage modulus, an electrically conductive layer and a base material in this order can have excellent flexibility and anti-migration effect, and have completed the present invention.

That is, the present invention includes the following.

[1] A laminate comprising a thermoplastic resin layer, an electrically conductive layer and a substrate in this order,

the moisture permeability of the thermoplastic resin layer is 5g/m²24h or less, a storage modulus at 25 ℃ of 1300MPa or less,

the conductive layer contains at least one element selected from 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 silyl group functionalized polymer is a silyl group modified product of a block copolymer.

[4] The laminate according to [2] or [3], wherein the silyl group-containing polymer is a silyl group-modified product of a copolymer of an aromatic vinyl monomer and a conjugated diene monomer.

[5] The laminate according to [4], wherein a hydrogenation rate of the unit based on the aromatic vinyl monomer is 90% or more, and a hydrogenation rate of the unit based on the conjugated diene monomer is 90% or more.

[6]According to [1]～[5]The laminate according to any one of the above items, wherein the thermoplastic resin layer has a storage modulus E at 100 ℃₂Storage modulus E at-40 ℃ with the above thermoplastic resin layer₁Ratio of (E)₂/E₁) Is 15 or less.

[7]According to [1]～[6]The laminate according to any one of the above items, wherein the substrate has a moisture permeability of 3g/m²24h 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 substrate contains a polymer having an alicyclic structure.

[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 inclined with respect to a width direction of the film.

[11] The laminate according to any one of [1] to [10], wherein the storage modulus of the base material at 25 ℃ is 2000 to 3000 MPa.

[12] The laminate according to any one of [1] to [11], wherein the thermoplastic resin layer has a retardation in an in-plane direction of 10nm or less.

[13] The laminate according to any one of [1] to [12], wherein a 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 a polarizing plate and the laminate according to any one of [1] to [13 ].

[15] A display device having the circularly polarizing plate of [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], which comprises a polarizing plate provided in contact with the thermoplastic resin layer of the laminate.

[19] The touch panel according to [17] or [18], which comprises the laminate and a polarizing plate,

an angle formed by an absorption axis of the polarizing plate and a slow axis of the substrate of the laminate is 45 °.

[20] A method for producing a laminate according to any one of [1] to [13], comprising:

a step 1 of forming the conductive layer on the substrate; and

a step 2 of forming the thermoplastic resin layer on the conductive layer,

the step 2 includes thermocompression bonding the thermoplastic resin layer or applying a solution containing a thermoplastic resin.

Effects of the invention

According to the present invention, a laminate having excellent flexibility and an excellent migration prevention effect, and a method for manufacturing the same can be provided; a circularly polarizing plate and a touch panel each having the laminate; and a display device having the above circularly polarizing plate.

Drawings

Fig. 1 is a sectional view schematically showing a laminate according to an embodiment of the present invention.

Detailed Description

The present invention will be described in detail below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples described below, and may be modified and implemented arbitrarily without departing from the scope and range equivalent to the scope of the present invention.

In the present application, a "long film" means a film having a length of 5 times or more, preferably 10 times or more, with respect to the width of the film, and more specifically means a film having a length of a degree of winding up in a roll shape for storage or transport. The upper limit of the ratio of the length to the width of the film is not particularly limited, and may be, for example, 100000 times or less.

In the present application, the in-plane retardation Re of the film is calculated from the formula Re ═ (nx-ny) × d. Here, nx is a refractive index in the slow axis direction (maximum in-plane refractive index) in the plane of the film, ny is a refractive index in the direction perpendicular to the slow axis in the plane of the film, and d is a thickness (nm) of the film. The measurement wavelength is not limited, and may be 590nm, which is a wavelength representative of the visible light region.

[1. outline of laminate ]

Fig. 1 is a sectional view schematically showing a laminate 10 according to an embodiment of the present invention.

As shown in fig. 1, a laminate 10 according to one embodiment of the present invention includes a thermoplastic resin layer 110, a conductive layer 120, and a substrate 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 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 has a moisture permeability of 5g/m²A layer having a storage modulus at 25 ℃ of 1300MPa or less for 24 hours or less. When the moisture permeability of the thermoplastic resin layer is in the above range and the storage modulus is in the above range, the adhesion between the thermoplastic resin layer and the conductive layer can be improved, the migration prevention effect can be improved, and the flexibility of the laminate can be improved.

The moisture permeability of the thermoplastic resin layer was 5g/m²24h or less, preferably 4g/m²24h or less, more preferably 3g/m²24h or less. The lower limit of the moisture permeability of the thermoplastic resin is not particularly limited, but is preferably 1g/m²24h or more, more preferably 2g/m²24h or more. When the moisture permeability is not more than the upper limit value, the adhesion between the thermoplastic resin layer and the conductive layer can be improved, and the migration prevention effect can be improved.

The moisture permeability of the thermoplastic resin layer can be measured by a Lyssy method (measuring apparatus L80-5000 (manufactured by Systech Illinois Co., Ltd.), under temperature conditions of 40 ℃ and humidity of 90%).

The thermoplastic resin layer has a storage modulus at 25 ℃ of 1300MPa or less, preferably 1100MPa or less, preferably 100MPa or more. By setting the storage modulus of the thermoplastic resin layer at 25 ℃ to the upper limit or less, the flexibility of the thermoplastic resin layer can be made excellent.

Storage modulus E of thermoplastic resin layer at 100 DEG C₂Storage modulus E at-40 ℃ with a thermoplastic resin layer₁Ratio of (E)₂/E₁) Preferably 15 or less, more preferably 12 or less. E₂/E₁The lower limit of (b) is not particularly limited, but is preferably 5 or more, and more preferably 8 or more. By making E₂/E₁When the temperature difference is less than the upper limit, the laminate can have excellent flexibility in an environment with a temperature difference.

Each storage modulus of the thermoplastic resin layer can be measured using a dynamic viscoelasticity measuring apparatus at a frequency of 1 Hz. The specific measurement conditions used in the examples described below can be employed.

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

[2.1. thermoplastic resin ]

As the thermoplastic resin forming the thermoplastic resin layer, a thermoplastic resin containing a polymer (hereinafter, also referred to as "polymer X") and, if necessary, an optional component can be used. The polymer X may be used alone or in combination of two or more kinds 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, the thermoplastic resin layer formed of the resin containing the silyl group functionalized polymer has excellent adhesion to the conductive layer, and therefore, can prevent the penetration of water or the like, effectively prevent migration, and improve the mechanical strength of the entire laminate.

The silyl group-containing polymer is preferably a silyl group-modified product of a block copolymer. Examples of the silyl group-modified product of the block copolymer include a silyl group-modified product obtained by introducing a silyl group into a block copolymer and a hydride thereof. Further, as the polymer having a silyl group, a silyl-modified product of a copolymer of an aromatic vinyl monomer and a conjugated diene monomer is preferable. Examples of the silyl group-modified product of the copolymer of an aromatic vinyl monomer and a conjugated diene monomer include a silyl group-modified product obtained by introducing a silyl group into a copolymer of an aromatic vinyl monomer and a conjugated diene monomer or a hydrogenated product thereof. However, the polymer and the constituent of the polymer used in the present invention are not limited to the production method.

The silyl group-containing polymer is more preferably a polymer obtained by introducing a silyl group into a hydrogenated product of a block copolymer comprising a polymer block [ A ] containing an aromatic vinyl monomer unit and a polymer block [ B ] containing a conjugated diene monomer unit; and a polymer obtained by introducing a silyl group into a hydrogenated product of a block copolymer comprising a polymer block [ A ] containing an aromatic vinyl monomer unit and a polymer block [ C ] containing an aromatic vinyl monomer unit and a conjugated diene monomer unit.

Hereinafter, a description will be given of a polymer obtained by introducing a silyl group into a hydrogenated product of a block copolymer comprising the polymer block [ A ] and the polymer block [ B ] or the polymer block [ C ], which is preferable as a polymer having a silyl group, but the present invention is not limited thereto. In the following description, a block copolymer comprising a polymer block [ A ] and a polymer block [ B ] or a polymer block [ C ] is sometimes referred to as a block copolymer [1 ]. Further, the hydride of the block copolymer [1] is sometimes referred to as a hydride [2 ].

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

The polymer block [ A ] is a polymer block containing an aromatic vinyl monomer unit. The aromatic vinyl monomer unit is a structural unit having a structure obtained 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 of the polymer block [ a ] include styrene; styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent, such as α -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2, 4-dimethylstyrene, 2, 4-diisopropylstyrene, 4-tert-butylstyrene, and 5-tert-butyl-2-methylstyrene; styrenes having a halogen atom as a substituent, such as 4-chlorostyrene, dichlorostyrene, and 4-monofluorostyrene; styrenes having an alkoxy group having 1 to 6 carbon atoms as a substituent, such as 4-methoxystyrene; styrenes having an aryl group as a substituent, such as 4-phenylstyrene; and vinylnaphthalenes such as 1-vinylnaphthalene and 2-vinylnaphthalene. These may be used alone or in combination of two or more in any ratio. Among them, styrene or an aromatic vinyl compound containing no polar group such as styrene having an alkyl group having 1 to 6 carbon atoms as a substituent is preferable because of its ability to reduce hygroscopicity, and styrene is particularly preferable because it is industrially easily available.

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. By increasing the amount of the aromatic vinyl monomer unit in the polymer block [ a ] as described above, the hardness and heat resistance of the thermoplastic resin layer can be improved.

The polymer block [ A ] may contain an arbitrary structural unit in addition to the aromatic vinyl monomer unit. The polymer block [ A ] may contain one arbitrary structural unit alone, or may contain two or more arbitrary structural units in combination at an arbitrary ratio.

Examples of the arbitrary structural unit that the polymer block [ a ] may contain include a conjugated diene monomer unit. The conjugated diene monomer unit is a structural unit having a structure obtained 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 ones as those of the conjugated diene compound corresponding to the conjugated diene monomer unit contained in the polymer block [ B ].

