Laminated body, optical member with laminated body, and image display device

Abstract

To provide a laminate which achieves excellent sliding properties regardless of whether or not a user's finger is wet with a liquid containing oil, an optical member with a laminate, and an image display device.SOLUTION: A laminate according to an embodiment of the present invention comprises a substrate and a functional layer that is disposed on one side of the substrate in the thickness direction. In a specific friction test carried out through Bowden surface contact, both a static friction coefficient and a dynamic friction coefficient on a surface of the functional layer are 0.11 or less, as measured using a contact element that is wet with an oil-in-water emulsion containing the following components (1) to (5). (1) 80-90 mass% water; (2) 2-5 mass% ethanol; (3) 2-5 mass% glycerin; (4) 2-5 mass% squalane; and (5) 0.5-1 mass% hexadecanol.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a laminate, an optical member with a laminate, and an image display device.

Background Art

[0002] Image display devices that also serve as touch panel input devices, such as smartphones and tablet personal computers (PCs), have become widespread. Typically, such image display devices use a laminate including a functional layer according to the application. As the laminate, for example, a hard coat film in which a hard coat layer is provided on one side of a transparent base film is known (for example, Patent Document 1). In recent years, the usage environments of image display devices that also serve as touch panel input devices have become diversified. For example, a smartphone may be used immediately after using cosmetics such as emulsion and cream, and the smartphone may be operated with the user's finger wet with a liquid containing oil. However, when the hard coat film described in Patent Document 1 is used for the front panel of an image display device, in both cases where the user's finger is wet with a liquid containing oil and where the user's finger is not wet, there is a limit to improving the slipperiness of the finger, and the operability of the image display device may be insufficient.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] The present invention has been made to solve the above conventional problems, and its main object is to provide a laminate, an optical member with a laminate, and an image display device that can achieve excellent slipperiness whether the user's finger is wet with a liquid containing oil or not wet.

Means for Solving the Problem

[0005] The laminate according to an embodiment of the present invention includes a base material and a functional layer disposed on one side in the thickness direction of the base material. In the following friction test by surface contact of the Boudouard method, the static friction coefficient and the dynamic friction coefficient of the surface of the functional layer measured using a contactor wetted with an oil-in-water emulsion containing the following components (1) to (5) are both 0.11 or less. (1) 80% by mass or more and 90% by mass or less of water (2) 2% by mass or more and 5% by mass or less of ethanol (3) 2% by mass or more and 5% by mass or less of glycerin (4) 2% by mass or more and 5% by mass or less of squalane (5) 0.5% by mass or more and 1% by mass or less of hexadecanol (Friction Test) Set the above laminate in an automatic friction and wear analysis device; as a first step, bring the above contactor into contact with the surface of the functional layer with a load of 200 g; as a second step, move the above contactor at a speed of 1.7 mm / s for 50 mm to measure the static friction force and the dynamic friction force on the surface of the functional layer; as a third step, separate the above contactor from the surface of the functional layer and return it to the initial position; repeat the above first step, the above second step, and the above third step in order 5 times, calculate the static friction coefficient of the surface of the functional layer from the static friction force on the surface of the functional layer, and calculate the dynamic friction coefficient of the surface of the functional layer from the dynamic friction force on the surface of the functional layer. In one embodiment, the absolute value of the surface force measured by the following surface force test of the above laminate is 110 μN or less. (Surface Force Test) Set the laminate on a surface force measuring device equipped with a probe having a surface layer formed of polydimethylsiloxane; place the probe at the initial position and bring the surface of the functional layer into contact with the surface layer. When the probe comes into contact with the functional layer, in the case of a highly adhesive substance such as polydimethylsiloxane, a phenomenon (wetting) occurs in which the probe is pulled downward when contacting. The occurrence of this wetting is used as a criterion for determining that the sample and the probe are in contact.; Next, after setting the displacement amount of the pulled-in probe to zero, move the probe in a direction away from the laminate, and calculate the absolute value of the surface force of the laminate from the minimum value of the load applied to the probe when the surface layer separates from the surface of the functional layer. In one embodiment, the carbon element ratio on the surface of the functional layer is 50 atomic% or less, and the fluorine element ratio on the surface of the functional layer is 30 atomic% or more. In one embodiment, in the C1s spectrum measured by X-ray photoelectron spectroscopy of the surface of the functional layer, the sum of the areas of the peaks located in the range of 293 eV to 295 eV is 30 area% or more with respect to the sum of the areas of the peaks located in the range of 280 eV to 300 eV, and the area of the peak located in the range of 293 eV to 294 eV is 1.5 or more and 2.5 or less with respect to the area of the peak located in the range of 294 eV to 295 eV. In one embodiment, the absolute value of the difference in the static friction coefficient before and after the following slidability test and the absolute value of the difference in the kinetic friction coefficient before and after the following slidability test are both 0.01 or less. (Slidability test) Set the laminate on a slidability test device; wet the surface of the functional layer with the water-in-oil type emulsion, and bring a contactor formed of a rubber material into contact with the surface of the functional layer with a load of 2 kg; then, reciprocate the contactor 1000 times in a range of 50 mm at a speed of 66.7 mm / s. In one embodiment, the kinetic friction coefficient before the slidability test is greater than the kinetic friction coefficient after the slidability test. In one embodiment, the functional layer includes an anti-fingerprint layer located on the outermost surface of the functional layer, and the anti-fingerprint layer is composed of a vapor deposition film of a fluorine-containing silane compound. The optical member with a laminate according to another aspect of the present invention includes the laminate and an optical member disposed on the side opposite to the functional layer with respect to the substrate. The image display device according to still another aspect of the present invention includes the laminate as a front panel.

