Film and layered body

Abstract

To provide a film with superior adhesion, and a layered body having the film.SOLUTION: A film 1 comprises a base material layer 3 and a cured resin layer 4 in this order toward one side in the thickness direction. When the one surface in the thickness direction of the cured resin layer 4 is subjected to measurements by X-ray photoelectron spectroscopy, the peak intensity ICC, attributed to the C-C bond at 285 eV, the peak intensity ICOO, attributed to the COO bond at 289 eV, and the peak intensity IO of the O1 s spectrum at 532 eV, satisfy the relationships (1) and (2). ICOO / ICC>0.5 (1) and IO / ICC>1.2 (2).SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a film and a laminate, and more particularly to a film and a laminate including the film. [Background technology]

[0002] In order to achieve weight reduction and high performance in electronics products, composite materials that combine organic and inorganic materials have been developed. For example, a laminated film that includes an organic substrate film and an inorganic layer on the substrate film is known as a composite material.

[0003] As such a laminated film, for example, a hard coat film having a film substrate and a hard coat layer in this order, an inorganic oxide primer layer, and an antireflection film having an antireflection layer in this order, have been proposed (see, for example, Patent Document 1).

[0004] In Patent Document 1, the hard coat layer is subjected to a plasma treatment before a primer layer is formed on the hard coat layer. Such a treatment can remove dirt and moisture from the surface of the hard coat film (hard coat layer) and improve the adhesion between the hard coat film and the antireflection layer. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2022-65437 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the substrate film (hard coat film) of Patent Document 1 has the drawback of insufficient adhesion, and therefore the substrate film (hard coat film) is required to have even better adhesion.

[0007] The present invention provides a film having excellent adhesion and a laminate including the film. [Means for solving the problem]

[0008] The present invention [1] is a method for manufacturing a cured resin film having a substrate layer and a cured resin layer in this order toward one side in the thickness direction, and a peak intensity I attributable to a C-C bond at 285 eV measured by X-ray photoelectron spectroscopy on one side in the thickness direction of the cured resin layer. CC , the peak intensity I at 289 eV assigned to the CO-O bond COO , and the peak intensity I of the O1s spectrum located at 532 eV O is a film that satisfies the following formula (1) and formula (2). I COO / I CC >0.5 (1) I O / I CC >1.2 (2)

[0009] The present invention [2] includes the film according to the above [1], wherein the cured resin layer includes a cured product of an acrylate resin.

[0010] The present invention [3] includes a laminate comprising the film according to [1] or [2] above and an inorganic layer in that order toward one side in the thickness direction.

[0011] The present invention [4] includes the laminate according to the above [3], in which the inorganic layer is an anti-reflection layer, and the anti-reflection layer comprises a plurality of layers having different refractive indices along the thickness direction.

[0012] The present invention [5] includes the laminate according to the above [3], in which the inorganic layer is a conductive layer. [Effects of the Invention]

[0013] The film of the present invention has a peak intensity I at 285 eV assigned to a C-C bond measured by X-ray photoelectron spectroscopy on one surface in the thickness direction of the cured resin layer. CC , the peak intensity I at 289 eV assigned to the CO-O bond COO , and the peak intensity I of the O1s spectrum located at 532 eV O However, the following formula (1) and formula (2) are satisfied, and therefore the adhesion can be improved. I COO / I CC >0.5 (1) I O / I CC >1.2 (2)

[0014] The laminate of the present invention includes the film of the present invention and an inorganic layer in this order toward one side in the thickness direction, and therefore has excellent adhesion between the film and the inorganic layer. [Brief explanation of the drawings]

[0015] [Figure 1] FIG. 1 shows one embodiment of the film of the present invention. [Figure 2] FIG. 2 is a perspective view showing the positional relationship between the low inductance antenna and the intermediate laminate. [Figure 3] FIG. 3 is a cross-sectional view showing the positional relationship between the low inductance antenna and the intermediate laminate. [Figure 4] FIG. 4 shows one embodiment of the laminate of the present invention. [Figure 5] FIG. 5 shows an embodiment of the stack in which the inorganic layer is an anti-reflective layer. DETAILED DESCRIPTION OF THE INVENTION

[0016] One embodiment of the film of the present invention will be described with reference to FIG.

[0017] In FIG. 1, the up-down direction of the paper is the up-down direction (thickness direction). The upper side of the paper is the top side (one side in the thickness direction). The lower side of the paper is the bottom side (the other side in the thickness direction). The left-right direction and the depth direction of the paper are surface directions that are perpendicular to the up-down direction. Specifically, they follow the directional arrows in each figure.

[0018] The film 1 has a film shape (including a sheet shape) with a predetermined thickness. The film 1 extends in a plane direction perpendicular to the thickness direction. The film 1 has a flat upper surface and a flat lower surface. The film 1 is preferably flexible.

[0019] The film 1 preferably has transparency. Specifically, the total light transmittance (JIS K 7375-2008) of the film 1 is, for example, 80% or more, or preferably 85% or more.

[0020] The thickness of the film 1 is, for example, 10 μm or more, preferably 20 μm or more, more preferably 35 μm or more, and from the viewpoint of handleability in the roll-to-roll method described later, for example, 200 μm or less, preferably 150 μm or less, more preferably 100 μm or less, and even more preferably 60 μm or less.

[0021] The thickness of the film 1 can be measured using a dial gauge (manufactured by PEACOCK, "DG-205").

[0022] The film 1 includes a base material layer 3 and a cured resin layer 4, arranged in this order toward one side in the thickness direction. Specifically, the film 1 includes the base material layer 3 and the cured resin layer 4, which is disposed directly on the upper surface (one surface in the thickness direction) of the base material layer 3. The film 1 preferably includes the base material layer 3 and the cured resin layer 4.