Examples of the optional structural unit that the polymer block [ a ] may contain include a structural unit having a structure obtained by polymerizing an optional unsaturated compound other than the aromatic vinyl compound and the chain-like conjugated diene compound. 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 them, from the viewpoint of hygroscopicity, a linear olefin having 2 to 20 carbon atoms per molecule, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-eicosene, 4-methyl-1-pentene, 4, 6-dimethyl-1-heptene, and the like, is preferable; vinyl compounds having no polar group such as cyclic olefins having 5 to 20 carbon atoms per molecule, such as vinylcyclohexane, more preferably linear olefins having 2 to 20 carbon atoms per molecule, and particularly preferably ethylene or propylene.

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

The polymer block [ B ] is a polymer block containing conjugated diene monomer units. As described above, the conjugated diene monomer unit refers to a structural unit having a structure formed by polymerizing, for example, 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 contained in the polymer block [ B ] include chain conjugated diene compounds such as 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene, and 1, 3-pentadiene. These may be used alone or in combination of two or more in any ratio. Among these, chain-like conjugated diene compounds containing no polar group are preferable because of their ability to reduce hygroscopicity, and 1, 3-butadiene and isoprene are particularly preferable.

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 in 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 arbitrary structural unit alone or two or more arbitrary structural units in combination at an arbitrary ratio.

Examples of the optional structural unit that can be contained in the polymer block [ B ] include an aromatic vinyl compound unit and a structural unit having a structure obtained by polymerizing an optional unsaturated compound other than an aromatic vinyl compound and a chain-like conjugated diene compound. Examples of the aromatic vinyl compound unit and the structural unit having a structure obtained by polymerizing an unsaturated compound other than an arbitrary unsaturated compound include the same ones as those exemplified as the structural unit that can be contained in the polymer block [ A ].

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. By setting the content of an arbitrary structural unit in the polymer block [ B ] within the above range, the flexibility of the thermoplastic resin layer can be improved.

The number of the polymer blocks [ B ] in one molecular block copolymer [1] is usually one or more, but may be two or more. When the number of the polymer blocks [ B ] in the block copolymer [1] is two or more, these 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 refers to, for example, a structural unit having a structure formed by polymerizing a conjugated diene compound, and is also referred to as a conjugated diene compound unit. The aromatic vinyl monomer unit is, for example, a structural unit having a structure obtained by polymerizing an aromatic vinyl monomer unit, and is also referred to as an aromatic vinyl compound unit.

Examples of the aromatic vinyl compound corresponding to the aromatic vinyl monomer unit of the polymer block [ C ] include aromatic vinyl compounds exemplified as the aromatic vinyl compounds corresponding to the aromatic vinyl monomer unit of the polymer block [ a ]. Examples of the conjugated diene compound corresponding to the conjugated diene monomer unit contained in the polymer block [ C ] include conjugated diene compounds exemplified as conjugated diene compounds 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 or less, and particularly preferably 55% by weight or less. By setting the content of the aromatic vinyl monomer unit in the polymer block [ C ] to the above range, the hardness and heat resistance of the thermoplastic resin layer can be improved.

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, more preferably 60% by weight or less. By setting the content of the conjugated diene monomer unit in the polymer block [ C ] to the above range, the flexibility of the thermoplastic resin layer can be improved.

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

Examples of the optional structural unit that can be contained in the polymer block [ C ] include a structural unit having a structure obtained by polymerizing an optional unsaturated compound other than the aromatic vinyl compound and the chain-like conjugated diene compound. Examples of the structural unit having a structure obtained by polymerizing an arbitrary unsaturated compound include the same ones as those exemplified as the structural unit that can 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. By setting the content of the arbitrary structural unit in the polymer block [ C ] within the above range, the flexibility of the thermoplastic resin layer can be improved.

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

The form of the block copolymer [1] may be a chain-type block or a radial-type block. Among these, the chain-type block is preferable because it is excellent in mechanical strength. When the block copolymer [1] has a form of a chain-type block, the blocking of the thermoplastic resin layer can be suppressed to a desired low value by making both ends of the molecular chain of the block copolymer [1] be the polymer blocks [ a ].

The form of the block copolymer [1] is particularly preferably: a triblock copolymer comprising a polymer block [ A ] and a polymer block [ B ] or [ C ] bonded to both ends of the polymer block [ A ] - [ B ] to [ A ] and [ A ] to [ C ] respectively; a pentablock copolymer in which a polymer block [ B ] or [ C ] represented by [ A ] - [ B ] - [ A ] and [ A ] - [ C ] - [ A ] is bonded to both ends of the polymer block [ A ] and the polymer block [ A ] is bonded to the other end of the two polymer block [ B ] or [ C ], respectively. Particularly, the triblock copolymers of [ A ] - [ B ] - [ A ] and [ A ] - [ C ] - [ A ] are particularly preferable because they can be easily produced and the physical properties can be easily controlled within a desired range.

In the block copolymer [1], the ratio (wA/wB) of the weight fraction wA of the polymer block [ A ] in the whole block copolymer [1] to the weight fraction wB of the polymer block [ B ] in the whole block copolymer [1] is preferably controlled to 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, more preferably 70/30 or less, and particularly preferably 55/45 or less. When the ratio wA/wB is not less than the lower limit of the above range, the rigidity and heat resistance of the thermoplastic resin layer can be improved, and birefringence can be reduced. Further, by setting the ratio wA/wB to be equal to or less than the upper limit of the above range, the flexibility of the thermoplastic resin layer can be improved. Here, the weight fraction wA of the polymer block [ A ] represents the weight fraction of the whole of the polymer block [ A ], and the weight fraction wB of the polymer block [ B ] represents the weight fraction of the whole of the polymer block [ B ].

In the block copolymer [1], the ratio (wA/wC) of the weight fraction wA of the polymer block [ A ] in the whole block copolymer [1] to the weight fraction wC of the polymer block [ C ] in the whole block copolymer [1] is preferably controlled to 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, more preferably 70/30 or less, and particularly preferably 55/45 or less. When the ratio wA/wC is equal to or higher than the lower limit of the above range, the rigidity and heat resistance of the thermoplastic resin layer can be improved, and birefringence can be reduced. Further, by setting the ratio wA/wC to the upper limit of the above range or less, the flexibility of the thermoplastic resin layer can be improved. Here, the weight fraction wA of the polymer block [ A ] represents the weight fraction of the whole of the polymer block [ A ], and the weight fraction wC of the polymer block [ C ] represents the weight fraction of the whole of the polymer block [ C ].

The weight average molecular weight (Mw) of the block copolymer [1] is preferably 30000 or more, more preferably 40000 or more, particularly preferably 50000 or more, preferably 200000 or less, more preferably 150000 or less, particularly preferably 100000 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 the molecular weight distribution (Mw/Mn) of the block copolymer [1] can be measured by Gel Permeation Chromatography (GPC) using Tetrahydrofuran (THF) as a solvent, and values in terms of polystyrene.

As the method for producing the block copolymer [1], for example, the method described in International publication No. 2015/099079 and Japanese patent application laid-open No. 2016-204217 can be used.

The hydride [2] is a polymer obtained by hydrogenating the unsaturated bond of the block copolymer [1 ]. The unsaturated bond of the block copolymer [1] to be hydrogenated includes any of aromatic and non-aromatic carbon-carbon unsaturated bonds in the main chain and side chain of the block copolymer [1 ].

Hydride [2]]The hydrogenation ratio (c) is preferably 90% or more, more preferably 97% or more, and particularly preferably 99% or more. In addition, in the case of hydrides [2]]Of these, the hydrogenation rate of the aromatic vinyl monomer unit is preferably 90% or more and the hydrogenation rate of the conjugated diene monomer unit is preferably 90% or more. Hydride [2]]The hydrogenation ratio of (3) is not particularly limited, and is a block copolymer [1]]The ratio of the bond to be hydrogenated in the aromatic and non-aromatic carbon-carbon unsaturated bonds in the main chain and the side chain of (2). The higher the hydrogenation ratio, the better the transparency, heat resistance and weather resistance of the thermoplastic resin layer can be made, and the birefringence of the thermoplastic resin layer can be reduced more easily. Here, the hydride [2]]The hydrogenation rate of (2) can be determined by using¹H-NMR was measured. The upper limit of the hydrogenation rate may be 100%.

In particular, the hydrogenation rate of the non-aromatic carbon-carbon unsaturated bond is preferably 95% or more, and 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 improved.

The hydrogenation ratio 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, and therefore the heat resistance of the thermoplastic resin layer can be effectively improved. Further, the photoelastic coefficient of the thermoplastic resin can be reduced.

The weight average molecular weight (Mw) of the hydride [2] is preferably 30000 or more, more preferably 40000 or more, still more preferably 45000 or more, preferably 200000 or less, more preferably 150000 or less, still more preferably 100000 or less. By controlling the weight average molecular weight (Mw) of the hydride [2] 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 easily reduced.

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. By controlling the molecular weight distribution (Mw/Mn) of the hydride [2] 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 easily reduced.

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

The above-mentioned hydride [2] can be produced by hydrogenating the block copolymer [1 ]. As the hydrogenation method, a hydrogenation method which can increase the hydrogenation rate and which causes less chain scission reaction of the block copolymer [1] is preferable. Examples of such hydrogenation methods include the methods described in International publication No. 2015/099079 and Japanese patent application laid-open No. 2016 and 204217.

As the hydride [2], a hydride in which a silyl group is introduced is preferable. Hereinafter, the hydride [2] in which a silyl group is particularly introduced into the hydride [2] may be referred to as a "silyl-modified product [3] as appropriate. By introducing the silyl group, the silyl-modified product [3] exhibited high adhesion to other materials. Therefore, the thermoplastic resin layer formed from the thermoplastic resin containing the silyl-modified product [3] has excellent adhesion to the conductive layer, and therefore the mechanical strength of the entire laminate can be improved.

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

The amount of silyl group introduced in the silyl-modified product [3] is preferably 0.1 part by weight or more, more preferably 0.2 part by weight or more, 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, based on 100 parts by weight of the hydride [2] before introduction of the silyl group. When the amount of silyl group introduced is controlled to the above range, the degree of crosslinking between silyl groups decomposed by moisture or the like can be suppressed from becoming excessively high, and therefore the adhesion of the thermoplastic resin layer can be maintained high.

The amount of silyl group introduced can be determined by¹H-NMR spectroscopy. In addition, when the amount of silyl group introduced is measured, the number of scans can be increased when the amount of silyl group introduced is small.

