Stacked body, optical member with stacked body, and image display device

Abstract

The present application provides a laminate capable of achieving excellent slidability regardless of whether or not a user's finger is wetted with water, an optical member with the laminate, and an image display device. The laminate of the embodiment of the present application has a substrate and a functional layer disposed on one side in the thickness direction of the substrate, and the static friction coefficient and the kinetic friction coefficient of the functional layer surface measured using a contact wetted with water are both 0.13 or less in a specific friction test based on a Bowden method of surface contact.

Description

Technical Field

[0001] This invention relates to laminates, optical components with laminates, and image display devices. Background Technology

[0002] Image display devices that also function as touch panel input devices, such as smartphones and tablet PCs, are becoming increasingly common. These image display devices typically utilize laminates that include functional layers appropriate to their intended use. For example, a hard coating film with a hard coating layer provided on one side of a transparent substrate film is known (e.g., Patent Document 1).

[0003] In recent years, the usage environments for image display devices that also function as touch panel input devices have become more diverse. For example, smartphones are sometimes used while showering or immediately after washing hands, and users may operate the smartphone with wet fingers.

[0004] However, if the hard coating described in Patent Document 1 is used on the front panel of an image display device, the improvement in finger gliding is limited both when the user's finger is wet and when the user's finger is not wet, raising concerns that the operability of the image display device may become insufficient.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent No. 5157819 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] The present invention was made to solve the above-mentioned existing problems. Its main objective is to provide a laminate, an optical component with a laminate, and an image display device that can achieve excellent gliding performance regardless of whether the user's fingers are wet or not.

[0010] Problem Solving Methods

[0011] The laminate according to an embodiment of the present invention comprises: a substrate and a functional layer disposed on one side of the substrate in the thickness direction. In the following friction test based on Bowden's method for surface contact, the static friction coefficient and dynamic friction coefficient of the surface of the functional layer, measured using a water-wetted contact, are both 0.13 or less.

[0012] (Friction test)

[0013] The aforementioned laminate is placed in an automatic tribological analysis device. As a first step, the contact is brought into contact with the surface of the functional layer under a load of 200g. As a second step, the contact is moved 50mm at a speed of 1.7mm / s, and the static and dynamic friction forces on the surface of the functional layer are measured. As a third step, the contact is separated from the surface of the functional layer and returned to its initial position. The first, second, and third steps are repeated 5 times in sequence. The static friction coefficient of the functional layer surface is calculated based on the static friction force, and the dynamic friction coefficient of the functional layer surface is calculated based on the dynamic friction force.

[0014] In one embodiment, the absolute value of the surface force of the above-mentioned laminate, as measured by the surface force test described below, is 110 μN or less.

[0015] (Surface force test)

[0016] The aforementioned laminate is placed in a surface force measuring device equipped with a probe having a surface layer formed of polydimethylsiloxane. The probe is positioned in an initial position so that the surface of the functional layer contacts the surface layer. If the probe contacts the functional layer, in the case of a highly adhesive substance such as polydimethylsiloxane, a phenomenon occurs where the probe is pulled downwards upon contact (wetting). The moment when this wetting occurs is used as a reference for determining whether the sample has made contact with the probe. Next, after setting the probe's pull-in displacement to zero, the probe is moved away from the laminate, and the absolute value of the surface force of the laminate is calculated based on the minimum load applied to the probe when the surface layer leaves the surface of the functional layer.

[0017] In one embodiment, the carbon content on the surface of the functional layer is 50 atomic% or less, and the fluorine content on the surface of the functional layer is 30 atomic% or more.

[0018] In one embodiment, in the C1s spectrum obtained by measuring the surface of the functional layer by X-ray photoelectron spectroscopy analysis, the total area of ​​the peaks in the range of 293 eV to 295 eV is more than 30% of the total area of ​​the peaks in the range of 280 eV to 300 eV, and the area of ​​the peaks in the range of 293 eV to 294 eV is more than 1.5 and less than 2.5 of the area of ​​the peaks in the range of 294 eV to 295 eV.

[0019] In one embodiment, the absolute value of the difference between the static friction coefficients before and after the sliding test and the absolute value of the difference between the dynamic friction coefficients before and after the sliding test are both 0.03 or less.

[0020] (Sliding test)

[0021] The above-mentioned laminate is placed in a sliding test apparatus; the surface of the functional layer is wetted with water, and a contact made of rubber material is brought into contact with the surface of the functional layer with a load of 2 kg; next, the contact is moved back and forth 1000 times within a range of 50 mm at a speed of 66.7 mm / s.