[0023] <Base material layer> The base layer 3 is a base material for ensuring the mechanical strength of the film 1.

[0024] The base layer 3 has a film shape and is preferably flexible.

[0025] The base layer 3 may be, for example, a polymer film.

[0026] Examples of polymer film materials include polyester resins, (meth)acrylic resins, olefin resins, polycarbonate resins, polyethersulfone resins, polyarylate resins, melamine resins, polyamide resins, polyimide resins, cellulose resins, and polystyrene resins. Examples of polyester resins include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Examples of (meth)acrylic resins include polymethyl methacrylate. Examples of olefin resins include polyethylene, polypropylene, and cycloolefin polymers. Examples of cellulose resins include triacetyl cellulose.

[0027] The polymer film is preferably made of a cellulose resin, and more preferably made of triacetyl cellulose.

[0028] The thickness of the base layer 3 is, from the viewpoint of ensuring mechanical strength, for example, 10 μm or more, preferably 20 μm or more, more preferably 30 μm or more, and from the viewpoint of handleability in the roll-to-roll system described below, for example, 200 μm or less, preferably 150 μm or less, more preferably 100 μm or less, and even more preferably 50 μm or less. A carrier film may be attached to the back surface of the film 1 to ensure transportability and handleability of the base layer 3 in the roll-to-roll system process.

[0029] The thickness of the base layer 3 can be measured using a dial gauge (manufactured by PEACOCK, "DG-205").

[0030] The base layer 3 preferably has transparency. Specifically, the total light transmittance (JIS K 7375-2008) of the base layer 3 is, for example, 80% or more, or preferably 85% or more.

[0031] <Cured resin layer> The cured resin layer 4 has a film shape. The cured resin layer 4 is disposed on the entire upper surface of the base layer 3 so as to be in contact with the upper surface of the base layer 3. The cured resin layer 4 is the uppermost layer of the film 1.

[0032] Examples of the cured resin layer 4 include a hard coat layer, an easy-adhesion layer, and an anti-blocking (AB) layer. A hard coat layer is preferably used as the cured resin layer 4. The hard coat layer is an abrasion protection layer that makes the film 1 less susceptible to scratches.

[0033] The hard coat layer is a cured product of a hard coat composition containing an acrylate resin. That is, the hard coat layer (cured resin layer 4) contains a cured product of an acrylate resin.

[0034] If the hard coat layer (cured resin layer 4) contains a cured product of an acrylate resin, the peak intensity I attributable to a C-C bond at 285 eV CC (See below), and the peak intensity I at 289 eV assigned to the COO bond. COO (described later), and the peak intensity I of the O1s spectrum located at 532 eV O (described later) can be adjusted to ensure that equation (1) described later and equation (2) described later are satisfied.

[0035] The cured product of the acrylate resin is a cured product of the curing component.

[0036] The curing component includes a urethane (meth)acrylate, an oligomer of a urethane (meth)acrylate, and a polyfunctional (meth)acrylic monomer.

[0037] Examples of polyfunctional (meth)acrylic monomers include tricyclodecane dimethanol diacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane triacrylate, pentaerythritol tetra(meth)acrylate, and dimethylolpropane tetraacrylate.Preferably, the polyfunctional (meth)acrylic monomer is pentaerythritol tri(meth)acrylate.More preferably, the polyfunctional (meth)acrylic monomer is pentaerythritol triacrylate.

[0038] When the curing component contains a urethane (meth)acrylate and / or a urethane (meth)acrylate oligomer and a polyfunctional (meth)acrylic monomer, the content of the urethane (meth)acrylate and / or the urethane (meth)acrylate oligomer relative to the curing component is, for example, 30% by mass or more, preferably 40% by mass or more, and for example, 70% by mass or less, preferably 60% by mass or less. The content of the polyfunctional (meth)acrylic monomer relative to the curing component is, for example, 30% by mass or more, preferably 40% by mass or more, and for example, 70% by mass or less, preferably 60% by mass or less.

[0039] Examples of the acrylate resin include ultraviolet-curable acrylate resin and thermosetting acrylate resin. The acrylate resin is preferably ultraviolet-curable acrylate resin. If the acrylate resin is ultraviolet-curable acrylate resin, it can be cured without heating, which improves the production efficiency of the film 1.

[0040] The content of the acrylate resin in the hard coat composition is, for example, 80 mass % or more, preferably 90 mass % or more, and for example, 99 mass % or less, preferably 96 mass % or less.

[0041] The hard coat composition optionally contains other curable resins (e.g., polyester resins, amide resins, silicone resins, epoxy resins, and melamine resins), particles, initiators (thermal polymerization initiators, photopolymerization initiators), leveling agents, and fillers (e.g., synthetic smectite).

[0042] Examples of particles include inorganic particles and organic particles. Examples of inorganic particles include inorganic oxide particles. Examples of inorganic oxide particle materials include silica, alumina, titania, zirconia, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide. Examples of organic particle materials include polymethyl methacrylate, polystyrene, polyurethane, acrylic-styrene copolymer, benzoguanamine, melamine, silicone, and polycarbonate. Preferred organic particle materials include polystyrene and silicone.

[0043] The content of inorganic particles is preferably low. The lower the content of inorganic particles, the more light scattering caused by the inorganic particles can be suppressed and the production cost can be reduced. From the viewpoint of visibility (described later), the content of inorganic particles in the hard coat composition is, for example, 20% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1% by mass or less, particularly preferably 0.5% by mass or less, most preferably 0.2% by mass or less, even 0.1% by mass or less, or even 0.0% by mass.

[0044] The hard coat composition can be diluted, if necessary, with a solvent, such as butyl acetate, ethyl acetate, toluene, and cyclopentanone.