Since the amount of the silyl group introduced is small, the weight average molecular weight (Mw) of the silyl-modified product [3] does not change much from the weight average molecular weight (Mw) of the hydride [2] before introduction of the silyl group. However, since the introduction of the silyl group generally causes a modification reaction of the hydride [2] in the presence of a peroxide, the hydride [2] undergoes a crosslinking reaction and a chain scission reaction, and the molecular weight distribution tends to change greatly. The weight average molecular weight (Mw) of the silyl-modified product [3] is preferably 30000 or more, more preferably 40000 or more, still more preferably 45000 or more, preferably 200000 or less, more preferably 150000 or less, still more preferably 100000 or less. The silyl-modified product [3] preferably has a molecular weight distribution (Mw/Mn) of 3.5 or less, more preferably 2.5 or less, particularly preferably 2.0 or less, and preferably 1.0 or more. When the weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) of the silyl-modified product [3] are in the above ranges, the thermoplastic resin layer can maintain good mechanical strength and tensile elongation.

The weight average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) of the silyl-modified product [3] can be measured by Gel Permeation Chromatography (GPC) using tetrahydrofuran as a solvent and values in terms of polystyrene.

The silyl-modified product [3] can be produced by introducing an alkoxysilyl group into the hydride [2] of the block copolymer [1 ]. Examples of the method for introducing an alkoxysilyl group into the hydride [2] include the methods described in International publication No. 2015/099079 and Japanese patent application laid-open No. 2016-204217.

The proportion of the polymer X such as the hydride [2] (including the silyl-modified product [3]) in the thermoplastic resin is preferably 80 to 100% by weight, more preferably 90 to 100% by weight, and particularly preferably 95 to 100% by weight. By controlling the ratio of the polymer in the resin B in the above range, the storage modulus of the resin B can be easily controlled in the above range.

The thermoplastic resin layer may contain any of the components in combination with the polymer X described above. Examples of the optional component include inorganic fine particles; stabilizers such as antioxidants, heat stabilizers, ultraviolet absorbers, and near infrared absorbers; resin modifiers such as lubricants and plasticizers; colorants such as dyes and pigments; and an antistatic agent. These optional components may be used alone or in combination of two or more in an optional 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 generally has high transparency. The specific total light transmittance of the thermoplastic resin layer is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more. The total light transmittance can be measured in the wavelength range of 400nm to 700nm using an ultraviolet-visible spectrometer. The upper limit of the total light transmittance is preferably 100%, and 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, and particularly preferably 60 μm or less. When the thickness of the thermoplastic resin layer is not less than the lower limit of the above range, the thermoplastic resin layer can suppress the penetration of moisture into the conductive layer, and effectively prevent migration. On the other hand, by setting the thickness of the thermoplastic resin layer to be equal to or less than the upper limit of the above range, the flexibility can be effectively improved.

The method for producing the thermoplastic resin layer is not limited. Examples of the method for producing the thermoplastic resin layer include a melt molding method and a solution casting method. Among these, the melt molding method is preferred because it is possible to suppress the residual of volatile components such as a solvent in the thermoplastic resin layer. Further, in order to obtain a thermoplastic resin layer excellent in mechanical strength and surface accuracy, among melt molding methods, extrusion molding, inflation molding and press molding are preferable, and extrusion molding is preferable from the viewpoint of enabling efficient and simple production of a thermoplastic resin layer.

[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 undergo migration, but in the present invention, the occurrence of migration can be prevented by the thermoplastic resin layer having a predetermined moisture permeability and a predetermined storage 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 kinds at an arbitrary ratio. When the conductive layer is formed using these metals, a transparent conductive layer can be obtained by forming the conductive layer into a thin wire shape. For example, a transparent conductive layer can be obtained by forming the conductive layer so as to form a mesh-like metal mesh layer.

The conductive layer is formed of a material containing the above-described element (hereinafter also referred to as a "conductive material"). Examples of such a conductive material include a metal material. The metal material as referred to herein is a material in which metal atoms are bonded to each other through a metal bond, unlike a so-called metal oxide. Examples of such a metal material include metal particles and metal nanowires. The conductive material may be used alone, or two or more of them may be used in combination at an arbitrary ratio.

The conductive layer can be formed by, for example, a formation method including applying a composition for forming a conductive layer containing metal particles. In this case, the conductive layer forming composition is printed in a predetermined mesh pattern, whereby a conductive layer as a metal mesh layer can be obtained. Further, for example, a conductive layer can be formed as a metal mesh layer by applying a composition for forming a conductive layer containing metal particles such as silver salt and silver nanoparticles, and forming fine metal wires into a predetermined mesh pattern by exposure treatment and development treatment. For details of such a conductive layer and a method for forming the same, reference is made to japanese patent laid-open nos. 2012 and 18634 and 2003 and 331654.

The metal nanowires are conductive substances having a shape of needles or wires and a diameter of nanometer size. The metal nanowire may be linear or curved. Such metal nanowires are formed in a mesh shape by forming gaps between the metal nanowires, and a good conductive path can be formed even with a small amount of metal nanowires, thereby realizing a conductive layer with low resistance. Further, by forming the metal wire in a mesh shape, an opening is formed in a gap of the mesh, and thus a conductive layer having high light transmittance can be obtained.

The ratio of the thickness d to the length L (aspect ratio: L/d) of the metal nanowire is preferably 10 to 100000, more preferably 50 to 100000, and particularly preferably 100 to 10000. When such a metal nanowire having a large aspect ratio is used, the metal nanowires cross well, and high conductivity can be exhibited by a small amount of the metal nanowire. As a result, a laminate having excellent transparency can be obtained. Here, the "thickness of the metal nanowire" means a diameter in the case where the cross section of the metal nanowire is circular, a minor diameter in the case of an elliptical shape, and a longest diagonal line in the case of a polygon. 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 nanowires is preferably less than 500nm, more preferably less than 200nm, still more preferably 10nm to 100nm, and particularly preferably 10nm to 50 nm. This can improve the transparency of the conductive layer.

The length of the metal nanowires is preferably 2.5 to 1000. mu.m, more preferably 10 to 500. mu.m, and particularly preferably 20 to 100. mu.m. This can improve the conductivity of the conductive layer.

As the metal contained in the metal nanowire, a metal having high conductivity is preferable. Preferred examples of the metal include gold, silver, and copper, and silver is more preferred. Further, a material obtained by subjecting the above metal to plating treatment (e.g., gold plating treatment) may be used. Further, the above-mentioned materials may be used singly or in combination of two or more kinds at an arbitrary ratio.

As the method for producing the metal nanowire, any appropriate method can be adopted. For example, a method of reducing silver nitrate in a solution; and a method of applying a voltage or a current to the tip portion of the probe to the surface of the precursor to extract the metal nanowire from the tip portion of the probe to form the metal nanowire continuously. In the method of reducing silver nitrate in a solution, silver nanowires can be synthesized by reducing silver salts such as silver nitrate in a liquid phase in the presence of a polyol such as ethylene glycol and polyvinylpyrrolidone. Silver nanowires of uniform size can be mass produced according to the methods described in, for example, Xia, Y.et., chem.Mater. (2002),14, 4736-.

The conductive layer containing the metal nanowires can be obtained by, for example, a formation method including coating a metal nanowire dispersion obtained by dispersing metal nanowires in a solvent and drying the same.

Examples of the solvent contained in the metal nanowire dispersion liquid include water, an alcohol-based solvent, a ketone-based solvent, an ether-based solvent, a hydrocarbon-based solvent, and an aromatic solvent, and among these, water is preferably used from the viewpoint of reducing the environmental load. In addition, one solvent may be used alone, or two or more solvents may be used in combination at an arbitrary ratio.

The concentration of the metal nanowires in the metal nanowire dispersion liquid is preferably 0.1 to 1 wt%. This enables formation of a conductive layer having excellent conductivity and transparency.

The metal nanowire dispersion may comprise any combination of ingredients with the metal nanowires and the solvent. Examples of the optional component include a corrosion inhibitor for inhibiting corrosion of the metal nanowire, a surfactant for inhibiting aggregation of the conductive nanowire, a binder polymer for holding the conductive nanowire in the conductive layer, and the like. In addition, any of the components may be used alone, or two or more of them may be used in combination at any 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, a spray coating method, a screen coating method, a dip coating method, a slot die coating method, a relief printing method, a gravure printing method, an intaglio printing method, and the like. As the drying method, any suitable drying method (for example, natural drying, air-blast drying, heat drying) can be employed. For example, in the case of heat drying, the drying temperature is 100 to 200 ℃ and the drying time is 1 to 10 minutes.

The proportion of the metal nanowires of the conductive layer is preferably 80 to 100 wt%, more preferably 85 to 99 wt%, with respect to the total weight of the conductive layer. This can provide a conductive layer having excellent conductivity and light transmittance.

The conductive layer may contain the above-described conductive material and any conductive material other than the above. Examples of the optional conductive material include carbon nanotubes and a conductive polymer.

Examples of the carbon nanotubes include so-called multi-wall carbon nanotubes, two-wall carbon nanotubes, and single-wall carbon nanotubes having a diameter of 0.3 to 100nm and a length of about 0.1 to 20 μm. Among them, from the viewpoint of high conductivity, a single-layer or two-layer carbon nanotube having a diameter of 10nm or less and a length of 1 μm to 10 μm is preferable. The aggregate of carbon nanotubes preferably does not contain impurities such as amorphous carbon and a catalyst metal. As the method for producing the carbon nanotube, any appropriate method can be adopted. Carbon nanotubes produced by arc discharge are preferably used. Carbon nanotubes produced by the arc discharge method are preferable because they have excellent crystallinity.

Examples of the conductive polymer include polythiophene-based polymers, polyacetylene-based polymers, polyparaphenylene-based polymers, polyaniline-based polymers, polyparaphenylene-vinylene-based polymers, polypyrrole-based polymers, polyphenylene-based polymers, and polyester-based polymers modified with acrylic polymers. Among them, polythiophene-based polymers, polyacetylene-based polymers, polyphenylene-based polymers, polyaniline-based polymers, polyparaphenylene vinylene-based polymers, and polypyrrole-based polymers are preferable.

