Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
  • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/11—Anti-reflection coatings
  • G02B1/113—Anti-reflection coatings using inorganic layer materials only
  • G02B1/115—Multilayers
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/11—Anti-reflection coatings
  • G02B1/113—Anti-reflection coatings using inorganic layer materials only
  • G02B1/115—Multilayers
  • G02B1/116—Multilayers including electrically conducting layers
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/16—Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings

Definitions

• the present invention relates to a laminated film.
• One known composite material is a laminate film that includes an organic base film and an inorganic layer on the base film.
• the surface of the base film is plasma treated to remove dirt and moisture from the surface. Removing dirt and moisture from the surface of the base film helps to improve the adhesion of the inorganic layer formed on the surface to the base film.
• Technology related to such laminate films is described, for example, in Patent Document 1 below.
• Patent Document 1 describes a laminated film as an anti-reflection film.
• This laminated film comprises a base film, an adhesion layer, and an inorganic layer as an anti-reflection layer, in that order in the thickness direction.
• the base film has a hard coat (HC) layer on the adhesion layer side.
• This HC layer contains nanosilica particles.
• the HC layer has surface irregularities on the adhesion layer side.
• the adhesion of the inorganic layer to the base film is improved by the anchor effect due to the surface irregularities of the HC layer and the physicochemical action of the adhesion layer. If the adhesion of the inorganic layer to the base film is insufficient, the inorganic layer will peel off from the base film.
• nanosilica particles are relatively expensive and increase the manufacturing costs of the laminated film.
• the present invention provides a laminated film that can ensure adhesion of the inorganic layer to the base film while suppressing manufacturing costs.
• the present invention [1] includes a laminate film comprising a base film, an adhesive layer on the base film, and an inorganic layer on the adhesive layer, in which, in a cross-sectional view in the thickness direction of the laminate film, the ratio of a second interface length at the interface between the adhesive layer and the inorganic layer to a first interface length at the interface between the base film and the adhesive layer is 1.10 or more.
• the present invention [2] includes the laminated film described in [1] above, in which the ratio is 2.0 or less.
• the present invention [3] includes the laminate film described in [1] or [2] above, in which the adhesion layer has a thickness of 1 nm or more and 50 nm or less.
• the present invention [4] includes the laminate film according to any one of [1] to [3] above, in which the adhesion layer is an inorganic oxide film containing at least one element selected from the group consisting of Si, In, Al, Sn, Ti, Zr, and Nb.
• the present invention [5] includes a laminate film according to any one of [1] to [4] above, in which the inorganic layer includes a conductive layer.
• the present invention [6] includes the laminate film according to any one of [1] to [5] above, in which the inorganic layer includes an anti-reflection layer, and the anti-reflection layer includes a plurality of transparent inorganic oxide films laminated in the thickness direction.
• the ratio of the second interface length at the interface between the adhesive layer and the inorganic layer to the first interface length at the interface between the base film and the adhesive layer is 1.10 or more.
• the ratio of the first and second interface lengths is 1.10 or more, so that the anchor effect of the adhesive layer to the inorganic layer is exerted, and the adhesion of the inorganic layer to the base film via the adhesive layer can be ensured. Therefore, the content of particles such as nanosilica particles in the surface layer on the adhesive layer side of the base film can be reduced. This allows the manufacturing cost of the laminate film to be reduced. Therefore, with the laminate film of the present invention, the adhesion of the inorganic layer to the base film can be ensured while suppressing manufacturing costs.
• FIG. 1 is a schematic cross-sectional view of one embodiment of a laminated film of the present invention.
• FIG. 1 shows a case where the laminate film has an anti-reflection layer as an inorganic layer.
• 3 shows an example of a method for producing the laminate film shown in Fig. 1.
• Fig. 3A shows a cured resin layer forming step
• Fig. 3B shows an adhesion layer forming step
• Fig. 3C shows an inorganic layer forming step.
• FIG. 2 is a schematic diagram of an apparatus for carrying out a plasma treatment step and a film formation step in the example of the method for producing the laminated film shown in FIG. 1 .
• FIG. 5 is a perspective view showing the positional relationship between a low inductance antenna and a base film in the plasma processing chamber shown in FIG. 4.
• 5 is a cross-sectional view showing the positional relationship between a low inductance antenna and a base film in the plasma processing chamber shown in FIG. 4.
• 3 is a schematic diagram of an observation image of a cross section of a sample in Example 1.
• FIG. FIG. 13 is a schematic diagram of an observation image of a cross section of a sample in Comparative Example 1.
• the laminate film X of one embodiment of the present invention comprises a base film 10, an adhesive layer 21, and an inorganic layer 22, in this order in the thickness direction H.
• the laminate film X extends in a direction (plane direction D) perpendicular to the thickness direction H.
• the laminate film X is, for example, an anti-reflective film or a transparent conductive film.
• the laminate film X may also be another type of film.
• the base film 10 includes a resin film 11 and a cured resin layer 12 in this order in the thickness direction H.
• the resin film 11 and the cured resin layer 12 are in contact with each other.
• the cured resin layer 12 forms a first surface 10a
• the resin film 11 forms a second surface 10b.
• the resin film 11 is an element that ensures the strength of the laminated film X.
• the resin film 11 is, for example, a transparent resin film having flexibility.
• the material of the resin film 11 include polyester resin, polyolefin resin, cellulose resin, acrylic resin, polycarbonate resin, polyethersulfone resin, polyarylate resin, melamine resin, polyamide resin, polyimide resin, and polystyrene resin.
• the polyester resin include polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate.
• the polyolefin resin include polyethylene, polypropylene, and cycloolefin polymer (COP).
• the cellulose resin include triacetyl cellulose (TAC).
• the material of the resin film 11 is preferably at least one selected from the group consisting of polyester resin, polyolefin resin, and cellulose resin, and more preferably at least one selected from the group consisting of PET, COP, and TAC. In addition, in this embodiment, the resin film 11 does not contain particles.
• the thickness of the resin film 11 is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, and even more preferably 30 ⁇ m or more, and is preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, and even more preferably 100 ⁇ m or less.
• the thickness of the resin film 11 is equal to or greater than the above lower limit, the strength of the laminated film X can be ensured.
• the thickness of the resin film 11 is equal to or less than the above upper limit, the handleability of the base film 10 in the roll-to-roll process described below can be ensured.
• a carrier film may be bonded to the second surface 10b of the resin film 11 in order to ensure the transportability and handleability of the base film 10 in the roll-to-roll process.
• the total light transmittance (JIS K 7375:2008) of the resin film 11 is preferably 80% or more, more preferably 90% or more, and even more preferably 95% or more, and is, for example, 100% or less.
• the total light transmittance of the resin film 11 is equal to or greater than the above lower limit, good transparency can be ensured in the laminate film X.
• the cured resin layer 12 is a functional layer that contains a resin.
• the cured resin layer 12 is a cured product of a curable resin composition that contains a curable resin.
• An example of a functional layer is a hard coat layer.
• the hard coat layer is a layer that makes it difficult for scratches to form on the exposed surface of the inorganic layer 22 (the upper surface in FIG. 1).
• the curable resin examples include polyester resin, acrylic urethane resin, acrylic resin (excluding acrylic urethane resin), urethane resin (excluding acrylic urethane resin), amide resin, silicone resin, epoxy resin, and melamine resin. These curable resins may be used alone or in combination of two or more types. From the viewpoint of ensuring the hardness of the cured resin layer 12, the curable resin is preferably at least one selected from the group consisting of acrylic urethane resin and acrylic resin.