Advantages of the Invention

[0006] According to the embodiment of the present invention, excellent slipperiness can be achieved whether the user's finger is wet with a liquid containing oil or not.

Brief Description of the Drawings

[0007]

Figure 1

Figure 2

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Figure 8

Embodiments for Carrying Out the Invention

[0008] Hereinafter, representative embodiments of the present invention will be described, but the present invention is not limited to these embodiments.

[0009] A. Overall Configuration of the Laminate FIG. 1 is a schematic cross-sectional view of a laminate according to one embodiment of the present invention; FIG. 2 is a schematic cross-sectional view of a laminate according to another embodiment of the present invention; FIG. 3 is an explanatory diagram for explaining a friction test. The laminate 1 in the illustrated example includes a base material 2 and a functional layer 3 disposed on one side in the thickness direction of the base material 2. The surface 3a of the functional layer 3 on the side opposite to the base material 2 is located on the outermost surface of the laminate 1. In the laminate 1, in the following friction test by surface contact of the Boudouard method, the static friction coefficient and the dynamic friction coefficient of the surface 3a of the functional layer measured using a contactor wetted with an oil-in-water emulsion containing the following components (1) to (5) are both 0.11 or less. (1) 80% by mass or more and 90% by mass or less of water (2) 2% by mass or more and 5% by mass or less of ethanol (3) 2% by mass or more and 5% by mass or less of glycerin (4) 2% by mass or more and 5% by mass or less of squalane (5) 0.5% by mass or more and 1% by mass or less of hexadecanol (Friction Test) Set the laminate 1 in the automatic friction and wear analysis device 4; as the first step, bring the above-described contact 41 into contact with the surface 3a of the functional layer with a load of 200 g; as the second step, move the contact 41 at a speed of 1.7 mm / s for 50 mm to measure the static friction force and the dynamic friction force on the surface 3a of the functional layer; as the third step, separate the contact 41 from the surface 3a of the functional layer and return it to the initial position; repeat the first step, the second step, and the third step in order 5 times, calculate the static friction coefficient of the surface 3a of the functional layer from the static friction force of the surface 3a of the functional layer, and calculate the dynamic friction coefficient of the surface 3a of the functional layer from the dynamic friction force of the surface 3a of the functional layer. Details of the friction test will be described in the examples below. In such a laminate, in the above friction test, the static friction coefficient (hereinafter, μs *乳液 shall be used.) and the dynamic friction coefficient (hereinafter, μk *乳液 shall be used.) of the surface of the functional layer measured using a contact wetted with an oil-in-water type emulsion are both below the above upper limit. Therefore, excellent slipperiness can be realized when the user's finger is wet with a liquid containing oil (for example, cosmetics such as emulsion and cream). Note that the lower limit of each of μs *乳液 and μk *乳液 is typically 0.05 or more.

[0010] Also, typically, in the above friction test, the static friction coefficient (hereinafter, μs *無 shall be used.) and the dynamic friction coefficient (hereinafter, μk *無 shall be used.) of the surface 3a of the functional layer measured using a dry contact are both 0.15 or less, preferably 0.13 or less, more preferably 0.11 or less. Therefore, excellent slipperiness can be realized even when the user's finger is not wet with a liquid containing oil. Note that the lower limit of each of μs *無 and μk *無 is typically 0.05 or more.

[0011] In one embodiment, the ratio of μs *無 to μs *乳液 (μs *乳液 / μs *無) is, for example, 0.8 or more, preferably 0.9 or more, and for example, 1.4 or less, preferably 1.3 or less. μs *乳液 / μs *無 If it is within the above range, even if the user's finger is wet with a liquid containing oil, the same slipperiness as when the finger is not wet can be stably achieved. In one embodiment, μk *無 The ratio of μk *乳液 to μk *乳液 / μk *無 ) is, for example, 0.8 or more, preferably 0.9 or more, and for example, 1.4 or less, preferably 1.3 or less. μk *乳液 / μk *無 If it is within the above range, even if the user's finger is wet with a liquid containing oil, the same slipperiness as when the finger is not wet can be more stably achieved.

[0012] Figures 4(a) to 4(c) are explanatory diagrams for explaining the surface force test. In one embodiment, the laminate 1 has an absolute value of the surface force measured by the following surface force test of 110 μN or less, preferably 105 μN or less. (Surface force test) Set the laminate 1 in the surface force measuring device 5 including the probe 51 having the surface layer 51a formed of polydimethylsiloxane; place the probe 51 at the initial position and bring the surface 3a of the functional layer into contact with the surface layer 51a; then move the probe 51 in a direction away from the laminate 1, and calculate the absolute value of the surface force of the laminate from the minimum value of the load applied to the probe 51 when the surface layer 51a is separated from the surface 3a of the functional layer. Details of the surface force test will be described in the examples described later. If the surface force of the laminate 1 measured by the above surface force test is equal to or greater than the above lower limit, the static friction coefficient and the dynamic friction coefficient of the surface of the functional layer can be stably adjusted within the above-described range. The absolute value of the surface force of the laminate is typically 80 μN or more.