Among them, polythiophene-based polymers are particularly preferable. By using the 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) such as poly (3-hexylthiophene)_1-8Alkyl-thiophenes); poly (3, 4-ethylenedioxythiophene), poly (3, 4-propylenedioxythiophene), poly [3,4- (1, 2-cyclohexylene) dioxythiophene]Isopoly (3, 4-cyclo) alkyldioxythiophenes); polythienylenevinylenes and the like. Here, "C" is_1-8The alkyl group represents an alkyl group having 1 to 8 carbon atoms. The conductive polymer may be used alone or in combination of two or more kinds at an arbitrary ratio.

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 polymers having a carboxyl group, a sulfonic acid group, or a salt thereof. An anionic polymer having a sulfonic acid group such as polystyrenesulfonic acid is preferably used.

The conductive layer is formed of the conductive material as described above, and therefore 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 use 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. or less, and particularly preferably 800 Ω/sq. or less. The lower limit of the surface resistance value of the conductive layer is not particularly limited, but is preferably 1 Ω/sq. or more, more preferably 2.5 Ω/sq. or more, and particularly preferably 5 Ω/sq. or more, from the viewpoint of ease of production.

The conductive layer may be formed over the entire area between the thermoplastic resin layer and the substrate, or may be formed locally between the thermoplastic resin layer and the substrate. For example, the conductive layer may be patterned to form a pattern having a prescribed planar shape. Here, the planar shape refers to 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 use of the laminate. For example, in the case where the laminate is used as a circuit substrate, the planar shape of the conductive layer may be formed into a pattern corresponding to the wiring shape of the circuit. Further, for example, when the laminate is used as a sensor film for a touch panel, the planar shape of the conductive layer is preferably a pattern that can be favorably handled as a touch panel (for example, a capacitive touch panel), and specific examples thereof include patterns described in japanese patent publication No. 2011-511357, japanese patent publication No. 2010-164938, japanese patent publication No. 2008-310550, japanese patent publication No. 2003-511799, and japanese patent publication No. 2010-541109.

The conductive layer generally has high transparency. Therefore, visible light rays can generally transmit the conductive layer. The specific transparency of the conductive layer can be adjusted according to the use of the laminate. The specific total light transmittance of the conductive layer is preferably 80% or more, more preferably 90% or more, and further preferably 95% or more.

The thickness of each conductive layer is preferably 0.01 to 10 μm, more preferably 0.05 to 3 μm, and particularly preferably 0.1 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, a film formed of a resin containing the polymer Y and further containing an optional component as necessary can be used. The polymer Y may be used alone, or two or more of them may be used in combination at an arbitrary ratio.

The polymer Y is preferably a polymer containing an alicyclic structure. Hereinafter, the alicyclic structure-containing polymer may be appropriately referred to as an "alicyclic structure-containing polymer".

The alicyclic structure-containing polymer is excellent in mechanical strength. Further, the alicyclic structure-containing polymer is generally excellent in transparency, low water absorption, moisture resistance, dimensional stability and lightweight property.

The alicyclic structure-containing polymer is a polymer having an alicyclic structure in a repeating unit, and examples thereof include a polymer obtainable by polymerization using a cyclic olefin as a monomer, and a hydrogenated product thereof. Further, as the alicyclic structure-containing polymer, any of a polymer having an alicyclic structure in the main chain and a polymer having an alicyclic structure in the side chain can be used. Among them, the alicyclic structure-containing polymer preferably contains an alicyclic structure in its main chain. Examples of the alicyclic structure include a cycloalkane structure and a cycloalkene structure, and a cycloalkane structure is preferable from the viewpoint of thermal stability and the like.

The number of carbon atoms included in one alicyclic structure is preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less. By making the number of carbon atoms included in one alicyclic structure within the above range, mechanical strength, heat resistance, and moldability can be highly balanced.

The proportion of the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer is preferably 30% by weight or more, more preferably 50% by weight or more, still more preferably 70% by weight or more, and particularly preferably 90% by weight or more. By increasing the proportion of the repeating unit having an alicyclic structure as described above, heat resistance can be improved.

In the alicyclic structure-containing polymer, the remaining portion other than the repeating unit having an alicyclic structure is not particularly limited and may be appropriately selected depending on the purpose of use.

The alicyclic structure-containing polymer may be a crystalline alicyclic structure-containing polymer or an amorphous alicyclic structure-containing polymer, or may be a combination of both. Here, the polymer having crystallinity means a polymer having a melting point Mp. Further, the polymer having a melting point Mp, i.e., the polymer having a melting point Mp can be observed with a Differential Scanning Calorimeter (DSC). Since the alicyclic structure-containing polymer having crystallinity is solvent-resistant, it can be used as a material for a base material, and a thermoplastic resin layer is formed by coating a thermoplastic resin dissolved in a solvent. Further, the use of the alicyclic structure-containing polymer having crystallinity as a material for the base material can particularly effectively improve the mechanical strength of the laminate. When the alicyclic structure-containing polymer having no crystallinity is used as a material for 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 them, the polymer (. beta.) is preferable as the alicyclic structure-containing polymer having crystallinity because a laminate excellent in heat resistance can be easily obtained.

Polymer (α): a ring-opened polymer of a cyclic olefin monomer having crystallinity.

Polymer (β): a hydride of the polymer (. alpha.) having crystallinity.

Polymer (γ): addition polymers of cyclic olefin monomers having crystallinity.

Polymer (δ): a hydride of the polymer (γ) having crystallinity.

Specifically, the alicyclic structure-containing polymer having crystallinity is more preferably a ring-opened polymer of dicyclopentadiene having crystallinity and a hydrogenated product of the ring-opened polymer of dicyclopentadiene having crystallinity, and particularly preferably a hydrogenated product of the ring-opened polymer of dicyclopentadiene having crystallinity. The ring-opened polymer of dicyclopentadiene is a polymer in which the proportion of the constituent unit derived from dicyclopentadiene is usually 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more, and still more preferably 100% by weight based on the total constituent units.

The alicyclic structure-containing polymer having crystallinity may not be crystallized before the production of the laminate. However, after the laminate is produced, the alicyclic structure-containing polymer having crystallinity contained in the laminate can generally have high crystallinity by crystallization. The specific range of crystallinity may be appropriately selected depending on the desired performance, and is preferably 10% or more, and more preferably 15% or more. When the crystallinity of the alicyclic structure-containing polymer contained in the laminate is not less than the lower limit of the above range, the laminate can be provided with high heat resistance and chemical resistance. The crystallinity can be measured by X-ray diffraction.

The melting point Mp of the alicyclic structure-containing polymer having crystallinity is preferably 200 ℃ or higher, more preferably 230 ℃ or higher, and preferably 290 ℃ or lower. By using the alicyclic structure-containing polymer having crystallinity and having such a melting point Mp, a laminate having a further excellent balance between moldability and heat resistance can be obtained.

The alicyclic structure-containing polymer having such crystallinity can be produced, for example, by the method described in international publication No. 2016/067893.

On the other hand, examples of the alicyclic structure-containing polymer having no crystallinity include (1) norbornene-based polymers, (2) monocyclic cyclic olefin polymers, (3) cyclic conjugated diene polymers, (4) vinyl alicyclic hydrocarbon polymers, and hydrogenated products thereof. Among them, norbornene polymers and hydrogenated products thereof 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 and other monomers capable of ring-opening copolymerization, and hydrogenated products thereof; addition polymers of norbornene monomers, addition copolymers of norbornene monomers and other copolymerizable monomers, and the like. Among them, the hydrogenated ring-opening polymer of a norbornene-based monomer is particularly preferable from the viewpoint of transparency.

The above-mentioned alicyclic structure-containing polymer may be selected from, for example, the polymers disclosed in Japanese patent laid-open publication No. 2002-321302.

Since there are various commercially available products as the resin containing the alicyclic structure-containing polymer having no crystallinity, a resin having desired characteristics can be appropriately selected from these products and used. Examples of the commercially available products include product groups having trade names of "ZEONOR" (manufactured by ZEON corporation), "art" (manufactured by JSR corporation), "APEL" (manufactured by Mitsui Chemicals, inc.), and "TOPAS" (manufactured by polyplatics co.

The weight average molecular weight (Mw) of the polymer Y contained in the base material is preferably 10000 or more, more preferably 15000 or more, particularly preferably 20000 or more, preferably 100000 or less, more preferably 80000 or less, and particularly preferably 50000 or less. The polymer Y having such a weight average molecular weight is excellent in the 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, more preferably 3.4 or less, and particularly preferably 3.3 or less. When the molecular weight distribution is not less than the lower limit of the above range, the productivity of the polymer Y can be improved and the production cost can be controlled. Further, by being equal to or less than the upper limit, the amount of the low-molecular component becomes small, so that relaxation at the time of high-temperature exposure can be suppressed, and the stability of the laminate can be improved.

The weight average molecular weight Mw and the number average molecular weight Mn of the polymer Y can be measured by gel permeation chromatography (hereinafter, abbreviated as "GPC") using cyclohexane (toluene in the case where the resin is insoluble) as a solvent and values in terms of polyisoprene (in terms of polystyrene in the case where the solvent is toluene).

From the viewpoint of obtaining a laminate having particularly excellent heat resistance and bending resistance, the proportion of the polymer Y in the base material is preferably 80 to 100% by weight, more preferably 90 to 100% by weight, even more preferably 95 to 100% by weight, and particularly preferably 98 to 100% by weight.

The substrate may comprise any of the ingredients in combination with the polymer Y described above. The same examples as those exemplified for the optional components that can be contained in the thermoplastic resin layer can be given as the optional components. Any of the components may be used alone, or two or more of them 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 ℃. By providing the resin Y with a high glass transition temperature Tg as described above, the heat resistance of the resin Y can be improved, and thus dimensional change of the substrate in a high-temperature environment can be suppressed. By providing the substrate with excellent heat resistance as described above, the conductive layer can be formed appropriately. In particular, when a conductive layer having a fine pattern shape is formed, it is useful that the base material has excellent heat resistance. From the viewpoint of facilitating the availability of the resin Y, the upper limit of the glass transition temperature of the resin Y is preferably 200 ℃ or lower, more preferably 190 ℃ or lower, and particularly preferably 180 ℃ or lower. The glass transition temperature can be measured by the method described in the examples described later.

