JP2025011541A - Films and Laminates - Google Patents

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

The present invention relates to a film and a laminate, and more specifically to a film and a laminate comprising the film.

In the field of electronics products, composite materials that combine organic and inorganic materials have been developed with the aim of reducing weight and improving functionality. One known composite material is a laminate film that has an organic base film and an inorganic layer on the base film.

As such a laminated film, for example, a hard coat film having a film substrate and a hard coat layer in that order, and an anti-reflection film having an inorganic oxide primer layer and an anti-reflection layer in that order have been proposed (see, for example, Patent Document 1).

In Patent Document 1, a plasma treatment is applied to the hard coat layer before a primer layer is formed on the hard coat layer. This treatment can remove dirt and moisture from the surface of the hard coat film (hard coat layer), and can improve the adhesion between the hard coat film and the anti-reflection layer.

JP 2022-65437 A

However, the base film (hard coat film) of Patent Document 1 has a drawback in that it has insufficient adhesion. Therefore, the base film (hard coat film) is required to have even better adhesion.

The present invention provides a film with excellent adhesion and a laminate including the film.

The present invention [1] is a film comprising a base layer and a cured resin layer in this order toward one side in a thickness direction, wherein a peak intensity I CC attributable to a C—C bond at 285 eV, a peak intensity _{I COO attributable} to a COO bond at 289 eV, and a peak intensity I _O of an O1s spectrum located at 532 eV, measured by X-ray photoelectron spectroscopy on one side in the thickness direction of the cured resin layer, satisfy the following formulas (1) and (2):
I _COO /I _CC >0.5 (1)
I _O /I _CC >1.2 (2)

The present invention [2] includes the film described in [1] above, in which the cured resin layer includes a cured product of an acrylate resin.

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

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

The present invention [5] includes the laminate described in [3] above, in which the inorganic layer is a conductive layer.

In the film of the present invention, the peak intensity I _CC assigned to a C-C bond at 285 eV, the peak intensity I _COO assigned to a COO bond at 289 eV, and the peak intensity I _O of an O1s spectrum located at 532 eV, measured by X-ray photoelectron spectroscopy on one surface in the thickness direction of the cured resin layer, satisfy the following formulas (1) and (2). Therefore, adhesion can be improved.
I _COO /I _CC >0.5 (1)
I _O /I _CC >1.2 (2)

The laminate of the present invention has the film of the present invention and an inorganic layer in order toward one side in the thickness direction. Therefore, there is excellent adhesion between the film and the inorganic layer.

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

One embodiment of the film of the present invention will be described with reference to Figure 1.

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

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

Film 1 is preferably transparent. Specifically, the total light transmittance (JIS K 7375-2008) of film 1 is, for example, 80% or more, preferably 85% or more.

The thickness of film 1 is, for example, 10 μm or more, preferably 20 μm or more, and more preferably 35 μm or more, and from the viewpoint of handleability in the roll-to-roll method described below, is, 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.

The thickness of film 1 can be measured using a dial gauge (PEACOCK, "DG-205").

The film 1 comprises a base layer 3 and a cured resin layer 4 in this order toward one side in the thickness direction. Specifically, the film 1 comprises a base layer 3 and a cured resin layer 4 that is disposed directly on the upper surface (one side in the thickness direction) of the base layer 3. The film 1 preferably comprises a base layer 3 and a cured resin layer 4.

<Base layer>
The substrate layer 3 is a substrate for ensuring the mechanical strength of the film 1 .

The substrate layer 3 has a film shape. The substrate layer 3 is preferably flexible.

An example of the substrate layer 3 is a polymer film.

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

As a material for the polymer film, a cellulose resin is preferable. As a material for the polymer film, triacetyl cellulose is more preferable.

The thickness of the base layer 3 is, for example, 10 μm or more, preferably 20 μm or more, more preferably 30 μm or more, from the viewpoint of ensuring mechanical strength, and, from the viewpoint of handleability in the roll-to-roll method described below, is, 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. In addition, 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 process.

