JP7279392B2 - laminate - Google Patents

Description

The present invention relates to laminates.

The optical film may be folded during use depending on its use. Therefore, the optical film is sometimes required to have bending resistance (see Patent Document 1, for example).

WO2016/152871

The aforementioned Patent Document 1 describes that the bending resistance is improved by a film provided with three layers containing a predetermined polymer.
In recent years, flexible image display elements have been developed, and members such as touch panels including such image display elements are also required to have bending resistance. An optical film used as a member of a touch panel is sometimes attached to the touch panel via an adhesive layer, an adhesive layer, or the like. Since layers such as adhesive layers and adhesive layers are usually soft layers, optical films that are attached via such layers tend to leave creases when released from the folded state after being folded. Improvement in bending resistance is required.

As a result of intensive studies by the present inventors to solve the above problems, the present inventors have found that, in a laminate including a laminated film containing a base material and an inorganic layer, and a resin layer provided directly on the laminated film, the tension of the resin layer The present inventors have found that the above problems can be solved by setting the elastic modulus within a predetermined range and making the tensile elastic modulus of the laminated film 5% or more higher than that of the substrate, and completed the present invention. That is, the present invention provides the following.

[1] A laminated film containing a substrate and an inorganic layer having a thickness of 50 μm or less;
and a resin layer provided directly on the laminated film,
The resin layer has a tensile modulus of 10 ¹ Pa or more and less than 10 ⁹ Pa,
The laminated body, wherein the tensile elastic modulus of the laminated film is 5% or more higher than the tensile elastic modulus of the substrate.
[2] The laminate according to [1], wherein the tensile modulus of the laminated film is 7% or more higher than the tensile modulus of the substrate.
[3] The laminate according to [1] or [2], wherein the substrate has a thickness of 30 μm or less.
[4] The laminate according to any one of [1] to [3], wherein the inorganic layer has a surface resistance value of 10 ⁹ Ω/□ or more.
[5] Any one of [1] to [4], wherein the inorganic layer is a layer containing one or more selected from silicon oxides and oxynitrides, and aluminum oxides and oxynitrides. The laminate according to item 1.
[6] The laminate according to any one of [1] to [5], wherein the base material has a stress relaxation rate of 10% or less.

ADVANTAGE OF THE INVENTION According to this invention, the laminated body with favorable bending resistance can be provided.

FIG. 1 is a cross-sectional view schematically showing the laminate of Embodiment 1. FIG. FIG. 2 is a cross-sectional view schematically showing laminates produced in Examples 1 and 2. FIG. FIG. 3 is a cross-sectional view schematically showing a bending resistance evaluation test method. FIG. 4 is a cross-sectional view schematically showing a laminate described in another embodiment.

Hereinafter, the present invention will be described in detail by showing embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and can be arbitrarily modified without departing from the scope of the claims of the present invention and their equivalents. Moreover, the same reference numerals may be given to the same elements, and the description thereof may be omitted.

In the following description, the terms "parallel", "perpendicular" and "perpendicular" for the directions of the elements include errors within a range that does not impair the effects of the present invention, for example, within a range of ±5°, unless otherwise specified. You can stay.

[Overview of Laminate of the Present Invention]
The laminate of the present invention includes a laminate film containing a base material and an inorganic layer having a thickness of 50 μm or less, and a resin layer provided directly on the laminate film. In the laminate of the present invention, the resin layer has a tensile modulus of 10 ¹ Pa or more and less than 10 ⁹ Pa, and the tensile modulus of the laminated film is 5% or more higher than that of the substrate.

[Embodiment 1]
A laminate according to Embodiment 1 of the present invention will be described below with reference to FIG. FIG. 1 is a cross-sectional view schematically showing a laminate according to Embodiment 1. FIG.

As shown in FIG. 1, the laminate 100 of the present embodiment includes a laminate film 20 including a substrate 11 having a thickness of 50 μm or less and an inorganic layer 12, and a resin layer 15 provided directly on the laminate film 20. include.

[1. Laminated film]
Laminated film 20 includes substrate 11 and inorganic layer 12 .

[1.1. Base material]
Examples of the base material 11 include a resin film containing a polymer. Examples of the polymer contained in such a resin film include a crystalline alicyclic structure-containing polymer and a crystalline polystyrene polymer (see JP-A-2011-118137). be done. Among them, a crystalline alicyclic structure-containing polymer is preferable because it is excellent in transparency, low hygroscopicity, dimensional stability and lightness. A polymer having crystallinity refers to a polymer having a melting point Mp [that is, the melting point Mp can be observed with a differential scanning calorimeter (DSC)]. In the description below, a polymer having crystallinity is sometimes referred to as a "crystalline polymer". The resin film may contain a polymer having no crystallinity.

The alicyclic structure-containing polymer is a polymer having an alicyclic structure in its molecule, and is a polymer obtained by a polymerization reaction using a cyclic olefin as a monomer or a hydrogenated product thereof. In addition, the alicyclic structure-containing polymer may be used singly or in combination of two or more at any ratio.

The alicyclic structure possessed by the alicyclic structure-containing polymer includes, for example, a cycloalkane structure and a cycloalkene structure. Among these, a cycloalkane structure is preferable because a base material having excellent properties such as thermal stability can be easily obtained. The number of carbon atoms contained in one alicyclic structure is preferably 4 or more, more preferably 5 or more, preferably 30 or less, more preferably 20 or less, and particularly preferably 15 or less. be. When the number of carbon atoms contained in one alicyclic structure is within the above range, mechanical strength, heat resistance, and moldability are highly balanced.

In the alicyclic structure-containing polymer, the ratio of structural units having an alicyclic structure to all structural units is preferably 30% by weight or more, more preferably 50% by weight or more, and particularly preferably 70% by weight or more. . Heat resistance can be improved by increasing the ratio of structural units having an alicyclic structure in the alicyclic structure-containing polymer as described above.
In addition, in the alicyclic structure-containing polymer, the remainder other than structural units having an alicyclic structure is not particularly limited and can be appropriately selected according to the purpose of use.

Examples of the crystalline alicyclic structure-containing polymer include the following polymers (α) to (δ). Among these, the polymer (β) is preferable because a substrate having excellent heat resistance can be easily obtained.
Polymer (α): A ring-opening polymer of a cyclic olefin monomer and having crystallinity.
Polymer (β): A hydrogenated product of polymer (α) and having crystallinity.
Polymer (γ): A crystalline addition polymer of cyclic olefin monomers.
Polymer (δ): A hydrogenated product of polymer (γ) and having crystallinity.

Specifically, the crystalline alicyclic structure-containing polymer includes a ring-opening polymer of dicyclopentadiene having crystallinity, and a hydrogenated product of a ring-opening polymer of dicyclopentadiene. and having crystallinity is more preferable, and a hydrogenated product of a ring-opening polymer of dicyclopentadiene having crystallinity is particularly preferable. Here, the ring-opening polymer of dicyclopentadiene means that the ratio of structural units derived from dicyclopentadiene to all structural units is usually 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more, More preferably, it refers to 100% by weight of polymer.

