KR102517501B1 - Optical film with antifouling layer - Google Patents

Abstract

The optical film (F) with an antifouling layer of the present invention includes a transparent substrate 11, a hard coat layer 12, an inorganic oxide base layer 13, and an antifouling layer 14 in this order. The antifouling layer 14 is a dry coating film disposed on the inorganic oxide base layer 13 . The product of the hardness (GPa) at 25°C measured by the nanoindentation method and the elastic recovery rate of the surface 14a on the opposite side to the inorganic oxide base layer 13 in the antifouling layer 14 is 0.8 or more. .

Description

Optical film with antifouling layer

The present invention relates to an optical film with an antifouling layer.

From the viewpoint of antifouling property, for example, an optical film with an antifouling layer is bonded to the outer surface on the image display side in displays such as touch panel displays. An optical film with an antifouling layer includes a transparent substrate and an antifouling layer disposed on an outermost surface of one side of the transparent substrate. The antifouling layer suppresses the adhesion of contaminants such as hand oil on the surface of the display, and facilitates removal of the contaminants adhering. A technology related to an optical film with such an antifouling layer is described in, for example, Patent Document 1 below.

Japanese Unexamined Patent Publication No. 2020-52221

At the time of use of the optical film on which the antifouling layer is formed, contaminants adhering to the antifouling layer are removed by, for example, a wiping operation. However, repetition of the wiping operation for the antifouling layer causes deterioration in the antifouling properties of the antifouling layer, and also causes peeling of the antifouling layer. From the viewpoint of the antifouling function of the optical film on which the antifouling layer is formed, deterioration in antifouling properties and peeling of the antifouling layer are undesirable.

The present invention provides an optical film with an antifouling layer suitable for suppressing a decrease in antifouling property while ensuring peeling resistance in the antifouling layer.

The present invention [1] is a dry coating film comprising a transparent substrate, a hard coat layer, an inorganic oxide base layer, and an antifouling layer in this order, and the antifouling layer disposed on the inorganic oxide base layer, An optical film with an antifouling layer, wherein the product of the hardness (GPa) at 25°C measured by the nanoindentation method and the elastic recovery rate of the surface opposite to the inorganic oxide base layer in the antifouling layer is 0.8 or more. do.

The present invention [2] includes the optical film with an antifouling layer described in [1] above, wherein the surface of the antifouling layer has an elastic recovery factor at 25°C of 0.76 or more as measured by the nanoindentation method.

The present invention [3] includes the optical film with an antifouling layer according to the above [1] or [2], wherein the antifouling layer has a thickness of 1 nm or more and 25 nm or less.

The present invention [4] includes the optical film with an antifouling layer according to any one of the above [1] to [3], wherein the inorganic oxide underlayer contains silicon dioxide.

This invention [5] includes the optical film with an antifouling layer according to any one of [1] to [4] above, wherein the inorganic oxide underlayer has a thickness of 50 nm or more.

The present invention [6] includes the optical film with an antifouling layer according to any one of [1] to [5], wherein the hard coat layer has a thickness of 1 μm or more and 50 μm or less.

As described above, the optical film with an antifouling layer of the present invention is a dry coating film in which the antifouling layer is disposed on the inorganic oxide base layer. Such a configuration is suitable for securing high bonding strength of the antifouling layer in an optical film with an antifouling layer, and therefore suitable for ensuring peeling resistance of the antifouling layer. Further, in the optical film with the antifouling layer, the product of the hardness (GPa) at 25°C measured by the nanoindentation method and the elastic recovery rate of the surface of the antifouling layer on the opposite side to the inorganic oxide underlayer is 0.8 or more. am. Such a configuration is suitable for suppressing the deterioration of the antifouling properties of the antifouling layer by resisting the wiping operation to the antifouling layer.

1 is a cross-sectional schematic diagram of an embodiment of an optical film of the present invention.
2 is a cross-sectional schematic diagram of a modified example of the optical film of the present invention (in this modified example, the optical film is provided with an antireflection layer).
3 shows the measurement results of the product of the surface hardness H and the elastic recovery rate R (horizontal axis) measured for each optical film of Examples 1 to 9 and Comparative Example 1 (horizontal axis) and the water contact angle θ ₂ (vertical axis) after the second eraser sliding test. is the plotted graph.

As shown in FIG. 1, the optical film (F) as an embodiment of the optical film with antifouling layer of the present invention includes a transparent substrate 11, a hard coat layer 12, and an inorganic oxide underlayer 13 and the antifouling layer 14 are provided in this order toward one side of the thickness direction T. In the present embodiment, the optical film (F) includes a transparent substrate 11, a hard coat layer 12, an adhesive layer 15, an inorganic oxide base layer 13, and an antifouling layer 14, It is provided in this order toward one side of the thickness direction T. In addition, the optical film F has a shape extending in a direction (surface direction) orthogonal to the thickness direction T.

The transparent substrate 11 is a transparent resin film having flexibility. Examples of the material of the transparent substrate 11 include polyester resins, polyolefin resins, polystyrene resins, acrylic resins, polycarbonate resins, polyethersulfone resins, polysulfone resins, polyamide resins, polyimide resins, and cellulose resins. , norbornene resins, polyarylate resins, and polyvinyl alcohol resins. Examples of the polyester resin include polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate. Examples of the polyolefin resin include polyethylene, polypropylene, and cycloolefin polymer (COP). As a cellulose resin, triacetyl cellulose (TAC) is mentioned, for example. These materials may be used independently, or two or more types may be used together. As the material of the transparent substrate 11, from the viewpoint of transparency and strength, one selected from the group consisting of polyester resins, polyolefin resins and cellulose resins is used, more preferably from the group consisting of PET, COP and TAC The one selected is used.

The surface on the side of the hard coat layer 12 in the transparent substrate 11 may be subjected to surface modification treatment. Examples of the surface modification treatment include corona treatment, plasma treatment, ozone treatment, primer treatment, gloss treatment, and coupling agent treatment.