• the curable resin examples include ultraviolet-curable resins and thermosetting resins.
• the curable resin is preferably an ultraviolet-curable resin.
• the curable resin can be cured without being heated to a high temperature, which improves the manufacturing efficiency of the laminated film X.
• the cured resin layer 12 contains fewer inorganic oxide particles.
• materials for inorganic oxide particles include silica, alumina, titania, zirconia, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide.
• the content of inorganic oxide particles in the cured resin layer 12 is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, even more preferably 1% by mass or less, even more preferably 0.5% by mass or less, even more preferably 0.2% by mass or less, even more preferably 0.1% by mass or less, and particularly preferably 0.0% by mass.
• the thickness of the cured resin layer 12 is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, and even more preferably 5 ⁇ m or more, and is preferably 30 ⁇ m or less, more preferably 25 ⁇ m or less, and even more preferably 20 ⁇ m or less.
• the thickness of the cured resin layer 12 is equal to or greater than the above lower limit, the function of the cured resin layer 12 can be ensured.
• the cured resin layer 12 is a hard coat layer, the scratch resistance of the inorganic layer 22 can be ensured.
• the thickness of the cured resin layer 12 is equal to or less than the above upper limit, the transparency of the cured resin layer 12 can be ensured.
• the total light transmittance (JIS K 7375:2008) of the base film 10 is preferably 80% or more, more preferably 90% or more, and even more preferably 95% or more, and is, for example, 100% or less.
• the total light transmittance of the base film 10 is equal to or greater than the above lower limit, good transparency can be ensured in the laminate film X.
• the surface roughness Sa (arithmetic mean height based on ISO 25178-2:2012) of the first surface 10a of the substrate film 10 is preferably 1.0 nm or more, more preferably 1.2 nm or more, even more preferably 1.3 nm or more, and is preferably 10.0 nm or less, more preferably 7.0 nm or less, even more preferably 4.5 nm or less.
• the surface roughness Sa of the first surface 10a is equal to or greater than the above lower limit, the fine irregularities of the first surface 10a have an anchoring effect on the adhesive layer 21, thereby enhancing the adhesion of the inorganic layer 22 to the substrate film 10 via the adhesive layer 21.
• the surface roughness Sa of the first surface 10a is equal to or less than the above upper limit, excessive irregularities at the interface in the inorganic layer 22 described below can be suppressed.
• the first surface 10a is, for example, a surface that has been plasma-treated.
• the plasma treatment is preferably a treatment by inductively coupled plasma using an oxygen-containing gas (oxygen-LAICP treatment) that is generated by applying high-frequency power to a low-inductance antenna.
• oxygen-LAICP treatment of the first surface 10a will be described in detail later with respect to the manufacturing method of the laminated film X.
• the adhesion layer 21 is disposed on one surface of the base film 10 in the thickness direction H. Specifically, the adhesion layer 21 is disposed on the first surface 10a of the base film 10. The adhesion layer 21 is in contact with the base film 10.
• the adhesion layer 21 is a layer that enhances the adhesion of the inorganic layer 22 to the base film 10. Examples of materials for the adhesion layer 21 include metals such as Si, In, Ni, Cr, Ar, Sn, Au, Ag, Pt, Zn, Ti, W, Zr, Nb, and Pd, alloys of two or more of these metals, and oxides of these metals.
• the adhesion layer 21 is preferably an inorganic oxide film containing at least one element selected from the group consisting of Si, In, Al, Sn, Ti, Zr, and Nb. From the viewpoint of achieving both adhesion to both the base film 10 and the inorganic layer 22 and transparency of the adhesion layer 21, indium tin oxide (ITO) or silicon oxide (SiOx) is more preferable as the material of the adhesion layer 21.
• ITO indium tin oxide
• SiOx silicon oxide
• the silicon oxide as the material of the adhesion layer 21 is preferably SiOx having a lower oxygen content than the stoichiometric composition, and more preferably SiOx with x being 1.2 or more and 1.9 or less.
• the thickness of the adhesion layer 21 is preferably 1 nm or more, more preferably 2 nm or more, even more preferably 3 nm or more, and is preferably 50 nm or less, more preferably 30 nm or less, even more preferably 10 nm or less, and even more preferably 5 nm or less.
• the thickness of the adhesion layer 21 is equal to or greater than the above lower limit, the adhesion between the base film 10 and the inorganic layer 22 can be ensured.
• the thickness of the adhesion layer 21 is equal to or less than the above upper limit, the transparency of the adhesion layer 21 can be ensured.
• the inorganic layer 22 is disposed on one surface of the adhesive layer 21 in the thickness direction H.
• the inorganic layer 22 is in contact with the adhesive layer 21.
• Examples of the inorganic layer 22 include an anti-reflective layer and a conductive layer.
• the anti-reflective layer is a layer having anti-reflective properties that suppress the reflection intensity of external light.
• the conductive layer is a layer having conductivity.
• the inorganic layer 22 may be another layer.
• the inorganic layer 22 may also be a composite layer including an anti-reflective layer and another layer.
• the inorganic layer 22 may be a composite layer including a conductive layer and another layer.
• the inorganic layer 22 as an anti-reflection layer preferably includes a plurality of transparent inorganic oxide films stacked in the thickness direction H.
• Figure 2 shows an example of such an inorganic layer 22.
• the inorganic layer 22 (anti-reflection layer) in Figure 2 includes a high refractive index layer 22a, a low refractive index layer 22b, a high refractive index layer 22c, and a low refractive index layer 22d, in this order from the adhesive layer 21 side in the thickness direction H.
• the high refractive index layer 22a is in contact with the adhesive layer 21.
• the high refractive index layer 22a is in contact with the low refractive index layer 22b.
• the low refractive index layer 22b is in contact with the high refractive index layer 22c.
• the high refractive index layer 22c is in contact with the low refractive index layer 22d.
• the high refractive index layers 22a and 22c are layers with a relatively high refractive index
• the low refractive index layers 22b and 22d are layers with a relatively low refractive index.
• the intensity of the reflected light is attenuated by interference between the reflected light at multiple interfaces in the high refractive index layers 22a, 22c and the low refractive index layers 22b, 22d.
• Such interference can be achieved by adjusting the optical film thickness (the product of the film's refractive index and thickness) of each layer of the inorganic layer 22.
• the high refractive index layer 22a (first high refractive index layer) is made of a high refractive index material having a refractive index of preferably 1.9 or more at a wavelength of 550 nm.
• high refractive index materials include niobium oxide (Nb 2 O 5 ), titanium oxide, zirconium oxide, indium tin oxide (ITO), and antimony tin oxide (ATO).
• the high refractive index material is preferably niobium oxide (refractive index 2.33).
• the optical thickness of the high refractive index layer 22a is, for example, 20 nm or more and, for example, 55 nm or less.
• the low refractive index layer 22b (first low refractive index layer) is made of a low refractive index material having a refractive index of preferably 1.6 or less at a wavelength of 550 nm.
• low refractive index materials include silicon dioxide (SiO 2 ) and magnesium fluoride. From the viewpoint of achieving both a low refractive index and low absorption of visible light, the low refractive index material is preferably silicon dioxide (refractive index 1.46).