[0022] In one embodiment, the coefficient of dynamic friction before the sliding test is greater than the coefficient of dynamic friction after the sliding test.

[0023] In one embodiment, the functional layer includes an anti-fingerprint layer located on the outermost surface of the functional layer, which is formed by vapor deposition of a fluorinated silane compound.

[0024] Another aspect of the present invention provides an optical component with a laminate, comprising: the laminate and an optical component disposed on the side of the substrate opposite to the functional layer.

[0025] In another aspect, the image display device of the present invention includes the above-described laminate as a front panel.

[0026] The effects of the invention

[0027] According to embodiments of the present invention, excellent glide is achieved regardless of whether the user's fingers are wet or not. Attached Figure Description

[0028] Figure 1 This is a cross-sectional schematic diagram of a laminated body according to one embodiment of the present invention.

[0029] Figure 2 This is a cross-sectional schematic diagram of a laminated body according to another embodiment of the present invention.

[0030] Figure 3 This is an explanatory diagram used to illustrate friction tests.

[0031] Figure 4 (a)~ Figure 4 (c) is an explanatory diagram used to illustrate the surface force test. Figure 4 (a) shows the state with the probe positioned in the initial position. Figure 4 (b) shows the state in which the probe is moved upward from its initial position. Figure 4 (c) shows the state in which the probe's surface layer leaves the surface of the functional layer.

[0032] Figure 5 (a) and Figure 5 (b) is an explanatory diagram used to illustrate the sliding test. Figure 5 (a) shows the state in which the contact moves back and forth. Figure 5(b) shows the friction test after the sliding test.

[0033] Figure 6 It is a graph showing the results (coefficient of friction) of a friction test using dry contacts.

[0034] Figure 7 It is a graph showing the results (coefficient of friction) of a friction test using contacts that were wetted with water.

[0035] Figure 8 It is a graph showing the difference in the coefficient of friction before and after the use of water in the sliding test.

[0036] Symbol Explanation

[0037] 1. Layered body

[0038] 2. Substrate

[0039] 3. Functional Layer

[0040] Surface of functional layer 3a

[0041] 4 Automatic Friction and Wear Analysis Device

[0042] 41 Contacts

[0043] 5. Surface force measuring device

[0044] 51 probes

[0045] 51a Surface layer

[0046] 6. Sliding test apparatus Detailed Implementation

[0047] The following describes representative embodiments of the present invention, but the present invention is not limited to these embodiments.

[0048] A. Overall composition of the laminated structure

[0049] Figure 1 This is a cross-sectional schematic diagram of a laminated body according to one embodiment of the present invention; Figure 2 This is a cross-sectional schematic diagram of a laminate according to another embodiment of the present invention; Figure 3 This is an explanatory diagram used to illustrate friction tests.

[0050] The laminate 1 shown in the figure includes a substrate 2 and a functional layer 3 disposed on one side of the substrate 2 in the thickness direction. The surface 3a of the functional layer 3 opposite to the substrate 2 is located on the outermost surface of the laminate 1.

[0051] In the following friction test of surface contact based on the Bowden method, the static friction coefficient and dynamic friction coefficient of the surface 3a of the functional layer of the laminate 1, measured using a water-wetted contact, are both 0.13 or less, preferably 0.11 or less.

[0052] (Friction test)

[0053] The laminate 1 is placed in the automatic tribological analysis device 4. As a first step, the contact 41 is brought into contact with the surface 3a of the functional layer under a load of 200g. As a second step, the contact 41 is moved 50mm at a speed of 1.7mm / s, and the static and dynamic friction forces on the surface 3a of the functional layer are measured. As a third step, the contact 41 is separated from the surface 3a of the functional layer and returned to its initial position. The first, second, and third steps are repeated five times. The static friction coefficient of the surface 3a of the functional layer is calculated based on the static friction force, and the dynamic friction coefficient of the surface 3a of the functional layer is calculated based on the dynamic friction force. It should be noted that detailed information regarding the friction test will be provided in the embodiments described later.

[0054] For such a laminate, the static friction coefficient (hereinafter denoted as μs) of the functional layer surface measured using a water-wetted contact in the above friction test is... ＊水 ) and the coefficient of kinetic friction (hereinafter denoted as μk) ＊水 All values ​​are below the aforementioned upper limit. Therefore, excellent glide performance is achieved even when the user's fingers are wet. It should be noted that μs... ＊水 and μk ＊水 Their respective lower limits are representatively above 0.05.