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

The substrate layer 3 is preferably transparent. Specifically, the total light transmittance (JIS K 7375-2008) of the substrate layer 3 is, for example, 80% or more, preferably 85% or more.

<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.

Examples of the cured resin layer 4 include a hard coat layer, an easy adhesion layer, and an anti-blocking (AB) layer. A preferred example of the cured resin layer 4 is a hard coat layer. The hard coat layer is an abrasion protection layer that makes it difficult for the film 1 to be scratched.

The hard coat layer is a cured product of a hard coat composition containing an acrylate resin. In other words, the hard coat layer (cured resin layer 4) contains a cured product of an acrylate resin.

When the hard coat layer (cured resin layer 4) contains a cured product of an acrylate resin, the peak intensity I _CC (described later) attributable to a C-C bond at 285 eV, the peak intensity I _COO (described later) attributable to a COO bond at 289 eV, and the peak intensity I _O (described later) of the O1s spectrum located at 532 eV can be adjusted so as to reliably satisfy the formula (1) described later and the formula (2) described later.

The cured product of acrylate resin is the cured product of the curing component.

The curing components include urethane (meth)acrylate, urethane (meth)acrylate oligomer, and polyfunctional (meth)acrylic monomer.

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. Examples of polyfunctional (meth)acrylic monomers include pentaerythritol tri(meth)acrylate, preferably. Examples of polyfunctional (meth)acrylic monomers include pentaerythritol triacrylate, more preferably.

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 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, relative to the curing component. The content of the polyfunctional (meth)acrylic monomer 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, relative to the curing component.

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

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

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).

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

A lower content of inorganic particles is preferable. The lower the content of inorganic particles, the more the scattering of light caused by inorganic particles can be suppressed, and the lower the manufacturing cost can be. 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, and even 0.0% by mass.

The hard coat composition can be diluted with a solvent, if necessary. Examples of solvents include butyl acetate, ethyl acetate, toluene, and cyclopentanone.

When the hard coat composition is diluted with a solvent, the solids 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.

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 the composition as necessary.

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

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.

<Peak intensity I _CC at 285 eV assigned to a C—C bond, peak intensity I _COO at 289 eV assigned to a COO bond, and peak intensity I _O of the O1s spectrum located at 532 eV>
In the film 1, on one side in the thickness direction of the cured resin layer 4, a peak intensity I _CC at 285 eV assigned to a C—C bond, a peak intensity I _COO at 289 eV assigned to a COO bond, and a peak intensity I _O of an O1s spectrum located at 532 eV, measured by X-ray photoelectron spectroscopy, satisfy the following formula (1) and the following formula (2):
I _COO /I _CC >0.5 (1)
I _O /I _CC >1.2 (2)

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

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

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

<Film manufacturing method>
The method for producing the film includes a first step of preparing a base layer 3, a second step of disposing a cured resin layer 4 on one surface in the thickness direction of the base layer 3, and a third step of performing a plasma treatment on one surface in the thickness direction of the cured resin layer 4. This method is preferably performed by a roll-to-roll method. 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. In the following description, the case where the cured resin layer 4 is a hard coat layer will be described in detail.

[First step]
In the first step, the base layer 3 is prepared.

[Second step]
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. In order to dispose a 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.

As drying conditions, the drying temperature is, for example, 50°C or higher and, for example, 120°C or lower. The drying time is, for example, 10 seconds or longer and, for example, 10 minutes or shorter.

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 the ultraviolet light is, for example, 100 mJ/ ^cm2 or more and, for example, 500 mJ/cm2 ^or less.

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.

This results in a hard coat layer (cured resin layer 4) being disposed on one thickness-wise surface of the substrate layer 3, producing an intermediate laminate 2 having the substrate layer 3 and the hard coat layer (cured resin layer 4) in that order.

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

Specific examples of plasma treatment include treatment using inductively coupled plasma of an oxygen-containing gas (oxygen-LAICP treatment) generated by applying high-frequency power to a low-inductance antenna.

A low-inductance antenna is an antenna that has a low inductance of 7.5 μH or less and can generate inductively coupled plasma by applying high-frequency power.