From the viewpoint of strength, the thickness of the transparent substrate 11 is preferably 5 μm or more, more preferably 10 μm or more, still more preferably 20 μm or more. The thickness of the transparent substrate 11 is preferably 300 μm or less, more preferably 200 μm or less, from the viewpoint of handleability.

The total light transmittance (JIS K 7375-2008) of the transparent substrate 11 is preferably 80% or more, more preferably 90% or more, still more preferably 95% or more. Such a structure is suitable for ensuring the transparency required of the optical film (F) when the surface of a display such as a touch panel display is provided with the optical film (F). The total light transmittance of the transparent substrate 11 is, for example, 100% or less.

The hard coat layer 12 is arranged on one side of the thickness direction T of the transparent substrate 11 . The hard coat layer 12 is a layer for preventing scratches from being formed on the exposed surface (upper surface in FIG. 1 ) of the optical film F.

The hard coat layer 12 is a cured product of curable resin composition. Examples of the curable resin contained in the curable resin composition include polyester resins, acrylic resins, urethane resins, acrylic urethane resins, amide resins, silicone resins, epoxy resins, and melamine resins. These curable resins may be used independently and two or more types may be used together. From the viewpoint of ensuring the high hardness of the hard coat layer 12, as the curable resin, an acrylic urethane resin is preferably used.

Moreover, as a curable resin composition, an ultraviolet curing type resin composition and a thermosetting type resin composition are mentioned, for example. Since it can be cured without heating at a high temperature, a UV-curable resin composition is preferably used as the curable resin composition from the viewpoint of being useful for improving the manufacturing efficiency of the optical film (F). The ultraviolet curable resin composition includes at least one selected from the group consisting of ultraviolet curable monomers, ultraviolet curable oligomers, and ultraviolet curable polymers. As a specific example of an ultraviolet curable resin composition, the composition for hard-coat layer formation of Unexamined-Japanese-Patent No. 2016-179686 is mentioned.

The curable resin composition may contain fine particles. Mixing of the fine particles into the curable resin composition is useful for adjusting the hardness, adjusting the surface roughness, adjusting the refractive index, and imparting anti-glare properties to the hard coat layer 12 . Examples of fine particles include metal oxide particles, glass particles, and organic particles. Examples of the material of the metal oxide particles include silica, alumina, titania, zirconia, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide. Examples of materials for organic particles include polymethyl methacrylate, polystyrene, polyurethane, acrylic/styrene copolymer, benzoguanamine, melamine, and polycarbonate.

The thickness of the hard coat layer 12 is preferably 1 µm or more, more preferably 3 µm or more, from the viewpoint of securing the hardness of the surface of the antifouling layer 14 by securing the hardness of the hard coat layer 12. Preferably it is 5 micrometers or more. The thickness of the hard coat layer 12 is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 35 μm or less, particularly preferably 30 μm or less, from the viewpoint of ensuring the flexibility of the optical film (F). less than μm.

The surface of the hard coat layer 12 on the side of the adhesion layer 15 may be subjected to surface modification treatment. Examples of the surface modification treatment include plasma treatment, corona treatment, ozone treatment, primer treatment, gloss treatment, and coupling agent treatment. From the viewpoint of ensuring high adhesion between the hard coat layer 12 and the adhesion layer 15, the surface on the side of the adhesion layer 15 in the hard coat layer 12 is preferably subjected to plasma treatment.

The adhesive layer 15 is a layer for ensuring the adhesion of the inorganic oxide layer (the inorganic oxide base layer 13 in this embodiment) to the transparent substrate 11 . The adhesive layer 15 is disposed on one side of the thickness direction T of the hard coat layer 12 . Examples of the material of the adhesive layer 15 include metals such as silicon, indium, nickel, chromium, aluminum, tin, gold, silver, platinum, zinc, titanium, tungsten, zirconium, and palladium, and two types of these metals. The above alloys and oxides of these metals are exemplified. Coexistence of adhesion between the organic layer (specifically, the hard coat layer 12) and the inorganic oxide layer (specifically, the inorganic oxide base layer 13 in this embodiment) and the transparency of the adhesive layer 15 In , as the material of the adhesive layer 15, indium tin oxide (ITO) or silicon oxide (SiOx) is preferably used. When silicon oxide is used as the material of the adhesive layer 15, preferably, SiOx having a smaller oxygen content than the stoichiometric composition is used, and more preferably, SiOx having an x of 1.2 or more and 1.9 or less is used.

The thickness of the adhesive layer 15 is preferably 1 nm or more and 10 from the viewpoint of ensuring the adhesive force between the hard coat layer 12 and the inorganic oxide base layer 13 and coexistence of the transparency of the adhesive layer 15. less than nm.

The inorganic oxide base layer 13 is a layer for securing peeling resistance in the antifouling layer 14 . Examples of the material for the inorganic oxide base layer 13 include silicon dioxide (SiO ₂ ) and magnesium fluoride, and silicon dioxide is preferably used.

The thickness of the inorganic oxide base layer 13 is preferably 50 nm or more, more preferably 65 nm or more, still more preferably 80 nm or more, from the viewpoint of ensuring peeling resistance in the antifouling layer 14. Especially preferably, it is 90 nm or more. The thickness of the inorganic oxide base layer 13 is, for example, 300 nm or less.

The antifouling layer 14 is a layer having an antifouling function. The antifouling layer 14 is disposed on one side of the thickness direction T of the inorganic oxide base layer 13 . The antifouling layer 14 has a surface 14a (outer surface) on one side of the thickness direction T. The antifouling function of the antifouling layer 14 includes a function of suppressing adhesion of contaminants such as hand oil to the film exposed surface during use of the optical film F, and a function of making it easy to remove the adhering contaminants. .

As a material of the antifouling layer 14, the organic compound containing a fluorine group is mentioned, for example. As the organic compound containing a fluorine group, an alkoxysilane compound having a perfluoropolyether group is preferably used. As an alkoxysilane compound which has a perfluoropolyether group, the compound represented by the following general formula (1) is mentioned, for example.