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

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

The glass transition temperature Tg of the crystalline polymer is not particularly limited, but is usually 85° C. or higher and usually 170° C. or lower.

The weight average molecular weight (Mw) of the crystalline polymer is preferably 1,000 or more, more preferably 2,000 or more, and preferably 1,000,000 or less, more preferably 500,000 or less. A crystalline polymer having such a weight-average molecular weight has an excellent balance between moldability and heat resistance.

The molecular weight distribution (Mw/Mn) of the crystalline polymer is preferably 1.0 or more, more preferably 1.5 or more, and preferably 4.0 or less, more preferably 3.5 or less. Here, Mn represents the number average molecular weight. A crystalline polymer having such a molecular weight distribution is excellent in moldability.
The weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the crystalline polymer can be measured as polystyrene equivalent values by gel permeation chromatography (GPC) using tetrahydrofuran as a developing solvent.

The range of crystallinity of the crystalline polymer can be appropriately selected according to the desired performance. The crystallinity of the crystalline polymer is preferably 10% or more, more preferably 15% or more, from the viewpoint of imparting high heat resistance and chemical resistance to the substrate. The crystallinity of a crystalline polymer can be measured by X-ray diffractometry.

The proportion of the crystalline polymer in the substrate is preferably 50% by weight or more, more preferably 70% by weight or more, and particularly preferably 90% by weight or more. By setting the ratio of the crystalline polymer to the lower limit of the above range or more, the heat resistance of the substrate can be effectively increased.

The substrate may contain optional ingredients in addition to the crystalline polymer. Optional components include, for example, antioxidants such as phenol antioxidants, phosphorus antioxidants, and sulfur antioxidants; light stabilizers such as hindered amine light stabilizers; petroleum waxes, Fischer-Tropsch waxes, Waxes such as polyalkylene waxes; nucleating agents such as sorbitol compounds, metal salts of organic phosphoric acid, metal salts of organic carboxylic acids, kaolin and talc; diaminostilbene derivatives, coumarin derivatives, azole derivatives (e.g., benzoxazole derivatives, Fluorescent whitening agents such as benzotriazole derivatives, benzimidazole derivatives, and benzothiazole derivatives), carbazole derivatives, pyridine derivatives, naphthalic acid derivatives, and imidazolone derivatives; benzophenone-based UV absorbers, salicylic acid-based UV absorbers, benzotriazole-based UV absorbers such as UV absorbers; inorganic fillers such as talc, silica, calcium carbonate, glass fiber; coloring agents; flame retardants; flame retardant aids; antistatic agents; , and any polymer other than a crystalline polymer, such as a soft polymer; Moreover, arbitrary components may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.

The substrate can be produced by resin molding methods such as injection molding, extrusion molding, press molding, inflation molding, blow molding, calendar molding, cast molding, and compression molding. Among these, it is preferable to manufacture the substrate by the extrusion molding method because the thickness can be easily controlled.

[Physical properties of base material]
In the present invention, the thickness of the substrate is 50 μm or less. The thickness of the substrate is preferably 30 μm or less, more preferably 25 μm or less, preferably 1 μm or more, more preferably 5 μm or more. When the thickness of the substrate is 50 μm or less, the laminate can be easily folded. High mechanical strength can be obtained by setting the thickness of the base material to be at least the above lower limit.

The tensile elastic modulus of the substrate (substrate tensile elastic modulus T1) is preferably 10 ⁹ Pa or more, more preferably 2×10 ⁹ Pa or more, and preferably 10 ¹¹ Pa or less, more preferably 10 ¹⁰ Pa or less. is. When the tensile elastic modulus T1 of the substrate is equal to or higher than the lower limit, creases are less likely to remain when the laminate is released from the folded state after being folded. The tensile modulus T1 of the base material is measured using a tensile tester with a constant temperature and humidity chamber ("5564 type" manufactured by Instron) as a measuring device under the conditions of a measurement temperature of 23 ° C. and a measurement humidity of 40% RH. I can.

The stress relaxation rate of the substrate is preferably 10% or less. When the stress relaxation rate of the substrate is equal to or less than the upper limit, creases are less likely to remain when the laminate is released from the folded state after being folded.

In the present invention, the stress relaxation rate can be measured, for example, by the following method.
As a measuring device, using a tensile tester with a constant temperature and humidity chamber ("5564 type" manufactured by Instron), under the conditions of a measurement temperature of 23 ° C. and a measurement humidity of 40% RH, the measurement object (base material) After applying a strain of 2.0% at 20 mm / min, an operation of holding for 10 minutes was performed, and the stress value σ ₀ at the time when the strain reached 2.0% and the stress value σ after 10 minutes, is measured, and the stress relaxation rate is calculated from the following formula (1).
Stress relaxation rate (%) = [(σ ₀ - σ)/σ ₀ ] × 100 Equation (1)

The substrate preferably has a high total light transmittance. Specifically, the total light transmittance of the substrate is preferably 80% or higher, more preferably 85% or higher, and particularly preferably 88% or higher. The total light transmittance of the substrate can be measured using a UV-visible spectrometer in the wavelength range of 400 nm to 700 nm.

[1.2. inorganic layer]
The inorganic layer is a layer that can suppress deformation of the laminate that may occur when the laminate is folded, and can make crease marks inconspicuous. An inorganic layer is a layer formed of an inorganic material.

[Material of Inorganic Layer]
Inorganic materials that form the inorganic layer generally include inorganic oxides (MO _X ), inorganic nitrides (MN _Y ), inorganic carbides (MC _Z ), inorganic oxide carbides (MO _X C _Z ), inorganic nitride carbides (MN _Y C _Z ), inorganic oxynitrides (MO _X N _Y ), mixtures thereof, and the like. Among these, inorganic oxides and inorganic oxynitrides are preferred. Examples of M include silicon, aluminum, and magnesium.

Specific examples of inorganic materials include silicon oxide, silicon oxynitride, aluminum oxide, aluminum oxynitride, aluminum magnesium oxynitride, silicon aluminum oxynitride, and mixtures thereof. Inorganic layers formed from these inorganic materials are suitable for optical applications because they are less colored.

In the present invention, the inorganic layer is more preferably a layer containing one or more selected from oxides and oxynitrides of silicon and oxides and oxynitrides of aluminum. Such a layer has high transparency and is suitable for optical applications.

[Physical property values of inorganic layer]
The thickness of the inorganic layer is preferably 10 nm or more, more preferably 40 nm or more, and preferably 500 nm or less, more preferably 200 nm or less. When the thickness of the inorganic layer is equal to or greater than the lower limit, creases are less likely to remain when the laminate is released from the folded state after being folded. When the thickness of the inorganic layer is equal to or less than the upper limit, the laminate can be easily bent.