[0045] When the hard coat composition is diluted with a solvent, the solid content concentration is, for example, 10% by mass or more, preferably 30% by mass or more, and for example, 70% by mass or less, preferably 60% by mass or less.

[0046] As will be described in detail later, the hard coat layer is formed by applying a hard coat composition to one surface in the thickness direction of the substrate layer 3, and drying and curing it as necessary.

[0047] The hard coat layer preferably has transparency. Specifically, the total light transmittance (JIS K 7375-2008) of the hard coat layer is, for example, 80% or more, preferably 85% or more.

[0048] The thickness of the cured resin layer 4 is, for example, 0.5 μm or more, preferably 2 μm or more, more preferably 3 μm or more, and for example, 30 μm or less, preferably 25 μm or less, more preferably 20 μm or less.

[0049] Peak intensity I assigned to CC bonds at <285 eV CC , the peak intensity I at 289 eV assigned to the CO-O bond COO , and the peak intensity I of the O1s spectrum located at 532 eV O > The film 1 has a peak intensity I at 285 eV attributed to a C-C bond measured by X-ray photoelectron spectroscopy on one side of the thickness direction of the cured resin layer 4. CC , the peak intensity I at 289 eV assigned to the CO-O bond COO , and the peak intensity I of the O1s spectrum located at 532 eV O satisfies the following formula (1) and formula (2). I COO / I CC >0.5 (1) I O / I CC >1.2 (2)

[0050] If the above formula (1) and formula (2) are satisfied, the adhesion can be improved.

[0051] On the other hand, if the above formula (1) and / or the above formula (2) is not satisfied, the adhesion will decrease.

[0052] To satisfy the above formulas (1) and (2), the surface of the cured resin layer 4 is subjected to oxygen-LAICP treatment (described below). During the oxygen-LAICP treatment, for example, the transfer speed (described below), the type of LA21 (described below), the oxygen concentration in the vacuum chamber during the oxygen-LAICP treatment (described below), the pressure in the vacuum chamber during the oxygen-LAICP treatment (described below), the frequency and magnitude of the high-frequency power applied to the LA21 during the oxygen-LAICP treatment (described below), and the plasma current density during the oxygen-LAICP treatment (described below) are adjusted.

[0053] <Film manufacturing method> The film manufacturing method includes a first step of preparing a base layer 3, a second step of disposing a cured resin layer 4 on one thickness-wise surface of the base layer 3, and a third step of subjecting one thickness-wise surface of the cured resin layer 4 to plasma treatment. This method is preferably carried out using a roll-to-roll system. In such a case, the conveying speed is, for example, 0.1 m / min or more and, for example, 20.0 m / min or less. The following description will be given in detail of the case where the cured resin layer 4 is a hard coat layer.

[0054] [1st step] In the first step, the base layer 3 is prepared.

[0055] [Second process] In the second step, a hard coat layer (cured resin layer 4) is disposed on one surface in the thickness direction of the substrate layer 3. To dispose the hard coat layer on one surface in the thickness direction of the substrate layer 3, a hard coat composition is applied to one surface in the thickness direction of the substrate layer 3, and then dried and cured as necessary to form the hard coat layer.

[0056] As for the drying conditions, the drying temperature is, for example, 50° C. or higher and, for example, 120° C. or lower, and the drying time is, for example, 10 seconds or higher and, for example, 10 minutes or lower.

[0057] When the hard coat composition contains an ultraviolet-curable acrylate resin, the ultraviolet-curable acrylate resin is cured by ultraviolet irradiation. Examples of the light source for ultraviolet irradiation include a high-pressure mercury lamp and an LED light. The cumulative irradiation amount of ultraviolet light is, for example, 100 mJ / cm. 2 or more, for example, 500 mJ / cm 2 The following is the result.

[0058] When the hard coat composition contains a thermosetting acrylate resin, the thermosetting acrylate resin is cured by heating. The heating temperature is, for example, 100° C. or higher and, for example, 150° C. or lower. The heating time is, for example, 10 seconds or higher and, for example, 10 minutes or shorter.

[0059] In this way, the hard coat layer (cured resin layer 4) is disposed on one surface of the base layer 3 in the thickness direction, and an intermediate laminate 2 having the base layer 3 and the hard coat layer (cured resin layer 4) in this order is produced.

[0060] [3rd step] In the second step, one surface in the thickness direction of the hard coat layer (cured resin layer 4) is subjected to plasma treatment.

[0061] Specifically, the plasma treatment may be a treatment using inductively coupled plasma of an oxygen-containing gas (oxygen-LAICP treatment) generated by applying high-frequency power to a low-inductance antenna.

[0062] The low-inductance antenna means an antenna that has a low inductance of 7.5 μH or less and is capable of generating inductively coupled plasma by application of high-frequency power.

[0063] 2 and 3, the low inductance antennas 21 (LA21) are supported by fixtures 22 and arranged in a state where they are covered with cover blocks 23 (omitted in FIG. 3) (a case where the number of LA21 is four is shown as an example). The multiple LA21 are arranged in a line so as to be aligned in the running direction of the intermediate laminate 2 and in a direction perpendicular to the running direction (the width direction of the intermediate laminate 2).

[0064] The LA21 is made of a conductor, such as copper or silver, preferably copper, and may be covered with an insulator. Insulators include, for example, glass and quartz.

[0065] The LA 21 is electrically connected to a high frequency power source (RF power source) via an impedance matching box.

[0066] The LA21 has an open loop shape. The open loop shape of the LA21 can reduce the inductance of the LA21. Therefore, the open loop shape of the LA21 can suppress an increase in voltage due to an increase in power applied to the LA21. This can suppress abnormal discharge during plasma processing. Suppressing abnormal discharge can suppress damage to the intermediate laminate 2 being plasma processed.

