Antireflection film

Abstract

This antireflection film X comprises a base material film (10), an adhesion layer (21) on the base material film (10), and an antireflection layer (22) on the adhesion layer (21). In the antireflection film X, the total reflectance of irradiation light having a wavelength of 380-780 nm from a standard light source D65 with respect to the antireflection layer (22) side is 0.40% or less. In the antireflection film X, the peeling rate of the antireflection layer 22 in a predetermined second test after a predetermined first test is less than 20%.

Description

Anti-reflective film

[0001] The present invention relates to an anti-reflection film.

[0002] Anti-reflection films are known that are placed on the outer surface of display screens of display devices such as liquid crystal displays and organic electroluminescence (EL) displays. The anti-reflection film suppresses reflection of external light and glare of images on the display screen (anti-reflection properties). The anti-reflection film includes, for example, an anti-reflection layer made of an inorganic oxide and a resin substrate film that supports the layer. Such an anti-reflection film is described, for example, in Patent Document 1 listed below.

[0003] Japanese Patent Application Laid-Open No. 2022-65437

[0004] The antireflection film described in Patent Document 1 comprises a substrate film, an adhesive layer, and an antireflection layer in this order in the thickness direction. The substrate film has a hard coat (HC) layer on the adhesive layer side. This HC layer contains silica particles. As a result, the HC layer has surface irregularities on the adhesive layer side. The anchor effect of the surface irregularities of the HC layer and the physicochemical action of the adhesive layer enhance the adhesion of the antireflection layer to the substrate film. If the adhesion of the antireflection layer to the substrate film is insufficient, the antireflection layer will peel off from the substrate film.

[0005] However, in the antireflection film of Patent Document 1, the surface of the antireflection layer (the surface opposite to the substrate film) also has surface irregularities that follow the surface irregularities of the HC layer. The surface irregularities of the antireflection layer scatter a portion of the light incident on the antireflection film. The silica particles in the HC layer also scatter a portion of the light incident on the antireflection film. In an antireflection film, the more the incident light is scattered, the lower the antireflection properties.

[0006] The present invention provides an anti-reflection film that can continuously provide a good anti-reflection effect.

[0007] The present invention [1] includes an antireflection film comprising a base film, an adhesive layer on the base film, and an antireflection layer on the adhesive layer, wherein the total reflectance of light irradiated from a standard illuminant D65 at a wavelength of 380 nm to 780 nm on the antireflection layer side is 0.40% or less, and the peeling rate of the antireflection layer in the second test described below after the first test described below is less than 20%.

[0008] First test: First, the substrate film side of the antireflection film is fixed to a glass plate. Next, the antireflection layer of the antireflection film on the glass plate is irradiated with light at a temperature of 85°C, a relative humidity of 45%, and an irradiation intensity (integrated illuminance at 290 nm to 450 nm) of 150 mW / cm. ２ The mixture was exposed to light for 32.5 hours under the conditions of

[0009] Second test: First, 11 parallel first incisions (2 mm apart) extending linearly in a first direction and 11 parallel second incisions (2 mm apart) extending linearly in a second direction perpendicular to the first direction are made in the anti-reflection layer and the adhesive layer of the anti-reflection film on the glass plate using a cutter knife, and 100 grids are formed by the first and second incisions. Next, isopropyl alcohol is continuously dropped at 2 mL / min on the 100 grid areas of the anti-reflection film, and a polyester wiper is slid over the wiper contact surface of 20 mm x 20 mm, with a load of 1.5 kg / 20 mm, a sliding speed of 50 mm / sec, and 1000 reciprocations. Next, 1 mm of the 100 grids is removed. ２ The number of squares where the above peeling occurred is counted, and then the counted number is divided by 100 to calculate the peeling rate (%).

[0010] The present invention [2] includes the antireflection film according to the above [1], wherein the difference between the total reflectance and the regular reflectance of the antireflection layer side when irradiated with light having a wavelength of 450 nm is 0.25% or less.

[0011] The present invention [3] includes the antireflection film according to the above [1] or [2], wherein the surface roughness Sa of the surface of the antireflection layer opposite to the substrate film is 4.5 nm or less.

[0012] The present invention [4] includes the antireflection film according to any one of the above [1] to [3], wherein the developed area ratio Sdr of the surface of the antireflection layer opposite to the substrate film is 3.0% or less.

[0013] The present invention [5] includes the antireflection film according to any one of the above [1] to [4], wherein the difference between the maximum peak height Sp and the maximum valley depth Sv on the surface of the antireflection layer opposite to the substrate film is 30 nm or less.

[0014] The present invention [6] includes the antireflection film according to any one of the above [1] to [5], wherein the root mean square slope Sdq of the surface of the antireflection layer opposite to the substrate film is 12 or less.

[0015] The present invention [7] includes the antireflection film according to any one of the above [1] to [6], wherein the surface of the substrate film on the antireflection layer side has a surface roughness Sa of 1.0 nm or more and 4.0 nm or less.

[0016] The present invention [8] includes the antireflection film according to any one of the above [1] to [7], wherein the developed area ratio Sdr of the surface of the base film on the antireflection layer side is 2.0% or more and 10% or less.

[0017] The present invention [9] includes the antireflection film according to any one of the above [1] to [8], wherein the difference between the maximum peak height Sp and the maximum valley depth Sv on the surface of the base film facing the antireflection layer is 10 nm or more and 50 nm or less.

[0018] The present invention

[10] includes the antireflection film according to any one of the above [1] to [9], wherein the root mean square slope Sdq of the surface of the base film on the antireflection layer side is 12 or more and 30 or less.

[0019] As described above, the antireflection film of the present invention has a total reflectance of 0.40% or less for light irradiated from a standard illuminant D65 at a wavelength of 380 nm to 780 nm on the antireflection layer side, and a peeling rate of the antireflection layer in the second test after the first test (accelerated weathering test) is less than 20%. When the total reflectance of the antireflection film is 0.40% or less, scattering of light incident on the film is reduced, ensuring the antireflection properties of the antireflection film. When the peeling rate of the antireflection layer is less than 20%, deterioration of the antireflection properties of the antireflection film due to peeling of the antireflection layer can be suppressed in practical use. Therefore, the antireflection film of the present invention can continuously obtain a good antireflection effect.

[0020] 2A is a cross-sectional schematic diagram of an embodiment of the antireflection film of the present invention. FIG. 2B shows an example of a method for producing the antireflection film shown in FIG. 1. FIG. 2A shows a cured resin layer forming step, FIG. 2B shows an adhesion layer forming step, and FIG. 2C shows an antireflection layer forming step. FIG. 2B is a schematic configuration diagram of an apparatus for carrying out a plasma treatment step and a film formation step in an example of a method for producing the antireflection film shown in FIG. 1. FIG. 3 is a perspective view showing the positional relationship between a low inductance antenna and a substrate film in the plasma treatment chamber shown in FIG. 3. FIG. 3 is a cross-sectional view showing the positional relationship between a low inductance antenna and a substrate film in the plasma treatment chamber shown in FIG. 3.

[0021] An anti-reflection film X according to one embodiment of the present invention comprises a substrate film 10, an adhesive layer 21, and an anti-reflection layer 22, in this order in the thickness direction H. The anti-reflection film X extends in a direction (plane direction D) perpendicular to the thickness direction H. The anti-reflection film X is disposed on the outer surface of a display screen of a display device, for example. Specifically, the substrate film 10 side of the anti-reflection film X is bonded to the outer surface of the display device via a bonding material such as a transparent adhesive sheet. Examples of display devices include liquid crystal displays and organic EL displays. In such an anti-reflection film X, the anti-reflection layer 22 has a surface 22A on the side opposite to the substrate film 10.

[0022] In this embodiment, the base film 10 includes a resin film 11 and a cured resin layer 12, which are arranged in this order in the thickness direction H. In this embodiment, the resin film 11 and the cured resin layer 12 are in contact with each other. In the base film 10, the cured resin layer 12 forms a first surface 10a, and the resin film 11 forms a second surface 10b.

[0023] The resin film 11 is an element that ensures the strength of the anti-reflection film X. The resin film 11 is, for example, a flexible, transparent resin film. Examples of materials for 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. Examples of polyester resins include polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate. Examples of polyolefin resins include polyethylene, polypropylene, and cycloolefin polymer (COP). Examples of cellulose resins include triacetyl cellulose (TAC). These materials may be used alone or in combination. From the viewpoints of transparency and strength, the material for 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.

[0024] The thickness of the resin film 11 is preferably 10 μm or more, more preferably 20 μm or more, even more preferably 30 μm or more, and is preferably 200 μm or less, more preferably 150 μm or less, even more preferably 100 μm or less. When the thickness of the resin film 11 is equal to or greater than the above-mentioned lower limit, the strength of the antireflection film X can be ensured. When the thickness of the resin film 11 is equal to or less than the above-mentioned upper limit, the handleability of the substrate film 10 in the roll-to-roll process described below can be ensured.

[0025] 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. When the total light transmittance of the resin film 11 is the above-mentioned lower limit or more, the antireflection film X can ensure good transparency.

[0026] The cured resin layer 12 is a functional layer containing a resin. Specifically, the cured resin layer 12 is a cured product of a curable resin composition containing a curable resin. An example of the 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 (the upper surface in FIG. 1 ) of the antireflection layer 22.

[0027] Examples of curable resins include polyester resins, acrylic urethane resins, acrylic resins (excluding acrylic urethane resins), urethane resins (excluding acrylic urethane resins), amide resins, silicone resins, epoxy resins, and melamine resins. These curable resins may be used alone or in combination of two or more. 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 resins and acrylic resins.

[0028] Examples of the curable resin include an ultraviolet-curable resin and a thermosetting resin. The curable resin is preferably an ultraviolet-curable resin. When the curable resin is an ultraviolet-curable resin, the curable resin can be cured without high-temperature heating, which can improve the production efficiency of the antireflection film X.