The substrate generally has high transparency. The specific total light transmittance of the substrate is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more. In the present invention, at least one of the thermoplastic resin layer and the base material layer preferably has a total light transmittance of 80% or more, and more preferably has a total light transmittance of 80% or more. If the total light transmittance of at least one layer is 80% or more, the laminate has high transparency, and is therefore preferable when used in a display device or the like.

The moisture permeability of the substrate is preferably 3g/m²24h or less, more preferably 2g/m²24h or less. The lower limit of the moisture permeability of the substrate is not particularly limited, but is preferably 0g/m²24h or more. By setting the moisture permeability of the base material to the upper limit value or less, 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 substrate can be measured by a Lyssy method (measuring apparatus L80-5000 (manufactured by Systech Illinois Co., Ltd.), under a temperature condition of 40 ℃ and a humidity of 90%).

The storage modulus of the substrate at 25 ℃ is preferably 2000MPa or more, more preferably 2500MPa or more, and preferably 3000MPa or less. By setting the storage modulus of the base material to be not more than the upper limit value, the laminate can be made to have excellent flexibility. The storage modulus of the substrate can be measured using a dynamic viscoelasticity measuring apparatus at a frequency of 1 Hz.

The thickness of the substrate 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, and particularly preferably 60 μm or less. When the thickness of the base material is not less than the lower limit of the above range, the base material can suppress the penetration of moisture into the conductive layer. Therefore, the occurrence of migration can be effectively suppressed. On the other hand, by setting the thickness of the base material to be equal to or less than the upper limit of the above range, the flexibility of the laminate can be effectively improved.

The phase difference Re in the in-plane direction of the substrate can be arbitrarily set according to the application of the laminate. Particularly, when the polarizing plate is used in combination with a linear polarizing plate as a circular polarizing plate, it preferably has a retardation Re in the in-plane direction that can function as an 1/4 wave plate. The in-plane retardation Re in this case is preferably 100nm or more, more preferably 110nm or more, preferably 180nm or less, and more preferably 170nm or less. In the case of other applications, the thickness is not particularly limited, but is preferably 10nm or less, and more preferably 5nm or less.

The method of manufacturing the substrate is not limited. Examples of the method for producing the substrate 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 residual of volatile components such as a solvent in the base material. 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, extrusion molding, inflation molding and press molding are preferable for obtaining a substrate excellent in mechanical strength and surface accuracy, and extrusion molding is particularly preferable from the viewpoint of enabling more efficient and simple production of a substrate.

The shape of the base material is not particularly limited, and a long film is preferable. Further, the base material is preferably a long film, and is a film having a slow axis in an oblique direction with respect to its width direction. The oblique direction refers to a direction that is not parallel to any of the longitudinal direction of the film and the width direction of the film among the in-plane directions of the film. A film having a slow axis in an oblique direction can be obtained by stretching a long film in an oblique direction with respect to the width direction. In the obliquely stretched film, the direction of the optical axis is an oblique direction with respect to the film width direction, and therefore when a film having a slow axis in an oblique direction (obliquely stretched film) is used as a base material, the laminate of the present invention can be easily produced by a roll-to-roll method, and is therefore preferable.

The method of the oblique stretching and the stretching machine for the oblique stretching are not particularly limited, and a conventionally known tenter can be used. The tenter includes a transverse single-screw stretcher, a simultaneous twin-screw stretcher, and the like, and any of various kinds of stretchers can be used as long as the long film can be continuously obliquely stretched.

[5. optional layers ]

The laminate may contain any layer in addition to the thermoplastic resin layer, the conductive layer, and the substrate. For example, the laminate may have any layer at a position such as a position opposite to the conductive layer of the thermoplastic resin layer, a position opposite to the conductive layer of the substrate, and the like. Examples of the optional layer include a support layer, a hard coat layer, a refractive index matching layer, an adhesive layer, a retardation layer, a polarizer layer, and an optical compensation layer.

In the laminate, the substrate and the conductive layer are preferably in direct contact. Further, the conductive layer and the thermoplastic resin layer are preferably in direct contact. Herein, the manner in which two layers are joined to each other is "directly" means that there is no other layer between the two layers. Further, the laminate is particularly preferably a film having a three-layer structure including only a substrate, 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, and still more preferably 90% or more. When the total light transmittance of the laminate is not less than the lower limit value, it is preferable in the application of the optical member.

From the viewpoint of improving the image clarity of an image display device incorporating the laminate, the haze of the laminate is preferably 5% or less, more preferably 3% or less, particularly preferably 1% or less, and ideally 0%.

The thickness of the laminate is preferably 2 μm or more, more preferably 5 μm or more, further preferably 7.5 μm or more, particularly preferably 10 μm or more, preferably 200 μm or less, more preferably 175 μm or less, and particularly preferably 150 μm or less. 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 improved and wrinkles can be prevented from occurring when the conductive layer is formed. Further, by setting the thickness of the laminate to be equal to or less than the upper limit of the above range, the laminate can be made to have good flexibility and can be made thinner.

[7] action and Effect of the present invention ]

In the present invention, the thermoplastic resin layer has a moisture permeability of 5g/m²A layer having a storage modulus at 25 ℃ of 1300MPa or less for 24 hours or less. That is, in the present invention, the thermoplastic resin layer has a moisture permeability in an appropriate range, and therefore, the adhesion to the conductive layer can be improved, thereby improving the migration prevention effect. In the present invention, the thermoplastic resin film has a storage modulus in an appropriate range, and therefore the laminate can have excellent flexibility. As a result, according to the present invention, a laminate having excellent flexibility and excellent migration prevention effect can be provided.

In addition, in the present invention, the laminate includes a base material and a thermoplastic resin layer, and the base material is flexible as a layer for supporting the conductive layer, and therefore, generally has excellent impact resistance and processability as compared with conductive glass. Further, the laminate is generally lighter than the conductive glass.

[8. method for producing laminate ]

The method for producing the laminate is not limited, and the laminate can be produced by a production method including, for example, step 1 of forming a conductive layer on a substrate and step 2 of forming a thermoplastic resin layer on the conductive layer. According to such a manufacturing method, the thermoplastic resin layer can be easily formed, and thus the manufacturing method can be simplified.

(step 1)

Step 1 is a step of forming a conductive layer on a substrate.

The base material used in step 1 can be formed of the resin Y by the above-described method for producing a base material, for example. In the case where an obliquely stretched film is used as the substrate, the stretching step is performed before the step 1.

In step 1, a conductive layer can be formed on the substrate by the above-described method for forming a conductive layer, for example. The conductive layer may be formed on the substrate via any interlayer grounding. However, it is preferable that the conductive layer is formed directly on the substrate.

(step 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 formed on the conductive layer via any interlayer grounding. For example, the conductive layer may be formed by bonding the thermoplastic resin layer produced by the above-described method for producing a thermoplastic resin layer to the conductive layer via an adhesive or a bonding agent. However, the thermoplastic resin layer is preferably formed directly on the conductive layer.

The step 2 preferably includes thermocompression bonding the thermoplastic resin layer or coating a solution containing the thermoplastic resin. According to this method, the manufacturing method can be simplified.

The method for thermocompression bonding the thermoplastic resin layer is as follows: if necessary, the thermoplastic resin layer produced by the above-described method for producing a thermoplastic resin layer is pressed against the surface of the conductive layer while being heated.

The method of applying the solution containing the thermoplastic resin is as follows: the thermoplastic resin layer is formed directly on the conductive layer by applying a solution containing a thermoplastic resin on the conductive layer and drying it as necessary. In the case where the material of the base material is solvent-resistant, the thermoplastic resin layer can be easily formed by this method. The solution containing the thermoplastic resin can be obtained by dissolving or dispersing the thermoplastic resin in a solvent.

The method for producing a laminate may further include any process in combination with the above-described process.

[9. use of laminate ]

The laminate of the present invention has excellent flexibility and excellent migration prevention effect, and therefore can be preferably used for optical applications such as a circularly polarizing plate and a touch panel, and applications such as a circuit board.

[10. circular polarizing plate ]

The circularly polarizing plate of the present invention comprises the laminate of the present invention and a polarizing plate. The circularly polarizing plate can be obtained by laminating polarizing plates on a laminate, for example, so that the angle θ 1 formed by the slow axis of the substrate and the absorption axis of the polarizing plate is 45 °. The angle θ 1 of the slow axis of the substrate to the absorption axis of the polarizer may include an error in the range of, for example, ± 5 °, ± 3 °, ± 2 °, or ± 1 °. In the case of such an embodiment, for example, when a circularly polarizing plate is used for a display device, it is possible to prevent display contents from being difficult to see due to reflected light of incident external light. When the polarizing plate is a long film having an absorption axis in the longitudinal direction or the width direction, it is preferable that the direction of the slow axis of the substrate and the direction of the absorption axis of the polarizing plate are easily set at an appropriate angle to facilitate the production of the circularly polarizing plate.

In the case where a long polarizing film is used as the polarizing plate, the polarizing film can be produced by, for example, subjecting a polyvinyl alcohol film to adsorption of iodine or a dichroic dye and then uniaxial stretching in a boric acid bath. Further, the polyvinyl alcohol film can be produced by, for example, adsorbing iodine or a dichroic dye to the polyvinyl alcohol film, stretching the film, and modifying a part of polyvinyl alcohol units in the molecular chain into polyvinyl units. Further, a polarizing film having a function of separating polarized light into reflected light and transmitted light, such as a grid polarizer and a multilayer polarizer, may be used. Among them, a polarizing film comprising polyvinyl alcohol is preferable. The polarization degree of the polarizing film is preferably 98% or more, and more preferably 99% or more.

When the polarizing plate and the laminate are laminated, 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-pack curing adhesive, an ultraviolet curing adhesive, and a pressure-sensitive adhesive. Among these, water-based adhesives are preferable, and polyvinyl alcohol-based water-based adhesives are particularly preferable. One kind of the adhesive may be used alone, or two or more kinds may be used in combination at an arbitrary ratio.