[0067] Specifically, the LA 21 has a U-shape with two free ends. For each LA 21, the two free ends are fixed to a fixture 22 so as to be aligned in the width direction of the intermediate laminate 2. More specifically, the LA 21 is fixed to the fixture 22 via a feedthrough 24, as shown in FIG. 3 .

[0068] Furthermore, the LA 21 has extending portions 21a on the side opposite to the two free ends. The extending portions 21a extend in the width direction of the intermediate laminate 2. Each extending portion 21a may extend in the running direction of the intermediate laminate 2 (two LA 21 may be arranged in this manner).

[0069] The LA21 extends from the fixture 22 toward the intermediate laminate 2. The LA21 extends perpendicularly to the fixture 22. The extension length d1 of the LA21 from the fixture 22 is, for example, 30 mm or more and, for example, 150 mm or less.

[0070] The maximum length d2 of the LA21 in the plane direction of the intermediate laminate 2 is, for example, 50 mm or more, and, for example, 150 mm or less.

[0071] The separation distance d3 between the LA21 and the intermediate laminate 2 is, for example, 50 mm or more and, for example, 200 mm or less.

[0072] Preferably, the extension length d1 and the separation distance d3 are the same.

[0073] The ratio (d3 / d1) of the separation distance d3 to the extension length d1 is, for example, not less than 0.5 and not more than 3.5.

[0074] The center-to-center distance d4 between adjacent LA21 in the running direction of the intermediate laminate 2 is, for example, 100 mm or more, and, for example, 500 mm or less. The number (number of rows) of LA21 spaced apart in the running direction of the intermediate laminate 2 may be 1, 2, or 3, or may be 4 or more if necessary, depending on the running speed of the intermediate laminate 2 (i.e., plasma treatment time).

[0075] The center-to-center distance d5 between adjacent LAs 21 in the width direction of the intermediate stack 2 is, for example, 200 mm or less, or, for example, 500 mm or less. The uniformity of the plasma density in the width direction of the intermediate stack 2 can be controlled.

[0076] Preferably, the center distance d4 and the center distance d5 are the same.

[0077] The centers of the extensions 21a of the four LAs 21 preferably form a square with the vertices as vertices. Such a set of LAs 21 can generate high-density plasma with high in-plane uniformity. For example, the high-frequency antenna for plasma generation described in JP 2013-258153 A can be used as the LAs 21.

[0078] Moreover, the LA21 may have a coil shape instead of an open loop shape.

[0079] The cover block 23 includes a block body 23A and multiple partition plates 23B. The block body 23A has multiple storage spaces 23a. Each storage space 23a stores one LA 21. The partition plates 23B are arranged to close the storage spaces 23a. The storage spaces 23a are sealed spaces. In the cover block 23, the block body 23A is made of, for example, aluminum. Examples of aluminum include aluminum A5052. The partition plates 23B are made of an insulating material. Examples of insulating materials include quartz and glass. The separation distance d' (shown in FIG. 3) between the traveling intermediate stack 2 and the cover block 23 is, for example, 50 mm or more and, for example, 200 mm or less. Such a cover block 23 helps to avoid damage and contamination of the LA21 due to plasma processing without excessively reducing the plasma conversion efficiency due to the power applied to the LA21, and also helps to suppress damage to the intermediate stack 2 being plasma processed.

[0080] In the oxygen-LAICP process, the LA 21 is placed in a vacuum chamber, and the intermediate laminate 2 is transported thereinto, and oxygen is supplied into the vacuum chamber.

[0081] From the viewpoint of improving adhesion, the oxygen concentration in the vacuum chamber is, for example, 30% by volume or more, more preferably 50% by volume or more, and even more preferably 80% by volume or more. From the viewpoint of improving adhesion, the oxygen concentration is, for example, 100% by volume or less, preferably 95% by volume or less, and more preferably 90% by volume or less.

[0082] In addition, an inert gas or an active gas other than oxygen may be introduced into the vacuum chamber. Examples of the inert gas include rare gases (argon, krypton, and xenon). Examples of the active gas include nitrogen and water vapor.

[0083] The pressure inside the vacuum chamber during the oxygen-LAICP treatment is, for example, 0.1 Pa or more, preferably 0.2 Pa or more, more preferably 0.3 Pa or more, and for example, 7.0 Pa or less, preferably 5.0 Pa or less, more preferably 3.0 Pa or less, and even more preferably 1.0 Pa or less. The pressure can be adjusted by the amount of oxygen supplied to the vacuum chamber.

[0084] The frequency of the high-frequency power applied to LA21 during oxygen-LAICP treatment is, for example, 1 MHz or more, preferably 3 MHz or more, more preferably 5 MHz or more, and even more preferably 10 MHz or more, and is, for example, 100 MHz or less, preferably 80 MHz or less, and more preferably 60 MHz or less.

[0085] The high frequency power is, for example, 1.0 kW or more, preferably 1.5 kW or more, more preferably 1.8 kW or more, and for example, 10 kW or less, preferably 8 kW or less, more preferably 6 kW or less.

[0086] In the oxygen-LAICP process, the plasma current density at the intermediate position between the LA 21 and the intermediate laminate 2 is, for example, 1.0 mA / cm 3 More than 2.0 mA / cm 3 More preferably, 3.0 mA / cm 3 More preferably, 4.0 mA / cm 3 or more, for example, 10 mA / cm 3 Preferably, 8mA / cm or less 3 Less than 5 mA / cm, more preferably 3 The following is the result.

[0087] The plasma current density can be adjusted by the amount of oxygen introduced, the frequency of the high frequency power, and the high frequency power.

[0088] In this way, plasma treatment is performed on one surface in the thickness direction of the hard coat layer (cured resin layer 4), and the film 1 is produced.