The surface resistance value of the inorganic layer is preferably 10 ⁹ Ω/□ or more, more preferably 10 ¹⁰ Ω/□ or more. When the surface resistance value is equal to or higher than the lower limit value, the laminate can have high insulating properties. The higher the surface resistance, the better, but it can be 10 ²⁰ Ω/□ or less.

The surface resistance value of the inorganic layer can be measured by the following method. An inorganic layer is formed on a substrate to form a laminated film, and the inorganic layer of the laminated film can be measured using a surface resistance measuring device (MCP-HT800 manufactured by Mitsubishi Chemical Analytic Tech).

The refractive index of the inorganic layer is preferably 1.4 or more, more preferably 1.5 or more, and preferably 2 or less, more preferably 1.8 or less. The refractive index of the inorganic layer can be measured by the following method. An inorganic layer is formed on a substrate to form a laminated film, and the inorganic layer of the laminated film can be measured using a spectroscopic ellipsometer M-2000U (manufactured by JA Woollam).

[1.3. Any layer that can be included in the laminated film]
The laminated film can be provided with any layer such as an optical functional layer in combination with the substrate and the inorganic layer.

[1.4. Laminated film manufacturing method]
A laminated film can be produced by forming an inorganic layer on a substrate. The inorganic layer can be formed by forming a film of the inorganic layer material (inorganic material) on the substrate. The film forming method is not particularly limited, and for example, a deposition method, a sputtering method, an ion plating method, an ion beam assisted deposition method, an arc discharge plasma deposition method, a thermal CVD method, a plasma CVD method, or the like can be used.

[1.5. Physical properties of laminated film]
The tensile elastic modulus (tensile elastic modulus T) of the laminated film is preferably 1.05×10 ⁹ Pa or more, more preferably 2.1×10 ⁹ Pa or more, and preferably 10 ¹¹ Pa or less, more preferably 10 ¹⁰ Pa or less. When the tensile modulus T is equal to or higher than the lower limit, creases are less likely to remain when the laminate is released from the folded state after being folded. The tensile modulus of the laminated film can be measured by applying a strain within a range that does not crack the inorganic layer, using a tensile tester with a constant temperature and humidity chamber ("5564 model" manufactured by Instron) as a measuring device.

In the present invention, the tensile modulus of the laminated film is 5% or more higher than that of the substrate. That is, the laminated film including the substrate and the inorganic layer has a tensile modulus 5% or more higher than that of the substrate. Therefore, in the laminate of the present invention containing the laminated film and the resin layer, when released from the folded state after folding, compared to the laminate in the aspect not containing the inorganic layer (laminate of only the base material and the resin layer) Does not easily leave crease marks.

The tensile modulus of the laminated film is preferably 7% or more, more preferably 15% or more, than the tensile modulus of the substrate. The value of Z (Z value) when the tensile elastic modulus of the laminated film is higher than the tensile elastic modulus of the substrate by Z % is calculated by the following formula (2). In formula (2), T is the tensile modulus of the laminated film, and T1 is the tensile modulus of the substrate.
Z = [(T-T1) / T1] × 100 Formula (2)

[2. resin layer]
The resin layer 15 is a layer provided directly on the laminated film 20 .
In this embodiment, the resin layer 15 is directly provided on the surface of the laminated film 20 on the inorganic layer 12 side, as shown in FIG. The resin layer can be a sticky or adhesive layer.

The resin layer 15 can be a layer made of a resin containing a thermoplastic resin. A thermoplastic resin usually contains a thermoplastic polymer and, if necessary, further contains optional components. A thermoplastic resin having tackiness or adhesiveness can be used.

[Thermoplastic resin]
The content of the thermoplastic polymer in the thermoplastic resin is preferably 55% by weight or more, more preferably 60% by weight or more, and still more preferably 65% by weight or more, relative to the total weight of the thermoplastic resin. be. The thermoplastic polymer content in the thermoplastic resin may be 100% by weight or less.

Examples of polymers contained in thermoplastic resins include, for example, aliphatic olefin polymers such as polyethylene and polypropylene; alicyclic olefin polymers; polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyarylene sulfides such as polyphenylene sulfide; Alcohol; polycarbonate; polyarylate; cellulose ester polymer; polyether sulfone; polysulfone; Polystyrene polymers containing copolymers; hydrides of copolymers of aromatic compounds such as styrene and conjugated dienes such as butadiene and isoprene (including aromatic ring hydrides); polyacrylonitrile; Methyl methacrylate; or multicomponent copolymers thereof, and the like. Optional monomers that can be used as monomers for polystyrene polymers include, for example, acrylonitrile, maleic anhydride, methyl methacrylate, and butadiene. One of these may be used alone, or two or more of them may be used in combination at any ratio.

The thermoplastic resin preferably contains a hydrogenated block copolymer [2] or a hydrogenated block copolymer [2] modified with an alkoxysilyl group [3].

[Block copolymer hydride [2]]
Block copolymer hydride [2] is a substance obtained by hydrogenating block copolymer [1] below. Hereinafter, block copolymer hydride [2] is also referred to as "hydride [2]".

[Block copolymer [1]]
Block copolymer [1] comprises two or more polymer blocks [A] per molecule of block copolymer [1] and one or more polymer blocks [A] per molecule of block copolymer [1]. B].

Polymer block [A] is a polymer block containing an aromatic vinyl compound unit. Here, the aromatic vinyl compound unit means a structural unit having a structure formed by polymerizing an aromatic vinyl compound.

Examples of the aromatic vinyl compound corresponding to the aromatic vinyl compound unit of the polymer block [A] include styrene; α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4 -Styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent, such as dimethylstyrene, 2,4-diisopropylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene; 4-chloro Styrenes having a halogen atom as a substituent, such as styrene, dichlorostyrene, and 4-monofluorostyrene; Styrenes having an alkoxy group having 1 to 6 carbon atoms as a substituent, such as 4-methoxystyrene; 4-phenylstyrene styrenes having an aryl group as a substituent such as; vinylnaphthalenes such as 1-vinylnaphthalene and 2-vinylnaphthalene; One of these may be used alone, or two or more of them may be used in combination at any ratio. Among these, aromatic vinyl compounds containing no polar group, such as styrene and styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent, are preferred because they can reduce hygroscopicity, and they are easy to obtain industrially. Therefore, styrene is particularly preferred.

The content of aromatic vinyl compound units in 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 compound unit in the polymer block [A] as described above, the hardness and heat resistance of the resin layer can be enhanced.

Polymer block [A] may contain any structural unit in addition to the aromatic vinyl compound unit. The polymer block [A] may contain any structural unit singly or may contain two or more types in combination at any ratio.

Arbitrary structural units that may be included in the polymer block [A] include, for example, chain conjugated diene compound units. Here, the chain conjugated diene compound unit means a structural unit having a structure formed by polymerizing a chain conjugated diene compound. Examples of the chain conjugated diene compound corresponding to the chain conjugated diene compound unit include the same examples as the chain conjugated diene compound corresponding to the chain conjugated diene compound unit of the polymer block [B]. mentioned.