• the optical film thickness of the low refractive index layer 22b is, for example, 15 nm or more and, for example, 70 nm or less.
• the high refractive index layer 22c (second high refractive index layer) is made of a high refractive index material having a refractive index of preferably 1.9 or more at a wavelength of 550 nm.
• high refractive index materials include the materials described above for the high refractive index layer 22a, and niobium oxide is preferred.
• the optical film thickness of the high refractive index layer 22c is, for example, 60 nm or more and, for example, 330 nm or less.
• the low refractive index layer 22d (second low refractive index layer) is made of a low refractive index material whose refractive index at a wavelength of 550 nm is preferably 1.6 or less.
• low refractive index materials include the materials described above for the low refractive index layer 22b, and silicon dioxide is preferred.
• the optical film thickness of the low refractive index layer 22d is, for example, 100 nm or more and, for example, 160 nm or less.
• the total thickness of the inorganic layer 22 as an anti-reflection layer is preferably 180 nm or more, more preferably 200 nm or more, and even more preferably 220 nm or more, and is preferably 320 nm or less, more preferably 280 nm or less, and even more preferably 250 nm or less.
• the total thickness of the inorganic layer 22 as an anti-reflection layer is the sum of the thicknesses of the high refractive index layers 22a, 22c and the low refractive index layers 22b, 22d.
• the inorganic layer 22 can ensure the function of attenuating the reflected light intensity.
• the total thickness of the inorganic layer 22 is equal to or less than the upper limit, cracking of the inorganic layer 22 can be suppressed.
• the inorganic layer 22 as a conductive layer is formed from a conductive material.
• conductive materials include metals and metal oxides.
• metals include copper, silver, gold, nickel, chromium, and alloys thereof.
• metal oxides include indium-containing conductive oxides and antimony-containing conductive oxides.
• indium-containing conductive oxides include indium tin oxide (ITO), indium zinc oxide (IZO), indium gallium oxide (IGO), and indium gallium zinc oxide (IGZO).
• antimony-containing conductive oxides include antimony tin oxide (ATO).
• the inorganic layer 22 has a surface 22A on the side opposite to the substrate film 10.
• the surface roughness Sa (arithmetic mean height based on ISO 25178-2:2012) of the surface 22A is preferably 4.5 nm or less, more preferably 3.0 nm or less, even more preferably 2.5 nm or less, even more preferably 2.0 nm or less, and even more preferably 1.7 nm or less.
• the surface roughness Sa of the surface 22A is equal to or less than the upper limit, light scattering on the surface 22A can be suppressed.
• the surface roughness Sa of the surface 22A is preferably 1.0 nm or more, more preferably 1.3 nm or more, even more preferably 1.5 nm or more, and even more preferably more than 1.5.
• the frictional force on the surface 22A can be reduced, and good transportability of the laminated film X can be ensured, for example, in a method for producing the laminated film X by a roll-to-roll method.
• the method for measuring the surface roughness Sa is as described below in the examples.
• the interface between the base film 10 and the adhesive layer 21 has fine irregularities (not shown).
• the interface between two adjacent layers in the inorganic layer 22 also has fine irregularities (not shown).
• Microscopic irregularities are, for example, irregularities on the order of nanometers.
• the ratio (L2/L1) of the second interface length L2 at the interface (second interface) between the adhesive layer 21 and the inorganic layer 22 to the first interface length L1 at the interface (first interface) between the base film 10 and the adhesive layer 21 is 1.10 or more, preferably 1.20 or more, more preferably 1.30 or more, and even more preferably 1.35 or more.
• the first interface length L1 is the length of the first interface included in a range of, for example, 70 nm in the planar direction D in one cross-sectional view.
• the second interface length L2 is the length of the second interface included in the same range in the planar direction D in the same cross-sectional view.
• the method for measuring the first interface length L1 and the second interface length L2 is as described later in the examples.
• the ratio (L2/L1) is equal to or greater than the lower limit, the adhesion of the inorganic layer 22 in the laminate film X can be increased by the anchor effect.
• the ratio (L2/L1) is preferably equal to or less than 2.00, more preferably equal to or less than 1.70, and more preferably equal to or less than 1.50.
• the ratio (L2/L1) is equal to or less than the upper limit, the surface roughness Sa of the surface 22A of the inorganic layer 22 can be suppressed.
• the inorganic layer 22 is an anti-reflective layer, the suppression of the surface roughness Sa of the surface 22A can suppress light scattering on the surface 22A.
• Examples of methods for adjusting the ratio (L2/L1) include adjusting the amount of oxygen gas introduced in the oxygen-LAICP treatment process, adjusting the frequency of the high-frequency power in the high-frequency power source, adjusting the magnitude of the applied power, and adjusting the treatment time.
• the second interface length L2 is preferably 90 nm or more, more preferably 100 nm or more, even more preferably 110 nm or more, even more preferably 115 nm or more, and is preferably 160 nm or less, more preferably 140 nm or less, even more preferably 130 nm or less.
• the second interface length L2 is equal to or greater than the lower limit, the adhesion of the inorganic layer 22 to the substrate film 10 via the adhesion layer 21 can be improved.
• the second interface length L2 is equal to or less than the upper limit, the roughness of the surface 22A of the inorganic layer 22 can be adjusted.
• the peeling rate of the inorganic layer 22 of the laminated film X in the second test described below after the first test (accelerated weather resistance test) described below is preferably 5% or less, more preferably 3% or less, and even more preferably 1% or less, from the viewpoint of ensuring the adhesion of the inorganic layer 22. More specifically, the methods of the first and second tests are as described later in the examples.
• the peeling rate of the inorganic layer 22 is equal to or less than the upper limit value, it is possible to suppress a decrease in the substantial function of the inorganic layer 22 due to peeling of the inorganic layer 22.
• Test 1 First, the side of the base film 10 of the laminated film X is fixed to a glass plate. Next, the inorganic layer 22 of the laminated film X on the glass plate is irradiated with light for 32.5 hours under conditions of a temperature of 85° C., a relative humidity of 45%, and an irradiation intensity (integrated illuminance from 290 nm to 450 nm) of 150 mW/ cm2 .
• Test 2 First, eleven parallel first incisions (1 mm apart) extending linearly in a first direction and eleven parallel second incisions (1 mm apart) extending linearly in a second direction perpendicular to the first direction are formed on the inorganic layer 22 and the adhesive layer 21 in the laminated film X on the glass plate after the first test using a cutter knife, and 100 squares are formed by the first and second incisions.
• isopropyl alcohol is continuously dripped at 2 mL/min on the area of the 100 squares in the laminated film X, while a polyester wiper is slid under the conditions of a wiper contact surface of 20 mm x 20 mm, a load of 1.5 kg/20 mm, a sliding speed of 50 mm/sec, and 1000 reciprocations.
• the number of squares in which peeling of 0.25 mm2 or more has occurred is counted among the 100 squares.
• the count number is divided by 100 to calculate the peeling rate (%).
• the ratio (L2/L1) of the second interface length L2 at the interface between the adhesive layer 21 and the inorganic layer 22 to the first interface length L1 at the interface between the base film 10 and the adhesive layer 21 in a cross-sectional view in the thickness direction H is 1.10 or more.