[0089] <Laminate> As shown in FIG. 4, the laminate 10 includes a film 1 (specifically, the film 1 of the first embodiment or the film 1 of the second embodiment) and an inorganic layer 11, arranged in this order toward one side in the thickness direction (note that FIG. 4 shows the case where the film 1 is the film 1 of the second embodiment). Specifically, the laminate 10 includes the film 1 and the inorganic layer 11 disposed directly on the upper surface (one side in the thickness direction) of the film 1. The laminate 10 preferably consists of the film 1 and the inorganic layer 11.

[0090] [film] The film 1 is disposed over the entire lower surface of the inorganic layer 11 so as to be in contact with the lower surface of the inorganic layer 11. The film 1 is the bottom layer in the laminate .

[0091] [Inorganic layer] The inorganic layer 11 has a film shape. The inorganic layer 11 is disposed on the entire upper surface of the film 1 so as to be in contact with the upper surface of the film 1. The inorganic layer 11 is the uppermost layer in the laminate 10.

[0092] Examples of the inorganic layer 11 include an anti-reflection layer and a conductive layer. Hereinafter, the cases where the inorganic layer 11 is an anti-reflection layer and a conductive layer will be described in detail.

[0093] (When the inorganic layer is an anti-reflection layer) With reference to FIG. 5, the case where the inorganic layer 11 is an anti-reflection layer will be described in detail.

[0094] When the inorganic layer 11 is an anti-reflection layer, the laminate 10 is an anti-reflection film.

[0095] The antireflection layer includes multiple layers with different refractive indices along the thickness direction. Specifically, the antireflection layer includes high-refractive-index layers with a relatively high refractive index and low-refractive-index layers with a relatively low refractive index, alternating in the thickness direction. In the antireflection layer, the net reflected light intensity is attenuated by interference between reflected light at multiple interfaces in the multiple thin layers (high-refractive-index layers, low-refractive-index layers) included therein. Furthermore, in the antireflection layer, the interference effect that attenuates the reflected light intensity can be exerted by adjusting the optical film thickness (product of refractive index and thickness) of each thin layer. Such an antireflection layer includes high-refractive-index layers 12 and low-refractive-index layers 13 alternately arranged in order toward one side in the thickness direction.

[0096] The antireflection layers (specifically, the high refractive index layer 12 and the low refractive index layer 13) preferably contain one selected from the group consisting of metals, alloys, metal oxides, metal nitrides, and metal fluorides, and more preferably contain one selected from the group consisting of metals, metal oxides, and metal nitrides, which allows the antireflection layers to suppress the reflection intensity of external light.

[0097] Examples of metals include silicon, nickel, chromium, aluminum, tin, gold, silver, platinum, zinc, titanium, tungsten, zirconium, niobium, and palladium. Examples of alloys include alloys of the above metals. Examples of metal oxides include metal oxides of the above metals. Examples of metal nitrides include metal nitrides of the above metals. Examples of metal fluorides include metal nitrides of metal fluorides of the above metals.

[0098] In particular, the material used for the anti-reflection layer is selected depending on the desired refractive index.

[0099] Specifically, examples of the high refractive index material constituting the high refractive index layer 12 include niobium oxide (Nb2O5), titanium oxide, zirconium oxide, indium tin oxide (ITO), and antimony-doped tin oxide (ATO). A preferred example of the high refractive index material is indium tin oxide (ITO).

[0100] Furthermore, examples of the low refractive index material that constitutes the low refractive index layer 13 include silicon dioxide (SiO2) and magnesium fluoride. As the low refractive index material, silicon dioxide (SiO2) is preferably used.

[0101] In the antireflection layer, the high refractive index layer 12 has a thickness of, for example, 1 nm or more, or preferably 3 nm or more, and for example, 15 nm or less, or preferably 10 nm or less.

[0102] The thickness of the low refractive index layer 13 is thicker than the thickness of the high refractive index layer 12, and is, for example, greater than 15 nm and is, for example, 50 nm or less, preferably 30 nm or less.

[0103] The ratio of the thickness of the low refractive index layer 13 to the thickness of the high refractive index layer 12 (thickness of the low refractive index layer 13 / thickness of the high refractive index layer 12) is, for example, more than 1, preferably 2 or more, more preferably 3 or more, and is, for example, 10 or less, preferably 5 or less.

[0104] The thickness of the antireflection layer is, for example, 20 nm or more, and, for example, 300 nm or less, preferably 250 nm or less, and more preferably 200 nm or less.

[0105] When the inorganic layer 11 is an anti-reflection layer, the laminate 10 can be produced by disposing the anti-reflection layer on one surface of the film 1 in the thickness direction by a known sputtering method.

[0106] In the antireflection layer, the number of high refractive index layers and low refractive index layers is not particularly limited.

[0107] (When the inorganic layer is a conductive layer) When the inorganic layer 11 is a conductive layer, the laminate 10 is a transparent conductive film.

[0108] Examples of materials for the conductive layer include metals and metal oxides. Examples of metals include copper, silver, gold, nickel, chromium, and alloys thereof. Examples of metal oxides include indium-containing conductive oxides and antimony-containing conductive oxides. Examples of indium-containing conductive oxides include indium tin composite oxide (ITO), indium zinc composite oxide (IZO), indium gallium composite oxide (IGO), and indium gallium zinc composite oxide (IGZO). Examples of antimony-containing conductive oxides include antimony tin composite oxide (ATO).

[0109] The conductive layer has a thickness of, for example, 1 nm or more, preferably 5 nm or more, and for example, 100 nm or less.

[0110] When the inorganic layer 11 is a conductive layer, the laminate 10 can be produced by disposing the conductive layer on one surface of the film 1 in the thickness direction by a known sputtering method.