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

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

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

When a plurality of different polymer blocks [A] are present in one molecule of the block copolymer [1], the weight average molecular weight of the polymer block having the maximum weight average molecular weight among the polymer blocks [A] is Mw. (A1), and the weight average molecular weight of the polymer block with the smallest weight average molecular weight is Mw (A2). At this time, the ratio "Mw (A1)/Mw (A2)" between Mw (A1) and Mw (A2) is preferably 4.0 or less, more preferably 3.0 or less, and particularly preferably 2.0 or less. is. As a result, variations in various physical property values can be suppressed.

Polymer block [B] is a polymer block containing a chain conjugated diene compound unit. As described above, the chain conjugated diene compound unit refers to a structural unit having a structure formed by polymerizing a chain conjugated diene compound.

Examples of the chain conjugated diene compound corresponding to the chain conjugated diene compound unit of the polymer block [B] include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1, 3-pentadiene and the like can be mentioned. One of these may be used alone, or two or more of them may be used in combination at any ratio. Among them, a linear conjugated diene compound containing no polar group is preferred, and 1,3-butadiene and isoprene are particularly preferred, since they can reduce hygroscopicity.

The content of chain conjugated diene compound units in the polymer block [B] is preferably 70% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more. By increasing the amount of chain conjugated diene compound units in the polymer block [B] as described above, the flexibility of the resin layer can be improved.

The polymer block [B] may contain any structural unit other than the chain conjugated diene compound unit. The polymer block [B] may contain any structural unit alone, or may contain two or more types in combination at any ratio.

The optional structural units that may be included in the polymer block [B] include, for example, aromatic vinyl compound units and any unsaturated compounds other than aromatic vinyl compounds and chain conjugated diene compounds that are polymerized to form A structural unit having a structure can be mentioned. These aromatic vinyl compound units and structural units having a structure formed by polymerizing any unsaturated compound include, for example, those exemplified as those that may be contained in the polymer block [A]. Same example as

The content of any structural unit in polymer block [B] is preferably 30% by weight or less, more preferably 20% by weight or less, and particularly preferably 10% by weight or less. The low content of any structural unit in the polymer block [B] can improve the flexibility of the resin layer.

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

When a plurality of different polymer blocks [B] are present in one molecule of the block copolymer [1], the weight average molecular weight of the polymer block having the maximum weight average molecular weight among the polymer blocks [B] is Mw. (B1), and the weight average molecular weight of the polymer block with the smallest weight average molecular weight is Mw (B2). At this time, the ratio "Mw (B1)/Mw (B2)" between Mw (B1) and Mw (B2) is preferably 4.0 or less, more preferably 3.0 or less, and particularly preferably 2.0 or less. is. As a result, variations in various physical property values can be suppressed.

The block form of the block copolymer [1] may be a linear block or a radial block. Among them, a chain type block is preferable because of its excellent mechanical strength. When the block copolymer [1] has the form of a chain type block, the polymer block [A] at both ends of the molecular chain of the block copolymer [1] reduces the stickiness of the resin layer to the desired low level. It is preferable because it can be suppressed to a value.

A particularly preferred block form of the block copolymer [1] is represented by [A]-[B]-[A], where the polymer block [A] is bound to both ends of the polymer block [B]. triblock copolymer; polymer block [B] is bound to both ends of polymer block [A] as represented by [A]-[B]-[A]-[B]-[A] and a pentablock copolymer in which polymer block [A] is bonded to the other end of both polymer blocks [B]. In particular, [A]-[B]-[A] triblock copolymers are particularly preferred because they are easy to produce and their physical properties can be easily adjusted within desired ranges.

In the block copolymer [1], the weight fraction wA of the polymer block [A] in the whole block copolymer [1] and the weight fraction wA of the polymer block [B] in the whole block copolymer [1] and the weight fraction wB (wA/wB) falls within a specific range. Specifically, the ratio (wA/wB) is usually 20/80 or more, preferably 25/75 or more, more preferably 30/70 or more, particularly preferably 40/60 or more, and usually 60/40. Below, preferably 55/45 or less. When the ratio wA/wB is equal to or higher than the lower limit of the range, the hardness and heat resistance of the resin layer can be improved, and the birefringence can be reduced. Further, when the ratio wA/wB is equal to or less than the upper limit of the range, the flexibility of the resin layer can be improved. Here, the weight fraction wA of the polymer block [A] indicates the weight fraction of the entire polymer block [A], and the weight fraction wB of the polymer block [B] indicates the entire polymer block [B]. shows the weight fraction of

The weight average molecular weight (Mw) of the block copolymer [1] is preferably 40,000 or more, more preferably 50,000 or more, particularly preferably 60,000 or more, and preferably 200,000 or less. More preferably 150,000 or less, particularly preferably 100,000 or less.
The molecular weight distribution (Mw/Mn) of 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. Here, Mn represents the number average molecular weight.
The weight-average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the block copolymer [1] were measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, and converted to polystyrene values. measurable.

As a method for producing the block copolymer [1], for example, a monomer composition (a) containing an aromatic vinyl compound and a monomer composition (b ) in which the monomer composition (a) containing an aromatic vinyl compound and the monomer composition (b) containing a chain conjugated diene compound are polymerized in order, followed by polymerizing the polymer block [B]. a method of coupling the ends with a coupling agent;

The content of the aromatic vinyl compound in the monomer composition (a) is preferably 90% by weight or more, more preferably 95% by weight or more, and particularly preferably 99% by weight or more. Moreover, the monomer composition (a) may contain any monomer component other than the aromatic vinyl compound. Examples of optional monomer components include chain conjugated diene compounds and optional unsaturated compounds. The amount of any monomer component is preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably 1% by weight or less based on the monomer composition (a).

The content of the linear conjugated diene compound in the monomer composition (b) is preferably 70% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more. Moreover, the monomer composition (b) may contain any monomer component other than the chain conjugated diene compound. Optional monomer components include aromatic vinyl compounds and optional unsaturated compounds. The amount of the optional monomer component is preferably 30% by weight or less, more preferably 20% by weight or less, particularly preferably 10% by weight or less, relative to the monomer composition (b).

Examples of the method of polymerizing the monomer composition to obtain each polymer block include radical polymerization, anionic polymerization, cationic polymerization, coordinated anionic polymerization, and coordinated cationic polymerization. From the viewpoint of facilitating the polymerization operation and the hydrogenation reaction in the post-process, a method of carrying out radical polymerization, anionic polymerization, cationic polymerization, or the like by living polymerization is preferred, and a method of carrying out living anionic polymerization is particularly preferred.

Polymerization may be carried out in the presence of a polymerization initiator. For example, in living anionic polymerization, as a polymerization initiator, n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, monoorganolithium such as phenyllithium; dilithiomethane, 1,4-dilithiobutane, 1,4-dilithio - polyfunctional organolithium compounds such as 2-ethylcyclohexane; One of these may be used alone, or two or more of them may be used in combination at any ratio.