• the ratio (L2/L1) being 1.10 or more provides an anchor effect of the adhesive layer 21 to the inorganic layer 22, and the adhesion of the inorganic layer 22 to the base film 10 via the adhesive layer 21 can be ensured. Therefore, the content of particles such as nanosilica particles in the surface layer on the adhesive layer 21 side of the base film 10 can be reduced. This allows the manufacturing cost of the laminate film X to be reduced. Therefore, with the laminate film X, the adhesion of the inorganic layer 22 to the base film 10 can be ensured while suppressing the manufacturing cost.
• FIGS. 3A to 3C show an example of a method for manufacturing laminated film X.
• This manufacturing method includes a cured resin layer forming process (FIG. 3A), a plasma treatment process, and a film forming process (FIGS. 3B and 3C).
• a cured resin layer 12 is formed on a long resin film 11. This results in a substrate film 10.
• the cured resin layer 12 can be formed by applying the above-mentioned curable resin composition to the resin film 11 to form a coating film, and then curing the coating film.
• the curable resin composition may contain other components other than the above-mentioned curable resin as necessary. Examples of the other components include a solvent and a leveling agent. Examples of the solvent include butyl acetate, ethyl acetate, toluene, and cyclopentanone.
• the curable resin composition when the curable resin composition contains an ultraviolet-curable resin as the curable resin group, the curable resin composition preferably contains a photopolymerization initiator.
• the curable resin composition when the curable resin composition contains a thermosetting resin as the curable resin, the curable resin composition preferably contains a thermal polymerization initiator.
• the coating on the resin film 11 is dried after the curable resin composition is applied.
• 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 higher and, for example, 10 minutes or shorter.
• the coating film on the resin film 11 is cured by ultraviolet irradiation.
• 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.
• the coating on the resin film 11 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.
• a long base film 10 can be produced.
• a roll of the long base film 10 is prepared. Specifically, the base film 10 is wound so that the first surface 10a of the base film 10 faces inward in the radial direction of the roll.
• the device Y shown in FIG. 4 is an example of a device for carrying out the plasma treatment process and the film formation process.
• the device Y includes a payout chamber R1, a winding chamber R2, a connection chamber C1, a plasma treatment chamber C2, a connection chamber C3, a film formation chamber C4, a connection chamber C5, a connection chamber C6, and a PEM device (not shown).
• the unwinding chamber R1 is equipped with a unwinding roller 51 for unwinding the work film W.
• a roll of a long base film 10 is attached to the unwinding roller 51 as the work film W.
• a predetermined number of guide rollers G for guiding the work film W are provided within the unwinding chamber R1.
• the winding chamber R2 is equipped with a winding roller 52 for winding up the work film W.
• a predetermined number of guide rollers G for guiding the work film W are provided within the winding chamber R2.
• connection chamber C1 is positioned next to the unwinding chamber R1 in the running direction of the work film W, and is positioned before the plasma processing chamber C2.
• a predetermined number of guide rollers G for guiding the work film W are provided inside the connection chamber C1.
• the connection chamber C1 is connected to a vacuum pump (not shown), and is configured so that the pressure inside the chamber can be adjusted.
• the pressure inside the connection chamber C1 is maintained at a predetermined pressure between the pressure inside the unwinding chamber R1 and the pressure inside the plasma processing chamber C2. This ensures a pressure difference between the unwinding chamber R1 and the plasma processing chamber C2.
• the plasma processing chamber C2 is disposed between the connection chamber C1 and the connection chamber C3 in the running direction of the workpiece film W. In the plasma processing chamber C2, the plasma processing process is carried out as described below.
• the plasma processing chamber C2 is equipped with a plurality of low inductance antennas (LA) 71.
• the low inductance antenna means an antenna that has a low inductance of 7.5 ⁇ H or less and is capable of generating inductively coupled plasma by application of high frequency power.
• the LA71 is supported by a mounting fixture 72 and covered by a cover block 73 (omitted in FIG. 5) as shown in FIGS. 5 and 6, and is placed inside the plasma processing chamber C2 (an example is shown in which the number of LA71 is four).
• the multiple LAs 71 are aligned in the running direction of the base film 10 and in the direction perpendicular to the running direction (the width direction of the base film 10).
• the fixture 72 is a vacuum flange. As shown in FIG. 6, the LAs 71 are fixed to the fixture 72 via a field through 74. As shown in FIG. 4, the fixture 72 is attached to an opening 75 provided in the wall of the plasma processing chamber C2. Specifically, the fixture 72 is attached to the opening 75 with a seal member (not shown) sandwiched between the wall of the plasma processing chamber C2 and the fixture 72.
• the LAs 71 are electrically connected to a high-frequency power source (RF power source) outside the plasma processing chamber C2 via an impedance matching device.
• RF power source high-frequency power source
• Such LAs 71 are formed of a conductor. Examples of conductors include copper and silver, and copper is preferable.
• the LAs 71 may be covered with an insulator. Examples of insulators include glass and quartz.
• the cover block 73 comprises a block body 73A and multiple partition plates 73B.
• the block body 73A has multiple storage spaces 73a.
• One LA 71 is stored in each storage space 73a.
• the partition plates 73B are arranged to close the storage spaces 73a.
• the storage spaces 73a are sealed spaces.
• the block body 73A is made of, for example, aluminum.
• An example of the aluminum is aluminum A5052.
• the partition plates 73B are made of an insulating material.
• An example of the insulating material is quartz and glass.
• the separation distance d' (shown in Figure 6) between the substrate film 10 running in the plasma processing chamber C2 and the cover block 73 is, for example, 50 to 200 mm.
• Such a cover block 73 helps to avoid damage and contamination of the LA71 due to plasma treatment without excessively reducing the plasma conversion efficiency due to the power applied to the LA71, and also helps to suppress damage to the substrate film 10 being plasma treated.
• the LA71 has an open loop shape in this embodiment.
• the open loop shape of the LA71 is advantageous in lowering the inductance of the LA71. Therefore, the open loop shape of the LA71 can suppress an increase in voltage due to an increase in the power applied to the LA71. This can suppress abnormal discharge during the plasma treatment described below. The suppression of abnormal discharge can suppress damage to the base film 10 being plasma treated.
• the LA71 has a U-shape with two free ends. For each LA71, the two free ends are fixed to the fixture 72 so as to be aligned in the width direction of the base film 10.
• the LA71 has an extension 71a on the opposite side to the two free ends.
• the extension 71a extends parallel to the base film 10 passing through the plasma processing chamber C2.
• the extension 71a extends in the width direction of the base film 10.
• Each extension 71a may extend in the running direction of the base film 10 (four LA71 may be arranged in this manner).
• the length of the extension 71a is, for example, 50 to 150 mm (FIG. 5 illustrates an example in which the length of the extension 71a is the same as the maximum length d2 of the LA71 described below).
• the LA71 may have a coil shape instead of an open loop shape.
• the LA 71 extends from the fixture 72 toward the base film 10.
• the LA 71 preferably extends perpendicularly to the fixture 72.
• the extension length d 1 of the LA 71 from the fixture 72 is, for example, 30 to 150 mm.
• the maximum length d 2 of the LA 71 in the surface direction of the base film 10 is, for example, 50 to 150 mm.
• the separation distance d 3 (shown in FIG. 6 ) between the LA 71 and the base film 10 is, for example, 50 to 200 mm.
• the extension length d 1 and the separation distance d 3 are preferably the same.