R^One-R²-X-(CH₂)_m-Si(OR³)₃ (One)

In the general formula (1), R ¹ represents a linear or branched fluoroalkyl group (eg, 1 to 20 carbon atoms) in which one or more hydrogen atoms in the alkyl group are substituted with fluorine atoms, preferably represents a perfluoroalkyl group in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms.

R ² represents a structure containing at least one repeating structure of a perfluoropolyether (PFPE) group, and preferably represents a structure containing two repeating structures of a PFPE group. Examples of the repeating structure of the PFPE group include a repeating structure of a linear PFPE group and a repeating structure of a branched PFPE group. As a repeating structure of the linear PFPE group, for example, a structure represented by -(OC _n F _2n ) _p - (n represents 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 below) can be mentioned. Examples of the repeating structure of the branched PFPE group include a structure represented by -(OC(CF ₃ ) ₂ ) _p - and a structure represented by -(OCF ₂ CF(CF ₃ )CF ₂ ) _p -. can 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 -.

R ³ represents an alkyl group having 1 or more and 4 or less carbon atoms, preferably a methyl group.

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

m represents an integer of 1 or greater. In addition, m is preferably an integer of 20 or less, more preferably 10 or less, still more preferably 5 or less.

Among the alkoxysilane compounds having such a perfluoropolyether group, a compound represented by the following general formula (2) is preferably used.

CF₃-(OCF₂)_q-(OC₂F₄)_r-O-(CH₂)₃-Si(OCH₃)₃ (2)

In 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.

Moreover, the alkoxysilane compound which has a perfluoropolyether group may be used independently, and 2 or more types may be used together.

The antifouling layer 14 is a film formed by a dry coating method (dry coating film). As a dry coating method, a sputtering method, a vacuum deposition method, and CVD are mentioned. The antifouling layer 14 is preferably a film formed by a vacuum deposition method (vacuum deposition film).

The material of the antifouling layer 14 contains an alkoxysilane compound having a perfluoropolyether group, and the antifouling layer 14 is a dry coating film (preferably a vacuum deposited film), the inorganic oxide base layer 13 It is suitable for securing high bonding strength of the antifouling layer 14 to the surface, and therefore suitable for securing peeling resistance of the antifouling layer 14. The fact that the peeling resistance of the antifouling layer 14 is high is useful for maintaining the antifouling function of the antifouling layer 14 .

The hardness (surface hardness H) at 25°C of the surface 14a of the antifouling layer 14 measured by the nanoindentation method is preferably 1.05 GPa or more, more preferably 1.1 GPa or more, and furthermore It is preferably 1.15 GPa or more, more preferably 1.2 GPa or more, still more preferably 1.25 GPa or more, and particularly preferably 1.3 GPa or more. Such a configuration is suitable for suppressing the deterioration of antifouling properties of the antifouling layer 14 by resisting the wiping operation to the antifouling layer 14 . The hardness (surface hardness H) at 25°C of the surface 14a of the antifouling layer 14 measured by the nanoindentation method is preferably 30 GPa or less, more preferably 20 GPa or less, still more preferably It is preferably 15 GPa or less. Such a configuration is suitable for securing the flexibility of the antifouling layer 14 and, therefore, suitable for ensuring the flexibility of the optical film F.

The nanoindentation method is a technique for measuring various physical properties of a sample on a nanometer scale. In this embodiment, the nanoindentation method is implemented based on ISO14577. In the nanoindentation method, a process of pressing an indenter into a sample set on a stage (load application process) and a process of extracting an indenter from the sample later (unloading process) are performed. Among a series of processes, the indenter - The load acting between the sample and the relative displacement of the indenter relative to the sample are measured (load-displacement measurement). By this, it is possible to obtain a load-displacement curve. From this load-displacement curve, it is possible to obtain physical properties such as hardness and modulus of elasticity based on nanometer-scale measurement of the measurement sample. For the load-displacement measurement of the surface of the antifouling layer by the nanoindentation method, a nanoindenter (trade name "Triboindenter", manufactured by Hysitron) can be used, for example. In the measurement, the measurement mode is single indentation measurement, the measurement temperature is 25 ° C, the indenter used is a Berkovich (triangular pyramid) type diamond indenter, and the maximum indentation depth of the indenter to the measurement sample in the process of applying the load (Maximum displacement H1) is 200 nm, the pushing speed of the indenter is 20 nm/sec, and the speed of extracting the indenter from the measurement sample in the unloading process is 20 nm/sec. Based on the load-displacement curve obtained by this measurement, the maximum load Pmax (the load acting on the indenter at the maximum displacement H1), the projected contact area Ap (the projected area of the contact area between the indenter and the sample at the time of maximum load) , and the amount of plastic deformation H2 on the sample surface after the unloading process (the depth of the concave portion maintained on the sample surface after separating the indenter from the sample surface) can be obtained. Then, the surface hardness of the antifouling layer (= Pmax/Ap) can be calculated from the maximum load Pmax and the contact projected area Ap. Further, from the maximum displacement H1 and the amount of plastic deformation H2, the later-described elastic recovery factor (= (H1-H2)/H1) of the surface of the antifouling layer subjected to load application and subsequent unloading can be calculated.

As a method for adjusting the surface hardness H in the antifouling layer 14, for example, hardness adjustment and thickness adjustment of the hard coat layer 12, and hardness adjustment of the base layer in the antifouling layer 14, thickness can be adjusted.