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

The method of laminating the polarizing plate laminate is not limited, and a method of applying an adhesive to one surface of the polarizing plate, and then bonding the polarizing plate and the laminate using a roll laminator and drying the same is preferable. Before bonding, the surface of the laminate may be subjected to treatment such as corona discharge treatment or plasma treatment. The drying time and the drying temperature may be appropriately selected depending on the type of the adhesive.

The circularly polarizing plate obtained is cut to an appropriate size as needed, and is used as an antireflection film for an organic electroluminescence display device (hereinafter, may be referred to as an "organic EL display device" as appropriate).

[11. display device ]

The display device of the present invention has the circularly polarizing plate of the present invention. As the display device of the present invention, an organic electroluminescence display device (hereinafter, sometimes referred to as an "organic EL display element" 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, by providing the circularly polarizing plate on the surface of the organic EL display device so that the surface on the polarizing plate side faces the viewing side, it is possible to suppress light incident from the outside of the device from being reflected inside the device and being emitted to the outside of the device, and as a result, it is possible to suppress undesirable phenomena such as glare on the display surface of the organic EL display device.

[12. touch Panel ]

The touch panel of the present invention has the laminate of the present invention.

In the touch panel, the arrangement direction of the laminate is not limited, and the laminate is preferably provided such that the thermoplastic resin layer, the conductive layer, and the base material are arranged in this order 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, the polarizing plate is preferably disposed such that an angle θ 2 formed by the absorption axis of the polarizing plate and the slow axis of the substrate of the laminate is 45 °. In this way, it is possible to prevent the display content from becoming illegible due to the reflected light of the incident external light. The angle θ 2 of the absorption axis of the polarizing plate to the slow axis of the substrate of the laminate may contain an error in a range of, for example, ± 5 °, ± 3 °, ± 2 °, or ± 1 °.

The touch panel is generally combined with a laminate and has an image display element. Examples of the image display element include a liquid crystal display element and an organic electroluminescence display element (hereinafter, may be referred to as an "organic EL display element" as appropriate). In general, the laminate is provided on the viewing side of the image display element.

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

In general, an organic EL display element includes a first electrode layer, a light-emitting layer, and a second electrode layer in this order on a substrate, and the light-emitting layer can emit light when a voltage is applied across the first electrode layer and the second electrode layer. Examples of the material constituting the organic light-emitting layer include materials of a polyparaphenylene vinylene system, a polyfluorene system, and a polyvinyl carbazole system. The light-emitting layer may have a laminate of a plurality of layers having different emission colors, or a mixed layer in which a layer of a certain pigment is doped with a pigment different from the layer. Further, the organic EL display device may be provided with 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.

Examples

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 modifications may be made without departing from the scope and the range of equivalents of the claims.

In the following description, "%" and "part" of the indicated amounts are based on weight unless otherwise specified. The following operations are performed under normal temperature and normal pressure, unless otherwise specified.

[ evaluation method ]

[ method for measuring molecular weight ]

The weight average molecular weight and the number average molecular weight of the polymer were measured at 38 ℃ in terms of standard polystyrene by gel permeation chromatography using tetrahydrofuran as an eluent. As a measuring apparatus, HLC8320GPC manufactured by TOSOH CORPORATION was used.

[ method for measuring hydrogenation Rate ]

The hydrogenation rate of the polymer is determined by¹H-NMR measurement was carried out.

[ method for measuring glass transition temperature Tg ]

The glass transition temperature Tg of the sample was determined by using a Differential Scanning Calorimeter (DSC) at a temperature rise of 10 ℃ per minute.

[ method for measuring in-plane retardation Re ]

Re of the base material and the thermoplastic resin layer used in the examples and comparative examples (hereinafter, also referred to as "examples") was measured at a wavelength of 590nm by using a retardation measuring apparatus (product name Axoscan, manufactured by Axometric).

[ measurement of Total light transmittance ]

The total light transmittance of the thermoplastic resin layer and the substrate was measured using an ultraviolet-visible spectrometer at a wavelength ranging from 400nm to 700 nm.

[ method for measuring storage modulus ]

The storage modulus of the thermoplastic resin layer and the base material used in each example was measured using a dynamic viscoelasticity device ("DMS 6100" manufactured by SEIKO INSTRUMENTS INC.) at 25 ℃ and a frequency of 1 Hz. The storage modulus at-40 ℃ and 100 ℃ was measured for the thermoplastic resin layer in addition to the storage modulus at 25 ℃. Using these measurement results, the storage modulus E at 100 ℃ was calculated₂And storage modulus at-40 ℃ E₁Ratio of (E)₂/E₁)。

[ method for measuring moisture permeability ]

The moisture permeability of the thermoplastic resin layer and the substrate used in each example was measured by the Lyssy method (measuring apparatus L80-5000 (manufactured by Systech Illinois Co., Ltd.), under temperature conditions of 40 ℃ and humidity conditions of 90%).

[ adhesion evaluation test (checkerboard peeling test) ]

The laminate produced in each example was formed in a checkered pattern in which 100 regions of 1mm × 1mm were engraved on the thermoplastic resin layer side. Transparent tapes (nickiban co., ltd., width 24mm) were attached to 100 of the above-described regions, peeled off within 1 second, and the number of the peeled substrate regions was counted and evaluated according to the following evaluation criteria.

< evaluation criteria >

A: in a 100-point checkerboard test (JIS standard), the number of peeled pieces is 3 or less.

B: in a 100-point checkerboard test (JIS standard), the number of peeling was 4 or more and 10 or less.

C: in a 100-point checkerboard test (JIS standard), the number of peeled pieces was 11 or more.

[ evaluation of anti-migration Effect ]

< production of evaluation substrates in examples 1 to 6 and comparative examples 2 to 6 >

A laminate having a comb-shaped conductive layer was produced as a substrate for evaluation. Specifically, Silver Ink (manufactured by Sigma-Aldrich Japan, "Silver Nanoparticle Ink") was applied to the substrate used in each example using a bar coater, and dried at 120 ℃ for 60 seconds. Thereby, a layer containing silver particles with a thickness of 0.7 μm was formed on the substrate. On which a positive photoresist ("zp 1700" manufactured by ZEON corporation) was applied, dried, exposed, and developed to form a resist pattern. Then, etching treatment is carried out by using an acidic etching solution to manufacture a comb-shaped electrode pattern, so as to obtain the conductive layer. The line width of each electrode was 400 μm, and the gap between the electrodes was 100 μm. Next, a thermoplastic resin layer was formed on the base material on which the conductive layer was formed, according to the material and the forming method of the thermoplastic resin layer used in each example, to manufacture a substrate for evaluation.

< production of evaluation substrate in comparative example 1 >

In the production of the laminate of comparative example 1, the laminate formed by forming the ITO layer in a comb shape was used as a substrate for evaluation.

< evaluation method >

The evaluation substrates of the examples were left to stand under wet heat conditions of 85 ℃ and 90% RH. In this state, a voltage of 50V was applied between the electrodes to perform a migration test. The resistance value of the comb electrode was measured, and the time (hours) until the resistance value rapidly decreased was measured. Here, "the resistance value sharply decreases" means that the resistance value decreases by 4 orders or more (conduction). The longer the above time, the better the anti-migration effect.

[ evaluation of surface Change by reverse-folding test ]

The laminates produced in the respective examples were subjected to a folding test. In the folding test, the laminate was folded back with a curvature radius of 5mm using a bending tester (YUASA SYSTEM co., ltd. "TCDM 111 LH"), and the number of times of folding was measured when at least one of the disconnection of the conductive layer and the peeling of each layer occurred. The more times the bending is performed, the higher the bending resistance.

Production example 1 production of thermoplastic resin layer A

(A-1. production of hydrogenated product of Block copolymer)

Referring to the method described in international publication No. 2014/077267, a triblock copolymer hydride (ia1) (weight average molecular weight Mw 81000; molecular weight distribution Mw/Mn 1.11; hydrogenation rate of carbon-carbon unsaturated bonds in the main chain and side chain and carbon-carbon unsaturated bonds in the aromatic ring ≈ 100%) is produced by sequentially polymerizing 25 parts of styrene, a mixture of 26 parts of styrene and 24 parts of isoprene, and 25 parts of styrene.

(A-2. production of silyl-modified product)

Further, by referring to the method described in International publication No. 2014/077267, 100 parts of the above-mentioned hydrogenated triblock copolymer (ia1) and 1.8 parts of vinyltrimethoxysilane were combined to produce pellets of an alkoxysilyl-modified triblock copolymer (ia1-s) hydrogenated product.

(A-3. production of thermoplastic resin layer)

The thermoplastic resin layer a was produced by the following method using a twin-screw extruder ("TEM-37B" manufactured by toshiba machine) having a side feeder and a T-die having a width of 400mm and a sheet tractor having a casting roll and a release film supplying device.

The alkoxysilyl-modified product (ia1-s) was fed to a twin-screw extruder and brought into a molten state. The alkoxysilyl-modified product (ia1-s) (molten resin) in a molten state was extruded from the T-die onto a casting roll and formed into a film shape. The extrusion is carried out under molding conditions of a molten resin temperature of 180 ℃, a T die temperature of 180 ℃ and a casting roll temperature of 40 ℃. The extruded molten resin was cooled by a casting roll to obtain a thermoplastic resin layer having a thickness of 50 μm.

One side of the thermoplastic resin layer extruded onto the casting roll was supplied onto a polyethylene terephthalate (PET) film (thickness: 50 μm) for mold release, and the thermoplastic resin layer and the PET film were wound in a roll form and recovered. Thus, a film roll of a multilayer film having a thermoplastic resin layer and a PET film was obtained.

The multilayer film was taken out from the roll of the multilayer film, and the PET film was peeled off to obtain a thermoplastic resin layer a. The moisture permeability of the thermoplastic resin layer A is 2g/m²24h, storage modulus at 25 ℃ 1000MPa, E₂/E₁Is 10. The total light transmittance of the thermoplastic resin layer A was 92% and the in-plane retardation Re was 10 nm.

Production example 2 production of thermoplastic resin layer B

(B-1. production of hydrogenated product of Block copolymer)

With reference to the method described in international publication No. 2014/077267, a triblock copolymer hydride (ib1) (weight average molecular weight Mw 48200, molecular weight distribution Mw/Mn 1.04, hydrogenation rate of carbon-carbon unsaturated bonds in the main chain and side chain and carbon-carbon unsaturated bonds in the aromatic ring 100%) was produced by sequentially polymerizing 25 parts of styrene, 50 parts of isoprene, and 25 parts of styrene.