[0055] Additionally, representatively, the static friction coefficient (hereinafter denoted as μs) of the surface 3a of the functional layer, obtained by measuring with a dry contact in the above friction test, is... ＊无 ) and the coefficient of kinetic friction (hereinafter denoted as μk) ＊无 The μs values ​​are all below 0.15, preferably below 0.13, and more preferably below 0.11. Therefore, excellent glide properties can be achieved even when the user's fingers are not wet. It should be noted that μs... ＊无 and μk ＊无 Their respective lower limits are representatively above 0.05.

[0056] In one implementation, μs ＊水 Relative to μs ＊无 The ratio (μs) ＊水 / μs ＊无 For example, it is 0.7 or more, preferably 0.8 or more, and for example, 1.3 or less, preferably 1.2 or less. μs ＊水 / μs＊无 When the above range is met, even if the user's fingers are wet, the same level of gliding performance can be achieved stably as if the fingers were not wet.

[0057] In one implementation, μk ＊水 Relative to μk ＊无 The ratio (μk) ＊水 / μk ＊无 For example, it is 0.7 or more, preferably 0.8 or more, and for example, 1.4 or less, preferably 1.3 or less. μk ＊水 / μk ＊无 When the above range is met, even if the user's fingers are wet, the same level of gliding stability can be achieved as if the fingers were not wet.

[0058] Figure 4 (a)~ Figure 4 (c) is an explanatory diagram used to illustrate the surface force test.

[0059] In one embodiment, the absolute value of the surface force of the laminate 1, as measured by the surface force test described below, is 110 μN or less, preferably 105 μN or less.

[0060] (Surface force test)

[0061] A laminate 1 is placed on a surface force measuring device 5 equipped with a probe 51, the probe 51 having a surface layer 51a formed of polydimethylsiloxane; the probe 51 is positioned in an initial position such that the surface 3a of the functional layer contacts the surface layer 51a; next, the probe 51 is moved away from the laminate 1, and the absolute value of the surface force of the laminate is calculated based on the minimum value of the load applied to the probe 51 when the surface layer 51a is away from the surface 3a of the functional layer. It should be noted that details regarding the surface force test will be described in the embodiments described later.

[0062] When the surface force of the laminate 1 measured by the above surface force test is below the upper limit, the static friction coefficient and dynamic friction coefficient of the functional layer surface can be stably adjusted to the above range. It should be noted that the absolute value of the surface force of the laminate is representatively 80 μN or more.

[0063] In one embodiment, the carbon content of the surface 3a of the functional layer is 50 atomic percent or less, preferably 40 atomic percent or less, and the fluorine content of the surface 3a of the functional layer is 30 atomic percent or more. The elemental ratios of the surface of the functional layer can be determined by X-ray photoelectron spectroscopy (ESCA). It should be noted that details regarding the determination of the elemental ratios will be described in the embodiments described later.

[0064] When the carbon element ratio of the surface 3a of the functional layer is below the aforementioned upper limit and the fluorine element ratio is above the aforementioned lower limit, the static friction coefficient and dynamic friction coefficient of the functional layer surface can be more stably adjusted to the aforementioned range. It should be noted that the carbon element ratio of the surface 3a of the functional layer is typically 20 atomic% or more, and the fluorine element ratio is typically 50 atomic% or less.

[0065] Furthermore, the nitrogen content of the surface 3a of the functional layer is, for example, less than 1.5 atomic%, preferably less than 1.3 atomic%, and for example, more than 0 atomic%. When the nitrogen content of the surface 3a of the functional layer is below the above-mentioned upper limit, the static friction coefficient and dynamic friction coefficient of the functional layer surface can be more stably adjusted to the above-mentioned range.

[0066] In one embodiment, in the C1s spectrum obtained by measuring the surface 3a of the functional layer using X-ray photoelectron spectroscopy, the total area of ​​peaks in the 293 eV–295 eV range is 30% or more of the total area of ​​peaks in the 280 eV–300 eV range, and the area of ​​peaks in the 293 eV–294 eV range is 1.5 or more and 2.5 or less of the area of ​​peaks in the 294 eV–295 eV range. It should be noted that details regarding the analysis of the C1s spectral waveform will be explained in the embodiments described later.

[0067] When the area ratio of peaks in the 293 eV–295 eV range in the C1s spectrum is above the lower limit mentioned above, and the area of ​​peaks in the 293 eV–294 eV range divided by the area of ​​peaks in the 294 eV–295 eV range falls within the range mentioned above, the static and dynamic friction coefficients of the functional layer surface can be adjusted to the ranges mentioned above more stably. It should be noted that the area ratio of peaks in the 293 eV–295 eV range in the C1s spectrum is typically 80 atomic percent or less.

[0068] Figure 5 (a) and Figure 5 (b) is an explanatory diagram used to illustrate the sliding test.