[0111] <Action and effect> The film 1 has a peak intensity I at 285 eV attributed to a C-C bond measured by X-ray photoelectron spectroscopy on one surface in the thickness direction of the cured resin layer 4. CC , the peak intensity I at 289 eV assigned to the CO-O bond COO , and the peak intensity I of the O1s spectrum located at 532 eV O satisfies the above formula (1) and formula (2), and therefore, the adhesion can be improved.

[0112] For details, the above peak intensity I COO is the intensity of the peak attributed to the CO-O bond, and the above peak intensity I Ois the intensity of the peak in the O1s spectrum. Both of these peaks are derived from bonds containing oxygen.

[0113] On the other hand, the above peak intensity I CC is a peak attributed to a C—C bond and is derived from a bond that does not contain oxygen.

[0114] In addition, the above peak intensity I CC , the above peak intensity I COO , and the above peak intensity I O is a peak intensity derived from one surface of the cured resin layer 4 in the thickness direction, since it is measured for one surface of the cured resin layer 4 in the thickness direction using X-ray photoelectron spectroscopy.

[0115] Satisfying the above formula (1) or (2) means that on one surface in the thickness direction of the cured resin layer 4, the proportion of bonds containing oxygen is higher than the proportion of bonds not containing oxygen.

[0116] The high proportion of bonds containing oxygen suggests that oxygen modification has been applied to the surface of the cured resin layer 4. This results in chemical bonding between the film 1 (cured resin layer 4) and the inorganic layer 11 via oxygen, improving adhesion.

[0117] The laminate 10 includes a film 1 and an inorganic layer 11 in this order toward one side in the thickness direction. Therefore, the adhesion between the film 1 and the inorganic layer 11 is excellent. [Example]

[0118] The present invention will be described in more detail below with reference to examples and comparative examples. It should be noted that the present invention is in no way limited to these examples and comparative examples. The specific numerical values ​​of the blending ratios (content ratios), physical property values, parameters, etc. used in the following description can be replaced with the corresponding upper limit values ​​(numeric values ​​defined as "equal to or less than" or "less than") or lower limit values ​​(numeric values ​​defined as "equal to or greater than" or "exceeding") of the blending ratios (content ratios), physical property values, parameters, etc. described in the "Description of the Invention" above.

[0119] Example 1 <Film manufacturing> [1st step] In the first step, a base layer was prepared. Specifically, a long TAC film (triacetyl cellulose film, length 100 m, width 340 mm, thickness 40 μm) was first prepared as the base layer.

[0120] [Second process] In the second step, a hard coat layer (cured resin layer) was disposed on one thickness-wise surface of the substrate layer. Specifically, first, 100 parts by mass (solid content equivalent) of a butyl acetate solution of urethane acrylate (product name "Luxidia 17-806", solid content concentration 80% by mass, manufactured by DIC Corporation), 5 parts by mass of a photopolymerization initiator (product name "Omnirad 907", manufactured by IGM Resins), 0.03 parts by mass of a leveling agent (product name "GRANDIC PC4100", manufactured by DIC Corporation), and butyl acetate as a solvent were mixed to adjust the solid content to 75% by mass. Next, cyclopentanone was added as a solvent to prepare a hard coat composition (solid content concentration 50% by mass).

[0121] Next, a hard coat composition was applied to one surface of the substrate layer in the thickness direction to form a coating film. Next, this coating film was dried by heating and then cured by ultraviolet irradiation. As a result, a hard coat layer (thickness 5 μm) was disposed on one surface of the substrate layer in the thickness direction.

[0122] The heating temperature was 100°C and the heating time was 60 seconds. For ultraviolet irradiation, a high-pressure mercury lamp was used as the light source, and ultraviolet rays with a wavelength of 365 nm were irradiated onto the coating film, with an integrated irradiation dose of 300 mJ / cm. 2 It was decided.

[0123] In this way, an intermediate laminate having the substrate layer and the hard coat layer (cured resin layer) in this order was produced.

[0124] [3rd step] In the third step, one surface of the hard coat layer in the thickness direction was subjected to plasma treatment.

[0125] Specifically, the intermediate laminate was transported into a vacuum chamber by a roll-to-roll method under vacuum at a transport speed of 1.0 m / min, and the plasma treatment was carried out on the intermediate laminate.

[0126] The plasma treatment was oxygen-LAICP treatment.The low-inductance antenna shown in Figures 2 and 3 was used.

[0127] In the low-inductance antenna, the extension length d1 is 88 mm, the maximum length d2 is 100 mm, the separation distance d3 is 112 mm, the center-to-center distance d4 is 290 mm, the center-to-center distance d5 is 280 mm, and the separation distance d' is 100 mm. Each low-inductance antenna is electrically connected to a high-frequency power supply (RF power supply, frequency 13.56 MHz) via an impedance matching box.

[0128] The ultimate vacuum of the vacuum chamber is 1.0 x 10 -4 After evacuating the apparatus until the pressure reached 0.5 Pa, oxygen gas (oxygen concentration 100% by volume) was introduced into the vacuum chamber, and the pressure inside the vacuum chamber was adjusted to 0.5 Pa. By applying high frequency power of 5.0 kW to the four low inductance antennas using a high frequency power supply, inductively coupled plasma of the oxygen-containing gas was formed around the antennas (the hard coat layer was treated with this plasma). The plasma current density at the midpoint between the low-inductance antenna and the intermediate laminate was 4.2 mA / cm. 3 It was decided.

[0129] This produced a film.

[0130] <Production of laminate> An anti-reflection layer was formed on one surface of the film in the thickness direction by sputtering.

