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

Abstract

To provide a laminate that, even if a user's finger is wet with any liquid, can satisfy sliding properties equivalent to those when the user's finger is not wet, 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. Both a static friction coefficient and a dynamic friction coefficient on a surface of the functional layer are 0.05 or more to 0.15 or less as measured in a specific friction test carried out through Bowden surface contact, using a contact element selected from the group consisting of dry contact elements, contact elements that are wet with water, contact elements that are wet with synthetic sweat stipulated in JIS L 0848, and contact elements that are wet with oil-in-water emulsions 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 surface 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, the opportunities to use smartphones in environments such as during sports, cooking, bathing, or immediately after using cosmetics such as lotions and creams have increased, and there are cases where the smartphone is operated with the user's finger wet with a liquid such as water, sweat, or oil. However, when the hard coat film described in Patent Document 1 is used for the front panel of an image display device, there is a problem that the slipperiness of the finger when the user's finger is wet with a liquid is different from the slipperiness of the finger when the user's finger is not wet, which affects the operability of the image display device.

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-described conventional problems, and its main object is to provide a laminate, an optical member with a laminate, and an image display device that can satisfy the same slipperiness as when the user's finger is not wet even when the user's finger is wet with a liquid.

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 Baudin method, the static friction coefficient and the dynamic friction coefficient of the surface of the functional layer measured using a contact selected from the group consisting of a dry contact, a contact wetted with water, a contact wetted with artificial sweat defined in JIS L 0848, and a contact wetted with an oil-in-water emulsion containing the following components (1) to (5) are both 0.05 or more and 0.15 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 contact into contact with the surface of the above functional layer with a load of 200 g; as a second step, move the above contact 50 mm at a speed of 1.7 mm / s to measure the static frictional force and the dynamic frictional force on the surface of the above functional layer; as a third step, separate the above contact from the surface of the above 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 above functional layer from the static frictional force on the surface of the above functional layer, and calculate the dynamic friction coefficient of the surface of the above functional layer from the dynamic frictional force on the surface of the above 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. Then, after setting the displacement amount of the pulled-in probe to zero, then 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 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. 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 0.03 or less. (Slidability test) Set the laminate on a slidability test device; wet the surface of the functional layer with one kind of liquid selected from the group consisting of water, the artificial sweat, and the water-in-oil emulsion, and bring a contactor formed of a rubber material into contact with the surface of the functional layer under 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 dynamic friction coefficient before the slidability test is larger than the dynamic 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 base material. 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, even when the user's finger is wet with liquid, it can satisfy the same slipperiness as when the finger is not wet.

Brief Description of the Drawings

[0007]

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DETAILED DESCRIPTION OF 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 view 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 selected from the group consisting of a dry contactor, a contactor wetted with water, a contactor wetted with artificial sweat defined in JIS L 0848, and a contactor wetted with an oil-in-water emulsion containing the following components (1) to (5) are both 0.05 or more and 0.15 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 mass% or more and 1 mass% or less of hexadecanol (Friction test) Set laminate 1 in the automatic friction and wear analysis device 4; as the first step, bring the above-mentioned 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 dynamic friction force of 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 coefficient of static friction of the surface 3a of the functional layer from the static friction force of the surface 3a of the functional layer, and calculate the coefficient of dynamic friction 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, regardless of which contact selected from the group consisting of a dry contact, a contact wet with water, a contact wet with artificial sweat, and a contact wet with the above water-in-oil emulsion is used, the coefficient of static friction and the coefficient of dynamic friction of the surface of the functional layer are within the above ranges. Therefore, even if the user's finger is wet with a liquid, it can satisfy the same slipperiness as when the finger is not wet.