The elastic recovery rate (elastic recovery rate R) at 25°C of the surface 14a of the antifouling layer 14 measured by the nanoindentation method is preferably 0.76 or more, more preferably 0.80 or more, still more preferably. It is preferably 0.815 or more, particularly preferably 0.85 or more. Such a configuration is suitable for suppressing the deterioration of antifouling properties of the antifouling layer 14 by resisting the wiping operation to the antifouling layer 14 . The elastic recovery factor (elastic recovery factor R) at 25°C of the surface 14a of the antifouling layer 14 measured by the nanoindentation method is preferably 1.0 or less, more preferably 0.95 or less. Such a configuration is suitable for securing the flexibility of the antifouling layer 14 and, therefore, suitable for ensuring the flexibility of the optical film F. As a method for adjusting the elastic recovery rate R in the antifouling layer 14, for example, hardness adjustment and elastic modulus adjustment of the hard coat layer 12, and hardness adjustment of the base layer in the antifouling layer 14 and elastic modulus adjustment.

The product of the surface hardness H (GPa) and the elastic recovery rate R in the antifouling layer 14 is 0.8 or more, preferably 0.9 or more, more preferably 1.0 or more, still more preferably 1.1 or more. Such a configuration is suitable for suppressing the deterioration of antifouling properties of the antifouling layer 14 by resisting the wiping operation to the antifouling layer 14 . The product of the surface hardness H (GPa) and the elastic recovery factor R in the antifouling layer 14 is preferably 2.0 or less, more preferably 1.7 or less, still more preferably 1.5 or less. Such a configuration is suitable for securing the flexibility of the antifouling layer 14 and, therefore, suitable for ensuring the flexibility of the optical film F.

The water contact angle (pure contact angle) of the surface 14a of the antifouling layer 14 is preferably 110° or more, preferably 111° or more, more preferably 112° or more, still more preferably 113° or more; Especially preferably, it is 114 degrees or more. A configuration in which the water contact angle on the surface 14a is so high is suitable for realizing high antifouling properties in the antifouling layer 14 . The animal contact angle is, for example, 130° or less. The water contact angle is obtained by forming a water droplet (pure water droplet) with a diameter of 2 mm or less on the surface 14a (exposed surface) of the antifouling layer 14, and measuring the contact angle of the water droplet with respect to the surface 14a. The water contact angle of the surface 14a is, for example, the composition of the antifouling layer 14, the roughness of the surface 14a, the composition of the hard coat layer 12, and the antifouling layer 14 of the hard coat layer 12 It can be adjusted by adjusting the surface roughness of the side.

The antifouling layer 14 has a thickness of preferably 1 nm or more, more preferably 3 nm or more, even more preferably 5 nm or more, and particularly preferably 7 nm or more. Such a configuration is suitable for realizing the surface hardness of the antifouling layer 14 described above. The thickness of the antifouling layer 14 is preferably 25 nm or less, more preferably 20 nm or less, still more preferably 18 nm or less. Such a structure is suitable for realizing the above water contact angle in the antifouling layer 14 .

The optical film (F), after preparing the transparent substrate 11, for example, in a roll-to-roll system, on the transparent substrate 11, the hard coat layer 12, the adhesive layer 15, and the antifouling layer ( 14) can be produced by sequentially forming.

The hard coat layer 12 can be formed, for example, by applying a curable resin composition on the transparent substrate 11 to form a coating film, and then curing the coating film. When curable resin composition contains ultraviolet curable resin, the said coating film is hardened by ultraviolet irradiation. When the curable resin composition contains a thermosetting resin, the coating film is cured by heating.

The exposed surface of the hard coat layer 12 formed on the transparent substrate 11 is subjected to surface modification treatment as needed. In the case of plasma treatment as the surface modification treatment, for example, argon gas is used as an inert gas. In addition, the discharge power in the plasma treatment is, for example, 10 W or more, and is, for example, 10000 W or less.

The inorganic oxide base layer 13 is formed by forming a material into a film by a dry coating method. As the dry coating method, sputtering method, vacuum evaporation method, and CVD are mentioned, and sputtering method is preferably used.

In the sputtering method, a negative voltage is applied to a target placed on a cathode while gas is introduced into the sputter chamber under vacuum conditions. Thereby, a glow discharge is generated to ionize gas atoms, and the gas ions collide with the target surface at high speed to repel the target material from the target surface, and the repelled target material is deposited on a predetermined surface. From the viewpoint of film formation speed, reactive sputtering is preferred as the sputtering method. In reactive sputtering, a metal target is used as a target, and a mixed gas of an inert gas such as argon and oxygen (reactive gas) is used as the gas described above. The ratio of oxygen contained in the inorganic oxide to be formed can be adjusted by adjusting the flow rate ratio (sccm) of the inert gas and oxygen.

As a power supply for performing the sputtering method, a DC power supply, an AC power supply, an RF power supply, and an MFAC power supply (an AC power supply having a frequency band of several kHz to several MHz) are exemplified. The discharge voltage in the sputtering method is, for example, 200 V or more, and is, for example, 1000 V or less. In addition, the film formation atmospheric pressure in the sputtering chamber where the sputtering method is performed is preferably 0.01 Pa or more, more preferably 0.05 Pa or more, still more preferably 0.1 Pa or more. Such a configuration is preferable from the viewpoint of forming the antifouling layer 14 in which materials are densely deposited. In addition, the film-forming atmospheric pressure is, for example, 2 Pa or less from the viewpoint of discharge stability.

The antifouling layer 14 is formed by forming, for example, a fluorine group-containing organic compound into a film on the inorganic oxide base layer 13 by a dry coating method. As a dry coating method, a vacuum deposition method, sputtering method, and CVD are mentioned, for example, The vacuum deposition method is used preferably.

For example, the optical film (F) can be manufactured as described above. As for the optical film (F), the side of the transparent substrate 11 is bonded to an adherend through an adhesive, for example, and used. As an adherend, the transparent cover arrange|positioned on the image display side in displays, such as a touch panel display, is mentioned, for example.

As described above, the optical film (F) is a dry coating film in which the antifouling layer (14) is disposed on the inorganic oxide base layer (13). Such a configuration is suitable for ensuring high bonding strength of the antifouling layer 14 in the optical film F, and therefore suitable for ensuring peeling resistance of the antifouling layer 14. The fact that the peeling resistance of the antifouling layer 14 is high is useful for maintaining the antifouling function of the antifouling layer 14 .