[0069] In one embodiment, the absolute value of the difference between the static friction coefficients before and after the sliding test and the absolute value of the difference between the dynamic friction coefficients before and after the sliding test are both 0.03 or less, preferably 0.02 or less.

[0070] (Sliding test)

[0071] The laminate 1 is placed on the sliding test device 6; the surface 3a of the functional layer is wetted with water, and a contact 61 made of rubber material is brought into contact with the surface 3a of the functional layer with a load of 2 kg; next, the contact 61 is moved back and forth 1000 times within a range of 50 mm at a speed of 66.7 mm / s.

[0072] Then, the contact 41 of the automatic friction and wear analysis device 4 is moistened with water, and the above-mentioned friction test is carried out.

[0073] When the absolute values ​​of the differences in static and dynamic friction coefficients before and after the sliding test are below the aforementioned upper limit, excellent sliding properties of the functional layer surface can be sufficiently ensured even when using a laminate and rubbing the surface of the functional layer with a finger or similar object. It should be noted that the absolute values ​​of the differences in static and dynamic friction coefficients before and after the sliding test are representatively greater than or equal to 0.0010.

[0074] Furthermore, the coefficient of kinetic friction before the sliding test is preferably greater than the coefficient of kinetic friction after the sliding test. Based on this configuration, the sliding properties of the functional layer surface can be improved with the use of the laminate.

[0075] B. Substrate

[0076] The substrate 2 can be composed of any suitable transparent resin. Specific examples of transparent resins include polyethylene terephthalate resins, polyethylene naphthalate resins, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyamide-imide resins, polyolefin resins, (meth)acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, polyarylate resins, and polyphenylene sulfide resins. These resins can be used alone or in combination.

[0077] Among transparent resins, polyethylene terephthalate resins and polyimide resins are preferred examples.

[0078] 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.

[0079] C. Functional Layer

[0080] The functional layer 3 is appropriately provided according to the required performance corresponding to the application of the laminate 1. There are no particular limitations as long as the surface 3a of the functional layer 3 has the aforementioned characteristics and / or configuration.

[0081] Examples of functional layer 3 include: a hard coating layer, an anti-reflective layer, an anti-fingerprint layer, and a conductive layer. Functional layer 3 can be a single layer or multiple layers stacked together.

[0082] Figure 1 The functional layer 3 shown is a hard coating 31, and the surface of the hard coating 31 on the side opposite to the substrate 2 corresponds to surface 3a.

[0083] The hard coating 31 can be typically formed as follows: a hard coating agent is applied to form a coating layer, and then the coating layer is irradiated with active energy rays (e.g., ultraviolet light) to cure it. The hard coating agent contains an active energy ray-curable (meth)acrylate as a base resin. Examples of active energy ray-curable (meth)acrylates include, for example, ultraviolet-curable (meth)acrylates and electron beam-curable (meth)acrylates, with ultraviolet-curable (meth)acrylates being preferred. The ultraviolet-curable (meth)acrylate contains ultraviolet-curable monomers, oligomers, polymers, etc. The ultraviolet-curable (meth)acrylate contains monomer components and oligomer components, preferably having two or more, more preferably having three to six ultraviolet-polymerizing functional groups. Typically, a photopolymerization initiator is incorporated into the ultraviolet-curable (meth)acrylate. The curing method can be free radical polymerization or cationic polymerization. It should be noted that, in this specification, (meth)acrylate refers to acrylates and / or methacrylates.

[0084] Hard coatings may further contain any suitable additives depending on the purpose. Examples of additives include: photopolymerization initiators, leveling agents, antiblocking agents, dispersing stabilizers, thixotropic agents, antioxidants, UV absorbers, defoamers, tackifiers, dispersants, surfactants, catalysts, fillers, lubricants, and antistatic agents. The types, combinations, and amounts of these additives can be appropriately determined based on the purpose and desired characteristics.

[0085] The cumulative light intensity (cumulative light intensity) of exposure to active energy rays (such as ultraviolet rays) is, for example, 150 mJ / cm². 2 ~400mJ / cm 2 If necessary, the coating layer can be heated before irradiation with active energy rays. The heating temperature is, for example, 70°C to 160°C, and the heating time is, for example, 1 minute to 4 minutes.

[0086] The thickness of the hard coating is, for example, greater than 3 μm and less than 20 μm.

[0087] Figure 2 The functional layer 3 shown includes: a hard coating layer 31, an anti-reflective layer 32 disposed on the side of the hard coating layer 31 opposite to the substrate 2, and an anti-fingerprint layer 33 disposed on the side of the anti-reflective layer 32 opposite to the substrate 2. The surface of the anti-fingerprint layer 33 opposite to the anti-reflective layer 32 is located at the outermost surface of the functional layer 3, which corresponds to the surface 3a of the functional layer 3.