[0010] In one embodiment, in the above friction test, the coefficient of static friction of the surface of the functional layer measured using a contact wet with the above liquid (any one of water, artificial sweat, and water-in-oil emulsion) (hereinafter, μs *液体 is denoted as follows.) and the coefficient of dynamic friction (hereinafter, μk *液体 is denoted as follows.) The upper limits of each are 0.13 or less, preferably 0.11 or less. If each of μs *液体 and μk *液体 is below the above upper limit, excellent slipperiness can be realized when the user's finger is wet with the above liquid (any one of water, artificial sweat, and water-in-oil emulsion). Note that the lower limits of each of μs *液体 and μk *液体 are typically 0.05 or more. In one embodiment, in the above friction test, the coefficient of static friction of the surface of the functional layer measured using a dry contact (hereinafter, μs *無Let it be μs.) with respect to *液体 The ratio of μs *液体 / μs *無 ) is, for example, 0.7 or more, preferably 0.8 or more, more preferably 0.9 or more, and for example, 1.4 or less, preferably 1.3 or less, more preferably 1.2 or less, and particularly preferably 1.1 or less. μs *液体 / μs *無 If μs / μs is within the above range, even if the user's finger is wet with the above liquid (any one of water, artificial sweat, and water-in-oil emulsion), the same slipperiness as when the finger is not wet can be stably achieved. In one embodiment, the coefficient of kinetic friction of the surface of the functional layer measured using a dried contact in the above friction test (hereinafter, μk *無 Let it be.) with respect to μk *液体 The ratio of μk *液体 / μk *無 ) is, for example, 0.7 or more, preferably 0.8 or more, more preferably 0.9 or more, and for example, 1.4 or less, preferably 1.3 or less, more preferably 1.2 or less. If μk / μk *液体 / μk *無 is within the above range, even if the user's finger is wet with the above liquid (any one of water, artificial sweat, and water-in-oil emulsion), the same slipperiness as when the finger is not wet can be even more stably achieved.

[0011] Also, hereinafter, when distinguishing μs *液体 according to the type of liquid, the coefficient of static friction of the surface of the functional layer measured using a contact wetted with water is μs *水 , the coefficient of static friction of the surface of the functional layer measured using a contact wetted with artificial sweat is μs *人工汗液 , and the coefficient of static friction of the surface of the functional layer measured using a contact wetted with water-in-oil emulsion is μs *乳液 Let it be. Also, when distinguishing μk *液体 according to the type of liquid, the coefficient of kinetic friction of the surface of the functional layer measured using a contact wetted with water is μk *水 , the coefficient of kinetic friction of the surface of the functional layer measured using a contact wetted with artificial sweat is μk *人工汗液Let the coefficient of kinetic friction of the surface of the functional layer measured using a contactor wetted with an oil-in-water emulsion be μk *乳液 Let it be so.

[0012] Figs. 4(a) to 4(c) are explanatory diagrams for explaining the surface force test. In one embodiment, the absolute value of the surface force measured by the following surface force test of the laminate 1 is 110 μN or less, preferably 105 μN or less. (Surface force test) Set the laminate 1 in a surface force measuring device 5 including a probe 51 having a 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 coefficient of static friction and the coefficient of kinetic friction of the surface of the functional layer can be stably adjusted within the above-described ranges. Note that 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 element ratio on the surface of the functional layer can be measured by X-ray photoelectron spectroscopy (ESCA). Details of the element ratio measurement will be described in the examples described later. If the carbon element ratio on the surface 3a of the functional layer is equal to or less than the above upper limit and the fluorine element ratio is equal to or more than the above lower limit, the coefficient of static friction and the coefficient of kinetic friction of the surface of the functional layer can be adjusted more stably within the above-described ranges. Note that the carbon element ratio on the surface 3a of the functional layer is typically 20 atomic% or more, and the fluorine element ratio is typically 50 atomic% or less. Further, 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, 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 the dynamic friction coefficient of 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 of 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 at 293 eV to 294 eV / the area of the peak at 294 eV to 295 eV is within the above range, the static friction coefficient and the dynamic friction coefficient of the surface of the functional layer can be adjusted more stably within the above ranges. Note that the area ratio of the peaks located in the range of 293 eV to 295 eV in the C1s spectrum is typically 80 atomic % or less.

[0015] FIG. 5(a) and FIG. 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 0.03 or less, preferably 0.02 or less. (Slidability test) The laminate 1 is set in the slidability test apparatus 6; the surface 3a of the functional layer is wetted with one kind of liquid selected from the group consisting of water, the above artificial sweat, and the above water-in-oil emulsion, and the contactor 61 formed of a rubber material is brought into contact with the surface 3a of the functional layer with a load of 2 kg; then, the contactor 61 is reciprocally moved 1000 times in a range of 50 mm at a speed of 66.7 mm / s. Thereafter, using the same liquid as the liquid that wets the surface 3a of the functional layer, the contact 41 of the automatic friction and wear analysis device 4 is wetted, and the above friction test is carried out. When the absolute value of the difference in the static friction coefficient (using the same liquid) before and after the slidability test and the absolute value of the difference in the dynamic friction coefficient (using the same liquid) are equal to or less than the above upper limit, even if the laminated body 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 slidability test are typically 0.0001 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 laminated body.