In the optical film (F), the product of the surface hardness H (GPa) and the elastic recovery factor R in the antifouling layer 14 is 0.8 or more as described above, preferably 0.9 or more, more preferably 1.0 or more; More preferably, it is 1.1 or more. Such a configuration is suitable for suppressing the deterioration of antifouling properties of the antifouling layer 14 by resisting the wiping operation to the antifouling layer 14 .

In addition to this, in the optical film (F), the elastic recovery factor R at 25°C measured by the nanoindentation method of the surface 14a of the antifouling layer 14 is preferably 0.76 or more as described above. , More preferably 0.80 or more, still more preferably 0.815 or more, and particularly preferably 0.85 or more. Such a configuration is suitable for suppressing the deterioration of antifouling properties of the antifouling layer 14 by resisting the wiping operation to the antifouling layer 14 .

As described above, the optical film (F) is suitable for suppressing a decrease in antifouling properties while ensuring peeling resistance in the antifouling layer 14 .

The optical film F may include a layer having a predetermined optical function (optical function layer). When the optical function layer contains a plurality of layers, it is preferable that the surface layer on the antifouling layer 14 side of such an optical function layer also serves as the above-mentioned inorganic oxide base layer 13.

2 shows the case where the optical film F is provided with the optical function layer 20 between the adhesive layer 15 and the antifouling layer 14. This optical function layer 20 has a layer that also serves as an inorganic oxide base layer 13 on the surface on the side of the antifouling layer 14 so as to be described later.

The optical function layer 20 is arranged on one side of the thickness direction T of the adhesive layer 15 . In this modified example, the optical function layer 20 is an antireflection layer for suppressing the reflected intensity of external light. That is, the optical film (F), in this modification, is an antireflection film with an antifouling layer.

The optical function layer 20 (antireflection layer) has a high refractive index layer having a relatively large refractive index and a low refractive index layer having a relatively small refractive index alternately in the thickness direction. In the antireflection layer, the net intensity of reflected light is attenuated by an interference action between reflected light at a plurality of interfaces in a plurality of thin layers (high refractive index layer and low refractive index layer) included in the same layer. Further, in the antireflection layer, an interference effect of attenuating the reflected light intensity can be developed by adjusting the optical film thickness (product of refractive index and thickness) of each thin layer. The optical function layer 20 as such an antireflection layer, in this embodiment, specifically, the first high refractive index layer 21, the first low refractive index layer 22, the second high refractive index layer 23 and , the second low refractive index layer 24 serving as the above-mentioned inorganic oxide base layer 13 is provided in this order toward one side of the thickness direction T.

The first high refractive index layer 21 and the second high refractive index layer 23 are each made of a high refractive index material having a refractive index of preferably 1.9 or more at a wavelength of 550 nm. From the viewpoint of coexistence of high refractive index and low absorption of visible light, examples of the high refractive index material include niobium oxide (Nb ₂ O ₅ ), titanium oxide, zirconium oxide, tin-doped indium oxide (ITO), and antimony-doped oxide. Tin (ATO) is exemplified, and niobium oxide is preferably used.

The optical film thickness (product of the refractive index and the thickness) of the first high refractive index layer 21 is, for example, 20 nm or more and, for example, 55 nm or less. The optical film thickness of the second high refractive index layer 23 is, for example, 60 nm or more and, for example, 330 nm or less.

The first low refractive index layer 22 and the second low refractive index layer 24 are each made of a low refractive index material having a refractive index of preferably 1.6 or less at a wavelength of 550 nm. From the viewpoint of both low refractive index and low absorption of visible light, examples of the low refractive index material include silicon dioxide (SiO ₂ ) and magnesium fluoride, and silicon dioxide is preferably used. As described above, SiO ₂ and magnesium fluoride are also preferable as a material for the inorganic oxide base layer 13 .

The optical film thickness of the first low refractive index layer 22 is, for example, 15 nm or more and, for example, 70 nm or less. The optical film thickness of the second low refractive index layer 24 is, for example, 100 nm or more and, for example, 160 nm or less.

The first high-refractive-index layer 21, the first low-refractive-index layer 22, and the second high-refractive-index layer 23 can each be formed by forming a film of a material by a dry coating method. The second low refractive index layer 24 serving as the inorganic oxide base layer 13 is formed by forming a film of a material by a dry coating method. As the dry coating method, sputtering method, vacuum evaporation method, and CVD are mentioned, and sputtering method is preferably used. As the sputtering method, reactive sputtering is preferable from the viewpoint of film formation speed. The conditions of the sputtering method are the same as those described above as the conditions of the sputtering method related to formation of the inorganic oxide underlayer 13 .

In the optical film F shown in FIG. 2 , the antifouling layer 14 is a dry coating film arranged on the second low refractive index layer 24 (inorganic oxide base layer 13). In the optical film F shown in FIG. 2 , the product of the surface hardness H (GPa) of the surface 14a of the antifouling layer 14 at 25° C. measured by the nanoindentation method and the elastic recovery factor R is 0.8 or more. , and is preferably 0.9 or more, more preferably 1.0 or more, still more preferably 1.1 or more. In the optical film F shown in FIG. 2 , the elastic recovery rate R at 25° C. of the surface 14a of the antifouling layer 14 measured by the nanoindentation method is preferably 0.76 or more, more preferably is 0.80 or more, more preferably 0.815 or more, particularly preferably 0.85 or more. Such an optical film (F) is suitable for suppressing a decrease in antifouling properties while ensuring peeling resistance in the antifouling layer 14 .

Example

The present invention will be described concretely by showing examples below. The present invention is not limited to the examples. In addition, specific numerical values such as compounding amounts (contents), physical property values, and parameters described below are described in the above-mentioned "mode for carrying out the invention", and the compounding amounts (contents), physical property values, and parameters corresponding to them are described. etc. can be replaced with the upper limit (numerical value defined as "below" or "less than") or lower limit (numerical value defined as "greater than" or "exceeds") of the description.