[0029] The curable resin may also contain, for example, a reactive diluent as described in JP-A-2008-88309. Specifically, the resin may contain a polyfunctional (meth)acrylate.

[0030] When the substrate film 10 has a cured resin layer 12, it is preferable that the cured resin layer 12 contain fewer inorganic oxide particles. The fewer inorganic oxide particles in the cured resin layer 12, the more the scattering of light incident on the anti-reflection film X caused by particles in the substrate film 10 can be suppressed, and the manufacturing cost of the anti-reflection film X can be reduced. Examples of materials for inorganic oxide particles include silica, alumina, titania, zirconia, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide. The inorganic oxide particle content of 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, still 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.

[0031] The thickness of the cured resin layer 12 is preferably 1 μm or more, more preferably 3 μm or more, even more preferably 5 μm or more, and is preferably 30 μm or less, more preferably 25 μm or less, even more preferably 20 μm or less. When the thickness of the cured resin layer 12 is equal to or greater than the above-mentioned lower limit, the functionality of the cured resin layer 12 can be ensured. Specifically, when the cured resin layer 12 is a hard coat layer, the scratch resistance of the antireflection layer 22 can be ensured. When the thickness of the cured resin layer 12 is equal to or less than the above-mentioned upper limit, cracking of the cured resin layer 12 can be suppressed, and good transportability in a roll-to-roll process can be ensured.

[0032] The total light transmittance (JIS K 7375:2008) of the substrate 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. When the total light transmittance of the substrate film 10 is the above-mentioned lower limit or more, good transparency can be ensured in the antireflection film X.

[0033] 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, even more preferably 1.5 nm or more, and still more preferably 1.7 nm or more, and is preferably 4.0 nm or less, more preferably 3.0 nm or less, even more preferably 2.5 nm or less, and even more preferably 2.0 nm or less. When the surface roughness Sa of the first surface 10a is equal to or greater than the above-mentioned lower limit, the fine irregularities on the first surface 10a have an anchoring effect on the adhesion layer 21, thereby improving the adhesion of the antireflection layer 22 to the substrate film 10 via the adhesion layer 21. Having the surface roughness Sa of the first surface 10a equal to or less than the above-mentioned upper limit is advantageous for suppressing a decrease in the scratch resistance of the surface 22A of the antireflection layer 22. The method for measuring the surface roughness Sa is as described below in the examples (the same applies to the measurement methods for other parameters related to surface properties described below based on ISO 25178-2:2012).

[0034] The developed area ratio Sdr of the first surface 10a (based on ISO 25178-2:2012) is preferably 2.0% or more, more preferably 3.0% or more, even more preferably 4.0% or more, even more preferably 5.0% or more, even more preferably 6.0% or more, and even more preferably 7.0% or more, and is preferably 10% or less, more preferably 8.0% or less, and even more preferably 7.5% or less. The developed area ratio Sdr represents the increase in the actual surface area of ​​a surface having an irregular shape within a given region from the hypothetical area assuming that the region is flat. When the developed area ratio Sdr of the first surface 10a is equal to or greater than the above-mentioned lower limit, the fine irregularities of the first surface 10a have an anchoring effect on the adhesion layer 21, thereby improving the adhesion of the antireflection layer 22 to the substrate film 10 via the adhesion layer 21. The developed area ratio Sdr of the first surface 10 a being equal to or less than the upper limit is suitable for suppressing a decrease in the scratch resistance of the surface 22 A of the antireflection layer 22 .

[0035] The difference (Sp - Sv) between the maximum peak height Sp (based on ISO 25178-2:2012) and the maximum valley depth Sv (based on ISO 25178-2:2012) on the first surface 10a is preferably 10 nm or more, more preferably 12 nm or more, even more preferably 13 nm or more, even more preferably 15 nm or more, and even more preferably 20 nm or more, and is preferably 50 nm or less, more preferably 42 nm or less, even more preferably 40 nm or less, even more preferably 30 nm or less, and even more preferably 25 nm or less. When the difference (Sp - Sv) on the first surface 10a is equal to or greater than the above-mentioned lower limit, the fine irregularities on the first surface 10a have an anchoring effect on the adhesion layer 21, thereby improving the adhesion of the antireflection layer 22 to the substrate film 10 via the adhesion layer 21. Having the difference (Sp - Sv) on the first surface 10a equal to or less than the above-mentioned upper limit is advantageous for suppressing a decrease in the scratch resistance of the surface 22A of the antireflection layer 22.

[0036] The root-mean-square slope Sdq (based on ISO 25178-2:2012) of the first surface 10a is preferably 12 or more, more preferably 14 or more, even more preferably 16 or more, even more preferably 18 or more, and even more preferably 20 or more, and is preferably 30 or less, more preferably 25 or less, and even more preferably 22 or less. The root-mean-square slope Sdq is a parameter calculated from the root-mean-square of the slopes at all points in a predetermined region. When the root-mean-square slope Sdq of the first surface 10a is equal to or greater than the above-mentioned lower limit, the fine irregularities on the first surface 10a have an anchoring effect on the adhesive layer 21, thereby improving the adhesion of the antireflection layer 22 to the substrate film 10 via the adhesive layer 21. Having the root-mean-square slope Sdq of the first surface 10a equal to or less than the above-mentioned upper limit is advantageous for suppressing a decrease in the scratch resistance of the surface 22A of the antireflection layer 22.

[0037] The first surface 10a is, for example, a surface that has been plasma-treated. The plasma treatment is preferably an inductively coupled plasma treatment using an oxygen-containing gas (oxygen-LAICP treatment) that is generated by applying high-frequency power to a low-inductance antenna. The oxygen-LAICP treatment of the first surface 10a will be specifically described later in relation to the manufacturing method of the antireflection film X.

[0038] The adhesion layer 21 is disposed on one surface of the substrate film 10 in the thickness direction H. Specifically, the adhesion layer 21 is disposed on the first surface 10a of the substrate film 10. The adhesion layer 21 is in contact with the substrate film 10. The adhesion layer 21 is a layer that enhances adhesion of the antireflection layer 22 to the substrate film 10. Examples of materials for the adhesion layer 21 include metals such as silicon, indium, nickel, chromium, aluminum, tin, gold, silver, platinum, zinc, titanium, tungsten, zirconium, palladium, and niobium, alloys of two or more of these metals, and oxides of these metals. From the viewpoint of achieving both adhesion to both the substrate film 10 and the antireflection layer 22 and transparency of the adhesion layer 21, indium tin oxide (ITO) or silicon oxide (SiOx) is preferred as the material for the adhesion layer 21. The silicon oxide used as the material for the adhesion layer 21 is preferably SiOx having a smaller amount of oxygen than the stoichiometric composition, and more preferably SiOx where x is 1.2 or more and 1.95 or less.

[0039] The thickness of the adhesion layer 21 is preferably 1 nm or more, more preferably 2 nm or more, and even more preferably 3 nm or more, and is preferably 10 nm or less, more preferably 7 nm or less, and even more preferably 5 nm or less. When the thickness of the adhesion layer 21 is equal to or greater than the above-mentioned lower limit, the adhesion between the substrate film 10 and the antireflection layer 22 can be ensured. When the thickness of the adhesion layer 21 is equal to or less than the above-mentioned upper limit, the transparency of the adhesion layer 21 can be ensured.

[0040] The antireflection layer 22 is disposed on one surface of the adhesive layer 21 in the thickness direction H. The antireflection layer 22 is in contact with the adhesive layer 21. The antireflection layer 22 is a layer that suppresses the reflection intensity of external light (antireflection properties).

[0041] In this embodiment, the antireflection layer 22 includes a high-refractive index layer 22a, a low-refractive index layer 22b, a high-refractive index layer 22c, a low-refractive index layer 22d, and an antifouling surface layer 22e, in this order from the adhesive layer 21 side in the thickness direction H. The antireflection layer 22 of this embodiment is an antireflection layer with an antifouling surface layer. 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 have relatively high refractive indexes, and the low-refractive index layers 22b and 22d have relatively low refractive indexes. In the antireflection layer 22, for example, the intensity of reflected light is attenuated by interference between reflected light at multiple interfaces in the high-refractive index layers 22a and 22c and the low-refractive index layers 22b and 22d. Such interference can be achieved by adjusting the optical film thickness (product of the refractive index and thickness of the film) of each layer of the antireflection layer 22 .

[0042] 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. Examples of high refractive index materials include niobium oxide (Nb ２ O ５ Examples of the high refractive index material include titanium oxide, zirconium oxide, indium tin oxide (ITO), and antimony tin oxide (ATO). From the viewpoint of achieving both a high refractive index and low absorption of visible light, the high refractive index material is preferably niobium oxide (refractive index 2.33). The optical film thickness of the high refractive index layer 22a is, for example, 20 nm or more and, for example, 55 nm or less.

[0043] 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. Examples of 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.

[0044] 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. Examples of high-refractive-index materials include the materials described above for the high-refractive-index layer 22a, with niobium oxide being preferred. The optical thickness of the high-refractive-index layer 22c is, for example, 60 nm or more and, for example, 330 nm or less.

[0045] The low-refractive-index layer 22d (second 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. Examples of low-refractive-index materials include the materials described above for the low-refractive-index layer 22b, with silicon dioxide being preferred. The optical thickness of the low-refractive-index layer 22d is, for example, 100 nm or more and, for example, 160 nm or less.

[0046] The total thickness of the antireflection layer 22, from the high refractive index layer 22a to the low refractive index layer 22d, 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. When the total thickness of the antireflection layer 22 is equal to or greater than the above-mentioned lower limit, the antireflection layer 22 can ensure the function of attenuating the reflected light intensity. When the total thickness of the antireflection layer 22 is equal to or less than the above-mentioned upper limit, cracking of the antireflection layer 22 can be suppressed.