[0016] B. Substrate The substrate 2 can be made 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 are mentioned. The thickness of the substrate 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 for the application of the laminated body 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 prevention layer, and a conductive layer. The functional layer 3 may be a single layer or may be composed of a plurality of layers laminated together.

[0018] The functional layer 3 shown in FIG. 1 is a hard coat layer 31, and the surface of the hard coat layer 31 on the side opposite to the base material 2 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 ultraviolet ray-curable (meth)acrylate and electron beam-curable (meth)acrylate, and preferably, ultraviolet ray-curable (meth)acrylate. The ultraviolet ray-curable (meth)acrylate contains ultraviolet ray-polymerizable functional groups, preferably two 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 this 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 thickening agent, a dispersant, a surfactant, a catalyst, a filler, a lubricant, and an antistatic agent. The type, combination, content, etc. of the additives contained can be appropriately set according to the purpose and desired properties. The irradiation amount (integrated light amount) of the active energy rays (for example, ultraviolet rays) is, for example, 150 mJ / cm 2 ~400 mJ / cm 2It is so. If necessary, the coating layer may be heated before irradiation with active energy rays. 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 a fingerprint prevention layer 33 disposed on the side opposite to the base material 2 with respect to the antireflection layer 32. The surface of the fingerprint prevention 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 having 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 the 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 the 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 the medium refractive index layer include titanium oxide (TiO2) and a mixture of a material that can form a low refractive index layer and a material that can form 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 above-described vapor deposition method, 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 on the viewing side of the optical member and used. 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 placed 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 liquid shown in Table 1 was impregnated into a contact 41 (Anticon, manufactured by CONTEC Co., Ltd., trade name Anticon Gold Super Soak 9-inch square bulk pack (AP)) of the automatic friction and wear analysis device 4, or the dry state was maintained without impregnating the liquid (none in Table 1). The material of the contact 41 is polyester fiber, 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. In addition, the water-in-oil type emulsion shown in Table 1 was manufactured by NOEVIA Co., Ltd., trade name Sana Smooth Main Store Emulsion NA 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 contactor 41 (the wet contactor 41 or the dry contactor 41 shown in Table 1) was brought into contact with the surface 3a of the functional layer under a load of 200 g. Specifically, the contactor 41 was held by the holder 42 of the automatic friction and wear analysis apparatus 4, and the contactor 41 was sandwiched between the holder 42 and the surface 3a of the functional layer, and the contactor 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 contactor 41 pressed against the surface 3a of the functional layer, it 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 frictional force and the dynamic frictional force of the surface 3a of the functional layer. Next, as the third step, the holder 42 was moved upward to separate the contactor 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 frictional force 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 frictional force of the surface of the functional layer measured in the second step. Also, from the dynamic frictional force of 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 when using a wet contactor to the static friction coefficient μs when using a dry contactor, and the ratio of the dynamic friction coefficient μk when using a wet contactor to the dynamic friction coefficient μk when using a dry contactor were calculated. The results are shown in Table 1. *無 with respect to the static friction coefficient μs when using a wet contactor, *水、人工汗液、乳液 and the ratio of the dynamic friction coefficient μk when using a wet contactor to the dynamic friction coefficient μk when using a dry contactor *無 were calculated. The results are shown in Table 1. *水、人工汗液、乳液 The results are shown in Table 1. Furthermore, regarding the friction test results (μs, μk, μk max , μk min and μkw), the case using a dry contactor is shown in Fig. 6, the case using a contactor wet with water is shown in Fig. 7, the case using a contactor wet with artificial sweat is shown in Fig. 8, and the case using a contactor wet with an emulsion is shown in Fig. 9. 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 was 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 ultrasonically cleaning a metal ball (SUJ2) with a diameter of 1 mm in an organic solvent (acetone) for 10 minutes, then rinsing with pure water, ultrasonically 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-alcohol type silicone adhesive (manufactured by Three Bond Co., silicone adhesive 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 the 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. 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 10 mm squares, 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, X-ray 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 carried out. 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 Waveform analysis was performed on the C1s spectrum calculated in (3) above using 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 ratio of the area 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 of the above-described examples and comparative examples after the friction test was set in a slidability 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 slidability test apparatus 6 such that the surface 3a of the functional layer was the upper surface. The slidability test apparatus 6 includes a contact 61 formed of a rubber material (manufactured by minoan Co., Ltd., trade name: RUBBER STICK, product code: 4004005007) and a holder 62 for holding the contact 61. Next, the surface 3a of the functional layer was wetted with the liquid shown in Table 3 (water, the above artificial sweat, or the above water-in-oil emulsion), and the contact 61 was brought into contact with the surface 3a of the functional layer under a load of 2 kg. Next, with the contact 61 pressed against the surface 3a of the functional layer, the contact 61 was reciprocally moved 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 an automatic friction and wear analysis apparatus 4 such that the contact 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, Δμk, Δμk max in the static friction coefficient, Δμk min in the minimum friction coefficient, and Δμkw are shown in Table 3. Also, regarding the friction test results (Δμs, Δμk, Δμk max , Δμk min and Δμkw) before and after the slidability test, the case of using water is shown in Fig. 10, the case of using artificial sweat is shown in Fig. 11, and the case of using an emulsion is shown in Fig. 12.