As shown in Figures 2 and 3, the low inductance antenna 21 (LA21) is supported by a mounting fixture 22 and is arranged covered with a cover block 23 (omitted in Figure 3) (a case where the number of LA21 is four is shown as an example). The multiple LA21 are arranged in an array 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).

LA21 is formed of a conductor. Examples of the conductor include copper and silver, and preferably copper. LA21 may be covered with an insulator. Examples of the insulator include glass and quartz.

LA21 is electrically connected to a radio frequency power source (RF power source) via an impedance matching device.

LA21 has an open loop shape. Having LA21 in an open loop shape can reduce the inductance of LA21. Therefore, with LA21 in an open loop shape, it is possible to suppress an increase in voltage caused by an increase in the power applied to LA21. This makes it possible to suppress abnormal discharge during plasma processing. By suppressing abnormal discharge, it is possible to suppress damage to the intermediate laminate 2 being plasma processed.

Specifically, the LA21 has a U-shape with two free ends. For each LA21, the two free ends are fixed to the fixture 22 so that they are aligned in the width direction of the intermediate laminate 2. More specifically, the LA21 is fixed to the fixture 22 via a feedthrough 24, as shown in FIG. 3.

The LA21 also has an extension 21a on the side opposite the two free ends. The extension 21a extends in the width direction of the intermediate laminate 2. Each extension 21a may extend in the running direction of the intermediate laminate 2 (two LA21 may be arranged in this manner).

The LA 21 extends from the fixture 22 toward the intermediate laminate 2. The LA 21 extends in a direction perpendicular to the fixture 22. The extension length _d1 of the LA 21 from the fixture 22 is, for example, 30 mm or more and, for example, 150 mm or less.

The maximum length _d2 of the LA21 in the surface direction of the intermediate laminate 2 is, for example, 50 mm or more and, for example, 150 mm or less.

The separation distance _d3 between the LA 21 and the intermediate laminate 2 is, for example, 50 mm or more and, for example, 200 mm or less.

Preferably, the extension length _d1 and the separation distance _d3 are the same.

The ratio (d ₃ /d ₁ ) of the separation distance d ₃ to the extension length d ₁ is, for example, not less than 0.5 and not more than 3.5.

The center distance _d4 between adjacent LAs 21 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 LAs 21 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).

In the width direction of the intermediate laminate 2, the center distance _d5 between adjacent LAs 21 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 laminate 2 can be controlled.

Preferably, the center distance _d4 and the center distance _d5 are the same.

The center points 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.

Also, LA21 may have a coil shape instead of an open loop shape.

The cover block 23 includes a block body 23A and a plurality of partition plates 23B. The block body 23A has a plurality of 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 running 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 laminate 2 being plasma processed.

Then, in the oxygen-LAICP process, the LA21 is placed in a vacuum chamber, and the intermediate laminate 2 is transported to supply oxygen into the vacuum chamber.

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

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

The pressure in the vacuum chamber during 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 above pressure can be adjusted by the amount of oxygen supplied to the vacuum chamber.

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, even more preferably 10 MHz or more, and is, for example, 100 MHz or less, preferably 80 MHz or less, more preferably 60 MHz or less.

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.

In addition, in the oxygen-LAICP treatment, the plasma current density at the intermediate position between the LA 21 and the intermediate laminate 2 is, for example, 1.0 mA/cm3 or ^more , preferably 2.0 mA/cm3 or ^more , more preferably 3.0 mA/cm3 or ^more , and even more preferably 4.0 mA/ ^cm3 or more, and for example, 10 mA/cm3 or ^less , preferably 8 mA/cm3 or ^less , and more preferably 5 mA/cm3 ^or less.

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.

This allows plasma treatment to be performed on one side of the thickness direction of the hard coat layer (cured resin layer 4), producing film 1.

<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 a 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 surface in the thickness direction) of the film 1. The laminate 10 preferably includes the film 1 and the inorganic layer 11.

[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 lowermost layer in the laminate 10.

[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.