[0047] The anti-fouling surface layer 22e is a layer having an anti-fouling function. The anti-fouling surface layer 22e is disposed on the low refractive index layer 22d. The anti-fouling function of the anti-fouling surface layer 22e includes a function of suppressing adhesion of contaminants such as hand oils to the exposed surface of the anti-reflection film X during use, and a function of facilitating removal of adhered contaminants.

[0048] Examples of materials for the antifouling surface layer 22e include organic fluorine compounds. As the organic fluorine compound, an alkoxysilane compound having a perfluoropolyether group is preferably used. Examples of the alkoxysilane compound having a perfluoropolyether group include compounds represented by the following general formula (1):

[0049] R １ -R ２ -X-(CH ２ )ｍ -Si(OR ３ ) ３ (1)

[0050] In general formula (1), R １ represents a linear or branched fluorinated alkyl group (having, for example, 1 to 20 carbon atoms) in which one or more hydrogen atoms in the alkyl group have been substituted with fluorine atoms, and preferably represents a perfluoroalkyl group in which all hydrogen atoms in the alkyl group have been substituted with fluorine atoms.

[0051] R ２ represents a structure containing at least one repeating unit of a perfluoropolyether (PFPE) group, and preferably represents a structure containing two repeating units of a PFPE group. Examples of the repeating unit of a PFPE group include a repeating unit of a linear PFPE group and a repeating unit of a branched PFPE group. Examples of the repeating unit of a linear PFPE group include -(OC ｎ F ２ｎ ) ｐ - (where n is an integer of 1 or more and 20 or less, and p is an integer of 1 or more and 50 or less; the same applies hereinafter). Examples of the repeating structure of the branched PFPE group include -(OC(CF ３ ) ２ ) ｐ - and -(OCF ２ CF(CF ３ )CF ２ ) ｐ The repeating structure of the PFPE group is preferably a repeating structure of a linear PFPE group, more preferably -(OCF ２ ) ｐ - and - (OC ２ F ４ ) ｐ - are listed.

[0052] R ３ represents an alkyl group having 1 to 4 carbon atoms, preferably a methyl group.

[0053] X represents an ether group, a carbonyl group, an amino group, or an amide group, and preferably represents an ether group.

[0054] m represents an integer of 1 or more, and preferably an integer of 20 or less, more preferably 10 or less, and even more preferably 5 or less.

[0055] Of these alkoxysilane compounds having a perfluoropolyether group, the compound represented by the following general formula (2) is preferably used.

[0056] CF ３ -(OCF ２ ) ｑ -(OC ２ F ４ ) ｒ -O-(CH ２ ) ３ -Si(OCH ３ ) ３ (2)

[0057] In the general formula (2), q represents an integer of 1 or more and 50 or less, and r represents an integer of 1 or more and 50 or less.

[0058] The alkoxysilane compounds having a perfluoropolyether group may be used alone or in combination of two or more kinds.

[0059] In this embodiment, the antifouling surface layer 22e is a film (dry coating film) formed by a dry coating method. Examples of dry coating methods include sputtering, vacuum deposition, and CVD. The antifouling surface layer 22e is preferably a dry coating film, and more preferably a vacuum deposition film.

[0060] The anti-fouling surface layer 22e is made of a material containing an alkoxysilane compound having a perfluoropolyether group, and is a dry coating film (preferably a vacuum-deposited film), which is suitable for ensuring high adhesion of the anti-fouling surface layer 22e to the substrate, and therefore is suitable for ensuring peel resistance of the anti-fouling surface layer 22e. The high peel resistance of the anti-fouling surface layer 22e helps to maintain the anti-fouling function of the anti-fouling surface layer 22e.

[0061] From the viewpoint of ensuring the peel resistance of the antifouling surface layer 22e, the thickness of the antifouling surface layer 22e is preferably 1 nm or more, more preferably 3 nm or more, even more preferably 5 nm or more, particularly preferably 7 nm or more, and is preferably 25 nm or less, more preferably 20 nm or less, even more preferably 18 nm or less.

[0062] The antireflection layer 22 has a surface 22A (the surface of the antifouling surface layer 22e) on the side opposite to the substrate film 10. The surface roughness Sa (arithmetic mean height according to 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 1.8 nm or less. When the surface roughness Sa of the surface 22A is equal to or less than the above upper limit, light scattering at the surface 22A can be suppressed. Furthermore, 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, even more preferably more than 1.5 nm, and even more preferably 1.6 nm or more. Having the surface roughness Sa of the surface 22A equal to or greater than the above lower limit is advantageous for reducing frictional force and ensuring good slipperiness at the surface 22A.

[0063] The developed area ratio Sdr of the surface 22A is preferably 3.0% or less, more preferably 2.5% or less, and even more preferably 2.2% or less. When the developed area ratio Sdr of the surface 22A is equal to or less than the above upper limit, light scattering on the surface 22A can be suppressed. Furthermore, the developed area ratio Sdr of the surface 22A is preferably 0.3% or more, more preferably 0.7% or more, even more preferably 1.0% or more, even more preferably 1.5% or more, and even more preferably 2.0% or more. Having the developed area ratio Sdr of the surface 22A equal to or greater than the above lower limit is advantageous for reducing frictional force and ensuring good slipperiness on the surface 22A.

[0064] The difference (Sp - Sv) between the maximum peak height Sp and the maximum valley depth Sv on the surface 22A is preferably 30 nm or less, more preferably 20 nm or less, and even more preferably 17 nm or less. When the difference (Sp - Sv) on the surface 22A is equal to or greater than the above-mentioned lower limit, light scattering on the surface 22A can be suppressed. Furthermore, the difference (Sp - Sv) between the maximum peak height Sp and the maximum valley depth Sv on the surface 22A is preferably 5 nm or more, more preferably 10 nm or more, even more preferably 12 nm or more, even more preferably 14 nm or more, and even more preferably 16 nm or more. Having the difference (Sp - Sv) on the surface 22A equal to or less than the above-mentioned upper limit is suitable for reducing frictional force and ensuring good slip properties on the surface 22A.

[0065] The root-mean-square slope Sdq of surface 22A is preferably 12 or less, more preferably 11.9 or less, and even more preferably 11.8 or less. When the root-mean-square slope Sdq of surface 22A is equal to or greater than the above-mentioned lower limit, light scattering at surface 22A can be suppressed. Furthermore, the root-mean-square slope Sdq of surface 22A is preferably 5 or more, more preferably 8 or more, even more preferably 10 or more, still more preferably 11 or more, even more preferably 11.2 or more, and even more preferably 11.6 or more. Having the root-mean-square slope Sdq of surface 22A equal to or less than the above-mentioned upper limit is advantageous for reducing frictional force and ensuring good slipperiness at surface 22A.

[0066] The total reflectance of light irradiated from a standard illuminant D65 at a wavelength of 380 nm to 780 nm on the antireflection layer 22 side of the antireflection film X is 0.40% or less, preferably 0.36% or less, more preferably 0.33% or less, and is, for example, 0.00% or more. When the total reflectance of the antireflection film X is equal to or less than the upper limit, the antireflection properties of the antireflection film X can be ensured. This makes it possible to suppress reflection of external light and glare of images on the display screen on which the antireflection film X is disposed in a display device. The method for measuring the total reflectance is as described below in the examples.

[0067] The difference ΔR between the total reflectance and specular reflectance of light irradiated at a wavelength of 450 nm on the antireflection layer 22 side of the antireflection film X is preferably 0.25% or less, more preferably 0.18% or less, even more preferably 0.16% or less, and even more preferably 0.14% or less, and is, for example, 0.01% or more. A difference ΔR of not more than the above upper limit is suitable for suppressing light scattering in the antireflection film X and, therefore, for reducing the cloudy appearance of the display screen of a display device to which the antireflection film X is provided. The method for measuring the difference ΔR is as described below in the examples.

[0068] The peeling rate of the antireflection layer 22 of the antireflection film X in the second test described below after the first test (accelerated weathering test) described below is preferably less than 20%, more preferably 15% or less, even more preferably 10% or less, and even more preferably less than 10%. The methods for the first and second tests are described more specifically below in the examples. When the peeling rate of the antireflection layer 22 is equal to or less than the upper limit described above, the antireflection properties of the antireflection film X can be prevented from deteriorating due to peeling of the antireflection layer 22 in practical use.

[0069] First test: First, the substrate film 10 side of the anti-reflection film X is fixed to a glass plate. Next, the anti-reflection layer 22 of the anti-reflection film X on the glass plate is irradiated with light at 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 / cm. ２ The mixture was exposed to light for 32.5 hours under the conditions of

[0070] Second test: First, 11 parallel first incisions (2 mm apart) extending linearly in a first direction and 11 parallel second incisions (2 mm apart) extending linearly in a second direction perpendicular to the first direction are made with a cutter knife on the anti-reflection layer 22 and the adhesive layer 21 of the anti-reflection film X on the glass plate after the first test, and 100 grids are formed by the first and second incisions. Next, isopropyl alcohol is continuously dropped at 2 mL / min on the 100 grid areas of the anti-reflection film X, and a polyester wiper is slid over the wiper contact surface of 20 mm x 20 mm, with a load of 1.5 kg / 20 mm, a sliding speed of 50 mm / sec, and 1000 reciprocations. Next, 1 mm of the 100 grids are cut. ２ The number of squares where the above peeling occurred is counted, and the count is then divided by 100 to calculate the peeling rate (%).

[0071] As described above, the antireflection film X has a total reflectance of 0.40% or less for light irradiated from a standard illuminant D65 at a wavelength of 380 nm to 780 nm on the antireflection layer 22 side, and the peeling rate of the antireflection layer 22 in the second test after the first test (accelerated weathering test) is less than 20%. When the antireflection film X has a total reflectance of 0.40% or less, scattering of light incident on the antireflection film X is reduced, ensuring the antireflection properties of the antireflection film X. When the antireflection layer 22 has a peeling rate of less than 20%, deterioration of the antireflection properties of the antireflection film X due to peeling of the antireflection layer 22 can be suppressed in practical use. Therefore, the antireflection film X can continuously obtain a good antireflection effect.