[0013] In one embodiment, the carbon element ratio on the surface 3a of the functional layer is 50 atomic % or less, preferably 40 atomic % or less, and the fluorine element ratio on the surface 3a of the functional layer is 30 atomic % or more. The elemental ratio on the surface of the functional layer can be measured by X-ray photoelectron spectroscopy (ESCA). Details of the elemental ratio measurement will be described in the examples below. If the carbon element ratio on the surface 3a of the functional layer is below the above upper limit and the fluorine element ratio is above the above lower limit, the static friction coefficient and kinetic friction coefficient on the surface of the functional layer can be stably adjusted within the above ranges. Typically, the carbon element ratio on the surface 3a of the functional layer is 20 atomic % or more, and the fluorine element ratio is typically 50 atomic % or less. In addition, the nitrogen element ratio on the surface 3a of the functional layer is, for example, less than 1.5 atomic %, preferably 1.3 atomic % or less, and is, for example, 0 atomic % or more. If the nitrogen element ratio on the surface 3a of the functional layer is below the above upper limit, the static friction coefficient and kinetic friction coefficient on the surface of the functional layer can be adjusted more stably within the above ranges.

[0014] In one embodiment, in the C1s spectrum measured by X-ray photoelectron spectroscopy for the surface 3a of the functional layer, the total area of the peaks located in the range of 293 eV to 295 eV is 30 area % or more with respect to the total area of the peaks located in the range of 280 eV to 300 eV, and the area of the peak located in the range of 293 eV to 294 eV is 1.5 or more and 2.5 or less with respect to the area of the peak located in the range of 294 eV to 295 eV. Details of the C1s spectrum waveform analysis will be described in the examples below. If the area ratio of the peaks located in the range of 293 eV to 295 eV in the C1s spectrum is above the above lower limit and the area of the peak in the range of 293 eV to 294 eV / the area of the peak in the range of 294 eV to 295 eV is in the above range, the static friction coefficient and kinetic friction coefficient on the surface of the functional layer can be adjusted more stably within the above ranges. Typically, the area ratio of the peaks located in the range of 293 eV to 295 eV in the C1s spectrum is 80 atomic % or less.

[0015] Figs. 5(a) and 5(b) are explanatory diagrams for explaining the slidability test. In one embodiment, the absolute value of the difference in the static friction coefficient before and after the following slidability test and the absolute value of the difference in the dynamic friction coefficient before and after the following slidability test are both 0.01 or less, preferably 0.008 or less. (Slidability test) Set the laminate 1 in the slidability test apparatus 6; wet the surface 3a of the functional layer with the above water-in-oil type emulsion, and bring the contactor 61 formed of a rubber material into contact with the surface 3a of the functional layer under a load of 2 kg; then, reciprocate the contactor 61 1000 times within a range of 50 mm at a speed of 66.7 mm / s. Thereafter, wet the contactor 41 of the automatic friction and wear analysis apparatus 4 with the above water-in-oil type emulsion, and perform the above friction test. When the absolute value of the difference in the static friction coefficient and the absolute value of the difference in the dynamic friction coefficient before and after the slidability test are below the above upper limit, even if the laminate is used and the surface of the functional layer is rubbed with a finger or the like, excellent slipperiness of the surface of the functional layer can be sufficiently ensured. Note that the absolute value of the difference in the static friction coefficient and the absolute value of the difference in the dynamic friction coefficient before and after the above slidability test are typically 0.0010 or more. Also, the dynamic friction coefficient before the slidability test is preferably larger than the dynamic friction coefficient after the slidability test. According to such a configuration, the slipperiness of the surface of the functional layer can be improved with the use of the laminate.

[0016] B. Substrate The substrate 2 can be composed of any suitable transparent resin. Specific examples of the transparent resin include polyethylene terephthalate-based resins, polyethylene naphthalate-based resins, acetate-based resins, polyethersulfone-based resins, polycarbonate-based resins, polyamide-based resins, polyimide-based resins, polyamideimide-based resins, polyolefin-based resins, (meth)acrylic-based resins, polyvinyl chloride-based resins, polyvinylidene chloride-based resins, polystyrene-based resins, polyvinyl alcohol-based resins, polyarylate-based resins, polyphenylene sulfide-based resins. These resins can be used alone or in combination. Among the transparent resins, preferably, polyethylene terephthalate-based resins and polyimide-based resins can be mentioned. The thickness of the base material 2 is, for example, 40 μm or more, preferably 50 μm or more, and for example, 100 μm or less, preferably 80 μm or less.

[0017] C. Functional layer The functional layer 3 is appropriately provided according to the performance required according to the use of the laminate 1. The functional layer 3 is not particularly limited as long as the surface 3a of the functional layer 3 has the above-described characteristics and / or configuration. Examples of the functional layer 3 include a hard coat layer, an antireflection layer, a fingerprint-proof layer, and a conductive layer. The functional layer 3 may be a single layer or may be composed of a plurality of layers laminated.