• the ratio (d 3 /d 1 ) of the separation distance d 3 to the extension length d 1 is, for example, 0.5 to 3.5.
• the number (number of rows) of the LAs 71 spaced apart in the running direction of the base film 10 may be 1, 2, or 3, or may be 4 or more if necessary, depending on the running speed (i.e., plasma treatment time) of the base film 10.
• the center-to-center distance d 4 between adjacent LAs 71 is, for example, 100 to 500 mm.
• the center-to-center distance d 5 between adjacent LAs 71 is, for example, 200 to 500 mm.
• the center-to-center distance d 4 and the center-to-center distance d 5 are preferably the same.
• the ratio (d 5 /d 4 ) of the center-to-center distance d 5 to the center-to-center distance d 4 is, for example, 0.5 to 2.0.
• the center points of the extensions 71a of the four LAs 71 preferably form a square with the vertices.
• a high density plasma with high in-plane uniformity can be generated by such a set of LAs 71.
• the LAs 71 for example, a high frequency antenna for plasma generation described in JP 2013-258153 A may be used.
• the plasma processing chamber C2 further includes a transport roller 53.
• the transport roller 53 is a main guide roller for transporting the workpiece film W within the plasma processing chamber C2.
• the transport roller 53 has a temperature adjustment function that allows the workpiece film W to be heated or cooled.
• the transport roller 53 is a transport roller with a temperature adjustment function.
• the transport roller 53 transports the base film 10 while contacting the second surface 10b of the base film 10.
• the LA 71 is disposed opposite the transport roller 53.
• the transport roller 53 with a temperature control function that contacts the base film 10 can perform plasma treatment on the base film 10 while cooling or heating the base film 10.
• the PEM device is a device for performing plasma emission monitoring (PEM) during plasma processing, and comprises a device body and an optical fiber for collecting light.
• the tip (one end) of the optical fiber is positioned in the plasma processing chamber C2, between the work film W and LA71 in the direction of separation between them.
• the other end of the optical fiber is connected to the device body.
• a first line L1 with a flow rate control valve for introducing gas into the chamber is connected to the plasma processing chamber C2.
• connection chamber C3 is located next to the plasma processing chamber C2 in the running direction of the work film W and before the film formation chamber C4.
• a predetermined number of guide rollers G for guiding the work film W are provided inside the connection chamber C3.
• the connection chamber C3 is connected to a vacuum pump (not shown) and is configured so that the pressure inside the chamber can be adjusted.
• the pressure inside the connection chamber C3 is maintained at a predetermined pressure between the pressure inside the plasma processing chamber C2 and the pressure inside the film formation chamber C4. This ensures a pressure difference between the plasma processing chamber C2 and the film formation chamber C4.
• the film-forming chamber C4 is disposed next to the connection chamber C3 in the running direction of the workpiece film W.
• the film-forming chamber C4 is also connected to a vacuum pump (not shown) and is configured so that the interior of the chamber can be adjusted to a predetermined vacuum level. In the film-forming chamber C4, the film-forming process is carried out as described below.
• the film-forming chamber C4 is a sputtering film-forming chamber.
• the film-forming chamber C4 includes a film-forming roller 54 and a plurality of sputtering chambers 60 (sputtering chambers 60a to 60e) (a case where the number of sputtering chambers 60 is 5 is illustrated as an example).
• the film-forming roller 54 is a main guide roller for transporting the workpiece film W within the film-forming chamber C4.
• the film-forming roller 54 has a temperature adjustment function that can heat or cool the workpiece film W.
• the sputtering chamber 60 is a partitioned space within the film-forming chamber C4.
• the plurality of sputtering chambers 60 are arranged along the circumferential direction of the film-forming roller 54.
• Each sputtering chamber 60 opens toward the film-forming roller 54.
• a cathode 61 is provided within the sputtering chamber 60.
• a target (not illustrated) is arranged on the cathode 61 as a film-forming material supply material. The target is arranged on the target so as to face the film-forming roller 54.
• Each sputtering chamber 60 is provided with a power supply (not shown) for applying a voltage to the target to generate a glow discharge.
• Examples of power supplies include DC power supplies, AC power supplies, MF power supplies, RF power supplies, and MF-AC power supplies.
• MF-AC power supplies refer to AC power supplies with a frequency band of several kHz to several MHz.
• Each sputtering chamber 60 is connected to a required number of second lines (not shown) equipped with flow rate control valves for introducing gas into the chamber.
• a predetermined number of guide rollers G for guiding the workpiece film W are provided in the deposition chamber C4.
• the connecting chamber C5 and the connecting chamber C6 are disposed in this order between the film forming chamber C4 and the winding chamber R2 in the running direction of the workpiece film W.
• a predetermined number of guide rollers G are provided in the connecting chamber C5 for guiding the workpiece film W.
• a predetermined number of guide rollers G are provided in the connecting chamber C6 for guiding the workpiece film W.
• the connecting chamber C5 is connected to a vacuum pump (not shown) and is configured to be able to adjust the pressure inside the chamber.
• the connecting chamber C6 is connected to a vacuum pump (not shown) and is configured to adjust the pressure inside the chamber.
• the pressure inside the connecting chambers C5 and C6 is maintained at a predetermined pressure between the pressure inside the film forming chamber C4 and the pressure inside the winding chamber R2. This ensures a pressure difference between the film forming chamber C4 and the winding chamber R2.
• the above-described device Y performs a plasma treatment process and a film formation process in sequence. Specifically, the process is as follows.
• the work film W is unwound from the unwinding chamber R1. After being unwound from the unwinding chamber R1, the work film W passes through the connection chamber C1, the plasma treatment chamber C2, the connection chamber C3, the film forming chamber C4, the connection chamber C5, and the connection chamber C6 in sequence, and is wound up in the winding chamber R2.
• the running speed of the work film W is, for example, 0.5 m/min or more, and, for example, 5 m/min or less.
• the series of lines from the unwinding chamber R1 to the winding chamber R2 is not opened to the atmosphere along the way, and the process is carried out in the line under a reduced pressure atmosphere.
• the reduced pressure atmosphere is preferably under vacuum. Under vacuum preferably means a reduced pressure atmosphere of 7 Pa or less.
• the plasma treatment process is carried out in the plasma treatment chamber C2.
• the first surface 10a of the substrate film 10 is plasma-treated in a reduced pressure atmosphere in the plasma treatment chamber C2 (chamber) while the plasma emission intensity is detected.
• the plasma treatment is a treatment using inductively coupled plasma of an oxygen-containing gas (oxygen-LAICP treatment) that is generated by applying high-frequency power to the LA71. Specifically, it is as follows.
• Oxygen is supplied into the plasma processing chamber C2 during plasma processing via the first line L1.
• an inert gas may be supplied into the plasma processing chamber C2.
• inert gas include argon, krypton, and xenon.
• the oxygen concentration of the gas (oxygen-containing gas) in the plasma processing chamber C2 is preferably 30% by volume or more, more preferably 50% by volume or more, even more preferably 80% by volume or more, even more preferably 90% by volume or more, even more preferably 95% by volume or more, and particularly preferably 100% by volume.
• the oxygen concentration is equal to or more than the lower limit, high-density oxygen plasma can be generated. This is useful for forming fine irregularities on the nanometer order on the first surface 10a of the substrate film 10 and for highly activating the first surface 10a by cleaning it.