[0072] 2A to 2C show an example of a method for manufacturing the antireflection film X. This manufacturing method includes a cured resin layer forming step (FIG. 2A), a plasma treatment step, and a film forming step (FIGS. 2B and 2C).

[0073] In the cured resin layer forming step, as shown in FIG. 2A , 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-described 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 besides the above-described 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. When the curable resin composition contains an ultraviolet-curable resin as the curable resin, the curable resin composition preferably contains a photopolymerization initiator. When the curable resin composition contains a thermosetting resin as the curable resin, the curable resin composition preferably contains a thermal polymerization initiator.

[0074] When the curable resin composition contains a solvent, after the curable resin composition is applied, the coating film on the resin film 11 is dried. 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.

[0075] When the curable resin composition contains an ultraviolet-curable resin, the coating film on the resin film 11 is cured by ultraviolet irradiation. Examples of the light source for ultraviolet irradiation include a high-pressure mercury lamp and an LED light. The cumulative irradiation amount of ultraviolet light is, for example, 100 mJ / cm. ２ or more, and for example, 500 mJ / cm ２ The following is the result.

[0076] When the curable resin composition contains a thermosetting resin, the coating film 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.

[0077] In this manner, a long substrate film 10 can be produced. In this embodiment, a roll of the long substrate film 10 is prepared. Specifically, the substrate film 10 is wound so that the first surface 10a of the substrate film 10 faces inward in the radial direction of the roll.

[0078] In this manufacturing method, the substrate film 10 is then transported as a workpiece film W by a roll-to-roll method under reduced pressure, while a plasma treatment process and a film formation process are sequentially performed. The apparatus Y shown in Figure 3 is an example of an apparatus for performing the plasma treatment process and the film formation process. The apparatus Y includes a feed chamber R1, a winding chamber R2, a connecting chamber C1, a plasma treatment chamber C2, a connecting chamber C3, a film formation chamber C4 (first film formation chamber), a connecting chamber C5, and a film formation chamber C6 (second film formation chamber).

[0079] The unwinding chamber R1 is equipped with a unwinding roller 51 for unwinding the workpiece film W. A roll of a long base film 10 is attached to the unwinding roller 51 as the workpiece film W. In addition, a predetermined number of guide rollers G for guiding the workpiece film W are provided within the unwinding chamber R1.

[0080] The winding chamber R2 is equipped with a winding roller 52 for winding up the workpiece film W. A predetermined number of guide rollers G for guiding the workpiece film W are provided in the winding chamber R2.

[0081] The connecting chamber C1 is located next to the unwinding chamber R1 in the running direction of the workpiece film W and before the plasma processing chamber C2. A predetermined number of guide rollers G for guiding the workpiece film W are provided within the connecting chamber C1. The connecting chamber C1 is connected to a vacuum pump (not shown) and is configured to adjust the pressure within the chamber. When the device Y is in operation, the pressure within the connecting chamber C1 is maintained at a predetermined pressure between the pressure within the unwinding chamber R1 and the pressure within the plasma processing chamber C2. This ensures a pressure difference between the unwinding chamber R1 and the plasma processing chamber C2.

[0082] The plasma processing chamber C2 is located between the connecting chambers C1 and C3 in the running direction of the workpiece film W. The plasma processing step is carried out in the plasma processing chamber C2, as will be described later. A first line L1 equipped with a flow control valve for introducing gas into the chamber is connected to the plasma processing chamber C2.

[0083] In this embodiment, the plasma processing chamber C2 is equipped with multiple low-inductance antennas (LA) 71. A low-inductance antenna is an antenna that has a low inductance of 7.5 μH or less and is capable of generating inductively coupled plasma when high-frequency power is applied. In this embodiment, the LAs 71 are supported by fixtures 72 and covered by cover blocks 73 (not shown in FIG. 4 ) and are arranged inside the plasma processing chamber C2 (an example is shown in which there are four LAs 71).

[0084] The multiple LAs 71 are aligned in the running direction of the base film 10 and in a 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. 5, the LAs 71 are fixed to the fixture 72 via a feedthrough 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 matcher. The LAs 71 are formed of a conductor. Examples of conductors include copper and silver, with copper being preferred. The LAs 71 may be covered with an insulator. Examples of insulators include glass and quartz.

[0085] The cover block 73 includes a block body 73A and multiple partition plates 73B. The block body 73A has multiple storage spaces 73a. Each storage space 73a stores one LA 71. The partition plates 73B are arranged to close the storage spaces 73a. The storage spaces 73a are sealed spaces. In the cover block 73, the block body 73A is made of, for example, aluminum. Examples of aluminum include aluminum A5052. The partition plates 73B are made of an insulating material. Examples of insulating materials include quartz and glass. The separation distance d' (shown in FIG. 5) between the substrate film 10 traveling within 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 LA 71 due to plasma treatment without excessively reducing the plasma conversion efficiency due to the power applied to the LA 71, and also helps to suppress damage to the substrate film 10 being plasma treated.

[0086] As shown in FIG. 4 , in this embodiment, the LA 71 has an open loop shape. Having an open loop shape for the LA 71 is advantageous for reducing the inductance of the LA 71. Therefore, the open loop LA 71 can suppress an increase in voltage due to an increase in power applied to the LA 71. This suppresses abnormal discharge during plasma processing, as described below. Suppressing abnormal discharge also suppresses damage to the substrate film 10 being plasma-treated. Specifically, the LA 71 has a U-shape with two free ends. For each LA 71, the two free ends are fixed to a fixture 72 so as to be aligned in the width direction of the substrate film 10. In this embodiment, the LA 71 also has an extension portion 71a on the side opposite the two free ends. The extension portion 71a extends parallel to the substrate film 10 passing through the plasma processing chamber C2. The extension portion 71a extends in the width direction of the substrate film 10. Each extension 71a may extend in the running direction of the base film 10 (four LAs 71 may be arranged in this manner). The length of the extension 71a is, for example, 50 to 150 mm (FIG. 4 shows the case where the length of the extension 71a is equal to or greater than the maximum length d of the LA 71, which will be described later). ２(The case where the LA 71 has a coil shape instead of an open loop shape is shown as an example.)

[0087] The LA 71 extends from the fixture 72 toward the base film 10. The LA 71 preferably extends in a direction perpendicular to the fixture 72. The extension length d of the LA 71 from the fixture 72 １ The maximum length d of LA71 in the surface direction of the base film 10 is, for example, 30 to 150 mm. ２ The distance d between the LA 71 and the base film 10 is, for example, 50 to 150 mm. ３ (shown in FIG. 5) is, for example, 50 to 200 mm. １ and separation distance d ３ It is preferable that the extension length d １ Separation distance d ３ The ratio (d ３ / d １ ) is, for example, 0.5 to 3.5. The number (number of rows) of 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 of the base film 10 (i.e., plasma treatment time). The center-to-center distance d between adjacent LAs 71 in the running direction of the base film 10 is ４ is, for example, 100 to 500 mm. The center-to-center distance d between adjacent LAs 71 in the width direction of the base film 10 ５ is, for example, 200 to 500 mm. ５ By adjusting the center distance d, it is possible to control the uniformity of the plasma density in the width direction of the substrate film 10, which will be described later. ４ and center distance d ５ It is preferable that the center distance d is the same as the center distance d. ４ Center distance d ５ The ratio (d ５ / d ４) is, for example, 0.5 to 2.0. The centers of the extensions 71a of the four LAs 71 preferably form a square with the vertices as vertices. Such a set of LAs 71 can generate high-density plasma. For example, the high-frequency antenna for plasma generation described in Japanese Patent Laid-Open No. 2013-258153 may be used as the LAs 71.

[0088] In this embodiment, 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-regulating function that allows it to heat or cool the workpiece film W. In other words, the transport roller 53 is a transport roller with a temperature-regulating function. During operation of the device Y, 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. With the device Y equipped with this plasma processing chamber C2, in the plasma processing step S2, the transport roller 53 with a temperature-regulating function that contacts the base film 10 can perform plasma processing on the base film 10 while cooling or heating the base film 10. By controlling the temperature of the base film 10, thermal deformation of the base film 10 can be suppressed, and the effect of this thermal deformation on the transport of the base film 10 can be suppressed.

[0089] The connecting chamber C3 is located next to the plasma processing chamber C2 in the running direction of the workpiece film W and before the film forming chamber C4. A predetermined number of guide rollers G for guiding the workpiece film W are provided within the connecting chamber C3. The connecting chamber C3 is connected to a vacuum pump (not shown) and is configured to be able to adjust the pressure within the chamber. When the device Y is in operation, the pressure within the connecting chamber C3 is maintained at a predetermined pressure between the pressure within the plasma processing chamber C2 and the pressure within the film forming chamber C4. This ensures a pressure difference between the plasma processing chamber C2 and the film forming chamber C4.

[0090] The film-forming chamber C4 is located next to the connecting 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) so that the chamber can be adjusted to a predetermined vacuum level. In the film-forming chamber C4, the film-forming process for the high-refractive index layer 22a to the low-refractive index layer 22d is carried out, as will be described later.

[0091] In this embodiment, the film-forming chamber C4 is a sputtering chamber. The film-forming chamber C4 includes a film-forming roller 54 and multiple sputtering chambers 60 (sputtering chambers 60a to 60e) (five sputtering chambers 60 are shown 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 control function that allows the workpiece film W to be heated or cooled. The sputtering chamber 60 is a partitioned space within the film-forming chamber C4. The multiple 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 shown) 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 control valves for introducing gas into the chamber. Furthermore, a predetermined number of guide rollers G for guiding the workpiece film W are provided within the deposition chamber C4.