The polymerization temperature is preferably 0° C. or higher, more preferably 10° C. or higher, particularly preferably 20° C. or higher, and preferably 100° C. or lower, more preferably 80° C. or lower, particularly preferably 70° C. or lower.

As the form of the polymerization reaction, for example, solution polymerization and slurry polymerization can be used. Among them, solution polymerization facilitates the removal of reaction heat.
When solution polymerization is carried out, an inert solvent in which the polymer obtained in each step can be dissolved can be used as the solvent. Examples of inert solvents include aliphatic hydrocarbon solvents such as n-butane, n-pentane, isopentane, n-hexane, n-heptane and isooctane; cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, decalin, bicyclo alicyclic hydrocarbon solvents such as [4.3.0]nonane and tricyclo[4.3.0.1 ^2,5 ]decane; aromatic hydrocarbon solvents such as benzene and toluene; One of these may be used alone, or two or more of them may be used in combination at any ratio. Among them, it is preferable to use an alicyclic hydrocarbon solvent as the solvent because it can be used as it is as an inert solvent for the hydrogenation reaction and the block copolymer [1] has good solubility. The amount of solvent used is preferably 200 to 2000 parts by weight per 100 parts by weight of the total monomers used.

When each monomer composition contains more than one type of monomer, a randomizer can be used to suppress chain lengthening of only one component. Especially when the polymerization reaction is carried out by anionic polymerization, it is preferable to use, for example, a Lewis base compound as a randomizer. Examples of Lewis base compounds include ether compounds such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, diphenyl ether, ethylene glycol diethyl ether, and ethylene glycol methylphenyl ether; tertiary amine compounds; alkali metal alkoxide compounds such as potassium-t-amyloxide and potassium-t-butyloxide; phosphine compounds such as triphenylphosphine; One of these may be used alone, or two or more of them may be used in combination at any ratio.

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

The hydrogenation rate is preferably 90% or more, more preferably 97% or more, of the carbon-carbon unsaturated bonds of the main chain and side chains and the carbon-carbon unsaturated bonds of the aromatic ring of the block copolymer [1], Particularly preferably, it is 99% or more. The higher the degree of hydrogenation, the better the transparency, heat resistance and weather resistance of the resin layer, and the easier it is to reduce the birefringence of the resin layer. Here, the hydrogenation rate of the hydride [2] can be determined by ¹ H-NMR measurement.

In particular, the hydrogenation rate of carbon-carbon unsaturated bonds in the main chain and side chains is preferably 95% or higher, more preferably 99% or higher. By increasing the hydrogenation rate of the carbon-carbon unsaturated bonds in the main chain and side chains, the light resistance and oxidation resistance of the resin layer can be further increased.

Also, the hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring is preferably 90% or more, more preferably 93% or more, and particularly preferably 95% or more. By increasing the hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring, the glass transition temperature of the polymer block obtained by hydrogenating the polymer block [A] is increased, so that the heat resistance of the resin layer is effectively improved. can be increased to

The weight average molecular weight (Mw) of the hydride [2] is preferably 40,000 or more, more preferably 50,000 or more, particularly preferably 60,000 or more, preferably 200,000 or less, more preferably 150. ,000 or less, particularly preferably 100,000 or less. By keeping the weight average molecular weight (Mw) of the hydride [2] within the above range, the mechanical strength and heat resistance of the resin layer can be improved, and the birefringence of the resin layer can be easily reduced.

The molecular weight distribution (Mw/Mn) of hydride [2] is preferably 3 or less, more preferably 2 or less, particularly preferably 1.5 or less, and preferably 1.0 or more. By keeping the molecular weight distribution (Mw/Mn) of the hydride [2] within the above range, the mechanical strength and heat resistance of the resin layer can be improved, and furthermore the birefringence of the resin layer can be easily reduced.

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

The aforementioned hydride [2] can be produced by hydrogenating the block copolymer [1]. As the hydrogenation method, a hydrogenation method capable of increasing the hydrogenation rate and causing less chain scission reaction of the block copolymer [1] is preferable. Examples of such a hydrogenation method include the methods described in International Publication No. 2011/096389 and International Publication No. 2012/043708.

Examples of specific hydrogenation methods include, for example, hydrogenation using a hydrogenation catalyst containing at least one metal selected from the group consisting of nickel, cobalt, iron, rhodium, palladium, platinum, ruthenium, and rhenium. There is a method of performing One type of hydrogenation catalyst may be used alone, or two or more types may be used in combination at an arbitrary ratio. Either a heterogeneous catalyst or a homogeneous catalyst can be used as the hydrogenation catalyst. Also, the hydrogenation reaction is preferably carried out in an organic solvent.

[Alkoxysilyl group-modified product [3]]
The alkoxysilyl group-modified product [3] is a polymer obtained by introducing an alkoxysilyl group into the hydride [2] of the block copolymer [1] described above. At this time, the alkoxysilyl group may be directly bonded to the hydride [2] described above, or may be indirectly bonded via a divalent organic group such as an alkylene group. The alkoxysilyl group-modified product [3] into which an alkoxysilyl group is introduced is particularly excellent in adhesiveness to an inorganic layer. Therefore, the resin layer usually has excellent adhesion to the inorganic layer.

The amount of the alkoxysilyl group introduced in the alkoxysilyl group-modified product [3] is preferably 0.1 parts by weight or more, more preferably 0.1 part by weight, relative to 100 parts by weight of the hydride [2] before the introduction of the alkoxysilyl group. It is 2 parts by weight or more, particularly preferably 0.3 parts by weight or more, preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and particularly preferably 3 parts by weight or less. When the amount of the alkoxysilyl group to be introduced is within the above range, the degree of cross-linking between the alkoxysilyl groups decomposed by moisture or the like can be prevented from becoming excessively high, so that the adhesiveness of the resin layer to the inorganic layer can be maintained at a high level. can be done.
The amount of alkoxysilyl groups introduced can be measured by ¹ H-NMR spectrum. When measuring the introduction amount of the alkoxysilyl group, if the introduction amount is small, the measurement can be performed by increasing the number of accumulations.

Alkoxysilyl group-modified product [3] can be produced by introducing an alkoxysilyl group into hydride [2] of block copolymer [1] described above. A method of introducing an alkoxysilyl group into the hydride [2] includes, for example, a method of reacting the hydride [2] with an ethylenically unsaturated silane compound in the presence of a peroxide.