• the pressure (first pressure) in the plasma processing chamber C2 during plasma processing is preferably 0.1 Pa or more, more preferably 0.2 Pa or more, even more preferably 0.3 Pa or more, and is preferably 7 Pa or less, more preferably 5 Pa or less, and even more preferably 3 Pa or less.
• first pressure is equal to or greater than the lower limit
• a plasma environment of sufficient density for surface modification processing of the first surface 10a of the substrate film 10 can be formed in the plasma processing chamber C2.
• the first pressure is equal to or less than the upper limit, thermal damage to the first surface 10a caused by excessively high-density plasma can be suppressed in the plasma processing, and excessive roughening of the first surface 10a can be suppressed. Suppression of excessive roughening helps to suppress a decrease in the mechanical strength of the first surface 10a.
• the first pressure can be adjusted by the amount of oxygen gas supplied into the plasma processing chamber C2.
• the frequency of the high frequency power applied to the LA71 during plasma treatment is preferably 1 MHz or more, more preferably 5 MHz or more, even more preferably 10 MHz or more, and also preferably 100 MHz or less, more preferably 80 MHz or less, and even more preferably 60 MHz or less.
• the frequency is equal to or greater than the lower limit, the plasma discharge can be stabilized while increasing the plasma current density during plasma treatment.
• the antenna potential can be suppressed, and therefore damage to the substrate film 10 caused by the plasma can be suppressed.
• the high frequency power is preferably 0.1 kW or more, more preferably 0.3 kW or more, even more preferably 1.0 kW or more, and is preferably 10 kW or less, more preferably 8 kW or less, and even more preferably 6 kW or less.
• the high frequency power is equal to or greater than the lower limit, a high density plasma environment can be formed in the plasma treatment chamber C2 during plasma treatment using inductively coupled plasma.
• the high frequency power is equal to or less than the upper limit, excessive damage to the substrate caused by the plasma can be suppressed.
• the plasma emission intensity during the plasma treatment is preferably monitored by a PEM device. Then, based on the monitoring results, the amount of oxygen gas introduced, the high frequency power, the travel speed, etc. are controlled.
• the plasma current density at the intermediate position between the LA 71 and the base film 10 is preferably 1.0 mA/cm3 or more , more preferably 2.0 mA/ cm3 or more, even more preferably 3.0 mA/ cm3 or more, and preferably 10 mA/cm3 or less , more preferably 8 mA/cm3 or less, even more preferably 4 mA/cm3 or less .
• the inductively coupled plasma treatment using a low inductance antenna can achieve a higher plasma current density (for example, a plasma density about 100 times higher) than the capacitively coupled plasma treatment described above.
• Methods for adjusting the plasma current density include, for example, adjusting the amount of oxygen gas introduced into the plasma processing chamber C2, adjusting the frequency of the high frequency power in the high frequency power supply, and adjusting the magnitude of the applied power.
• an adhesion layer 21 and an inorganic layer 22 are formed in sequence on the first surface 10a of the substrate film 10 by a sputtering method in a reduced pressure atmosphere.
• the reduced pressure atmosphere is preferably a vacuum.
• a sputtering gas (inert gas) is introduced into each sputtering chamber 60 via a second line, while a negative voltage is applied to a target (film-forming material) placed on a cathode 61 in the sputtering chamber 60.
• a glow discharge to ionize gas atoms, and the gas ions collide with the target surface at high speed, ejecting the target material from the target surface, which is then deposited on the workpiece film W.
• sputtering gases include argon, krypton, and xenon.
• the sputtering method may be a reactive sputtering method.
• oxygen a reactive gas
• the oxygen is introduced into the sputtering chamber 60 via another second line.
• the target is, for example, a metal in the metal oxide that forms each layer.
• the pressure (second pressure) in the sputtering chamber 60 is, for example, 0.1 to 5.0 Pa depending on the type of layer to be formed.
• the film formation temperature (the temperature of the workpiece film W, which is adjusted by the film formation roller 54) is, for example, -10°C to 150°C.
• an adhesive layer 21 is formed on the substrate film 10 by a sputtering method in the sputtering chamber 60a.
• an ITO layer is formed as the adhesive layer 21
• an ITO target is used as the target placed on the cathode 61 in the sputtering chamber 60a.
• sputtering is performed while introducing argon into the sputtering chamber 60a.
• reactive sputtering is performed while introducing argon and oxygen into the sputtering chamber 60a.
• an inorganic layer 22 is formed on the adhesion layer 21 by sputtering in at least one sputtering chamber selected from sputtering chambers 60b to 60e.
• sputtering chambers 60b to 60e For example, when forming an inorganic layer 22 (FIG.
• a high refractive index layer 22a is formed on the adhesion layer 21 in sputtering chamber 60b
• a low refractive index layer 22b is formed on the high refractive index layer 22a in sputtering chamber 60c
• a high refractive index layer 22c is formed on the low refractive index layer 22b in sputtering chamber 60d
• a high refractive index layer 22d is formed on the high refractive index layer 22c in sputtering chamber 60e.
• the laminated film X serving as the work film W passes through the connection chambers C5 and C6 and enters the winding chamber R2, where it is wound up by the winding roller 52.
• Example 1 The laminated film of Example 1 was produced by carrying out the following steps in sequence.
• a hard coat layer was formed on one side of a triacetyl cellulose (TAC) film as a resin film to prepare a substrate film (preparation step).
• TAC triacetyl cellulose
• 100 parts by mass (solid content equivalent value) of a butyl acetate solution of an ultraviolet-curable acrylic urethane resin 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
• butyl acetate as a solvent were mixed to prepare a first resin composition with a solid content concentration of 75% by mass.
• cyclopentanone was added as an additional solvent to the first resin composition to prepare a second resin composition with a solid content concentration of 50% by mass.
• a long TAC film (length 100 m, width 340 mm, thickness 40 ⁇ m) was prepared.
• the second resin composition was applied to one side of the TAC film to form a coating film.
• the coating film was dried by heating and then cured by ultraviolet irradiation.
• HC hard coat
• a high-pressure mercury lamp was used as a light source, and ultraviolet rays with a wavelength of 365 nm were irradiated onto the coating film, with an integrated irradiation amount of 300 mJ/cm 2. In this manner, a TAC film with an HC layer was produced as a substrate film.
• the first apparatus includes a payout chamber, a plasma treatment chamber, a film formation chamber, and a winding chamber.
• the payout chamber, the plasma treatment chamber (first plasma treatment), the film formation chamber, and the winding chamber are arranged in this order and communicate with each other.
• the payout chamber includes a payout roller.
• a roll of the base film was set on the payout roller as the work film.
• the plasma treatment chamber includes a temperature-adjusting transport roller (transport roller 53 in FIG.
• each low inductance antenna has an extension (extension 71a in FIG. 5) parallel to the base film.
• the extension length d 1 is 88 mm
• the maximum length d 2 is 100 mm
• the separation distance d 3 is 112 mm
• the center distance d 4 is 290 mm
• the center distance d 5 is 280 mm (FIGS. 5 and 6).
• 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 outside the plasma processing chamber.
• the separation distance d' between the base film traveling in the plasma processing chamber and the cover block is 100 mm.
• the film formation chamber is a sputtering film formation chamber, and includes a film formation roller (film formation roller 54 in FIG. 4) and first and second sputtering chambers (sputtering chambers 60a, 60b in FIG. 4).