(B-2. production of silyl-modified product)

Further, by referring to the method described in International publication No. 2014/077267, 100 parts of the above-mentioned hydrogenated triblock copolymer (ib1) and 1.8 parts of vinyltrimethoxysilane were combined to produce pellets of an alkoxysilyl-modified triblock copolymer (ib 1-s).

(B-3. production of thermoplastic resin layer)

Using the sheet drawing 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. The hydrogenated polybutene (product "PARLEAM (registered trademark) 24" manufactured by NOF corporation) was continuously supplied from a side feeder at a ratio of 20 parts of hydrogenated polybutene (product "PARLEAM (registered trademark)) to 100 parts of the alkoxysilyl-modified product (ib1-s), to obtain a molten resin containing the above alkoxysilyl-modified product (ib1-s) and hydrogenated polybutene. Then, the molten resin was extruded from the T-die onto a casting roll and formed into a film shape. The extrusion is carried out under molding conditions of a molten resin temperature of 180 ℃, a T die temperature of 180 ℃, and a casting roll temperature of 40 ℃. The extruded molten resin was cooled by a casting roll to obtain a thermoplastic resin layer having a thickness of 50 μm.

A polyethylene terephthalate (PET) film (50 μm thick) for mold release was supplied to one side of the thermoplastic resin layer extruded onto the casting roll, and the thermoplastic resin layer and the PET film were wound in a roll form and recovered. Thus, a film roll of a multilayer film having a thermoplastic resin layer and a PET film was obtained.

The multilayer film was taken out from the 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 is 5g/m²24h, storage modulus at 25 ℃ of 128MPa, E₂/E₁Is 10. The total light transmittance of the thermoplastic resin layer B was 92%.

The thermoplastic resin layer B was produced by the following method.

The multilayer film was drawn from a roll of the multilayer film having the thermoplastic resin layer and the PET film obtained by the above-described method, and the PET film was peeled off to obtain a thermoplastic resin layer B. The moisture permeability of the thermoplastic resin layer B is 5g/m²24h, storage modulus at 25 ℃ of 12.8MPa, E₂/E₁Is 10. The total light transmittance of the thermoplastic resin layer B was 90% and the in-plane retardation Re was 10 nm.

Production example 3 production of thermoplastic resin layer C

Using the hydrogenated triblock copolymer (ib1) (polymer before silylation) obtained in (B-1) of production example 2, a thermoplastic resin layer C was produced by the following method.

(C-3) production of thermoplastic resin layer C

The thermoplastic resin layer C was produced using the sheet pulling machine used in (a-3) of production example 1.

A thermoplastic resin layer having a thickness of 50 μm was obtained in the same manner as in (A-3) of production example 1, except that the hydrogenated triblock copolymer (ib1) was fed to a twin-screw extruder in place of the alkoxysilyl-modified product (ia1-s) in (A-3) of production example 1.

A polyethylene terephthalate (PET) film (50 μm thick) for releasing was supplied to one side of the thermoplastic resin layer extruded onto the casting roll, and the thermoplastic resin layer and the PET film were wound in a roll form and recovered. Thus, a film roll of a multilayer film having a thermoplastic resin layer and a PET film was obtained.

The multilayer film was taken out from the roll of the multilayer film, and the PET film was peeled off to obtain a thermoplastic resin layer C. The thermoplastic resin layer C had a moisture permeability of 10g/m²24h, storage modulus at 25 ℃ of 128MPa, E₂/E₁Is 10. The total light transmittance of the thermoplastic resin layer C was 92% and the in-plane retardation Re was 10 nm.

Production example 4 production of thermoplastic resin layer D

A thermoplastic resin layer D was produced by the following method using the triblock copolymer hydride (ib1) (polymer before silylation) obtained in production example 2 (B-1) and a silane coupling agent.

(D-3) production of thermoplastic resin layer D

The thermoplastic resin layer D was produced using the sheet pulling machine used in (a-3) of production example 1.

A thermoplastic resin layer having a thickness of 50 μm was obtained in the same manner as in (a-3) of production example 1, except that 5 parts of a silane coupling agent (3-aminopropyltriethoxysilane (KE903 Shin-Etsu Chemical co., ltd.)) per 100 parts of the triblock copolymer hydride (ib1) and the triblock copolymer hydride was supplied to a twin-screw extruder instead of the alkoxysilyl-modified product (ia1-s) in (a-3) of production example 1.

The multilayer film was drawn from the roll of the multilayer film, and the PET film was peeled off to obtain a thermoplastic resin layer D. The thermoplastic resin layer D had a moisture permeability of 10g/m²24h, storage modulus at 25 ℃ of 128MPa, E₂/E₁Is 10. The total light transmittance of the thermoplastic resin layer D was 90% and the in-plane retardation Re was 10 nm.

[ example 1]

(1-1) preparation of substrate A

As the substrate, a resin Film (manufactured by ZEON CORPORATION, Inc. 'Zeonor Film ZF 16'; thickness 50 μm; glass transition temperature of resin 160 ℃, hereinafter also referred to as "substrate A") made of a norbornene-based polymer containing an alicyclic structure polymer having no crystallinity was prepared. The storage modulus of the substrate A at 25 ℃ was measured, and the result was 2300 MPa. Further, the moisture permeability of the substrate A was 2g/m²24h and an in-plane retardation Re of 5 nm. The total light transmittance of substrate a was 90%.

The surface of the substrate a was subjected to plasma treatment. The substrate A was irradiated with plasma at a resonance frequency of 25kHz and a moving speed of 5 cm/min while introducing 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 distance between the plasma generation source and the film was set to 5 mm.

(1-2) formation of conductive layer

Silver Ink (Silver Nanoparticle Ink manufactured by Sigma-Aldrich Japan) was prepared as a composition for forming a conductive layer containing Silver nanoparticles as metal particles.

The silver ink was coated on the plasma-treated substrate a using a bar coater, and dried at 120 ℃ for 60 seconds. Thereby, a layer containing silver particles having a thickness of 0.7 μm was formed on the substrate a. On the substrate a, a positive photoresist (ZPP 1700, manufactured by ZEON corporation) was applied, dried, exposed, and developed to form a pattern, and then an etching treatment was performed with an acidic etching solution to form a conductive layer on the substrate a. Thereby obtaining a substrate a having a conductive layer.

(1-3) production of laminate

A laminate was produced using the thermoplastic resin layer a produced in production example 1 as a thermoplastic resin layer.

After heating the substrate a having the conductive layer to about 100 ℃ on a hot plate, the thermoplastic resin layer a was placed on the conductive layer, and thermocompression bonding treatment was performed at a pressure of 0.3 MPa. Thereby, a laminate in which the thermoplastic resin layer is thermocompression bonded to the conductive layer is obtained. The obtained laminate was subjected to a folding test, 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 was performed by a method of applying a solution containing a thermoplastic resin using a crystalline resin film (substrate B) produced by the following method instead of the substrate a, thereby obtaining a laminate. The method for producing the laminate of this example will be described below.

(2-1) preparation of substrate B

(2-1-1) crystalline resin: production of crystalline COP resin (y1) containing hydride of ring-opened polymer of dicyclopentadiene

After the metal pressure-resistant reactor was sufficiently dried, nitrogen substitution was performed. 154.5 parts of cyclohexane, 42.8 parts (30 parts as dicyclopentadiene) of a 70% cyclohexane solution containing dicyclopentadiene (the content of an internal form is 99% or more) and 1.9 parts of 1-hexene were charged into the pressure resistant reactor and heated to 53 ℃.

0.014 part of tetrachlorotunglbenzimide (tetrahydrofuran) complex was dissolved in 0.70 part of toluene to prepare a solution. To the solution was added 0.061 parts of a 19% strength diethyl aluminum ethoxide/n-hexane solution, and stirred for 10 minutes to prepare a catalyst solution.

The catalyst solution is added into a pressure-resistant reactor to initiate ring-opening polymerization. Then, the reaction was carried out for 4 hours while maintaining 53 ℃ to obtain a solution of a ring-opened polymer of dicyclopentadiene. The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the obtained ring-opened polymer of dicyclopentadiene were 8750 and 28100, respectively, and the molecular weight distribution (Mw/Mn) determined therefrom was 3.21.

To 200 parts of the obtained solution of the ring-opened polymer of dicyclopentadiene, 0.037 part of 1, 2-ethanediol as a terminator was added, heated to 60 ℃ and stirred for 1 hour to terminate the polymerization reaction. At this time, 1 part of a hydrotalcite-like compound (KYOWAAD (registered trademark) 2000, manufactured by Kyowa Chemical Industry co., ltd.) was added, and the mixture was heated to 60 ℃ and stirred for 1 hour. Then, 0.4 part of a filter aid (SHOWA PAINT & coatngs co., ltd. "Radiolite (registered trademark) # 1500") was added, and the adsorbent and the solution were filtered using a PP pleated cartridge (ADVAN techthelologies JAPAN corp. "TCP-HX").

100 parts of cyclohexane was added to 200 parts (30 parts of the amount of the polymer) of the filtered solution of the ring-opened polymer of dicyclopentadiene, 0.0043 part of ruthenium carbonyl chloride hydride was added thereto, and hydrogenation was carried out at 180 ℃ for 4 hours under a hydrogen pressure of 6 MPa. Thereby, a reaction solution containing a hydride of the ring-opened polymer of dicyclopentadiene is obtained. In the reaction solution, a hydride precipitates to become a slurry solution.

The hydride and the solution contained in the reaction solution were separated by a centrifuge, and dried at 60 ℃ under reduced pressure for 24 hours to obtain 28.5 parts of a hydride of a ring-opened polymer of dicyclopentadiene having crystallinity. The hydrogenation rate of the hydride is 99% or more, the glass transition temperature Tg is 93 ℃, the melting point Mp is 262 ℃, and the ratio of syndiotactic diads is 89%.