Examples of the inorganic layer 11 include an anti-reflective layer and a conductive layer. Below, the cases where the inorganic layer 11 is an anti-reflective layer and a conductive layer will be described in detail.

(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.

When the inorganic layer 11 is an anti-reflective layer, the laminate 10 is an anti-reflective film.

The anti-reflection layer has multiple layers with different refractive indices along the thickness direction. Specifically, the anti-reflection layer has high refractive index layers with a relatively high refractive index and low refractive index layers with a relatively low refractive index alternately in the thickness direction. In the anti-reflection layer, the net reflected light intensity is attenuated by the interference between reflected light at multiple interfaces in the multiple thin layers (high refractive index layers, low refractive index layers) contained therein. In addition, in the anti-reflection layer, the interference effect that attenuates the reflected light intensity can be expressed by adjusting the optical film thickness (product of refractive index and thickness) of each thin layer. Such an anti-reflection layer has high refractive index layers 12 and low refractive index layers 13 alternately in order toward one side in the thickness direction.

The anti-reflection layer (specifically, the high refractive index layer 12 and the low refractive index layer 13) preferably contains one selected from the group consisting of metals, alloys, metal oxides, metal nitrides, and metal fluorides, and more preferably contains one selected from the group consisting of metals, metal oxides, and metal nitrides. This allows the anti-reflection layer to suppress the reflection intensity of external light.

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.

In particular, the material used for the anti-reflective layer is selected according to the desired refractive index.

Specifically, examples of the high refractive index material constituting the high refractive index layer 12 include niobium oxide (Nb ₂ O ₅ ), titanium oxide, zirconium oxide, indium tin oxide (ITO), and antimony-doped tin oxide (ATO). A preferable example of the high refractive index material is indium tin oxide (ITO).

Examples of the low refractive index material constituting the low refractive index layer 13 include silicon dioxide (SiO ₂ ) and magnesium fluoride. As the low refractive index material, silicon dioxide (SiO ₂ ) is preferable.

In addition, in the anti-reflection layer, the thickness of the high refractive index layer 12 is, for example, 1 nm or more, preferably 3 nm or more, and, for example, 15 nm or less, preferably 10 nm or less.

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, for example, 50 nm or less, preferably 30 nm or less.

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.

The thickness of the anti-reflection 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.

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

In addition, the number of high refractive index layers and low refractive index layers in the above anti-reflection layer is not particularly limited.

(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.

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).

The thickness of the conductive layer is, for example, 1 nm or more, preferably 5 nm or more, and, for example, 100 nm or less.

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

<Action and effect>
In the film 1, the peak intensity I _CC assigned to a C-C bond at 285 eV, the peak intensity I _COO assigned to a COO bond at 289 eV, and the peak intensity I _O of the O1s spectrum located at 532 eV, measured by X-ray photoelectron spectroscopy on one surface in the thickness direction of the cured resin layer 4, satisfy the above formulas (1) and (2). Therefore, the adhesion can be improved.

Specifically, the peak intensity I _COO is the intensity of a peak attributed to a COO bond, and the peak intensity I _O is the intensity of a peak in the O1s spectrum. Both of these are peaks derived from bonds containing oxygen.

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

In addition, the above peak intensities I _CC , I _COO , and I _O are measured using X-ray photoelectron spectroscopy for one surface in the thickness direction of the cured resin layer 4, and therefore are peak intensities originating from one surface in the thickness direction of the cured resin layer 4.

And, 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.

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

The laminate 10 has a film 1 and an inorganic layer 11 arranged in that order toward one side in the thickness direction. Therefore, there is excellent adhesion between the film 1 and the inorganic layer 11.

The present invention will be described in more detail below with reference to examples and comparative examples. Note that the present invention is in no way limited to the examples and comparative examples. Furthermore, the specific numerical values of the blending ratio (content ratio), physical property values, parameters, etc. used in the following description can be replaced with the upper limit values (numerical values defined as "equal to or less than") or lower limit values (numerical values defined as "equal to or more than" or "exceeding") of the corresponding blending ratio (content ratio), physical property values, parameters, etc. described in the above "Form for carrying out the invention."