[0018] The functional layer 3 shown in FIG. 1 is a hard coat layer 31, and the surface on the side opposite to the base material 2 in the hard coat layer 31 corresponds to the surface 3a. Typically, the hard coat layer 31 is formed by applying a coating agent for hard coat to form a coating layer and irradiating the coating layer with active energy rays (for example, ultraviolet rays) for curing. The coating agent for hard coat contains an active energy ray-curable (meth)acrylate as a base resin. Examples of the active energy ray-curable (meth)acrylate include an ultraviolet ray-curable (meth)acrylate and an electron beam-curable (meth)acrylate, and preferably an ultraviolet ray-curable (meth)acrylate. The ultraviolet ray-curable (meth)acrylate contains an ultraviolet ray-polymerizable functional group, preferably 2 or more, more preferably 3 to 6 monomer components and oligomer components. Typically, a photopolymerization initiator is blended in the ultraviolet ray-curable (meth)acrylate. The curing method may be a radical polymerization method or a cationic polymerization method. In the present specification, (meth)acrylate means acrylate and / or methacrylate.

[0019] The coating agent for hard coat may further contain any appropriate additive according to the purpose. Examples of the additive include a photopolymerization initiator, a leveling agent, an antiblocking agent, a dispersion stabilizer, a thixotropic agent, an antioxidant, an ultraviolet absorber, an antifoaming agent, a thickener, a dispersant, a surfactant, a catalyst, a filler, a lubricant, and an antistatic agent. The type, combination, content, etc. of the additive contained can be appropriately set according to the purpose and desired properties. The irradiation amount (integrated light amount) of the active energy ray (for example, ultraviolet ray) is, for example, 150 mJ / cm 2 ~400 mJ / cm 2 is. If necessary, the coating layer may be heated before irradiation with the active energy ray. The heating temperature is, for example, 70°C to 160°C. The heating time is, for example, 1 minute to 4 minutes. The thickness of the hard coat layer is, for example, 3 μm or more and 20 μm or less.

[0020] The functional layer 3 shown in FIG. 2 includes a hard coat layer 31, an antireflection layer 32 disposed on the side opposite to the base material 2 with respect to the hard coat layer 31, and an antifingerprint layer 33 disposed on the side opposite to the base material 2 with respect to the antireflection layer 32. The surface of the antifingerprint layer 33 on the side opposite to the antireflection layer 32 is located on the outermost surface of the functional layer 3 and corresponds to the surface 3a of the functional layer 3.

[0021] As the configuration of the antireflection layer 32, any appropriate configuration can be adopted. Representative configurations of the antireflection layer 32 include: (1) a single layer of a low refractive index layer with an optical film thickness of 120 nm to 140 nm and a refractive index of about 1.35 to 1.55; (2) a laminate having a medium refractive index layer, a high refractive index layer, and a low refractive index layer; (3) an alternating multilayer laminate of a high refractive index layer and a low refractive index layer.

[0022] Examples of materials that can form a low refractive index layer include silicon oxide (SiO2) and magnesium fluoride (MgF2). The refractive index of the low refractive index layer is typically about 1.35 to 1.55. Examples of materials that can form a high refractive index layer include titanium oxide (TiO2), niobium oxide (Nb2O3 or Nb2O5), tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), and ZrO2-TiO2. The refractive index of the high refractive index layer is typically about 1.60 to 2.20. Examples of materials that can form a medium refractive index layer include titanium oxide (TiO2) and a mixture of materials that can form a low refractive index layer and a high refractive index layer (for example, a mixture of titanium oxide and silicon oxide). The refractive index of the medium refractive index layer is typically about 1.50 to 1.85. The thicknesses of the low refractive index layer, the medium refractive index layer, and the high refractive index layer can be set so as to achieve an appropriate optical film thickness according to the layer structure of the antireflection layer, the desired antireflection performance, and the like.

[0023] The antireflection layer 32 is typically formed by a dry process. Specific examples of the dry process include the PVD (Physical Vapor Deposition) method and the CVD (Chemical Vapor Deposition) method. Examples of the PVD method include the vacuum evaporation method, the reactive evaporation method, the ion beam assist method, the sputtering method, and the ion plating method. Examples of the CVD method include the plasma CVD method. The dry process for forming the antireflection layer 32 is preferably the sputtering method. The thickness of the antireflection layer 32 is, for example, 20 nm to 300 nm.

[0024] As the configuration of the fingerprint prevention layer 33, any appropriate configuration can be adopted. The fingerprint prevention layer 33 typically consists of a vapor deposition film of a fluorine-containing silane compound. Examples of the fluorine-containing silane compound include an alkoxysilane compound having a perfluoropolyether group. The fingerprint prevention layer 33 is typically formed by the vapor deposition method described above, and preferably by the vacuum evaporation method. The thickness of the fingerprint prevention layer 33 is, for example, 1 nm to 50 nm.

[0025] D. Optical member with laminate and image display device The laminate described in Items A to C above can be disposed and used on the visible side of the optical member. Therefore, one embodiment of the present invention also includes an optical member with a laminate including the laminate and the optical member. The optical member is disposed on the side opposite to the functional layer with respect to the base material. Representative examples of the optical member include a polarizing plate and a retardation plate. In addition, such an optical member with a laminate can be applied to an image display device. Therefore, one embodiment of the present invention also includes an image display device using such an optical member with a laminate. The image display device typically also serves as a touch panel type input device. Representative examples of the image display device include a liquid crystal display device and an organic EL display device. The image display device according to the embodiment of the present invention typically includes the above laminate as a front panel. The image display device includes an image display panel. The image display panel includes an image display cell. Note that the image display device may be referred to as an optical display device, the image display panel may be referred to as an optical display panel, and the image display cell may be referred to as an optical display cell.