[0131] Specifically, after evacuating the vacuum chamber, 1.0 × 10 -4 The pressure was reduced to 10 Pa, and argon gas was introduced as the sputtering gas. An ITO target (SnO ratio 10 mass%, length 600 mm x width 150 mm x thickness 5 mm, single cathode system) was used as the target to deposit a high refractive index layer (ITO film, thickness 5 nm) (input power 1.0 kW, deposition chamber pressure: 0.3 Pa, DC discharge). Next, a pure Si target (length 600 mm x width 50 mm x thickness 5 mm, dual cathode system) was used as the target to deposit a low refractive index layer (SiO2 film, thickness 20 nm) (input power 3.0 kW, deposition pressure 0.3 Pa, O2 / Ar = 0.3, MFAC power supply 60 kHz).

[0132] In this way, a laminate was produced.

[0133] Comparative Example 1 <Film manufacturing> An intermediate laminate was prepared based on the same procedures as in the first and second steps of Example 1.

[0134] In the third step, one surface of the hard coat layer in the thickness direction was subjected to a bombardment treatment with argon ions.

[0135] Specifically, the intermediate laminate was transported into a vacuum chamber by a roll-to-roll method at a transport speed of 1.0 m / min under vacuum.

[0136] The vacuum chamber is equipped with a pair of flat electrodes for generating plasma: a cathode electrode and an anode electrode (both rectangular electrodes made of SUS304). The pair of flat electrodes are spaced 50 mm apart and arranged parallel to the intermediate laminate passing through the vacuum chamber. The anode electrode is positioned so that it remains in contact with the intermediate laminate passing through the vacuum chamber, and is grounded outside the vacuum chamber. The cathode electrode is positioned 35 mm away from the intermediate laminate and is electrically connected to a high-frequency power supply (RF power supply, 13.56 MHz) via an impedance matcher. The length of each electrode in the film running direction is 110 mm, and its length in the width direction is 430 mm.

[0137] The ultimate vacuum of the vacuum chamber is 1.0 x 10 -4 After evacuating the apparatus until the pressure reached 0.5 Pa, argon gas was introduced as an inert gas into the vacuum chamber, and the pressure inside the vacuum chamber was adjusted to 0.5 Pa. Capacitively coupled plasma (CCP) was generated by applying 550 W of power between the planar electrodes using a high-frequency power supply. In this plasma environment, the surface of the hard coat layer was bombarded with argon ions. <Production of laminate> A laminate was produced according to the same procedure as in Example 1.

[0138] Comparative Example 2 An intermediate laminate was prepared based on the same procedures as in the first and second steps of Example 1. Thereafter, the third step was not performed. Thereafter, a laminate was prepared based on the same procedures as in Example 1.

[0139] Example 2 <Film manufacturing> [1st step] Based on the same procedure as in Example 1, a base layer was prepared.

[0140] [Second process] In the second step, a hard coat layer (cured resin layer) was formed on one surface of the substrate layer in the thickness direction. Specifically, 50 parts by mass of pentaerythritol triacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name "Viscoat #300"), 50 parts by mass of urethane acrylate prepolymer (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name "UA-53H-80BK"), 3.5 parts by mass of silicone particles (manufactured by Momentive Performance Materials Japan, LLC, trade name "Tospearl 130", weight average particle size: 3 μm, refractive index: 1.42), 2 parts by mass of synthetic smectite (organic clay, manufactured by Co-op Chemical Co., Ltd., trade name "Lucentite SAN"), 3 parts by mass of photopolymerization initiator (manufactured by BASF, trade name "Irgacure 907"), and 0.2 parts by mass of leveling agent (manufactured by DIC Corporation, trade name "PC4100", solid content concentration 10%) were mixed and diluted with a toluene / cyclopentanone (CPN) mixed solvent (mass ratio 70 / 30) to prepare a hard coat composition (solid content concentration 35% by mass). The synthetic smectite was diluted with toluene to a solid content concentration of 6% by mass.

[0141] Next, a hard coat composition was applied to one surface of the substrate layer in the thickness direction to form a coating film. Next, this coating film was dried by heating and then cured by ultraviolet irradiation. As a result, a hard coat layer (thickness 6.3 μm) was disposed on one surface of the substrate layer in the thickness direction.

[0142] The heating temperature was 80°C and the heating time was 60 seconds. For ultraviolet irradiation, a high-pressure mercury lamp was used as the light source, and ultraviolet rays with a wavelength of 365 nm were irradiated onto the coating film, with an integrated irradiation dose of 300 mJ / cm. 2 It was decided.

[0143] In this way, an intermediate laminate having the substrate layer and the hard coat layer (cured resin layer) in this order was produced.

[0144] [3rd step] In the third step, based on the same procedure as in Example 1, one surface of the hard coat layer in the thickness direction was subjected to plasma treatment.

[0145] <Production of laminate> A laminate was produced according to the same procedure as in Example 1.

[0146] Comparative Example 3 <Film manufacturing> An intermediate laminate was prepared based on the same procedures as in the first and second steps of Example 2.

[0147] In the third step, based on the same procedure as in Comparative Example 1, one surface of the hard coat layer in the thickness direction was subjected to a bombardment treatment with argon ions.

[0148] <Production of laminate> A laminate was produced according to the same procedure as in Example 1.

[0149] Comparative Example 4 An intermediate laminate was prepared based on the same procedures as in the first and second steps of Example 2. Thereafter, the third step was not performed. Thereafter, a laminate was produced based on the same procedures as in Example 1.

[0150] Example 3 <Film manufacturing> [1st step] Based on the same procedure as in Example 1, a base layer was prepared.