[0092] The connecting chamber C5 is disposed between the connecting chamber C4 and the film forming chamber C6 in the running direction of the workpiece film W. A predetermined number of guide rollers G for guiding the workpiece film W are provided in the connecting chamber C5.

[0093] The film-forming chamber C6 is disposed between the connection chamber C5 and the winding chamber R2 in the running direction of the workpiece film W. In this embodiment, the film-forming chamber C6 is a vacuum deposition chamber. The film-forming chamber C6 includes a material holding section 62 and a deposition amount adjustment valve (not shown) whose opening is controllable. The film-forming chamber C6 is connected to a vacuum pump (not shown) so that the pressure inside the chamber can be adjusted. A predetermined number of guide rollers G are provided inside the film-forming chamber C6 to guide the workpiece film W. The film-forming process for the antifouling surface layer 22e is carried out in this film-forming chamber C6.

[0094] A film-forming material supply (not shown) is disposed in the material holding section 62 so as to face the workpiece film W being transported within the film-forming chamber C6. The material holding section 62 may be provided with a built-in resistance heating means, a built-in high-frequency induction heating means, or an electron beam heating means as a means for heating the film-forming material supply.

[0095] The plasma processing step and the film forming step are carried out in sequence by the above-described apparatus Y. Specifically, the steps are as follows.

[0096] The workpiece film W is unwound from the unwinding chamber R1. After being unwound from the unwinding chamber R1, the workpiece film W passes through the connecting chamber C1, the plasma treatment chamber C2, the connecting chamber C3, the film forming chamber C4, the connecting chamber C5, and the film forming chamber C6 in sequence, and is then wound up in the winding chamber R2. The running speed of the workpiece film W is, for example, 0.5 m / min or more and, for example, 15 m / min or less. Furthermore, the entire line from the unwinding chamber R1 to the winding chamber R2 is not open to the atmosphere along the way, and the process is carried out in this line under a reduced pressure atmosphere. The reduced pressure atmosphere is preferably a vacuum. By "vacuum," we mean a reduced pressure atmosphere of preferably 7 Pa or less.

[0097] A plasma treatment step is carried out in the plasma treatment chamber C2. In the plasma treatment step, the first surface 10a of the substrate film 10 is plasma-treated in a reduced pressure atmosphere in the plasma treatment chamber C2 (chamber). In this embodiment, the plasma treatment is a treatment using inductively coupled plasma of an oxygen-containing gas (oxygen-LAICP treatment) generated by applying high-frequency power to the LA 71. Specifically, the process is as follows.

[0098] During plasma treatment, oxygen is supplied into the plasma treatment chamber C2 via the first line L1. In addition to oxygen, an inert gas may be supplied into the plasma treatment chamber C2. Examples of inert gas include argon, krypton, and xenon. The gas in the plasma treatment chamber C2 may also contain gases other than the inert gas. Examples of other gases include oxygen, nitrogen, hydrogen, and water vapor. The oxygen concentration of the gas (oxygen-containing gas) in the plasma treatment 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. When the oxygen concentration is above the lower limit, high-density oxygen plasma can be generated. This is useful for creating nanometer-order micro-roughness on the first surface 10a of the substrate film 10 and for purifying and highly activating the first surface 10a.

[0099] The pressure (first pressure) within 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 preferably 7 Pa or less, more preferably 5 Pa or less, and even more preferably 3 Pa or less. When the first pressure is equal to or greater than the above-mentioned lower limit, a plasma environment of sufficient density for surface modification of the first surface 10a of the substrate film 10 can be formed within the plasma processing chamber C2. When the first pressure is equal to or less than the above-mentioned upper limit, thermal damage to the first surface 10a caused by excessively high-density plasma can be suppressed, and excessive roughening of the first surface 10a can be suppressed. Suppressing excessive roughening helps to prevent 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.

[0100] The frequency of the high-frequency power applied to the LA 71 during plasma treatment is preferably 1 MHz or higher, more preferably 5 MHz or higher, even more preferably 10 MHz or higher, and preferably 100 MHz or lower, more preferably 80 MHz or lower, and even more preferably 60 MHz or lower. When the frequency is equal to or higher than the lower limit, plasma discharge can be stabilized while increasing the plasma current density during plasma treatment. When the frequency is equal to or lower than the upper limit, the antenna potential can be suppressed, thereby suppressing damage to the substrate film 10 caused by the plasma. Furthermore, the high-frequency power is preferably 0.1 kW or higher, more preferably 0.3 kW or higher, even more preferably 1.0 kW or higher, and is preferably 10 kW or lower, more preferably 8 kW or lower, and even more preferably 6 kW or lower. When the high-frequency power is equal to or higher than the lower limit, a high-density plasma environment can be formed in the plasma treatment chamber C2 during inductively coupled plasma treatment. When the high-frequency power is equal to or lower than the upper limit, excessive damage to the substrate caused by the plasma can be suppressed.

[0101] In the plasma treatment step, the plasma current density at the intermediate position between the LA 71 and the substrate film 10 is preferably 1.0 mA / cm ３ More preferably, 2.0 mA / cm ３ More preferably, 3.0 mA / cm３ or more, and preferably 10 mA / cm ３ Less than or equal to 8mA / cm ３ Less than 4mA / cm, more preferably ３ The following is true. Inductively coupled plasma processing using a low-inductance antenna can achieve a higher plasma current density than capacitively coupled plasma processing (for example, a plasma density about 100 times higher). When the plasma current density is equal to or greater than the lower limit, sufficient plasma-converted oxygen particles can be secured in the plasma processing chamber C2 during plasma processing, allowing for appropriate surface modification of the first surface 10a of the substrate film 10. When the plasma current density is equal to or less than the upper limit, damage to the first surface 10a due to excessively high density plasma-converted oxygen particles can be suppressed during plasma processing. 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.

[0102] In the film formation step, first, in the film formation chamber C4, following the plasma treatment step, the adhesive layer 21 and the inorganic layer 22 are formed in sequence on the first surface 10a of the substrate film 10 by sputtering in a reduced pressure atmosphere. The reduced pressure atmosphere is preferably a vacuum.

[0103] In the sputtering method, 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. This generates a glow discharge, ionizing the gas atoms, causing the gas ions to collide with the target surface at high speed, ejecting the target material from the target surface and depositing the ejected target material on the workpiece film W. Examples of sputtering gases include argon, krypton, and xenon.

[0104] When the film forming material is a metal oxide, the sputtering method may be a reactive sputtering method. In the reactive sputtering method, oxygen (reactive gas) is introduced into the sputtering chamber 60 in addition to the sputtering gas. The oxygen is introduced into the sputtering chamber 60 via another second line. In the reactive sputtering method, the target is made of, for example, a metal in the metal oxide that forms each layer.

[0105] In the sputtering method, the pressure (second pressure) inside 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 adjusted by the film formation roller 54) is, for example, -10°C to 150°C.

[0106] In the film formation process, first, an adhesive layer 21 is formed on the substrate film 10 by sputtering in the sputtering chamber 60a. When 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. Then, reactive sputtering is performed while introducing argon and oxygen into the sputtering chamber 60a (reactive sputtering is similarly performed in the following sputtering methods in the sputtering chambers 60b to 60e).

[0107] Next, a high refractive index layer 22a is formed on the adhesive layer 21 by sputtering in the sputtering chamber 60b. ２ O ５ When forming the layer, a Nb target is used as the target placed on the cathode 61 in the sputtering chamber 60b.

[0108] Next, a low refractive index layer 22b is formed on the high refractive index layer 22a by sputtering in the sputtering chamber 60c. ２ When forming a layer, a Si target is used as the target placed on the cathode 61 in the sputtering chamber 60c.

[0109] Next, a high refractive index layer 22c is formed on the low refractive index layer 22b by sputtering in the sputtering chamber 60d. ２ O５ When forming the layer, a Nb target is used as the target placed on the cathode 61 in the sputtering chamber 60d.

[0110] Next, a low refractive index layer 22d is formed on the high refractive index layer 22c by sputtering in the sputtering chamber 60e. ２ When forming a layer, a Si target is used as the target placed on the cathode 61 in the sputtering chamber 60e.

[0111] In the film formation process, the antifouling surface layer 22e is further formed in the film formation chamber C6. In this step, the antifouling surface layer 22e is formed on the low refractive index layer 22d of the workpiece film W by vacuum deposition, which is a dry coating method, in the film formation chamber C6. Specifically, with the pressure inside the film formation chamber C6 reduced to a vacuum by operating a vacuum pump, a film formation material supply (not shown) placed in the material holding section 62 is heated to a predetermined temperature, and the vacuum deposition method is performed.

[0112] In the device Y, after the plasma treatment process and the film forming process, the anti-reflection film X as the workpiece film W reaches the winding chamber R2 and is wound up by the winding roller 52.

[0113] In this manner, a long antireflection film X can be produced.

[0114] The antireflection layer 22 of the antireflection film X does not have to include the above-mentioned antifouling surface layer 22e. In that case, the surface of the low refractive index layer 22d opposite to the substrate film 10 becomes the surface 22A of the antireflection layer 22. The antireflection film X not including the antifouling surface layer 22e can be produced by omitting the step in the film-forming chamber C6 in the above-mentioned production process of the antireflection film X.

[0115] The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples. The specific numerical values ​​of the blending amounts (contents), physical property values, parameters, etc. described below can be substituted with the upper limits (numerical values ​​defined as "equal to or less than") or lower limits (numerical values ​​defined as "equal to or more than") of the corresponding blending amounts (contents), physical property values, parameters, etc. described in the above-mentioned "Description of the Invention."

[0116] Example 1 The anti-reflection film of Example 1 was produced by carrying out the following steps in order.