• Each sputtering chamber is a space partitioned within the film formation chamber.
• the first and second sputtering chambers are arranged in this order along the circumferential direction of the deposition roller and in the running direction of the base film.
• Each sputtering chamber has a cathode arranged opposite the deposition roller.
• Each sputtering chamber is connected to a required number of second lines (not shown) equipped with flow rate control valves for introducing gas into the chamber.
• the winding chamber has a winding roller.
• the HC surface (first surface) of the base film was plasma treated in the plasma treatment chamber (plasma treatment process).
• the running speed of the base film was 0.5 m/min.
• the temperature of the temperature-controlled transport roller was -8°C.
• the plasma treatment conditions were as follows:
• the inside of the apparatus was evacuated until the ultimate vacuum in the plasma treatment chamber reached 1.0 ⁇ 10 -4 Pa, and then oxygen gas was introduced into the plasma treatment chamber to set the atmospheric pressure in the plasma treatment chamber to 0.5 Pa.
• High frequency power of 5.0 kW was applied from a high frequency power source to the four low inductance antennas, thereby forming an inductively coupled plasma of an oxygen-containing gas around the antennas (the surface of the HC layer of the substrate film was treated with this plasma).
• an adhesive layer and an inorganic layer were successively formed on the substrate film after plasma treatment (film formation process: adhesive layer formation process and inorganic layer formation process). Specifically, while the substrate film was cooled and transported by the film formation roll in the film formation chamber, an adhesive layer was formed on the HC layer of the substrate film in the first sputtering chamber, and an inorganic layer was formed on the adhesive layer in the second sputtering chamber.
• the film formation temperature temperature of the film formation roll was set to -8°C. More specifically, it is as follows.
• the film formation chamber was evacuated to an ultimate vacuum of 1.0 ⁇ 10 ⁇ 4 Pa, and then argon was introduced as an inert gas into the first sputtering chamber to set the pressure in the first sputtering chamber to 0.3 Pa.
• argon was introduced as an inert gas into the first sputtering chamber to set the pressure in the first sputtering chamber to 0.3 Pa.
• a sintered body of indium oxide and tin oxide ITO with a tin oxide concentration of 10 mass%) was used.
• the power source for applying a voltage to the target a DC power source was used. The discharge power was 1.0 kW.
• a 20 nm thick SiO2 layer was formed as an inorganic layer by reactive sputtering.
• argon as an inert gas and oxygen as a reactive gas were introduced into the second sputtering chamber, and the pressure in the second sputtering chamber was set to 0.3 Pa.
• the amount of oxygen introduced per 100 parts by volume of argon introduced into the second sputtering chamber was 30 parts by volume.
• a Si target was used as the target.
• An MF-AC power supply 60 kHz
• the discharge power was 3.0 kW.
• the laminated film of Example 1 includes a substrate film with an HC layer, an adhesive layer (ITO) on the HC layer, and an inorganic layer (SiO 2 ) on the adhesive layer.
• the substrate film of the laminated film of Example 1 has a plasma-treated HC layer surface. This plasma treatment is a treatment by inductively coupled plasma using an oxygen-containing gas generated by application of high-frequency power to a low-inductance antenna (oxygen-LAICP treatment).
• Example 2 A laminated film of Example 2 was produced in the same manner as the laminated film of Example 1, except for the following: The running speed of the base film was 1.0 m/min, and the high-frequency power applied in the plasma treatment step was 3.5 kW.
• a second device capable of performing a roll-to-roll process on the work film was used for the plasma treatment process and film formation process.
• the second device has the same configuration as the first device, except that it has a second plasma treatment chamber instead of the first plasma treatment.
• the second plasma treatment chamber has a cathode electrode and an anode electrode (both rectangular electrodes made of SUS304) as a pair of flat electrodes for generating plasma.
• the pair of flat electrodes are arranged parallel to the substrate film passing through the second plasma treatment chamber, with a gap of 50 mm between them.
• the anode electrode is arranged at a position 35 mm away from the substrate film passing through the second plasma treatment chamber, and is grounded outside the plasma treatment chamber.
• the cathode electrode is arranged to face the HC layer surface of the substrate film, and is electrically connected to a high-frequency power source (RF power source, 13.56 MHz) via an impedance matcher.
• RF power source 13.56 MHz
• the length of each electrode facing the base film in the film running direction is 110 mm, and the length in the width direction is 430 mm.
• the HC surface (first surface) of the base film was plasma treated (bombardment treatment).
• the running speed of the base film (film running speed) was 1.0 m/min.
• the plasma treatment conditions were as follows:
• argon was introduced into the second plasma treatment chamber, and the pressure in the plasma treatment chamber was set to 0.5 Pa.
• Capacitively coupled plasma was generated by applying a power of 550 W between the planar electrodes by a high-frequency power source.
• a bombardment treatment with argon ions Ar-BB treatment was performed on the surface of the HC layer of the substrate film.
• an adhesive layer and an inorganic layer were formed in sequence on the substrate film after the plasma treatment, in the same manner as described above for Example 1.
• the laminated film of Comparative Example 1 includes a substrate film with an HC layer, an adhesive layer (ITO) on the HC layer, and an inorganic layer (SiO 2 ) on the adhesive layer.
• the substrate film of the laminated film of Comparative Example 1 has a plasma-treated HC layer surface. This plasma treatment is an ion bombardment treatment (Ar-BB treatment) by capacitively coupled plasma using an argon-containing gas.
• Comparative Example 2 A laminated film of Comparative Example 2 was produced in the same manner as the laminated film of Example 1, except for the following: The running speed of the base film was 1.0 m/min, and the high-frequency power applied in the plasma treatment step was 2.0 kW.
• the substrate film after plasma treatment and before the formation of the adhesive layer in the manufacturing process of the laminated film was sampled, and a sample film of a predetermined size was cut out from the substrate film.
• the sample film was placed on a horizontally arranged slide glass. Specifically, the sample film was placed on the slide glass so that the plasma-treated surface (HC layer surface) of the sample film was facing up.
• 2 ⁇ L of a predetermined liquid was dropped onto the plasma-treated surface of the sample film on the slide glass to form a droplet (droplet formation).
• the contact angle of the droplet with respect to the sample film surface was measured by a contact angle meter (product name "DMs-401", manufactured by Kyowa Interface Science Co., Ltd.) (contact angle measurement).
• a contact angle meter product name "DMs-401", manufactured by Kyowa Interface Science Co., Ltd.
• contact angle measurement As the liquids, water (H 2 O), methylene iodide (CH 2 I 2 ), and 1-bromonaphthalene were used.
• a series of operations including droplet formation and subsequent contact angle measurement were performed five times. The measurements were performed within 24 hours after the plasma treatment of the substrate film. The average of five measurements for each liquid was taken as the contact angle for that liquid. In this manner, the contact angle ⁇ w of water, the contact angle ⁇ i of methylene iodide, and the contact angle ⁇ b of 1-bromonaphthalene for the sample film were obtained.
• the Kitazaki-Hata theory is described, for example, in Vol. 8, No. 3, pp. 131-141 (1972) of the Journal of the Japan Adhesion Association.
• ⁇ d is the dispersion component of the surface free energy
• ⁇ p is the polar component of the surface free energy
• ⁇ h is the hydrogen bond component of the surface free energy.