Example 1
<Film Production>
[First 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.

[Second step]
In the second step, a hard coat layer (cured resin layer) was disposed on one surface in the thickness direction of the substrate layer. Specifically, first, 100 parts by mass (solid content equivalent value) of a butyl acetate solution of urethane acrylate (product name "Luxidia 17-806", solid content concentration 80 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 concentration to 75 mass%. Next, cyclopentanone was added as a solvent to prepare a hard coat composition (solid content concentration 50 mass%).

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

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

By the above steps, an intermediate laminate was produced that had a base layer and a hard coat layer (cured resin layer) in that order.

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

Specifically, the intermediate laminate was transported to a vacuum chamber using a roll-to-roll method at a transport speed of 1.0 m/min under vacuum, and plasma treatment was performed on the intermediate laminate.

The plasma treatment was performed using oxygen-LAICP. The low-inductance antenna shown in Figures 2 and 3 was used.

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 distance _d4 is 290 mm, the 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 source (RF power source, frequency 13.56 MHz) via an impedance matching device.

The inside of the device was evacuated until the ultimate vacuum of the vacuum chamber reached 1.0×10 ⁻⁴ Pa, and then oxygen gas (oxygen concentration 100% by volume) was introduced into the vacuum chamber, and the pressure in the vacuum chamber was set to 0.5 Pa. By applying high-frequency power of 5.0 kW to the four low-inductance antennas by a high-frequency power source, an inductively coupled plasma of an oxygen-containing gas was formed around the antennas (the hard coat layer was treated by this plasma). The plasma current density at the midpoint between the low-inductance antennas and the intermediate laminate was set to 4.2 mA/cm ³ .

This is how the film was produced.

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

Specifically, after evacuating the inside of the vacuum chamber, the pressure was reduced to 1.0×10 ⁻⁴ Pa, argon gas was introduced as a sputtering gas, and a high refractive index layer (ITO film, thickness 5 nm) was formed using an ITO target (SnO ratio 10 mass%, length 600 mm × width 150 mm × thickness 5 mm, single cathode system) as a target (input power 1.0 kW, deposition chamber pressure: 0.3 Pa, DC discharge). Next, a low refractive index layer (SiO ₂ film, thickness 20 nm) was formed using a pure Si target (length 600 mm × width 50 mm × thickness 5 mm, dual cathode system) as a target (input power: 3.0 kW, deposition pressure 0.3 Pa, O ₂ /Ar=0.3, MFAC power supply 60 kHz).

This produced a laminate.

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

In the third step, argon ion bombardment was performed on one side of the hard coat layer in the thickness direction.

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

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 arranged with a gap of 50 mm between them, parallel to the intermediate laminate passing through the vacuum chamber. The anode electrode is arranged 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 arranged 35 mm away from the intermediate laminate, and is electrically connected to a high-frequency power source (RF power source, 13.56 MHz) via an impedance matcher. The length of each electrode in the film running direction is 110 mm, and the length in the width direction is 430 mm.

The inside of the device was evacuated until the ultimate vacuum of the vacuum chamber reached 1.0×10 ⁻⁴ Pa, and then argon gas was introduced as an inert gas into the vacuum chamber, and the pressure inside the vacuum chamber was set to 0.5 Pa. Capacitively coupled plasma (CCP) was generated by applying a power of 550 W between the planar electrodes by a high-frequency power source. 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.

Comparative Example 2
An intermediate laminate was prepared based on the same procedures as 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 Example 1.

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

[Second step]
In the second step, a hard coat layer (cured resin layer) was disposed on one surface in the thickness direction of the base layer. Specifically, first, 50 parts by mass of pentaerythritol triacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., product name "Viscoat #300"), 50 parts by mass of urethane acrylate prepolymer (manufactured by Shin-Nakamura Chemical Co., Ltd., product name "UA-53H-80BK"), 3.5 parts by mass of silicone particles (manufactured by Momentive Performance Materials Japan, LLC, product 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 Co., Ltd., trade name "Irgacure 907"), and 0.2 parts by mass of leveling agent (manufactured by DIC Co., Ltd., trade name "PC4100", solid content concentration 10%) are mixed, and diluted with toluene/cyclopentanone (CPN) mixed solvent (mass ratio 70/30) to prepare a hard coat composition (solid content concentration 35% by mass). Note that the synthetic smectite is used by diluting with toluene so that the solid content concentration becomes 6% by mass.