As the ethylenically unsaturated silane compound, a compound capable of graft polymerization with the hydride [2] and introducing an alkoxysilyl group into the hydride [2] can be used. Examples of such ethylenically unsaturated silane compounds include alkoxysilanes having a vinyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane; allyltrimethoxysilane, allyltriethoxysilane; alkoxysilanes having an allyl group such as; alkoxysilanes having a p-styryl group such as p-styryltrimethoxysilane and p-styryltriethoxysilane; 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropylmethyldimethoxysilane , 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, etc., alkoxysilanes having a 3-methacryloxypropyl group; 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, etc. alkoxysilanes having a 3-acryloxypropyl group of; alkoxysilanes having a 2-norbornen-5-yl group such as 2-norbornen-5-yltrimethoxysilane; Among these, vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, allyltrimethoxysilane, allyltriethoxysilane, and p-styryltrimethoxysilane are preferred because the effects of the present invention are more likely to be obtained. Silanes are preferred. Also, the ethylenically unsaturated silane compounds may be used singly or in combination of two or more at any ratio.

The amount of the ethylenically unsaturated silane compound is preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, and particularly It is preferably 0.3 parts 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.

In the thermoplastic resin, the proportion of the hydride [2] or the alkoxysilyl group-modified product [3] is preferably 80% to 100% by weight, more preferably 90% to 100% by weight, and particularly preferably 95% by weight. ~100% by weight.

[Optional components other than thermoplastic resin]
The resin forming the resin layer may contain any component in addition to the thermoplastic resin. Optional ingredients include, for example, liquid paraffins such as hydrogenated polybutenes.

Any component other than the thermoplastic resin in the resin layer is preferably 45% by weight or less, more preferably 40% by weight or less. Any component other than the thermoplastic resin in the resin layer may be 0% by weight or more.

[Physical properties of resin layer]
The thickness of the resin layer is preferably 100 µm or less, more preferably 50 µm or less, and preferably 1 µm or more, more preferably 5 µm or more. When the thickness of the resin layer is equal to or less than the upper limit, the laminate can be easily bent.

The tensile elastic modulus (tensile elastic modulus T2) of the resin layer is 10 ¹ Pa or more and less than 10 ⁹ Pa. The tensile modulus T2 is preferably 10 ² Pa or more, more preferably 10 ⁵ Pa or more, and preferably 8×10 ⁸ Pa or less, more preferably 5×10 ⁸ Pa or less. When the tensile elastic modulus T2 is within the above range, the laminate can be easily bent, and the laminate can be made difficult to peel off from the object to which it is bonded. The tensile modulus of the resin layer can be measured using a tensile tester with a constant temperature and humidity chamber ("5564 model" manufactured by Instron).

[Laminate production method]
A laminate can be produced by providing a resin layer directly on a laminate film. Specifically, a method of applying or printing a resin liquid (resin composition) containing components constituting a resin layer onto a laminated film, and a resin layer formed by applying the resin liquid onto a release film. can be formed by a method of laminating on a laminate film, a method of laminating a resin layer obtained by forming a film of pellets composed of the components constituting the resin layer on the laminate film, or the like.

[3. Any layer that the laminate may contain]
The laminate may contain any layer in addition to the laminated film and the resin layer depending on the purpose of use of the laminate. Examples of such an optional layer include a protective layer that prevents foreign matter from adhering to the resin layer.

[4. Application of laminate]
The laminate of the present invention can be used for various optical applications. For example, it can be used as a member of a touch panel.
Since the laminate of the present invention has good bending resistance, it can be used particularly in combination with a flexible image display element (flexible display element), such as a flexible touch panel. It can be a device having

[5. Action/effect]
In the present embodiment, the laminate 100 includes a laminate film 20 including a substrate 11 and an inorganic layer 12 having a thickness of 50 μm or less, and a resin layer 15 provided directly on the laminate film 20. The tensile modulus is 5% or more greater than the tensile modulus of the substrate 11 . Therefore, in the laminate 100 of the present embodiment including the laminate film 20 and the resin layer 15, after folding the laminate, the laminate does not contain an inorganic layer (laminate consisting only of the base material and the resin layer). Fold marks are less likely to remain when released from the folded state. As a result, according to this embodiment, it is possible to provide a laminate having good bending resistance.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to Examples. However, the present invention is not limited to the examples shown below, and can be arbitrarily modified without departing from the scope of the claims of the present invention and their equivalents.
In the following description, "%" and "parts" representing amounts are by weight unless otherwise specified. In addition, unless otherwise specified, the operations described below were performed under normal temperature and pressure conditions.

[Evaluation method]
[Method for measuring weight average molecular weight and number average molecular weight]
The weight-average molecular weight and number-average molecular weight of the polymer were measured using a gel permeation chromatography (GPC) system ("HLC-8320" manufactured by Tosoh Corporation) in terms of polystyrene. During the measurement, an H-type column (manufactured by Tosoh Corporation) was used as the column, and tetrahydrofuran was used as the solvent. Moreover, the temperature at the time of measurement was 40°C.

[Method for measuring polymerization conversion]
The polymerization conversion rate during the synthesis of the polymer was measured by GPC.

[Method for measuring hydrogenation rate of hydrogenated block copolymer]
The hydrogenation rate of the polymer was measured by ¹ H-NMR measurement at 145° C. using ortho-dichlorobenzene-d ₄ as a solvent.

[Thickness measurement method]
For the laminate (film) to be measured, the thickness was measured at arbitrary four points with a snap gauge (manufactured by Mitutoyo), and the average value was obtained as the thickness (film thickness).

[Measurement of tensile modulus]
The tensile modulus of the film to be measured was measured according to JIS K7127. A type 1B dumbbell-shaped test piece was punched out from the film to be measured and used as a measurement sample. As a measurement sample, 5 pieces along the flow direction (MD direction) of the film at the time of melt extrusion or injection molding, and 5 pieces along the film width direction (TD direction) perpendicular to the flow direction, a total of 10 pieces. was punched out of the film. A tensile tester with a constant temperature and humidity chamber (“5564 model” manufactured by Instron) was used as a measuring device. The measurement was performed under the measurement conditions of a measurement temperature of 23° C. and a measurement humidity of 40% RH. In addition, the tensile speed was 20 mm / min, and the average tensile modulus of the test piece (N = 5) punched along the MD direction and the test piece (N = 5) punched along the TD direction The value was taken as the tensile modulus of the film.

[Measurement of surface resistance]
The surface resistance value of the inorganic layer of the laminated film obtained by forming the inorganic layer on the substrate was measured using a surface resistance measuring device (MCP-HT800 manufactured by Mitsubishi Chemical Analytic Tech).

[Measurement of refractive index of inorganic layer]
The refractive index of the inorganic layer of the laminated film obtained by forming the inorganic layer on the substrate was measured using a spectroscopic ellipsometer M-2000U (manufactured by JA Woollam).

[Bending resistance test]
Laminates of Examples, laminates of Comparative Examples, and films of Reference Examples (hereinafter also simply referred to as "laminates") were tested using a desktop endurance tester ("DLDMLH-FS" manufactured by Yuasa System Co., Ltd.). , an evaluation test for bending resistance was performed (see FIG. 3). FIG. 3 is a cross-sectional view schematically showing a bending resistance evaluation test method.