Examples

[0026] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. The measurement methods for each characteristic are as follows.

[0027] (1) Friction test As shown in FIG. 3, the laminate 1 obtained in each example and each comparative example was set in an automatic friction and wear analysis device 4 (manufactured by Kyowa Interface Science Co., Ltd., trade name TSf-503, measurement method: surface contact of the Bowden method). Specifically, the laminate 1 was horizontally disposed on a stage (not shown) of the automatic friction and wear analysis device 4 such that the surface 3a of the functional layer was the upper surface. Next, 64 μL of the following water-in-oil type emulsion was impregnated into the contact 41 (anti-con, manufactured by CONTEC Co., Ltd., product name: Anti-Con Gold Super Soak 9-inch square bulk pack (AP)) of the automatic friction and wear analysis apparatus 4, or the dry state was maintained without impregnating the water-in-oil type emulsion (none in Table 1). The material of the contact 41 is polyester fiber, and the density of the contact 41 is 23.5 g / cm 3 , and the size of the contact 41 was 1 cm in length × 1 cm in width × 0.56 mm in thickness. Also, the water-in-oil type emulsion was "Sana Smooth Main Store Emulsion NA" manufactured by NOEVIR Co., Ltd., 150 mL, and contained the following components (1) to (5). (1) Water: 85% by mass (2) Ethanol: 3.3% by mass (3) Glycerin: 3.6% by mass (4) Squalane: 2.3% by mass (5) Hexadecanol: 0.81% by mass Next, as the first step, the contact 41 (the contact 41 wetted with the water-in-oil type emulsion or the dry contact 41) was brought into contact with the surface 3a of the functional layer under a load of 200 g. Specifically, the contact 41 was held by the holder 42 of the automatic friction and wear analysis apparatus 4, sandwiched between the holder 42 and the surface 3a of the functional layer, and the contact 41 was pressed against the surface 3a of the functional layer with the above load by the holder 42. Next, as the second step, with the contact 41 pressed against the surface 3a of the functional layer, the contact 41 was moved 50 mm at a speed of 1.7 mm / s in the long side direction of the laminate 1 to measure the static friction force and the dynamic friction force of the surface 3a of the functional layer. Next, as the third step, the holder 42 was moved upward to separate the contact 41 from the surface 3a of the functional layer and return it to the initial position before the first step. Thereafter, the first step, the second step, and the third step were repeated in order 5 times, and the static friction coefficient μs of the surface 3a of the functional layer was calculated from the average value of the static friction forces of the surface 3a of the functional layer measured in the second step, and the dynamic friction coefficient μk of the surface 3a of the functional layer was calculated from the average value of the dynamic friction forces of the surface of the functional layer measured in the second step. Also, from the kinetic frictional force on the surface of the functional layer measured in the second step, the maximum friction coefficient μk max and the minimum friction coefficient μk min were calculated, and the difference μkw between the maximum friction coefficient μk max and the minimum friction coefficient μk min was calculated. Also, the ratio of the static friction coefficient μs *無 when using a dry contact to the static friction coefficient μs *乳液 when using a contact wetted with an oil-in-water type emulsion, and the ratio of the kinetic friction coefficient μk *無 when using a dry contact to the kinetic friction coefficient μk *乳液 when using a contact wetted with an oil-in-water type emulsion were calculated. The results are shown in Table 1. Furthermore, regarding the friction test results (μs, μk, μk max , μk min and μkw), the case of using a dry contact is shown in Fig. 6, and the case of using a contact wetted with an emulsion is shown in Fig. 7. Note that the environmental conditions in the friction test were 30°C and 50% RH.

[0028] (2) Surface force test As shown in Fig. 4, the laminate 1 obtained in each example and each comparative example was set in a surface force measuring device 5 (manufactured by ELIONIX, trade name ENT-NEXUS). Specifically, the laminate 1 was horizontally placed on a stage 52 of the surface force measuring device 5 such that the surface 3a of the functional layer became the upper surface. The surface force measuring device 5 includes a probe 51 having a surface layer 51a formed of polydimethylsiloxane (PDMS). The probe 51 is movable in the vertical direction. The probe 51 was obtained by subjecting a metal ball (SUJ2) with a diameter of 1 mm to ultrasonic cleaning in an organic solvent (acetone) for 10 minutes, then rinsing with pure water, ultrasonic cleaning in an aqueous solution of a neutral detergent for 10 minutes, rinsing with pure water, and then applying a one-component solvent-free de-alcoholic silicone adhesive (manufactured by Three Bond Co., silicone adhesive and sealant for electric and electronic use) which is polydimethylsiloxane to the surface of the metal ball. The surface layer 51a has elasticity, the tensile strength E' of the surface layer 51a is 2.2 MPa, and the hardness (durometer A) F' is 20. The thickness of the surface layer 51a is 1 μm. Next, as shown in Fig. 4(a), the probe 51 was placed at the initial position, and the surface 3a of the functional layer was brought into contact with the surface layer 51a without substantially applying a load. Next, as shown in Figs. 4(b) and 4(c), the probe 51 was moved in a direction away from the laminate 1 (specifically, upward) at a speed of 50 μN / s, and the absolute value of the surface force was calculated from the minimum value of the load applied to the probe 51 when the surface layer 51a separated from the surface 3a of the functional layer. The above surface force test was repeated three times (n1 to n3). The results are shown in Table 2. In addition, the environmental conditions in the surface force test were 30°C and 50% RH.