[0117] First, 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). Specifically, 100 parts by mass (solids equivalent) of a butyl acetate solution of ultraviolet-curable acrylic urethane resin (product name "Luxidia 17-806", solids concentration 80% by mass, manufactured by DIC Corporation) was mixed with 5 parts by mass of a photopolymerization initiator (product name "IRGACURE 906", manufactured by BASF Corporation), and 0.01 parts by mass of a leveling agent (product name "GRANDIC PC4100", manufactured by DIC Corporation) to obtain a mixed solution. Next, a mixed solvent of cyclopentanone (CPN) and propylene glycol monomethyl ether (PGM) (mass ratio of CPN to PGM: 45:55) was added to adjust the solids concentration of the mixed solution to 36% by mass. This resulted in the preparation of a first resin composition. On the other hand, a long TAC film (product name "KC4UY", thickness 40 μm, manufactured by Konica Minolta Advanced Layer) was prepared. Next, a first resin composition was applied to one side of the TAC film to form a coating film. Next, this coating film was dried by heating and then cured by ultraviolet irradiation. In this way, a hard coat (HC) layer with a thickness of 7 μm was formed on the TAC film. The heating temperature was 90°C, and the heating time was 1 minute. For ultraviolet irradiation, a high-pressure mercury lamp was used as the light source, and ultraviolet rays with a wavelength of 365 nm were irradiated onto the coating film, with an accumulated irradiation light amount of 300 mJ / cm. ２ In this manner, a TAC film with an HC layer was produced as a substrate film.

[0118] Next, a plasma treatment process and a subsequent film formation process were performed on the substrate film while the substrate film was transported in a vacuum using a roll-to-roll method (roll-to-roll process). For the plasma treatment and film formation processes, an apparatus (first apparatus) capable of performing roll-to-roll processes on a workpiece film was used. The first apparatus included a payout chamber, a plasma treatment chamber (first plasma treatment), a first film formation chamber, a second film formation chamber, and a winding chamber. The payout chamber, plasma treatment chamber, first film formation chamber, second film formation chamber, and winding chamber were arranged in this order and connected to each other. The payout chamber included a payout roller. A roll of the above-mentioned substrate film was set on the payout roller as the workpiece film. The plasma treatment chamber included a temperature-controlled transport roller (transport roller 53 in FIG. 4 ) and four low-inductance antennas (LA71 in FIG. 4 and FIG. 5 ) covered by cover blocks (cover block 73 in FIG. 5 ), as shown in FIG. 4 and FIG. 5 . Each low inductance antenna has an extension portion (extension portion 71a in FIG. 4) parallel to the base film. １ is 88 mm, and the maximum length d ２ (length of extension) is 100 mm, and the separation distance d ３ is 112 mm, and the center distance d ４ is 290 mm, and the center distance d ５The distance d' between the substrate film traveling within the plasma processing chamber and the cover block is 280 mm (see Figures 4 and 5). Each low-inductance antenna is electrically connected to a high-frequency power source (RF power source, frequency 13.56 MHz) via an impedance matcher outside the plasma processing chamber. The separation distance d' between the substrate film traveling within the plasma processing chamber and the cover block is 100 mm. The first film-forming chamber is a sputtering chamber and includes a film-forming roller (film-forming roller 54 in Figure 3) and first to fifth sputtering chambers (sputtering chambers 60a to 60e in Figure 3). Each sputtering chamber is a partitioned space within the first film-forming chamber. The first to fifth sputtering chambers are arranged in this order along the circumferential direction of the film-forming roller in the traveling direction of the substrate film. Each sputtering chamber includes a cathode positioned opposite the film-forming roller. Each sputtering chamber is connected to a required number of second lines (not shown) equipped with flow control valves for introducing gas into the chamber. The second film-forming chamber is a vacuum deposition chamber and includes a material holding section (material holding section 62 in FIG. 3). The winding chamber includes a winding roller.

[0119] In the roll-to-roll process, the HC surface (first side) of the substrate film was plasma treated in the plasma treatment chamber (plasma treatment step). The running speed of the substrate film (film running speed) was 1.0 m / min. The temperature of the temperature-controlled transport roller was -8°C. The plasma treatment conditions were as follows:

[0120] The ultimate vacuum of the plasma processing chamber is 1.0 x 10 －４ After evacuating the apparatus until the pressure reached 1.5 Pa, oxygen was introduced into the plasma treatment chamber, and the pressure in the plasma treatment chamber was set to 1.5 Pa. A high-frequency power of 2 kW was applied to the four low-inductance antennas by a high-frequency power supply, 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). The plasma current density at the midpoint between the low-inductance antennas and the substrate film was 1.3 mA / cm. ３ The plasma current density was measured by a Langmuir probe for plasma measurement.

[0121] In the first film-forming chamber, an adhesive layer, a first high-refractive index layer, a first low-refractive index layer, a second high-refractive index layer, and a second low-refractive index layer were sequentially formed on the plasma-treated substrate film. Specifically, while the substrate film was cooled and transported by the film-forming roll in the first film-forming chamber, an adhesive layer was formed on the HC layer of the substrate film in the first sputtering chamber, a first high-refractive index layer was formed on the adhesive layer in the second sputtering chamber, a first low-refractive index layer was formed on the first high-refractive index layer in the third sputtering chamber, a second high-refractive index layer was formed on the first low-refractive index layer in the fourth sputtering chamber, and a second low-refractive index layer was formed on the second high-refractive index layer in the fifth sputtering chamber. The film-forming temperature (temperature of the film-forming roll) was set to -8°C. More specifically, the process is as follows.

[0122] In the first sputtering chamber, a 4 nm thick ITO layer was formed as an adhesive layer by reactive sputtering. In this process, the ultimate vacuum in the first film formation chamber was 1.0×10 －４ After the chamber was evacuated to a vacuum of 0.2 Pa, argon as an inert gas and oxygen as a reactive gas were introduced into the first sputtering chamber, and the pressure inside the first sputtering chamber was set to 0.2 Pa. The amount of oxygen introduced per 100 parts by volume of argon introduced into the first sputtering chamber was 10 parts by volume. A sintered body of indium oxide and tin oxide (ITO with a tin oxide concentration of 10% by mass) was used as the target. An MF-AC power supply was used as the power source for applying voltage to the target (the same applies to the second to fifth sputtering chambers described below). The discharge power was 4.3 kW.

[0123] In the second sputtering chamber, a 14 nm thick Nb ２ O ５ A layer (refractive index 2.33) was formed as the first high refractive index layer. In this process, after the first film formation chamber was evacuated as described above, 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 0.5 Pa. The amount of oxygen introduced was 5 parts by volume per 100 parts by volume of argon introduced into the second sputtering chamber. A Nb target was used as the target. The discharge power was 13 kW.

[0124] In the third sputtering chamber, a 28 nm thick SiO ２ A layer (refractive index 1.46) was formed as the first low refractive index layer. In this process, after the first film formation chamber was evacuated as described above, argon as an inert gas and oxygen as a reactive gas were introduced into the third sputtering chamber, and the pressure in the third sputtering chamber was set to 0.2 Pa. The amount of oxygen introduced per 100 parts by volume of argon introduced into the third sputtering chamber was 30 parts by volume. A Si target was used. The discharge power was 25 kW.

[0125] In the fourth sputtering chamber, a 105 nm thick Nb ２ O ５ A layer (refractive index 2.33) was formed as the second high refractive index layer. In this process, after the first film formation chamber was evacuated as described above, argon as an inert gas and oxygen as a reactive gas were introduced into the fourth sputtering chamber, and the pressure in the fourth sputtering chamber was set to 0.5 Pa. The amount of oxygen introduced per 100 volume parts of argon introduced into the fourth sputtering chamber was 13 volume parts. A Nb target was used. The discharge power was 27.5 kW.

[0126] In the fifth sputtering chamber, a SiO film having a thickness of 84 nm was deposited by reactive sputtering. ２ A layer (refractive index 1.46) was formed as the second low refractive index layer. In this process, after the first film formation chamber was evacuated as described above, argon as an inert gas and oxygen as a reactive gas were introduced into the fifth sputtering chamber, and the pressure in the fifth sputtering chamber was set to 0.2 Pa. The amount of oxygen introduced per 100 volume parts of argon introduced into the fifth sputtering chamber was 30 volume parts. A Si target was used. The discharge power was 20.5 kW.

[0127] In the second film-forming chamber, an anti-fouling surface layer was formed on the second low-refractive index layer. Specifically, an 8-nm-thick anti-fouling surface layer was formed on the second low-refractive index layer by vacuum deposition using a perfluoropolyether group-containing alkoxysilane compound as a deposition source. The deposition source was a solid obtained by drying "OPTOOL UD509" manufactured by Daikin Industries, Ltd. (a perfluoropolyether group-containing alkoxysilane compound represented by the above general formula (2), solid content concentration 20% by mass). The heating temperature of the deposition source in the vacuum deposition method was 260°C.

[0128] As described above, an antireflection film of Example 1 was produced. The antireflection film of Example 1 included a substrate film with an HC layer, an adhesive layer on the HC layer, and an antireflection layer (first high refractive index layer / first low refractive index layer / second high refractive index layer / second low refractive index layer / antifouling surface layer) on the adhesive layer. The substrate film of the antireflection film of Example 1 had a plasma-treated HC layer surface. This plasma treatment was an inductively coupled plasma treatment using an oxygen-containing gas generated by application of high-frequency power to a low-inductance antenna (oxygen-LAICP treatment).

[0129] [Example 2] The anti-reflection film of Example 2 was produced in the same manner as the anti-reflection film of Example 1, except for the following: In the preparation step, the second resin composition was used instead of the first resin composition to form an HC layer on the TAC film. Specifically, the following is true.