• the value ( ⁇ ) obtained by adding ⁇ d , ⁇ p , and ⁇ h was determined as the surface free energy of the plasma-treated surface of the sample film.
• the values required for derivation were as follows: dispersion component ⁇ d in the surface free energy of water was set to 29.1 mN/m, polar component ⁇ p was set to 1.3 mN/m, and hydrogen bond component ⁇ h was set to 42.4 mN/m.
• the dispersion component ⁇ d in the surface free energy of methylene iodide was set to 46.8 mN/m
• polar component ⁇ p was set to 4.0 mN/m
• hydrogen bond component ⁇ h was set to 0.0 mN/m.
• the dispersion component ⁇ d in the surface free energy of 1-bromonaphthalene was set to 44.4 mN/m
• polar component ⁇ p was set to 0.1 mN/m
• hydrogen bond component ⁇ h was set to 0.0 mN/m.
• the surface free energy (mN/m) of the plasma-treated surface of the sample film is shown in Table 1.
• ⁇ Surface roughness> The surface roughness of the first surface of the base film was examined for each of the laminated films of Examples 1 and 2 and Comparative Examples 1 and 2. Specifically, first, the base film after plasma treatment and before the formation of the adhesive layer in the manufacturing process of the laminated film was sampled, and the surface roughness Sa (arithmetic mean height based on ISO 25178) of the first surface (HC layer surface) of the base film was measured in an observation image of 1 ⁇ m square by an atomic force microscope (product name "Dimension Edge", manufactured by Bruker). In this measurement, the measurement mode was set to tapping mode, and an antimony-doped Si cantilever (product name "RTESP-300", manufactured by Bruker) was used as a probe. The measurement results are shown in Table 1.
• FIG. 7 shows a schematic view of the cross-section of the sample of Example 1 as an example.
• the HC layer 11, the adhesion layer 21, and the inorganic layer 22 of the base film 10 were observed.
• FIG. 8 shows a schematic view of the cross-section of the sample of Comparative Example 1 as another example.
• the observation image of Comparative Example 1 the HC layer 11', the adhesive layer 21', and the inorganic layer 22' of the base film 10' were observed.
• the observation image was analyzed using image processing software ImageJ.
• the first interface length L1 of the interface between the base film 10 (10') and the adhesive layer 21 (21') and the second interface length L2 of the interface between the adhesive layer 21 (21') and the inorganic layer 22 (22') in a predetermined image range in the observation image (cross-sectional view) were obtained.
• the ratio (L2/L1) of the second interface length L2 to the first interface length L1 was calculated. The values are shown in Table 1.
• Test 1 First, the substrate film side of the laminated film was fixed to a glass plate. Next, the inorganic layer of the laminated film on the glass plate was irradiated with light from a metal halide lamp for 32.5 hours under the conditions of a temperature of 85°C, a relative humidity of 45%, and an irradiation intensity (290 nm to 450 nm integrated illuminance) of 150 mW/ cm2 (accelerated weather resistance test). This test was performed using Iwasaki Electric's "Eye Super UV Tester SUV-W161".
• Test 2 First, eleven parallel first incisions (1 mm apart) extending linearly in the first direction and eleven parallel second incisions (1 mm apart) extending linearly in the second direction perpendicular to the first direction were formed with a cutter knife on the inorganic layer and the adhesive layer of the laminated film on the glass plate after the first test, and 100 squares were formed by the first and second incisions.
• a polyester wiper (trade name "Anticon Gold", manufactured by Sanplatec Co., Ltd.) was slid on the 100 squares of the laminated film under the conditions of a wiper contact surface of 20 mm x 20 mm, a load of 1.5 kg/20 mm, a sliding speed of 50 mm/sec, and 1000 reciprocations, while isopropyl alcohol was continuously dripped at 2 mL/min.
• the number of squares that had peeled off by 0.25 mm2 or more was counted out of the 100 squares.
• the count number was divided by 100 to calculate the peeling rate (%).
• the HC layer of the base film does not contain particles. Therefore, as shown in FIG. 8, the surface of the base film 10' (the surface on the adhesive layer 21' side) does not have unevenness caused by particles.
• the plasma treatment in the manufacturing process of the laminated film of Comparative Example 1 is, as described above, an ion bombardment treatment (Ar-BB treatment) by capacitively coupled plasma using argon-containing gas.
• the Ar-BB treatment cannot activate the base film surface as compared with the oxygen-LAICP treatment. This is reflected in the fact that the surface free energy of the plasma-treated surface of the base film in Comparative Example 1 is smaller than the surface free energy of the plasma-treated surface of the base film in Example 1.
• the inventors have found that the Ar-BB treatment cannot roughen the base film surface as compared with the oxygen-LAICP treatment.
• the ratio (L2/L1) of the second interface length L2 to the first interface length L1 was significantly lower than 1.10. Therefore, in the laminated film of Comparative Example 1, the adhesion of the inorganic layer could not be ensured.
• the HC layer of the base film does not contain particles, so the surface of the base film (the surface on the adhesive layer side) does not have irregularities caused by particles.
• the plasma treatment in the manufacturing process of the laminate film of Comparative Example 2 is an inductively coupled plasma treatment (oxygen-LAICP treatment) using an oxygen-containing gas, which is generated by applying high-frequency power to a low-inductance antenna, but the applied high-frequency power is insufficient.
• oxygen-LAICP treatment oxygen-LAICP treatment
• the ratio of the second interface length L2 to the first interface length L1 (L2/L1) was significantly lower than 1.10. Therefore, the adhesion of the inorganic layer could not be ensured in the laminate film of Comparative Example 2.
• the HC layer of the base film does not contain particles. Therefore, as shown in FIG. 7, the surface of the base film 10 (the surface on the adhesive layer 21 side) does not have unevenness caused by particles.
• the plasma treatment in the manufacturing process of the laminated film of Example 1 is a treatment by inductively coupled plasma using an oxygen-containing gas generated by application of high-frequency power to a low-inductance antenna (oxygen-LAICP treatment), and the applied high-frequency power is sufficiently large.
• oxygen-LAICP treatment oxygen-LAICP treatment
• the surface of the base film can be roughened with fine unevenness on the nanometer order, and the surface of the base film can be activated, compared to Ar-BB treatment and oxygen-LAICP treatment with insufficient applied power.
• the HC layer of the base film does not contain particles. Therefore, like the laminated film of Example 1, the surface of the base film 10 (the surface on the adhesive layer 21 side) does not have unevenness caused by particles.
• the plasma treatment in the manufacturing process of the laminated film of Example 2 like the plasma treatment in Example 1, is a treatment by inductively coupled plasma using an oxygen-containing gas generated by application of high-frequency power to a low-inductance antenna (oxygen-LAICP treatment), and the applied high-frequency power is sufficiently large.
• the surface of the base film can be roughened with fine unevenness on the nanometer order and the surface of the base film can be activated, compared to the Ar-BB treatment and the oxygen-LAICP treatment with insufficient applied power.
• unevenness is formed that originates from the fine unevenness of the highly active surface of the base film 10 and grows from the fine unevenness during the film formation process of the adhesive layer.
• the ratio (L2/L1) of the second interface length L2 to the first interface length L1 was 1.10 or more. Therefore, in the laminate film of Example 2, the adhesion of the inorganic layer was ensured.
• the laminated film of the present invention is suitable for use, for example, as an anti-reflection film.

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