[0151] [Second process] In the second step, a hard coat layer (cured resin layer) was formed on one surface of the substrate layer in the thickness direction. Specifically, 50 parts by weight of pentaerythritol triacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name "Viscoat #300"), 50 parts by weight of urethane acrylate prepolymer (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name "UA-53H-80BK"), 1.7 parts by weight of silicone particles (manufactured by Momentive Performance Materials Japan, LLC, trade name "Tospearl 130", weight average particle size: 3 μm, refractive index: 1.42), and 1.7 parts by weight of polystyrene particles (manufactured by Sekisui Plastics Co., Ltd., trade name "Techpolymer" ", weight average particle size: 3 μm, refractive index: 1.59) 2.3 parts by weight of synthetic smectite (organic clay, manufactured by Co-op Chemical Co., Ltd., trade name "Lucentite SAN"), 2 parts by weight of photopolymerization initiator (manufactured by BASF, trade name "Irgacure 907"), and 0.2 parts by weight of leveling agent (manufactured by DIC Corporation, trade name "PC4100", solid content concentration 10%) were mixed and diluted with a toluene / cyclopentanone (CPN) mixed solvent (weight ratio 70 / 30) to prepare a hard coat composition (solid content concentration 35% by mass). The synthetic smectite was diluted with toluene to a solid content concentration of 6% by mass.

[0152] Next, a hard coat composition was applied to one surface of the substrate layer in the thickness direction to form a coating film. Next, this coating film was dried by heating and then cured by ultraviolet irradiation. As a result, a hard coat layer (thickness 6.3 μm) was disposed on one surface of the substrate layer in the thickness direction.

[0153] The heating temperature was 80°C and the heating time was 60 seconds. For ultraviolet irradiation, a high-pressure mercury lamp was used as the light source, and ultraviolet rays with a wavelength of 365 nm were irradiated onto the coating film, with an integrated irradiation dose of 300 mJ / cm. 2 It was decided.

[0154] In this way, an intermediate laminate having the substrate layer and the hard coat layer (cured resin layer) in this order was produced.

[0155] [3rd step] In the third step, based on the same procedure as in Example 1, one surface of the hard coat layer in the thickness direction was subjected to plasma treatment.

[0156] <Production of laminate> A laminate was produced according to the same procedure as in Example 1.

[0157] Comparative Example 5 <Film manufacturing> An intermediate laminate was prepared based on the same procedures as in the first and second steps of Example 3.

[0158] In the third step, based on the same procedure as in Comparative Example 1, one surface of the hard coat layer in the thickness direction was subjected to a bombardment treatment with argon ions.

[0159] <Production of laminate> A laminate was produced according to the same procedure as in Example 1.

[0160] Comparative Example 6 An intermediate laminate was prepared based on the same procedures as in the first and second steps of Example 3. Then, the third step was not performed. Then, a laminate was produced based on the same procedures as in Example 1.

[0161] <Evaluation> [X-ray photoelectron spectroscopy] For the films of each Example and Comparative Example, narrow scan measurements were carried out on the surface of the hard coat layer in the vicinity of the C1s spectrum and O1s spectrum under the conditions below to obtain spectra. {conditions} Equipment: ULVAC-PHI Quantera SXM X-ray source: Monochrome Al Kα X-Ray Setting: 100μmφ[15kV, 25W] Photoelectron take-off angle: 45° to the sample surface Neutralization conditions: Use of a neutralization gun and an Ar ion gun (neutralization mode) Bond energy correction: The peak due to the CC bond in the C1s spectrum is corrected to 285.0 eV

[0162] The film was cut out from the center of the width direction (340 mm width) into a piece of about 1 cm square and used as a sample.

[0163] Peak intensity I at 285 eV assigned to CC bond CC , the peak intensity I at 289 eV assigned to the CO-O bond COO , and the peak intensity I of the O1s spectrum located at 532 eV O are shown in Table 1.

[0164] [Adhesion] The laminates of each example and comparative example were cut into a 50 mm x 50 mm size sample. Next, cuts were made at 1 mm intervals on the treated surface of the sample to create a grid of 100 squares, and then the sample was placed in a weathering tester under the following conditions. {conditions} SUV irradiation conditions Temperature and humidity conditions: 85℃45%Rh Light source used: Metal halide lamp Irradiation conditions: 150mW / cm 2 (290-450nm)

[0165] Next, 2 mL of isopropyl alcohol was continuously dripped onto the surface of the anti-reflection layer to prevent it from drying out, and a polyester wiper (Anticon Gold, manufactured by Sanplatec) fixed to a 20 mm square SUS jig was slid across the grid (load: 1.5 kg, 1000 strokes). A grid where the anti-reflection layer had peeled off over more than 1 / 4 of the grid's area was counted as "peeling." Adhesion was evaluated based on the following criteria. The results are shown in Table 1. {standard} ○: Peeling was 5 squares or less. ×: Peeling exceeded 5 squares.

[0166] [Table 1] [Explanation of symbols]

[0167] 1 film 3 Base material layer 4 Cured resin layer 10 Laminate 11 Inorganic layer

Claims

1. A substrate layer and a cured resin layer are provided in this order toward one side in a thickness direction, The peak intensity I attributable to a C—C bond at 285 eV measured using X-ray photoelectron spectroscopy on one side in the thickness direction of the cured resin layer ＣＣ , the peak intensity I at 289 eV assigned to the COO bond ＣＯＯ , and the peak intensity I of the O1s spectrum located at 532 eV Ｏ A film that satisfies the following formula (1) and the following formula (2). I ＣＯＯ / I ＣＣ >0.5 (1) I Ｏ / I ＣＣ >1.2 (2)

2. The film according to claim 1 , wherein the cured resin layer comprises a cured product of an acrylate resin.

3. A laminate comprising the film according to claim 1 or 2 and an inorganic layer in this order toward one side in the thickness direction.

4. the inorganic layer is an anti-reflection layer, The laminate according to claim 3 , wherein the antireflection layer comprises a plurality of layers having different refractive indices along the thickness direction.

5. The laminate according to claim 3 , wherein the inorganic layer is a conductive layer.

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