[0130] In the preparation step, first, 17 parts by mass (solid content equivalent) of a nanosilica particle-containing acrylic monomer composition (product name "NC035HS", nanosilica concentration 60% by mass, manufactured by Arakawa Chemical Industries, Ltd.), 83 parts by mass (solid content equivalent) of a UV-curable multifunctional urethane acrylate (product name "Beamset 580", solid content concentration 70% by mass, manufactured by Arakawa Chemical Industries, Ltd.), 1.5 parts by mass of a photopolymerization initiator (product name "OMNIRAD127D", manufactured by IGM Resins), 0.15 parts by mass (solid content equivalent) of a leveling agent (product name "LE303", solid content concentration 40% by mass, manufactured by Kyoeisha Chemical Co., Ltd.), and butyl acetate were mixed to prepare a second resin composition with a solid content concentration of 42% by mass. Meanwhile, a long TAC film (product name "KC4UY", thickness 40 μm, manufactured by Konica Minolta Advanced Layer) was prepared. Next, a second resin composition was applied to one side of the TAC film to form a coating film. This coating film was then dried by heating and then cured by ultraviolet irradiation. This resulted in a 7 μm-thick HC layer being formed on the TAC film. The heating temperature was 90°C, and the heating time was 1 minute. For ultraviolet irradiation, a high-pressure mercury lamp was used as the light source, and ultraviolet rays with a wavelength of 365 nm were irradiated onto the coating film, with an integrated irradiation dose of 300 mJ / cm. ２ In this way, a TAC film with an HC layer was prepared as a substrate film. The HC layer of the substrate film in Example 2 contained 10% by mass of nanosilica particles.

[0131] [Example 3] The anti-reflection film of Example 3 was produced in the same manner as the anti-reflection film of Example 1, except for the following: In the preparation step, the following resin composition was used instead of the first resin composition to form an HC layer on a TAC film. Specifically, the following is the procedure.

[0132] In the preparation step, 80 parts by mass (solid content equivalent) of ultraviolet-curable acrylic urethane resin (product name "UT-7314", manufactured by Mitsubishi Chemical Corporation), 20 parts by mass (solid content equivalent) of a multifunctional acrylate (product name "Viscoat #300", manufactured by Osaka Organic Chemical Industry Co., Ltd.) mainly composed of pentaerythritol triacrylate, 1.5 parts by mass of a photopolymerization initiator (product name "Omnirad 127D", manufactured by BASF Corporation), and 0.06 parts by mass of a leveling agent (product name "Polyflow LE-303", a leveling agent containing a silicone compound, manufactured by Kyoeisha Chemical Co., Ltd.) were mixed to obtain a mixed solution. Next, a mixed solvent of butyl acetate and cyclopentanone (CPN) (mass ratio of butyl acetate to CPN was 70:30) was added to the mixed solution as a solvent to prepare a resin composition having a solid content of 40% by mass.

[0133] Comparative Example 1 An antireflection film of Comparative Example 1 was produced in the same manner as the antireflection film of Example 1, except for the following: In the plasma treatment step, argon was introduced into the plasma treatment chamber instead of oxygen, and plasma treatment was performed. This plasma treatment was an inductively coupled plasma treatment (Ar-LAICP treatment) using an argon-containing gas generated by applying high-frequency power to a low-inductance antenna.

[0134] Comparative Example 2 First, in the same manner as in Example 1, an HC layer was formed on one side of a TAC film to prepare a substrate film (TCA film / HC layer).

[0135] Next, a plasma treatment process and a subsequent film formation process were performed on the substrate film while the substrate film was transported in a vacuum using a roll-to-roll method (roll-to-roll process). A second device capable of performing roll-to-roll processes on workpiece films was used for the plasma treatment and film formation processes. The second device had the same configuration as the first device, except that it included a second plasma treatment chamber instead of the first plasma treatment chamber. The second plasma treatment chamber included a pair of planar electrodes for generating plasma: a cathode electrode and an anode electrode (both rectangular electrodes made of SUS304). The pair of planar electrodes were spaced 50 mm apart and parallel to the substrate film passing through the second plasma treatment chamber. The anode electrode was positioned 35 mm away from the substrate film passing through the plasma treatment chamber and was grounded outside the plasma treatment chamber. The cathode electrode was positioned facing the HC layer surface of the substrate film and electrically connected to a high-frequency power source (RF power source, 13.56 MHz) via an impedance matcher. Each electrode facing the base film had a length of 110 mm in the film running direction and a length of 430 mm in the width direction.

[0136] In the second plasma treatment chamber, the HC surface (first side) of the substrate film was subjected to plasma treatment (bombardment treatment). The running speed of the substrate film (film running speed) was 1.0 m / min. The plasma treatment conditions were as follows:

[0137] The ultimate vacuum of the second plasma processing chamber is 1.0×10 －４ After evacuating the apparatus until the pressure reached 0.5 Pa, argon was introduced into the second plasma treatment chamber, and the pressure in the plasma treatment chamber was set to 0.5 Pa. A power of 550 W was applied between the planar electrodes by a high-frequency power supply to generate capacitively coupled plasma (CCP). In this plasma environment, the surface of the HC layer of the substrate film was subjected to argon ion bombardment treatment (Ar-BB treatment).

[0138] In the first film-forming chamber, layers from the adhesive layer to the second low refractive index layer were formed in order on the plasma-treated substrate film in the same manner as described above for Example 1. In the second film-forming chamber, an antifouling surface layer was formed on the second low refractive index layer in the same manner as described above for Example 1.

[0139] [Comparative Example 3] The anti-reflection film of Comparative Example 3 was produced in the same manner as the anti-reflection film of Comparative Example 2, except for the following: In the preparation step, the third resin composition was used instead of the first resin composition to form an HC layer on the TAC film. Specifically, the following is true.

[0140] In the preparation step, 83 parts by mass (solids equivalent) of a nanosilica particle-containing acrylic monomer composition (product name "NC035HS", nanosilica concentration 60% by mass, manufactured by Arakawa Chemical Industries, Ltd.), 17 parts by mass (solids equivalent) of a UV-curable multifunctional urethane acrylate (product name "Beamset 580", solids concentration 70% by mass, manufactured by Arakawa Chemical Industries, Ltd.), 1.5 parts by mass of a photopolymerization initiator (product name "OMNIRAD127D", manufactured by IGM Resins), 0.15 parts by mass (solids equivalent) of a leveling agent (product name "LE303", solids concentration 40% by mass, manufactured by Kyoeisha Chemical Co., Ltd.), and butyl acetate were mixed to prepare a second resin composition with a solids concentration of 42% by mass. Meanwhile, a long TAC film (product name "KC4UY", thickness 40 μm, manufactured by Konica Minolta Advanced Layer) was prepared. Next, a second resin composition was applied to one side of the TAC film to form a coating film. This coating film was then dried by heating and then cured by ultraviolet irradiation. This resulted in a 4 μm-thick HC layer being formed on the TAC film. The heating temperature was 90°C, and the heating time was 1 minute. For ultraviolet irradiation, a high-pressure mercury lamp was used as the light source, and ultraviolet rays with a wavelength of 365 nm were irradiated onto the coating film, with an integrated irradiation dose of 300 mJ / cm. ２ In this way, a TAC film with an HC layer was produced as a substrate film. The HC layer of the substrate film in Comparative Example 3 contained 50 mass % of nanosilica particles.

[0141] [Comparative Example 4] The antireflection film of Comparative Example 4 was produced in the same manner as the antireflection film of Comparative Example 2, except for the following: In the preparation step, the second resin composition was used instead of the first resin composition to form an HC layer (nanosilica particle content 10% by mass) on a TAC film.

[0142] <Surface Properties> The surface properties of the antireflection layer surface were investigated for each of the antireflection films of Examples 1 to 3 and Comparative Examples 1 to 4. Specifically, the exposed surface of the antireflection layer in each antireflection film was first observed and photographed using an atomic force microscope (product name "Dimension Edge SPC-160113-01", manufactured by Bruker) (first observation). The observation was performed in tapping mode, using an antimony-doped Si cantilever (product name "RTESP-300", manufactured by Bruker) as a probe (first observation conditions). Next, the surface roughness (arithmetic mean height) Sa, the developed area ratio Sdr, the maximum peak height Sp, the maximum valley depth Sv, and the root-mean-square slope Sdq were determined from the observation image of a 1 μm square area. These are parameters based on ISO 25178-2:2012. Table 1 shows the surface roughness Sa (nm), developed area ratio Sdr (%), difference between maximum peak height Sp (nm) and maximum valley depth Sv (nm), and root mean square slope Sdq for the surface of the antireflection layer.

[0143] Meanwhile, the surface properties of the first side of the substrate film were investigated for each of the antireflection films of Examples 1 to 3 and Comparative Examples 1 to 4. Specifically, first, a sample of the substrate film was taken after plasma treatment and before the formation of the adhesive layer during the antireflection film manufacturing process, and the first side of the substrate film was observed and imaged using the atomic force microscope (second observation). The conditions for the second observation were the same as those for the first observation. Next, the surface roughness (arithmetic mean height) Sa, the developed area ratio Sdr, the maximum peak height Sp, the maximum valley depth Sv, and the root-mean-square slope Sdq were determined from the observation image of a 1 μm square. Table 1 shows the surface roughness Sa (nm), the developed area ratio Sdr (%), the difference between the maximum peak height Sp (nm) and the maximum valley depth Sv (nm), and the root-mean-square slope Sdq for the first side of the substrate film.

[0144] <Reflectance Measurement> The total reflectance and regular reflectance of each of the antireflection films of Examples 1 to 3 and Comparative Examples 1 to 4 were measured as follows.