Next, a hard coat composition was applied to one surface of the substrate layer in the thickness direction to form a coating film. This coating film was then dried by heating and cured by UV 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.

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

By the above steps, an intermediate laminate was produced that had a base layer and a hard coat layer (cured resin layer) in that order.

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

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

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

In the third step, argon ion bombardment was performed on one side of the hard coat layer in the thickness direction, following the same procedure as in Comparative Example 1.

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

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

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

[Second step]
In the second step, a hard coat layer (cured resin layer) was disposed on one surface in the thickness direction of the base layer. Specifically, first, 50 parts by weight of pentaerythritol triacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., product name "Viscoat #300"), 50 parts by weight of urethane acrylate prepolymer (manufactured by Shin-Nakamura Chemical Co., Ltd., product name "UA-53H-80BK"), 1.7 parts by weight of silicone particles (manufactured by Momentive Performance Materials Japan, LLC, product 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 Chemical Co., Ltd., product name "Techpolymer ", weight average particle size: 3 μm, refractive index: 1.59) 2.3 parts by weight, synthetic smectite (organic clay, manufactured by Co-op Chemical Co., Ltd., trade name "Lucentite SAN") 2 parts by weight, photopolymerization initiator (manufactured by BASF, trade name "Irgacure 907") 3 parts by weight, and leveling agent (manufactured by DIC, trade name "PC4100", solid content concentration 10%) 0.2 parts by weight 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 used by diluting it with toluene so that the solid content concentration was 6% by mass.

Next, a hard coat composition was applied to one surface of the substrate layer in the thickness direction to form a coating film. This coating film was then dried by heating and cured by UV 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.

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

By the above steps, an intermediate laminate was produced that had a base layer and a hard coat layer (cured resin layer) in that order.

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

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

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

In the third step, argon ion bombardment was performed on one side of the hard coat layer in the thickness direction, following the same procedure as in Comparative Example 1.

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

Comparative Example 6
An intermediate laminate was prepared based on the same procedures as the first and second steps of Example 3. Thereafter, the third step was not performed. Thereafter, a laminate was manufactured based on the same procedures as Example 1.

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

The film was cut from the center of the width (340 mm width) into a piece approximately 1 cm square and used as a sample.

Table 1 shows the peak intensity I _CC at 285 eV assigned to the C—C bond, the peak intensity I _COO at 289 eV assigned to the COO bond, and the peak intensity I _O of the O1s spectrum located at 532 eV.

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

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

REFERENCE SIGNS LIST 1 film 3 substrate layer 4 cured resin layer 10 laminate 11 inorganic layer

Claims (5)

A base material layer and a cured resin layer are provided in this order toward one side in a thickness direction,
A film in which a peak intensity I _CC at 285 eV assigned to a C-C bond, a peak intensity I COO at 289 eV assigned to a _COO bond, and a peak intensity I _O of an O1s spectrum located at 532 eV, which are measured by X-ray photoelectron spectroscopy on one side in the thickness direction of the cured resin layer, satisfy the following formula (1) and the following formula (2):
I _COO /I _CC >0.5 (1)
I _O /I _CC >1.2 (2) The film according to claim 1, wherein the cured resin layer comprises a cured product of an acrylate resin. A laminate comprising the film according to claim 1 or 2 and an inorganic layer in that order toward one side in the thickness direction. the inorganic layer is an anti-reflection layer,
The laminate according to claim 3 , wherein the antireflection layer comprises a plurality of layers having mutually different refractive indices along a thickness direction. The laminate according to claim 3 , wherein the inorganic layer is a conductive layer.

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