[0029] (3) Functional group quantitative measurement The laminate 1 obtained in each example and each comparative example was cut into a 10 mm square, fixed to a scanning X-ray photoelectron spectrometer (manufactured by ULVAC-PHI, trade name Quantum 2000), and then wide scan measurement was performed on the outermost surface of the sample (X-ray source: monochromatic AlKα, Xray Setting: 200 μmφ [15 kV, 30 W], photoelectron extraction angle: 45 degrees with respect to the sample surface, correction of binding energy: the peak derived from the C-C bond of the C1s spectrum was corrected to 285.0 eV, neutralization condition: combined use of a neutralization gun and an Ar ion gun (neutralization mode)), and qualitative analysis was performed. Also, for the elements shown in Table 2, narrow scan measurement was performed under the same conditions as the wide scan measurement, and the elemental ratio (atomic %) was calculated. The above functional group quantitative measurement was repeated twice (n1 and n2). The results are shown in Table 2.

[0030] (4) C1s spectrum waveform analysis For the C1s spectrum calculated in (3) above, waveform analysis was performed at the peaks shown in Table 2. In the obtained C1s spectrum, Peaks 1 to 7 shown in Table 2 were confirmed in the range of binding energy values from 280 eV to 300 eV. Based on the binding energy values, the constituent functional group components corresponding to Peaks 1 to 7 were identified as shown in Table 2. Also, the area % of each peak with respect to the total area of the peaks located in the range of 280 eV to 300 eV (the total area of Peaks 1 to 7), and the area ratio of Peak 6 to the area of Peak 7 are shown in Table 2.

[0031] (5) Sliding property test As shown in Fig. 5(a), the laminate 1 obtained in each example and each comparative example after the above friction test was set in a sliding property test apparatus 6 (manufactured by Ogawa Seiki Co., Ltd., trade name 10-pen tester). Specifically, the laminate 1 was horizontally placed on a stage (not shown) of the sliding property test apparatus 6 such that the surface 3a of the functional layer was the upper surface. The sliding property test apparatus 6 includes a contactor 61 formed of a rubber material (manufactured by minoan, trade name RUBBER STICK, product code 4004005007) and a holder 62 for holding the contactor 61. Next, the surface 3a of the functional layer was wetted with the above water-in-oil emulsion, and the contactor 61 was brought into contact with the surface 3a of the functional layer under a load of 2 kg. Next, with the contactor 61 pressed against the surface 3a of the functional layer, it was reciprocated 1000 times in a range of 50 mm at a speed of 66.7 mm / s in the long side direction of the laminate 1. The environmental conditions in the slidability test were 25°C and 50% RH. Next, as shown in Fig. 5(b), the laminate 1 after the slidability test was set in the automatic friction and wear analysis device 4 so that the contactor 41 contacted the sliding trace 61a, and in the same manner as the above friction test, the static friction coefficient μs, kinetic friction coefficient μk, and maximum friction coefficient μk max and minimum friction coefficient μk min of the surface 3a of the functional layer after the slidability test were calculated. The differences Δμs in the static friction coefficient, Δμk in the kinetic friction coefficient, Δμk max in the maximum friction coefficient, and Δμk min in the minimum friction coefficient, and Δμkw are shown in Table 3. Also, the friction test results (Δμs, Δμk, Δμk max , Δμk min and Δμkw) before and after the slidability test are shown in Fig. 8.

[0032] [Example 1] [Preparation of Coating Agent A for Hard Coating] 100 parts by mass of a polyfunctional acrylate (manufactured by Aica Kogyo Co., Ltd., trade name Z-850-27ALL) as a base resin, 0.5 parts by mass of a leveling agent (manufactured by DIC Corporation, trade name GRANDIC PC-4100), and 3.9 parts by mass of a photopolymerization initiator (manufactured by Ciba Japan Co., Ltd., trade name Irgacure 907) were mixed and diluted with methyl isobutyl ketone so that the solid content concentration became 40% by mass, thereby preparing a coating agent A for hard coating. [Preparation of Coating Agent B for Hard Coating] 100 parts by mass of a polyfunctional acrylate (manufactured by Aica Kogyo Co., Ltd., trade name Z-850-16ALL) as a base resin, 0.15 parts by mass of a leveling agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KY-1203), and 3 parts by mass of a photopolymerization initiator (manufactured by Ciba Japan Co., Ltd., trade name Irgacure 127) were mixed and diluted with methyl isobutyl ketone so that the solid content concentration became 50% by mass, thereby preparing a coating agent B for a hard coat. <Fabrication of laminate> On one side of a transparent polyimide film (manufactured by KOLON Co., Ltd., trade name CPITMC_80, thickness 80 μm) as a base material, coating agent A was applied to form a coating layer, and the coating layer was heated at 120 °C for 1 minute together with the transparent polyimide film. Next, ultraviolet rays were irradiated onto the coating layer using a high-pressure mercury lamp with an integrated light quantity of 200 mJ / cm 2 to form a hard coat layer (HC) A as a functional layer. The thickness of the hard coat layer A was 5 μm. Next, coating agent B was applied onto the hard coat layer A to form a coating layer, and the coating layer was heated at 85 °C for 1 minute together with the transparent polyimide film. Then, ultraviolet rays were irradiated onto the coating layer using a high-pressure mercury lamp with an integrated light quantity of 250 mJ / cm 2 to form a hard coat layer (HC) B. The thickness of the hard coat layer B was 5 μm. Thus, a laminate including a transparent polyimide film (base material), and hard coat layers A and B was fabricated.