[0145] First, the side of the anti-reflection film opposite the anti-reflection layer side was bonded to a black acrylic plate (2 mm thick) via a specified transparent acrylic adhesive. This resulted in a laminated film. Next, a film strip for measurement was cut out from the laminated film. Next, the spectrum of total reflected light (including specular reflected light) was measured for the film strip using a spectrophotometer (product name "UH4150", manufactured by Hitachi High-Tech Science Corporation) (first reflectance measurement). For the measurement, standard illuminant D65 was used as the light source, and the film strip was placed in the spectrophotometer so that light was incident on the anti-reflection layer side of the film strip. The measurement was performed using the integrating sphere measurement mode of the spectrophotometer. The measured reflectance was the total reflectance of light irradiated from the standard illuminant D65 with wavelengths of 380 nm to 780 nm toward the anti-reflection layer side of the film strip (anti-reflection film). The measurement results are shown in Table 1. Furthermore, the spectrum of specular reflected light for the film strip was measured using the spectrophotometer (UH4150) (second reflectance measurement). The measurement conditions were the same as those for the first reflectance measurement. Then, based on the spectrum obtained in the first reflectance measurement and the spectrum obtained in the second reflectance measurement, the difference ΔR between the total reflectance and the regular reflectance of the irradiated light with a wavelength of 450 nm was calculated. The results are shown in Table 1.

[0146] <Adhesion> For each of the antireflection films of Examples 1 to 3 and Comparative Examples 1 to 4, the following first and second tests were carried out to examine the adhesion of the antireflection layer.

[0147] First test: First, the substrate film side of the anti-reflection film was fixed to a glass plate. Then, the anti-reflection layer of the anti-reflection film on the glass plate was irradiated with light at 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 / cm. ２ The test was carried out using an "Eye Super UV Tester SUV-W161" manufactured by Iwasaki Electric Co., Ltd., and the test piece was exposed to light for 32.5 hours under the conditions of:

[0148] Second test: First, after the first test, 11 parallel first incisions (2 mm apart) extending linearly in the first direction and 11 parallel second incisions (2 mm apart) extending linearly in the second direction perpendicular to the first direction were made with a cutter knife on the anti-reflection layer and the adhesive layer of the anti-reflection film on the glass plate, and 100 grids were formed by the first and second incisions. Next, isopropyl alcohol was continuously dropped at 2 mL / min on the 100 grid areas of the anti-reflection film, and a polyester wiper (trade name "Anticon Gold", manufactured by Sanplatec Co., Ltd.) was slid over the 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. Next, 1 mm out of the 100 grids was cut. ２ The number of squares where the above peeling occurred was counted, and the counted number was then divided by 100 to calculate the peeling rate (%).

[0149] A peeling rate of less than 10% was evaluated as "excellent," a peeling rate of 10% or more but less than 20% was evaluated as "good," a peeling rate of 20% or more but less than 80% was evaluated as "poor," and a peeling rate of 80% or more was evaluated as "very poor." The results are shown in Table 1.

[0150] [Evaluation] In the antireflection film of Comparative Example 1, the HC layer of the substrate film does not contain particles, so the substrate film surface does not have irregularities caused by particles. In addition, as described above, the plasma treatment in the manufacturing process of the antireflection film of Comparative Example 1 is an inductively coupled plasma treatment using argon-containing gas (Ar-LAICP treatment). Compared to the oxygen-LAICP treatment, the Ar-LAICP treatment does not roughen the substrate film surface. In such an antireflection film of Comparative Example 1, the adhesion of the antireflection layer could not be ensured.

[0151] In the anti-reflection film of Comparative Example 2, the HC layer of the substrate film does not contain particles, so the substrate film surface does not have irregularities caused by particles. In addition, the plasma treatment in the manufacturing process of the anti-reflection film of Comparative Example 2 is, as described above, ion bombardment treatment (Ar-BB treatment) using capacitively coupled plasma with argon-containing gas. Ar-BB treatment does not roughen the substrate film surface as easily as oxygen-LAICP treatment. In the anti-reflection film of Comparative Example 2, the adhesion of the anti-reflection layer could not be ensured.

[0152] In the antireflection film of Comparative Example 3, the HC layer of the substrate film contained 50% by mass of nanosilica particles. The surface of the HC layer of the substrate film 10 (the surface on the adhesive layer 21 side) had irregularities caused by the particles, and the surface roughness Sa was large at 7.65 nm. Therefore, in the antireflection film of Comparative Example 3, the surface roughness Sa of the antireflection layer was large at 5.01 nm. Therefore, the total reflectance of the antireflection film of Comparative Example 3 was large at 0.46%.

[0153] The antireflection film of Comparative Example 4 did not have good adhesion to the antireflection layer, and such a film could not provide a good, sustained antireflection effect.

[0154] In the antireflection film of Example 1, the HC layer of the substrate film does not contain particles. Therefore, the surface of the HC layer of the substrate film (the surface on the adhesive layer 21 side) does not have irregularities due to particles. Therefore, the surface roughness Sa of the antireflection layer in the antireflection film of Example 1 was small, at 1.53 nm. Therefore, the total reflectance of the antireflection film of Example 1 was 0.31%, which was smaller than the total reflectance (0.46%) in Comparative Example 3. Furthermore, as described above, the plasma treatment in the manufacturing process of the antireflection film of Example 1 was an inductively coupled plasma treatment using an oxygen-containing gas (oxygen-LAICP treatment) generated by applying high-frequency power to a low-inductance antenna. Compared to Ar-LAICP treatment and Ar-BB treatment, oxygen-LAICP treatment can roughen the substrate film surface with fine irregularities on the nanometer order. Therefore, the antireflection film of Example 1 ensured adhesion of the antireflection layer. Therefore, the antireflection film of Example 1 (which has a low total reflectance and ensures adhesion of the antireflection layer) can continuously achieve a good antireflection effect. The same is true for Example 3.

[0155] In the antireflection film of Example 2, the HC layer of the substrate film contains particles. However, because the particle content is low, the surface of the HC layer of the substrate film (the surface on the adhesive layer 21 side) does not have irregularities caused by particles. Therefore, in the antireflection film of Example 2, the surface roughness Sa of the antireflection layer was small, at 1.50 nm. Therefore, the total reflectance of the antireflection film of Example 2 was 0.33%, which was smaller than the total reflectance (0.46%) of Comparative Example 3. Furthermore, as described above, the plasma treatment in the manufacturing process of the antireflection film of Example 2 was oxygen-LAICP treatment. Therefore, the antireflection film of Example 2 was able to ensure the adhesion of the antireflection layer. Therefore, the antireflection film of Example 2 (which has a low total reflectance and ensures the adhesion of the antireflection layer) can continuously obtain a good antireflection effect.

[0156]

[0157] The above invention is provided as an exemplary embodiment of the present invention, but this is merely an example and should not be interpreted as limiting. Modifications of the present invention that are obvious to those skilled in the art are intended to be included in the scope of the following claims.

[0158] The anti-reflection film of the present invention is suitably used in the manufacture of display devices such as liquid crystal displays and organic EL displays.

[0159] X: Anti-reflection film H: Thickness direction D: Surface direction 10: Base film 10a: First surface 10b: Second surface 11: Resin film 12: Cured resin layer 21: Adhesion layer 22: Anti-reflection layer 22a, 22c: High refractive index layers 22b, 22d: Low refractive index layers 22e: Anti-fouling surface layer

Claims

1. An anti-reflective film comprising a base film, an adhesive layer on the base film, and an anti-reflective layer on the adhesive layer, wherein the total reflectance of light having a wavelength of 380 nm to 780 nm from a standard light source D65 on the anti-reflective layer side is 0.40% or less, and the peeling rate of the anti-reflective layer in the second test described below after the first test described below is less than 20%. First test: First, the side of the base film in the antireflection film is fixed to a glass plate. Next, the antireflection layer of the antireflection film on the glass plate is irradiated with light at a temperature of 85° C., a relative humidity of 45%, and an irradiation intensity (integrated illuminance at 290 nm to 450 nm) of 150 mW / cm. ２ The light is irradiated for 32.5 hours under the conditions of 1. 2nd test: First, 11 parallel first incisions (2 mm apart) extending linearly in a first direction and 11 parallel second incisions (2 mm apart) extending linearly in a second direction perpendicular to the first direction are formed in the anti-reflection layer and the adhesive layer of the anti-reflection film on the glass plate using a cutter knife, and 100 grids are formed by the first and second incisions. Next, isopropyl alcohol is continuously dropped at 2 mL / min on the area of ​​the 100 grids on the anti-reflection film, while a polyester wiper is slid on the area 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. Next, 1 mm of the 100 grids are cut into 1 mm. ２ The number of squares in which peeling of this magnitude or more has occurred is counted. Next, the count is divided by 100 to calculate the peeling rate (%).

2. The anti-reflection film according to claim 1, wherein the difference between the total reflectance and the regular reflectance for light having a wavelength of 450 nm on the anti-reflection layer side is 0.25% or less.

3. The antireflection film according to claim 1, wherein the surface roughness Sa of the surface of the antireflection layer opposite to the substrate film is 4.5 nm or less.

4. The anti-reflection film according to claim 1, wherein the developed area ratio Sdr of the surface of the anti-reflection layer opposite to the substrate film is 3.0% or less.

5. The antireflection film according to claim 1, wherein the difference between the maximum peak height Sp and the maximum valley depth Sv on the surface of the antireflection layer opposite to the substrate film is 30 nm or less.

6. The antireflection film according to claim 1, wherein the root mean square slope Sdq of the surface of the antireflection layer opposite to the substrate film is 12 or less.

7. The anti-reflection film according to any one of claims 1 to 6, wherein the surface roughness Sa of the surface of the substrate film on the side of the anti-reflection layer is 1.0 nm or more and 4.0 nm or less.

8. The anti-reflection film according to any one of claims 1 to 6, wherein the developed area ratio Sdr of the surface of the base film on the anti-reflection layer side is 2.0% or more and 10% or less.

9. The anti-reflection film according to any one of claims 1 to 6, wherein the difference between the maximum peak height Sp and the maximum valley depth Sv on the surface of the base film facing the anti-reflection layer is 10 nm or more and 50 nm or less.

10. The antireflection film according to any one of claims 1 to 6, wherein the root mean square slope Sdq of the surface of the base film on the antireflection layer side is 12 or more and 30 or less.

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