[Example 1]

First, a hard coat layer was formed on one side of a polyethylene terephthalate (PET) film (trade name "50U48", thickness 50 µm, manufactured by Toray Corporation) as a transparent substrate (hard coat layer forming step). Specifically, first, 100 mass of a butyl acetate solution (trade name "Unidic 17-806", solid content concentration: 80% by mass, manufactured by DIC) of a mixture of ultraviolet curable monomers and oligomers (containing urethane acrylate as a main component) Part (in terms of solid content), 5 parts by mass of a photopolymerization initiator (trade name "IRGACURE906", manufactured by BASF), and 0.01 part by mass of a leveling agent (trade name "GRANDIC PC4100", manufactured by DIC) were mixed to obtain a liquid mixture. Next, the solid content concentration of the liquid mixture was adjusted to 36% by mass by adding a mixed solvent of cyclopentanone (CPN) and propylene glycol monomethyl ether (PGM) (the mass ratio of CPN and PGM was 45:55). Thus, an ultraviolet curable resin composition (varnish) was prepared. Then, the composition was applied to one side of the PET film to form a coating film. Next, after drying this coating film by heating, it was hardened by ultraviolet irradiation. The heating temperature was 90°C, and the heating time was 60 seconds. In the ultraviolet irradiation, a high-pressure mercury lamp was used as a light source, and an ultraviolet ray having a wavelength of 365 nm was used, and the integrated irradiation light amount was 300 mJ/cm ² . This formed a hard coat (HC) layer with a thickness of 5 μm on the PET film.

Next, the surface of the HC layer of the PET film on which the HC layer was formed was subjected to plasma treatment in a vacuum atmosphere of 1.0 Pa using a roll-to-roll type plasma processing apparatus. In this plasma treatment, argon gas was used as an inert gas, and the discharge electric power was 780 W.

Next, on the HC layer of the PET film on which the HC layer was formed after plasma treatment, an adhesive layer and an inorganic oxide base layer were sequentially formed (sputter film formation process). Specifically, an indium tin oxide (ITO) layer with a thickness of 2.0 nm as an adhesive layer and a thickness of 165 nm as an inorganic oxide underlayer were formed on the HC layer of a PET film on which an HC layer was formed by a roll-to-roll sputter film deposition apparatus. nm SiO ₂ layers were sequentially formed. In the formation of the adhesion layer, an ITO target is used, argon gas as an inert gas, and oxygen gas as a reactive gas of 10 parts by volume per 100 parts by volume of the argon gas are used, the discharge voltage is set to 350 V, and the air pressure in the film formation chamber is reduced. The ITO layer was formed into a film by MFAC sputtering at a (film forming atmospheric pressure) of 0.4 Pa. In the formation of the inorganic oxide base layer, a Si target is used, 100 parts by volume of argon gas and 30 parts by volume of oxygen gas are used, the discharge voltage is set to 350 V, the film formation pressure is set to 0.3 Pa, and SiO is formed by MFAC sputtering. _Two layers were formed.

Next, an antifouling layer was formed (antifouling layer forming step). Specifically, an antifouling layer having a thickness of 12 nm was formed on the inorganic oxide base layer by a vacuum deposition method using an alkoxysilane compound containing a perfluoropolyether group as a deposition source. The evaporation source is a solid content obtained by drying "KY1903-1" (a perfluoropolyether group-containing alkoxysilane compound, solid content concentration: 20% by mass) manufactured by Shin-Etsu Chemical Co., Ltd. In addition, the heating temperature of the evaporation source in the vacuum evaporation method was 260 degreeC.

As described above, the optical film of Example 1 was produced. The optical film of Example 1 includes a transparent substrate (resin film), a hard coat layer, an adhesive layer, an inorganic oxide base layer, and an antifouling layer in this order toward one side in the thickness direction.

[Example 2]

An optical film of Example 2 was produced in the same manner as the optical film of Example 1, except that the thickness of the HC layer was changed to 10 µm instead of 5 µm.

[Example 3]

Optical film of Example 3 in the same manner as in the optical film of Example 1, except that the thickness of the HC layer was changed to 10 μm instead of 5 μm, and the thickness of the inorganic oxide underlayer was changed to 100 nm instead of 165 nm. was produced.

[Example 4]

The optical film of Example 4 was produced in the same manner as in the optical film of Example 1, except that the deposition air pressure at the time of forming the inorganic oxide underlayer was 0.1 Pa instead of 0.3 Pa.

[Example 5]

Example 1 was carried out in the same manner as in the optical film of Example 1, except that the thickness of the HC layer was changed to 10 μm instead of 5 μm, and the deposition air pressure at the time of forming the inorganic oxide underlayer was changed to 0.1 Pa instead of 0.3 Pa. The optical film of 5 was produced.

[Example 6]

The optical film of Example 6 was produced in the same manner as the optical film of Example 1, except that the thickness of the antifouling layer was changed to 8 nm instead of 12 nm.

[Example 7]

The optical film of Example 7 was produced in the same manner as the optical film of Example 1, except that the thickness of the antifouling layer was changed to 6 nm instead of 12 nm.

[Example 8]

The optical film of Example 8 was produced in the same manner as the optical film of Example 1, except that the thickness of the antifouling layer was changed to 16 nm instead of 12 nm.