[0033] [Example 2] <Fabrication of laminate> On one side of a polyethylene terephthalate (PET) film (manufactured by Toray Industries, Inc., trade name 50U48, thickness 50 μm) as a base material, a coating agent A for a hard coat was applied to form a coating film. Next, after this coating film was dried by heating, it was cured 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, ultraviolet rays with a wavelength of 365 nm were used, and the integrated irradiation light quantity was 300 mJ / cm 2It was thus formed a hard coat layer (HC) with a thickness of 5 μm on the PET film. Next, the surface of the HC layer of the PET film with the HC layer was plasma-treated in a vacuum atmosphere of 1.0 Pa by a roll-to-roll type plasma processing apparatus. In this plasma treatment, argon gas was used as an inert gas, and the discharge power was set to 780 W. Next, an antireflection layer was formed on the HC layer of the PET film with the HC layer after plasma treatment. Specifically, by a roll-to-roll type sputtering film forming apparatus, a 2.0 nm thick indium tin oxide (ITO) layer as an adhesion layer and a 165 nm thick SiO2 layer as an inorganic oxide underlayer were sequentially formed on the HC layer of the PET film with the HC layer. In the formation of the adhesion layer, an ITO target was used, argon gas as an inert gas and oxygen gas as a reactive gas in a volume ratio of 10 parts per 100 parts by volume of argon gas were used, the discharge voltage was set to 350 V, the atmospheric pressure in the film forming chamber (film forming atmospheric pressure) was set to 0.4 Pa, and the ITO layer was formed by MFAC sputtering. In the formation of the inorganic oxide underlayer, 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, the film forming atmospheric pressure was set to 0.3 Pa, and the SiO2 layer was formed by MFAC sputtering. Next, a fingerprint-proof layer was formed on the antireflection layer. Specifically, a 6 nm thick fingerprint-proof layer was formed on the inorganic oxide underlayer by a vacuum evaporation method using a perfluoropolyether group-containing alkoxysilane compound as an evaporation source. The evaporation source was a solid content obtained by drying "KY1903-1" (perfluoropolyether group-containing alkoxysilane compound, solid content concentration 20 mass%) manufactured by Shin-Etsu Chemical Co., Ltd. Further, the heating temperature of the evaporation source in the vacuum evaporation method was set to 260 °C. By the above, a laminate including a PET film (base material), a hard coat layer, an antireflection layer (adhesion layer and inorganic oxide underlayer), and a fingerprint-proof layer was produced.

[0034] [Comparative Example 1] [Preparation of Coating Agent C for Hard Coat] A resin solution (manufactured by DIC Corporation, trade name: Unidic 17-806, solid content concentration: 80% by mass) in which a mixture of an ultraviolet-curable resin monomer and oligomer mainly composed of urethane acrylate is dissolved in butyl acetate was added with 5 parts by mass of a photoinitiator (manufactured by BASF Corporation, trade name: IRGACURE 906) and 0.01 part of a leveling agent (manufactured by DIC Corporation, trade name: Grandic PC4100) per 100 parts by mass of the solid content in the solution. Cyclopentanone and propylene glycol monomethyl ether were added to the above mixture solution at a ratio of 45:55 so that the solid content concentration in the above solution became 36% by mass. Thus, a coating agent C for hard coat was prepared. <Fabrication of laminate> Next, the hard coat coating agent C was applied onto a transparent plastic film substrate (cellulose triacetate film, manufactured by Konica Minolta Advanced Layer, trade name: KC4UY, thickness: 40 μm, refractive index: 1.48) as a substrate to form a coating film such that the thickness of the cured hard coat layer (HC) became 7.8 μm. Then, it was dried at 90 °C for 1 minute, and thereafter, irradiated with ultraviolet rays having an integrated light amount of 300 mJ / cm 2 to cure the above coating film. Through the above steps, a laminate comprising a cellulose triacetate film (substrate) and a hard coat layer was fabricated.