(Evaluation of bending resistance under the condition of a bending radius of 3 mm)
The laminates of Examples and Comparative Examples were bent so as to have a bending radius of 3 mm and left to stand for 24 hours. The laminate was folded and left at rest by adjusting the distance X between the two plates P1 and P2 (see FIG. 3). After that, the laminate was taken out from the apparatus, and the state of deformation was visually observed (first visual observation). Furthermore, after the laminate after the first visual observation was allowed to stand on a horizontal table for 12 hours, the second visual observation was performed and evaluation was performed according to the following evaluation criteria. Table 1 shows the results. If the evaluation result is A, the bending resistance is good.
(Evaluation criteria)
A: No deformation is observed in the laminate (film) in the first visual observation.
B: Deformation is observed in the first visual observation, but no deformation is observed in the second visual observation.
C: Deformation is observed in both the first and second visual observations.

(Evaluation of bending resistance under the condition of a bending radius of 2 mm)
For the laminates of Examples, the laminates of Comparative Examples, and the films of Reference Examples, except that the bending radius was set to 2 mm, the same operation as when the bending radius was 3 mm was performed, and the bending radius was 3 mm. The bending resistance was evaluated according to the same evaluation criteria as. The results are shown in Tables 1 and 2. The condition "bending radius 2 mm" is stricter than "bending radius 3 mm", so if the evaluation result is A for the bending radius 2 mm, the bending resistance is particularly good.

[Measurement of stress relaxation rate]
From the resin film A produced in Production Example 1 and the films of Reference Examples 1 to 3, a test piece having a shape of type 1B defined in JIS K2127 was punched out and used as a measurement sample. As a measuring device, a tensile tester with a constant temperature and humidity chamber ("5564 type" manufactured by Instron) was used, and the strain was 2.0% at a measurement temperature of 23°C, a measurement humidity of 40% RH, and a tensile speed of 20 mm/min. After applying, the operation is held for 10 minutes, and the stress value σ ₀ at the time when the strain reaches 2.0% and the stress value σ after 10 minutes are measured, and the stress relaxation rate is calculated by the following formula Calculated from (1). Table 2 shows the results.
Stress relaxation rate (%) = [(σ ₀ - σ)/σ ₀ ] × 100 Equation (1)

[Production Example 1: Production of base material]
(1-1. Production of hydrogenated product of ring-opening polymer of dicyclopentadiene)
After sufficiently drying the metal pressure-resistant reactor, the atmosphere was replaced with nitrogen. In this metal pressure-resistant reactor, 154.5 parts of cyclohexane, 42.8 parts of a 70% cyclohexane solution of dicyclopentadiene (the content of endo bodies is 99% or more) (30 parts as the amount of dicyclopentadiene), and 1- Add 1.9 parts of hexene and heat to 53°C.

To a solution of 0.014 parts of tetrachlorotungstenphenylimide (tetrahydrofuran) complex dissolved in 0.70 parts of toluene, 0.061 parts of a 19% diethylaluminum ethoxide/n-hexane solution was added and stirred for 10 minutes. to prepare a catalyst solution.
This catalyst solution was added to the pressure reactor to initiate the ring-opening polymerization reaction. Thereafter, the mixture was allowed to react for 4 hours while maintaining the temperature at 53° C. to obtain a solution of a ring-opening polymer of dicyclopentadiene.
The obtained ring-opening polymer of dicyclopentadiene had a number average molecular weight (Mn) and a weight average molecular weight (Mw) of 8,750 and 28,100, respectively. was 3.21.

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

To 200 parts of the solution of the ring-opening polymer of dicyclopentadiene after filtration (polymer amount: 30 parts), 100 parts of cyclohexane was added, 0.0043 parts of chlorohydridocarbonyltris(triphenylphosphine)ruthenium was added, and hydrogen was added. A hydrogenation reaction was carried out at a pressure of 6 MPa and 180° C. for 4 hours. As a result, a reaction liquid containing the hydrogenated product of the ring-opening polymer of dicyclopentadiene was obtained. This reaction solution was a slurry solution with precipitation of the hydrogenated product.

The hydrogenated product and the solution contained in the reaction solution are separated using a centrifugal separator and dried under reduced pressure at 60° C. for 24 hours to obtain a hydrogenated product of a crystalline ring-opening polymer of dicyclopentadiene. 28.5 parts were obtained. This hydrogenated product had a hydrogenation rate of 99% or more, a glass transition temperature Tg of 93°C, a melting point Mp of 262°C, and a ratio of racemo dyads of 89%.

(1-2. Production of resin film A (substrate))
An antioxidant (tetrakis[methylene-3-(3′,5′-di-t-butyl-4′- Hydroxyphenyl)propionate]methane; "Irganox (registered trademark) 1010" manufactured by BASF Japan Co., Ltd.) was mixed with 1.1 parts to obtain a resin serving as a base material.

The above resin was put into a twin-screw extruder (“TEM-37B” manufactured by Toshiba Machine Co., Ltd.) equipped with four die holes with an inner diameter of 3 mmΦ. Using the twin-screw extruder, the resin was molded into a strand-like molding by hot-melt extrusion molding. This compact was cut into small pieces with a strand cutter to obtain resin pellets. The operating conditions of the twin-screw extruder are shown below.
・Barrel setting temperature: 270°C to 280°C
・Die setting temperature: 250°C
・Screw rotation speed: 145 rpm
・Feeder rotation speed: 50 rpm

The resulting pellets were subsequently fed to a hot-melt extrusion film former equipped with a T-die. Using this film forming machine, a resin film A (thickness: 15 μm, width: 120 mm) composed of the above resin was produced by winding onto a roll at a speed of 6.7 m/min. The operating conditions of the film forming machine are shown below.
・Barrel temperature setting: 280°C to 290°C
・Die temperature: 270°C
・Screw rotation speed: 30 rpm
When the stress relaxation rate of resin film A was measured, it was 9%.

[Production Example 2: Production of resin film B (film of Reference Example 3)]
In Production Example 1 (1-2), the same operation as in Production Example 1 was performed except that the winding speed of the hot-melt extrusion film forming machine was changed to 2.5 m / min, and a resin film B having a thickness of 40 μm was prepared. got

[Production Example 3: Production of film X (resin layer)]
(3-1. Production of alkoxysilyl-modified product (a1-s) of hydrogenated triblock copolymer)
With reference to the method described in International Publication No. 2014/077267, 25 parts of styrene, 50 parts of isoprene and 25 parts of styrene are polymerized in this order to obtain a hydrogenated triblock copolymer (a1) (weight average molecular weight Mw = 48,200; molecular weight distribution Mw/Mn = 1.04; carbon-carbon unsaturated bonds of the main chain and side chains, and hydrogenation rate of carbon-carbon unsaturated bonds of the aromatic ring was almost 100%). . Furthermore, with reference to the method described in International Publication No. WO 2014/077267, 2 parts of vinyltrimethoxysilane are bonded to 100 parts of the hydrogenated triblock copolymer (a1) to obtain a triblock copolymer. Pellets of alkoxysilyl-modified polymer hydride (a1-s) were produced.