To 100 parts of the hydrogenated product of the ring-opened dicyclopentadiene polymer obtained, 1.1 parts of an antioxidant (tetrakis [ methylene-3- (3 ', 5 ' -di-t-butyl-4 ' -hydroxyphenyl) propionate ] methane, "Irganox (registered trademark) 1010" manufactured by BASF GROUP corporation) was mixed and then charged into a twin-screw extruder (TEM-37B "manufactured by toshiba mechanical corporation) having 4 die holes with an inner diameter of 3mm Φ. The resin was molded by hot-melt extrusion using a twin-screw extruder to obtain a strand-shaped molded article, and then cut by a stranding machine to obtain pellets of a crystalline alicyclic structure polymer-containing resin (crystalline COP resin) (y 1). The crystalline COP resin (y1) is a resin containing a hydrogenated product of a ring-opening polymer of dicyclopentadiene, which is a polymer having a crystalline alicyclic structure.

The operating conditions of the twin-screw extruder described above are as follows.

The drum set temperature is 270 to 280 ℃.

The die set temperature was 250 ℃.

The screw speed was 145 rpm.

The feeder speed was 50 rpm.

(2-1-2) production of crystalline resin film

The crystalline COP resin (y1) obtained in 2.1.1 was supplied to a T-die at an extrusion screw temperature of 280 ℃, discharged from the T-die at a die extrusion temperature of 280 ℃, and cast on a cooling roll adjusted to a temperature of 60 ℃ to produce a film having a thickness of 15 μm and made of the crystalline COP resin. This film was annealed in an oven at 170 ℃ for 30 seconds to obtain a crystalline resin film (substrate B).

The base material B has a storage modulus of 2500MPa at 25 ℃ and a moisture permeability of 2g/m²24h and an in-plane retardation Re of 5 nm. The total light transmittance of substrate B was 90%.

(2-1-3) plasma treatment of substrate B

The substrate B was subjected to the plasma treatment in the same manner as the plasma treatment of the substrate a in (1-1) of example 1.

(2-2) formation of conductive layer

The same operation as in (2-1) of example 1 was performed except that the base material B was used instead of the base material a, and a conductive layer was formed on the base material B. Thereby obtaining a substrate B having a conductive layer.

(2-3) production of laminate

The thermoplastic resin layer a produced in production example 1 was dissolved in cyclohexane to prepare a solution (resin solution) containing 20 wt% of a thermoplastic resin. The resin solution was slit coated on a substrate B having a conductive layer, and then heated on a hot plate at 90 ℃ for 60 seconds to obtain a laminate having a thermoplastic resin layer A with a thickness of 35 μm. The obtained laminate was subjected to a folding test, and the results are shown in table 1.

[ example 3]

A laminate was obtained in the same manner as in example 1, except that a polyethylene terephthalate (PET) film (manufactured by TEIJIN limited., "PET film," substrate C ") was used instead of the substrate a. The obtained laminate was subjected to a folding test, and the results are shown in table 1.

The base material C has a storage modulus of 2300MPa at 25 ℃ and a moisture permeability of 10g/m²24h and an in-plane retardation Re of 150 nm. The total light transmittance of substrate C was 88%.

[ example 4]

A laminate was obtained in the same manner 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. The obtained laminate was subjected to a folding test, and the results are shown in table 1.

[ example 5]

A laminate was obtained in the same manner 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 and the substrate B was used instead of the substrate a. The obtained laminate was subjected to a folding test, and the results are shown in table 1.

[ example 6]

A laminate was obtained in the same manner 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 and a film containing a cycloaliphatic structure-free polymer having no crystallinity (Zeonor film ZD series, thickness 80 μm, "substrate D") having a slow axis in a direction of 45 ° with respect to the longitudinal direction was used instead of the substrate a. The obtained laminate was subjected to a folding test, and the results are shown in table 1. The base material D had a storage modulus of 2000MPa at 25 ℃ and a moisture permeability of 2g/m²24h and an in-plane retardation Re of 140 nm. The total light transmittance of the substrate D was 92%.

Comparative example 1

A laminate was obtained in the same manner as in example 1 except that a film of a resin containing an ethylene vinyl acetate copolymer (UBE-MARUZEN POLYETHYLENE, manufactured by UBE POLYETHYLENE V115, EVA film, thickness 100 μm) was used instead of the thermoplastic resin layer a. The obtained laminate was subjected to a folding test, and the results are shown in table 2.

The EVA film has a moisture permeability of 50g/m²24h, storage modulus at 25 ℃ 15MPa, E₂/E₁Is 250. The total light transmittance of the EVA film is89% and the in-plane retardation Re was 10 nm.

Comparative example 2

A laminate was obtained in the same manner as in example 1, except that an EVA film was used instead of the thermoplastic resin layer a, and a substrate C was used instead of the substrate a. The obtained laminate was subjected to a folding test, and the results are shown in table 2. The same EVA film as that used in comparative example 1 was used.

Comparative example 3

A laminate was obtained in the same manner as in example 1, except that the thermoplastic resin layer C (thermoplastic resin layer containing a hydrogenated triblock copolymer before silylation) produced in production example 3 was used instead of the thermoplastic resin layer a. The obtained laminate was subjected to a folding test, and the results are shown in table 2.

Comparative example 4

A laminate was obtained in the same manner as in example 1, except that the thermoplastic resin layer D (thermoplastic resin layer containing a hydrogenated triblock copolymer before silylation and a silane coupling agent) produced in production example 4 was used instead of the thermoplastic resin layer a. The obtained laminate was subjected to a folding test, and the results are shown in table 2.

Comparative example 5

A laminate was obtained in the same manner as in example 1, except that a resin film containing a copolymer of tetrafluoroethylene and ethylene (hereinafter referred to as "Fluon" in agcinc, ETFE film having a thickness of 100 μm) was used instead of the thermoplastic resin layer a. The obtained laminate was subjected to a folding test, and the results are shown in table 2.

The ETFE film has a moisture permeability of 3g/m²24h, storage modulus at 25 ℃ 2400MPa, E₂/E₁Is 30. The total light transmittance of the ETFE film was 90% and the in-plane retardation Re was 100 nm.

[ example 7]

The circularly polarizing plate of a commercial display device (organic EL display element) having the circularly polarizing plate disposed on the outermost surface was peeled off, and the laminate of example 6 was mounted so that the thermoplastic resin layer was on the outermost surface, to obtain a display device having a laminate. Reflectance before and after mounting the laminate on the display surface of the display device was measured by the optical splitter MCP-9800 for reflectance measurement made by OTSUKA ELECTRONICS co, Ltd, and as a result, reflectance of external light from the display device was suppressed to 95%.

The physical property values and evaluation test results of examples 1 to 6 and comparative examples 1 to 5 are shown in tables 1 and 2 below. In the following tables, the meanings of abbreviations are as follows.

"HSIS silyl modification": block copolymer hydride silyl modification.

"Ag-NW": silver nanowires.

"EVA": an EVA film.

"HSIS": block copolymer hydride.

"ETFE": an ETFE membrane.

"HSIS silyl modification": block copolymer hydride silyl modification.

"1000 <": more than 1000 times.

"100000 <": over 100000 hours.

[ Table 1]

TABLE 1

[ Table 2]

TABLE 2

[ results ]

As shown in tables 1 and 2, it is understood that the laminate of the example satisfying the requirements of the present invention is excellent in migration prevention effect and excellent in bending resistance. As a result, the laminate of the example satisfying the requirements of the present invention was excellent in migration prevention effect and flexibility.

Description of the reference numerals

10 … laminate

110 … thermoplastic resin layer

120 … conductive layer

130 … base material

Claims

1. A laminate comprising a thermoplastic resin layer, an electrically conductive layer and a substrate in this order,

the moisture permeability of the thermoplastic resin layer is 5g/m²A storage modulus at 25 ℃ of 1300MPa or less for 24 hours or less,

the conductive layer includes at least one element of Sn, Pb, Ag, Cu, and Au.

2. The laminate according to claim 1, wherein the thermoplastic resin layer comprises a polymer having a silyl group.

3. The laminate according to claim 2, wherein the polymer having a silyl group is a silyl-modified product of a block copolymer.

4. The laminate according to claim 2 or 3, wherein the polymer having a silyl group is a silyl-modified product of a copolymer of an aromatic vinyl monomer and a conjugated diene monomer.

5. 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.

6. The laminate according to any one of claims 1 to 5, wherein the thermoplastic resin layer has a storage modulus E at 100 ℃₂Storage modulus E at-40 ℃ with the thermoplastic resin layer₁Ratio of (E)₂/E₁) Is 15 or less.

7. The laminate according to any one of claims 1 to 6, wherein the substrate has a moisture permeability of 3g/m²24h or less.

8. The laminate of any one of claims 1 to 7, wherein the substrate is a polymer film comprising a polymer.

9. The laminate of any one of claims 1-8, wherein the substrate comprises a polymer comprising an alicyclic structure.

10. The laminate according to any one of claims 1 to 9, wherein the base material is an elongated film having a slow axis in an oblique direction with respect to a width direction of the film.

11. The laminate according to any one of claims 1 to 10, wherein the substrate has a storage modulus at 25 ℃ of 2000 to 3000 MPa.

12. The laminate according to any one of claims 1 to 11, wherein the thermoplastic resin layer has a phase difference in the in-plane direction of 10nm or less.

13. The laminate according to any one of claims 1 to 12, wherein at least one of the thermoplastic resin layer and the substrate has a total light transmittance of 80% or more.

14. A circularly polarizing plate comprising the laminate according to any one of claims 1 to 13 and a polarizing plate.

15. A display device having the circularly polarizing plate of claim 14.

16. The display device according to claim 15, wherein the display device is an organic electroluminescent device.

17. A touch panel comprising the laminate according to any one of claims 1 to 13.

18. The touch panel according to claim 17, comprising a polarizing plate provided in contact with the thermoplastic resin layer of the laminate.

19. The touch panel according to claim 17 or 18, which has the laminate and a polarizing plate,

the absorption axis of the polarizing plate forms an angle of 45 ° with the slow axis of the substrate of the laminate.

20. A method for producing a laminate according to any one of claims 1 to 13, comprising:

step 1 of forming the conductive layer on the substrate; and

a step 2 of forming the thermoplastic resin layer on the conductive layer,