[Example 9]

First, a hard coat layer was formed on one side of a PET film (trade name "50U48", thickness 50 µm, manufactured by Toray Industries) as a transparent substrate. Specifically, first, an ultraviolet curable polyfunctional acrylate resin (trade name "Z-850-50H-D", solid content concentration: 44 mass%, manufactured by Aika Kogyo) 100 parts by mass (in terms of solid content) and a photopolymerization initiator (trade name "OMNIRAD2959", manufactured by BASF) and 0.05 parts by mass of a leveling agent (trade name "LE-303", manufactured by Kyoeisha Chemical Co., Ltd.) were mixed to obtain a liquid mixture. Next, the solid content concentration of the liquid mixture was adjusted to 40% by mass by adding methyl isobutyl ketone to the liquid mixture. Thus, an ultraviolet curable resin composition (varnish) was prepared. Then, the composition was applied to one side of the PET film to form a coating film. Next, after drying this coating film by heating, it was hardened by ultraviolet irradiation. The heating temperature was 80°C, and the heating time was 60 seconds. In the ultraviolet irradiation, a high-pressure mercury lamp was used as a light source, and an ultraviolet ray having a wavelength of 365 nm was used, and the integrated irradiation light amount was 300 mJ/cm ² . Thus, a hard coat (HC) layer having a thickness of 5 μm was formed on the PET film.

Next, the surface of the HC layer of the PET film on which the HC layer was formed was subjected to plasma treatment in a vacuum atmosphere of 1.0 Pa using a roll-to-roll type plasma processing apparatus. In this plasma treatment, argon gas was used as an inert gas, and the discharge electric power was 150 W.

Subsequently, an adhesive layer and an antireflection layer were sequentially formed on the HC layer of the PET film on which the HC layer was formed after plasma treatment. Specifically, an indium tin oxide (ITO) layer having a thickness of 1.5 nm as an adhesive layer and a first high refractive index were placed on the HC layer of a PET film on which the HC layer after plasma treatment was formed by a roll-to-roll sputter film deposition apparatus. A 12 nm thick Nb ₂ O ₅ layer as a layer, a 28 nm thick SiO ₂ layer as a first low refractive index layer, a 100 nm thick Nb ₂ O ₅ layer as a second high refractive index layer, and a second low refractive index layer. An SiO ₂ layer with a thickness of 85 nm as , was sequentially formed. In the formation of the adhesion layer, an ITO target is used, argon gas as an inert gas, and oxygen gas as a reactive gas of 10 parts by volume per 100 parts by volume of the argon gas are used, the discharge voltage is set to 400 V, and the air pressure in the film formation chamber is reduced. The ITO layer was formed into a film by MFAC sputtering at a (film forming atmospheric pressure) of 0.2 Pa. In formation of the first high refractive index layer, a Nb target was used, 100 parts by volume of argon gas and 5 parts by volume of oxygen gas were used, the discharge voltage was set to 415 V, and the deposition pressure was set to 0.7 Pa by MFAC sputtering. A Nb ₂ O ₅ layer was formed. In the formation of the first low refractive index layer, a Si target was used, 100 parts by volume of argon gas and 30 parts by volume of oxygen gas were used, the discharge voltage was set to 350 V, and the deposition atmospheric pressure was set to 0.7 Pa by MFAC sputtering. A SiO ₂ layer was deposited. In the formation of the second high refractive index layer, a Nb target was used, 100 parts by volume of argon gas and 13 parts by volume of oxygen gas were used, the discharge voltage was set to 460 V, the deposition pressure was set to 0.7 Pa, by MFAC sputtering. A Nb ₂ O ₅ layer was formed. In the formation of the second low refractive index layer, a Si target was used, 100 parts by volume of argon gas and 30 parts by volume of oxygen gas were used, the discharge voltage was set to 340 V, and the deposition pressure was set to 0.7 Pa, by MFAC sputtering. A SiO ₂ layer was deposited. As described above, on the HC layer of the PET film on which the HC layer was formed, an antireflection layer (the first high refractive index layer, the first low refractive index layer, the second high refractive index layer, and the second low refractive index layer) was applied through the adhesive layer. layered formation. In this embodiment, the second low refractive index layer is an inorganic oxide base layer in the antifouling layer.

Next, an antifouling layer was formed on the formed antireflection layer (i.e., on the second low refractive index layer). Specifically, it is the same as the antifouling layer formation process in Example 1.

As described above, the optical film of Example 9 was produced. The optical film of Example 9 includes a transparent substrate (resin film), a hard coat layer, an adhesive layer, an antireflection layer (including a second low refractive index layer as an inorganic oxide base layer), and an antifouling layer in the thickness direction It is provided in this order toward one side.

[Comparative Example 1]

Optical film of Comparative Example 1 in the same manner as in the optical film of Example 1, except that the thickness of the HC layer was changed to 10 μm instead of 5 μm, and the thickness of the inorganic oxide underlayer was changed to 30 nm instead of 165 nm. was produced.

<Hardness and elastic recovery rate of the surface of the antifouling layer>

The surface of the antifouling layer of each optical film of Examples 1 to 9 and Comparative Example 1 was subjected to load-displacement measurement by a nanoindentation method. Specifically, first, a measurement sample (5 mm × 5 mm) was cut out from the optical film. Next, using a nanoindenter (trade name "Triboindenter", manufactured by Hysitron), a load-displacement measurement of the surface of the antifouling layer in the measurement sample was performed based on ISO14577, and a load-displacement curve was obtained. In this measurement, the measurement mode is single indentation measurement, the measurement temperature is 25 ° C, the indenter used is a Berkovich (triangular pyramid) type diamond indenter, and the maximum indentation depth of the indenter into the measurement sample during the load application process ( The maximum displacement H1) was 200 nm, the pushing speed of the indenter was 20 nm/sec, and the speed of extracting the indenter from the measurement sample in the unloading process was 20 nm/sec. Based on the obtained load-displacement curve, the maximum load Pmax (the load acting on the indenter at the maximum displacement H1), the projected contact area Ap (the projected area of the contact area between the indenter and the sample at the time of maximum load), and the unloading process The amount of plastic deformation H2 (the depth of the concave portion held on the sample surface after separating the indenter from the sample surface) on the subsequent sample surface was obtained. Then, the surface hardness of the antifouling layer (= Pmax/Ap) was calculated from the maximum load Pmax and the projected contact area Ap. In addition, from the maximum displacement H1 and the amount of plastic deformation H2, an elastic recovery factor (= (H1-H2)/H1) described below of the surface of the antifouling layer subjected to load application and subsequent unloading was calculated. Table 1 shows these surface hardness (GPa) and elastic recovery rate (%).