A film X having a thickness of 10 μm was obtained by injection molding using the obtained modified product (a1-s). The tensile modulus of the obtained film X was measured and found to be 360 MPa (3.6×10 ⁸ Pa).

[Production Example 4: Production of film Y (film of Reference Example 1)]
Using pellets of the alkoxysilyl-modified triblock copolymer hydride (a1-s) obtained in Production Example 3, a film Y having a thickness of 40 μm was obtained by injection molding.

[Example 1: Production of laminate]
Using the resin film A produced in Production Example 1 as a substrate, a laminate shown in FIG. 2 was produced. FIG. 2 is a cross-sectional view schematically showing laminates 200 of Examples 1 and 2. As shown in FIG. In FIG. 2, 11 is a substrate, 12 is an inorganic layer, 15 is a resin layer, and 20 is a laminated film. The laminate 200 is composed of two laminated films 20 and a resin layer 15 provided between the laminated films 20 . The surfaces of the two laminated films 20 on the inorganic layer 12 side are in direct contact with the resin layer 15 . The laminate 200 was manufactured by the following method.

On the resin film A (thickness 15 μm), a silicon oxynitride (SiO _X N _Y , _X : _Y =1:0) having a thickness of 200 nm is formed by a sputtering method so as to have a refractive index of about 1.7. Layers 1 to 2) were formed to obtain laminated film A1. Two sample films each having a size of 5×10 cm were cut out from this laminated film A1. Using the film X produced in Production Example 3, two sample films were laminated together by a heating laminator to obtain a laminate. The inorganic layer (SiON layer) side of each sample film was placed on the film X when the laminate was produced. The resulting laminate had a structure in which laminated film A1, film X, and laminated film A1 were laminated in this order (laminated film A1/film X/laminated film A1) (see FIG. 2). The thickness of this laminate was 40 μm.
When the obtained laminate was subjected to a bending test, no crease was observed under any of the conditions of R=3 mm and R=2 mm.

[Example 2]
A laminate was obtained in the same manner as in Example 1, except that instead of the laminated film A1, a laminated film B1 produced by the following method was used. The resulting laminate had a structure in which laminated film B1, film X, and laminated film B1 were laminated in this order (laminated film B1/film X/laminated film B1). The thickness of this laminate was 40 μm. A bending test was performed on this laminate. Table 1 shows the results.

(Manufacturing method of laminated film B1)
Silicon oxynitride (SiO _X N _Y ) having a thickness of 100 nm was deposited on the resin film A (thickness 15 μm) produced in Production Example 1 by sputtering so as to have a refractive index of about 1.7. A laminated film B was produced by forming a layer of

[Comparative Example 1]
A laminate was obtained in the same manner as in Example 1, except that the resin film A (thickness: 15 μm) produced in Production Example 1 was used instead of the laminate film A1. The resulting laminate had a structure in which resin film A, film X, and resin film A were laminated in this order (resin film A/film X/resin film A), and had a thickness of 40 μm. A bending test was performed on this laminate. Table 1 shows the results. The laminate of Comparative Example 1 does not contain an inorganic layer.

In Tables 1 and 2, "a crease (R = 3 mm)" means a case where the bending radius is 3 mm in the bending resistance test, and "a crease (R = 2 mm)" means bending resistance. This means that the test was performed under the condition of a bending radius of 2 mm.
In Table 1, the surface resistance value of 10 ¹⁰ Ω/□ or more means that it exceeded the upper limit value (10 ¹⁰ Ω/□) of the measurement range of the surface resistance value measuring device.

[Reference Examples 1 to 3]
The films of the following reference examples were measured for tensile modulus and stress relaxation rate, and subjected to a bending resistance test. Table 2 shows the results.
Reference Example 1: A film Y produced in Production Example 4, which is made of the same material as Film X (corresponding to the resin layer) of Production Example 3 and has a thickness of 40 μm.
Reference Example 2: Polyethylene terephthalate (PET) film (manufactured by Mitsubishi Chemical Corporation, thickness 40 μm).
Reference Example 3: Resin film B produced in Production Example 2, which is made of the same material as resin film A (corresponding to the substrate) of Production Example 1 and has a thickness of 40 μm.

As shown in Table 1, the laminate of the example containing the laminated film containing the substrate and the inorganic layer, and the resin layer provided directly on the laminated film is the laminate of the comparative example that does not contain the inorganic layer. In comparison, it can be seen that deformation after bending is less likely to occur (a crease scar is less likely to remain). From the above results, according to the laminates of Examples 1 and 2, which satisfy the requirements defined in the present invention, laminates having good bending resistance can be realized.

[Other embodiments]
(1) In the above-described embodiments and examples, the laminated body in which the resin layer is formed directly on the inorganic layer of the laminated film is shown, but the present invention is not limited to this. For example, the laminated body 300 shown in FIG. 4 may be used. FIG. 4 is a cross-sectional view schematically showing the laminate described in this embodiment. This laminate 300 is a mode in which the resin layer 15 is formed directly on the substrate 11 of the laminate film 20 .

DESCRIPTION OF SYMBOLS 100,200,300... Laminate 11... Base material 12... Inorganic layer 15... Resin layer 20... Laminated film

Claims (5)

A laminated film comprising a base material having a thickness of 50 μm or less and an inorganic layer;
and a resin layer provided directly on the laminated film,
The substrate is a resin film containing one or more selected from the group consisting of a crystalline alicyclic structure-containing polymer and a crystalline polystyrene polymer,
The resin layer has a tensile modulus of 10 ¹ Pa or more and less than 10 ⁹ Pa,
The resin layer is a block copolymer hydride [2] having a weight average molecular weight of 40,000 or more and 200,000 or less, or the block copolymer having a weight average molecular weight of 40,000 or more and 200,000 or less. The block copolymer hydride [2] is a block copolymer containing a polymer block [A] and a polymer block [B]. It is a hydride of [1], the polymer block [A] is a polymer block containing aromatic vinyl compound units, and the polymer block [B] contains chain conjugated diene compound units. is a polymer block that
The thickness of the resin layer is 1 μm or more and 100 μm or less,
The inorganic layer is a layer containing silicon oxynitride, and the thickness of the inorganic layer is 10 nm or more and 500 nm or less,
The laminated body, wherein the tensile elastic modulus of the laminated film is 5% or more higher than the tensile elastic modulus of the substrate. The laminate according to claim 1, wherein the tensile elastic modulus of the laminated film is 7% or more higher than the tensile elastic modulus of the substrate. 3. The laminate according to claim 1, wherein the base material has a thickness of 30 [mu]m or less. The laminate according to any one of claims 1 to 3, wherein the inorganic layer has a surface resistance value of 10 ⁹ Ω/□ or more. The laminate according to any one of claims 1 to 4 , wherein the stress relaxation rate of the base material is 10% or less.

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