[0035] [Comparative Example 2] <Preparation of antiglare layer forming material> As the resin contained in the anti-glare layer forming material, 100 parts by weight of an ultraviolet curable urethane acrylate resin (manufactured by DIC Corporation, trade name Unidic 17-806, solid content 80% by mass) was prepared. Per 100 parts by mass of the resin solid content of the resin, 14 parts by mass of styrene crosslinked particles (manufactured by Soken Chemical & Engineering Co., Ltd., trade name MX-350H, weight average particle diameter 3.5 μm, refractive index 1.59) as anti-glare layer forming particles, 2.5 parts by mass of synthetic smectite (manufactured by Kunimine Industries Co., Ltd., trade name Smecton SAN) which is an organic viscosity as a thixotropy imparting agent, 5 parts by weight of a photoinitiator (manufactured by BASF Corporation, trade name OMNIRAD 907), and 0.5 parts by weight of a leveling agent (manufactured by DIC Corporation, trade name Megafac F-556, solid content 100% by mass) were mixed. This mixture was diluted with a toluene / ethyl acetate mixed solvent (weight ratio 90 / 10) so that the solid content concentration became 30% by mass to prepare an anti-glare layer forming material (coating liquid). <Fabrication of laminate> Next, a transparent plastic film substrate (TAC film, manufactured by Fujifilm Corporation, trade name TG60UL, thickness 60 μm) was prepared as the substrate. On one side of the transparent plastic film substrate, an anti-glare layer forming material (coating liquid) was used to form a coating film using a bar coater. Then, the transparent plastic film substrate on which this coating film was formed was conveyed to a drying process. In the drying process, the coating film was dried by heating at 110 °C for 1 minute. Thereafter, ultraviolet rays with an integrated light amount of 300 mJ / cm 2 were irradiated with a high-pressure mercury lamp to cure the coating film and form an anti-glare layer with a thickness of 5.0 μm. As described above, a laminate including a TAC film (substrate) and an anti-glare layer was fabricated.

[0036]

Table 1

[0037]

Table 2

[0038]

Table 3

Industrial Applicability

[0039] The laminate of the present invention can be suitably used for an optical member with a laminate, an image display device (typically, a liquid crystal display device, an organic EL display device).

Explanation of Signs

[0040] 1 Laminate 2 Base material 3 Functional layer 3a Surface of the functional layer 4 Automatic friction and wear analysis device 41 Contact 5 Surface force measuring device 51 Probe 51a Surface layer 6 Sliding property test device

Claims

1. a base material; and a functional layer disposed on one side in the thickness direction of the base material, wherein the functional layer includes a hard coat layer, the thickness of the hard coat layer is 3 μm or more and 20 μm or less, in the following friction test by surface contact of the Boudouard method, the static friction coefficient and the dynamic friction coefficient of the surface of the functional layer measured using a contactor wetted with an oil-in-water emulsion containing the following components (1) to (5) are both 0.11 or less, the carbon element ratio on the surface of the functional layer is 50 atomic% or less, the fluorine element ratio on the surface of the functional layer is 30 atomic% or more, a laminate: (1) 80% by mass or more and 90% by mass or less of water (2) 2% by mass or more and 5% by mass or less of ethanol (3) 2% by mass or more and 5% by mass or less of glycerin (4) 2% by mass or more and 5% by mass or less of squalane (5) 0.5% by mass or more and 1% by mass or less of hexadecanol (Friction test) Set the laminate in an automatic friction and wear analysis device; As a first step, bring the contactor into contact with the surface of the functional layer with a load of 200 g; As a second step, move the contactor at a speed of 1.7 mm / s for 50 mm to measure the static frictional force and the dynamic frictional force on the surface of the functional layer; As a third step, separate the contactor from the surface of the functional layer and return it to the initial position; Repeat the first step, the second step, and the third step in order 5 times, calculate the static friction coefficient of the surface of the functional layer from the static frictional force on the surface of the functional layer, and calculate the dynamic friction coefficient of the surface of the functional layer from the dynamic frictional force on the surface of the functional layer.

2. The laminate according to claim 1, wherein the absolute value of the surface force of the laminate measured by the following surface force test is 110 μN or less: (Surface force test) Set the laminate in a surface force measuring device equipped with a probe having a surface layer formed of polydimethylsiloxane; Place the probe at the initial position and bring the surface of the functional layer into contact with the surface layer; Next, move the probe in a direction away from the laminate, and calculate the absolute value of the surface force of the laminate from the minimum value of the load applied to the probe when the surface layer separates from the surface of the functional layer.

3. In the C1s spectrum measured by X-ray photoelectron spectroscopy of the surface of the functional layer, the total area of the peaks located in the range of 293 eV to 295 eV is 30 area% or more with respect to the total area of the peaks located in the range of 280 eV to 300 eV, The area of the peak located in the range of 293 eV to 294 eV is 1.5 or more and 2.5 or less with respect to the area of the peak located in the range of 294 eV to 295 eV. The laminate according to claim 1 or 2.

4. The absolute value of the difference in the static friction coefficient before and after the following slidability test and the absolute value of the difference in the kinetic friction coefficient before and after the following slidability test are both 0.01 or less. The laminate according to any one of claims 1 to 3: (Slidability test) Set the laminate in a slidability test apparatus; Wet the surface of the functional layer with the water-in-oil type emulsion, and bring a contact made of a rubber material into contact with the surface of the functional layer under a load of 2 kg; Next, reciprocate the contact 1000 times within a range of 50 mm at a speed of 66.7 mm / s.

5. The kinetic friction coefficient before the slidability test is greater than the kinetic friction coefficient after the slidability test. The laminate according to claim 4.

6. The functional layer includes an anti-fingerprint layer located on the outermost surface of the functional layer, The anti-fingerprint layer is composed of a vapor deposition film of a fluorine-containing silane compound. The laminate according to any one of claims 1 to 5.

7. The laminate according to any one of claims 1 to 6, and An optical member disposed on the side opposite to the functional layer with respect to the substrate. An optical member with a laminate.

8. An image display device including the laminate according to any one of claims 1 to 6 as a front panel.

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