[0032] [Example 1] [Preparation of Coating Agent A for Hard Coating] 100 parts by mass of a polyfunctional acrylate as a base resin (manufactured by Aica Kogyo Co., Ltd., trade name Z-850-27ALL), 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 coat. <Preparation of Coating Agent B for Hard Coat> 100 parts by mass of a polyfunctional acrylate as a base resin (manufactured by Aica Kogyo Co., Ltd., trade name Z-850-16ALL), 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 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. Next, 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> A coating agent A for hard coat was applied to one side of a polyethylene terephthalate (PET) film (manufactured by Toray Industries, Inc., trade name 50U48, thickness 50 μm) as a substrate to form a coating film. Next, this coating film was dried by heating and then 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 light with a wavelength of 365 nm was used, and the integrated irradiation light amount was 300 mJ / cm 2 2. Thus, a hard coat layer (HC) with a thickness of 5 μm was formed 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 using a roll-to-roll type plasma treatment apparatus. In this plasma treatment, argon gas was used as an inert gas and the discharge power was 780 W. Next, an antireflection layer was formed on the HC layer of the PET film with the HC layer after the plasma treatment. Specifically, 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 using a roll-to-roll type sputtering film formation apparatus. 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 an amount of 10 parts by volume with respect to 100 parts by volume of argon gas were used, the discharge voltage was 350 V, the pressure in the film formation chamber (film formation pressure) was 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 350 V, the film formation pressure was 0.3 Pa, and the SiO2 layer was formed by MFAC sputtering. Next, an anti-fingerprint layer was formed on the anti-reflection layer. Specifically, a 6-nm-thick anti-fingerprint layer was formed on the inorganic oxide underlayer by a vacuum deposition method using a perfluoropolyether group-containing alkoxysilane compound as a deposition source. The deposition source was the 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. Also, the heating temperature of the deposition source in the vacuum deposition method was set to 260°C. Thus, a laminate including a PET film (substrate), a hard coat layer, an anti-reflection layer (adhesion layer and inorganic oxide underlayer), and an anti-fingerprint layer was produced.

[0034] [Comparative Example 1] <Preparation of Coating Agent C for Hard Coat> To 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 was dissolved in butyl acetate, 5 parts by mass of a photoinitiator (manufactured by BASF Corporation, trade name: IRGACURE906) and 0.01 part of a leveling agent (manufactured by DIC Corporation, trade name: GRANDIC PC4100) were added 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, coating agent C for hard coat was produced. <Production of Laminate> Next, coating agent C for hard coat 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, the coating film was cured by irradiating ultraviolet rays with an integrated light amount of 300 mJ / cm 2 thereof. Thus, a laminate including a cellulose triacetate film (substrate) and a hard coat layer was produced.

[0035] [Comparative Example 2] <Preparation of Anti-Glare 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: Smeton SAN) having an organic viscosity as a thixotropy imparting agent, 5 parts by weight of a photopolymerization initiator (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 solution). <Production 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 solution) 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 produced.

[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 measurement 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 according to the Bauden method, the static friction coefficient and the dynamic friction coefficient of the surface of the functional layer measured using a contact selected from the group consisting of a dried contact, a contact wetted with water, a contact wetted with artificial sweat defined in JIS L 0848, and a contact wetted with an oil-in-water emulsion containing the following components (1) to (5) are both 0.05 or more and 0.15 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 contact into contact with the surface of the functional layer with a load of 200 g; As a second step, move the contact 50 mm at a speed of 1.7 mm / s to measure the static frictional force and the dynamic frictional force on the surface of the functional layer; As a third step, separate the contact 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 including 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 is separated 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 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, 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 0.03 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 one liquid selected from the group consisting of water, the artificial sweat, and the water-in-oil 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; Then, 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 larger 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, 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.

Images