<Water contact angle>

For each optical film of Examples 1 to 9 and Comparative Example 1, the contact angle of water on the surface of the antifouling layer was investigated. First, water droplets were formed on the surface of the antifouling layer of the optical film by dropping about 1 µL of pure water. Next, the angle between the surface of the water droplets on the surface of the antifouling layer and the surface of the antifouling layer was measured. For the measurement, a contact angle meter (trade name "DMo-501", manufactured by Kyowa Interface Science Co., Ltd.) was used. The measurement results are shown in Table 1 as the initial water contact angle θ ₀ .

<Eraser sliding test>

For each optical film of Examples 1 to 9 and Comparative Example 1, the degree of deterioration in antifouling properties of the surface of the antifouling layer by passing through an eraser sliding test was investigated. Specifically, first, a sliding test was conducted in which an eraser was reciprocated while sliding on the surface of the antifouling layer of the optical film (first eraser sliding test). In this test, an eraser (Φ6 mm) manufactured by Minoan was used, the load of the eraser on the surface of the antifouling layer was 1 kg/6 mmΦ, and the sliding distance (one way in reciprocation) of the eraser on the surface of the antifouling layer was 20 mm, the sliding speed of the eraser was 40 rpm, and the number of times the eraser was reciprocated with respect to the surface of the antifouling layer was 3000 reciprocations. Next, the water contact angle at the sliding point of the eraser on the surface of the antifouling layer of the optical film was measured by the same method as the measuring method of the initial water contact angle θ ₀ . The measurement results are shown in Table 1 as the water contact angle θ ₁ after the first eraser sliding test.

Subsequently, a sliding test was conducted in which the surface of the antifouling layer of the optical film was reciprocated while sliding an eraser again (second eraser sliding test). The sliding conditions are the same as those in the first eraser sliding test (the number of times the eraser is reciprocated is a total of 6000 reciprocations in the first eraser sliding test and the second eraser sliding test thereafter). Next, the water contact angle at the sliding point of the eraser on the surface of the antifouling layer of the optical film was measured by the same method as the measuring method of the initial water contact angle θ ₀ . The measurement results are shown in Table 1 as the water contact angle θ ₂ after the second eraser sliding test. 3 is a graph in which the product of the surface hardness H and the elastic recovery rate R and the water contact angle θ ₂ in each of the optical films of Examples 1 to 9 and Comparative Example 1 are plotted. In the graph of FIG. 3 , the horizontal axis represents the product (R×H) of the surface hardness H (GPa) and the elastic recovery rate R, and the vertical axis represents the water contact angle θ ₂ (°). In FIG. 3 , plots E1 to E9 show measurement results in Examples 1 to 9, and plot C1 shows measurement results in Comparative Example 1.

<evaluation>

In each optical film of Examples 1 to 9, compared to the optical film of Comparative Example 1, the water contact angle at the surface of the antifouling layer by passing through the eraser sliding test (first eraser sliding test, second eraser sliding test) The degree of degradation is significantly small, and therefore, the decrease in antifouling properties is significantly small (on the surface of the antifouling layer, the smaller the decrease in water contact angle, the smaller the decrease in antifouling properties).

The embodiment described above is an illustration of the present invention, and the present invention should not be interpreted limitedly by the embodiment. Modifications of the present invention obvious to those skilled in the art are included in the claims described later.

industrial applicability

The optical film with an antifouling layer of the present invention can be applied to, for example, an antireflection film with an antifouling layer, a transparent conductive film with an antifouling layer, and an electromagnetic wave shielding film with an antifouling layer.

F: Optical film (optical film with antifouling layer)
11: transparent substrate
12: hard coat layer
13: inorganic oxide under layer
14: antifouling layer
14a: surface
15: adhesion layer
20: optical functional layer
21: first high refractive index layer
22: first low refractive index layer
23: second high refractive index layer
24: second low refractive index layer

Claims (6)

A transparent substrate, a hard coat layer, an inorganic oxide base layer, and an antifouling layer are provided in this order,
The inorganic oxide underlayer contains silicon dioxide,
the antifouling layer is a vacuum deposited film of an alkoxysilane compound containing a perfluoropolyether group disposed on the inorganic oxide underlayer, and has a thickness of 7 nm or more;
The perfluoropolyether group-containing alkoxysilane compound is a compound represented by the following general formula (1),
R ¹ -R ² -X-(CH ₂ ) _m -Si(OR ³ ) ₃ (1)
In the general formula (1), R ¹ represents a perfluoroalkyl group, and R ² represents a repeating structure of a perfluoropolyether group including -(OCF ₂ ) _p - and -(OC ₂ F ₄ ) _p - , p represents an integer of 1 or more and 50 or less, R ³ represents an alkyl group having 1 or more and 4 or less carbon atoms, X represents an ether group, a carbonyl group, an amino group or an amide group, m represents an integer of 1 or more,
The product of the hardness (GPa) and the elastic recovery factor at 25° C. measured by the nanoindentation method of the surface of the antifouling layer on the opposite side to the inorganic oxide underlayer is 0.8 or more,
An optical film with an antifouling layer having the hardness of 1.05 GPa or more. According to claim 1,
The optical film with an antifouling layer, wherein the surface of the antifouling layer has an elastic recovery factor at 25°C of 0.76 or more as measured by a nanoindentation method. According to claim 1 or 2,
An optical film with an antifouling layer, wherein the antifouling layer has a thickness of 25 nm or less. According to claim 1 or 2,
An optical film with an antifouling layer, wherein the inorganic oxide underlayer has a thickness of greater than 100 nm. According to claim 1 or 2,
The optical film with an antifouling layer, wherein the hard coat layer has a thickness of 1 μm or more and 50 μm or less. delete

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