[0088] As a component of the antireflective layer 32, any suitable configuration can be adopted. Representative configurations of the antireflective layer 32 include: (1) a single layer of low refractive index layer with an optical film thickness of 120nm to 140nm and a refractive index of about 1.35 to 1.55; (2) a stack of layers having a medium refractive index layer, a high refractive index layer and a low refractive index layer; and (3) a multilayer stack of alternating high refractive index layer and low refractive index layer.

[0089] Examples of materials suitable for forming low-refractive-index layers include silicon oxide (SiO2) and magnesium fluoride (MgF2). The refractive index of a low-refractive-index layer is typically around 1.35 to 1.55. Examples of materials suitable for forming high-refractive-index layers include titanium oxide (TiO2), niobium oxide (Nb2O3 or Nb2O5), indium tin oxide (ITO), tin oxide (ATO), and ZrO2-TiO2. The refractive index of a high-refractive-index layer is typically around 1.60 to 2.20. Examples of materials suitable for forming medium-refractive-index layers include titanium oxide (TiO2) and mixtures of materials suitable for forming low-refractive-index layers and materials suitable for forming high-refractive-index layers (e.g., a mixture of titanium oxide and silicon oxide). The refractive index of a medium-refractive-index layer is typically around 1.50 to 1.85. The thicknesses of the low-refractive-index, medium-refractive-index, and high-refractive-index layers can be set to achieve appropriate optical film thicknesses corresponding to the layer structure of the anti-reflective layer and the desired anti-reflective performance.

[0090] The antireflective layer 32 is typically formed using a dry process. Specific examples of dry processes include PVD (Physical Vapor Deposition) and CVD (Chemical Vapor Deposition). Examples of PVD methods include vacuum evaporation, reactive evaporation, ion beam assisted deposition, sputtering, and ion plating. Examples of CVD methods include plasma CVD. The preferred dry process for forming the antireflective layer 32 is sputtering.

[0091] The thickness of the anti-reflective layer 32 is, for example, 20 nm to 300 nm.

[0092] The anti-fingerprint layer 33 can be any suitable composition. The anti-fingerprint layer 33 is typically formed by the vapor deposition of a fluorinated silane compound. Examples of fluorinated silane compounds include alkoxysilane compounds having a perfluoropolyether group. The anti-fingerprint layer 33 is typically formed by the vapor deposition method described above, preferably by vacuum vapor deposition.

[0093] The thickness of the anti-fingerprint layer 33 is, for example, 1nm to 50nm.

[0094] D. Optical components and image display devices with stacked structures

[0095] The laminates described in items A through C above can be disposed on the visible side of an optical component for use. Therefore, one embodiment of the present invention also includes an optical component with a laminate and an optical component. The optical component is disposed on the side of the substrate opposite to the functional layer. Representative examples of optical components include polarizers and retardation plates.

[0096] Furthermore, such laminated optical components can be applied to image display devices. Therefore, one embodiment of the present invention also includes an image display device using such laminated optical components. The image display device typically also functions as a touch panel type input device. Examples of image display devices include liquid crystal displays and organic EL displays. The image display device of the embodiment of the present invention typically includes the aforementioned laminated structure as a front panel. The image display device includes an image display panel. The image display panel includes image display units. It should be noted that sometimes an image display device is referred to as an optical display device, sometimes an image display panel is referred to as an optical display panel, and sometimes an image display unit is referred to as an optical display unit.

[0097] Example

[0098] The present invention will now be specifically described through examples, but the present invention is not limited to these examples. It should be noted that the methods for measuring each characteristic are as follows.

[0099] (1) Friction test

[0100] like Figure 3 As shown, the laminate 1 obtained in each embodiment and comparative example is placed in an automatic tribology analysis apparatus 4 (manufactured by Kyowa Interface Science Co., Ltd., trade name TSf-503, measurement method: Bowden method for surface contact). Specifically, the laminate 1 is horizontally arranged on a stage (not shown) of the automatic tribology analysis apparatus 4 with the surface 3a of the functional layer as the upper surface.

[0101] Next, immerse 64 μL of water into the contact 41 (Anticon, CONTEC, trade name Anticanon Gold Super Sorb, 9 inches square, bulk (AP)) of the automatic tribological analysis device 4, or keep it dry without water immersion (none in Table 1). The contact 41 is made of polyester fiber with a density of 23.5 g / cm³. 3 The dimensions of contact 41 are 1cm in length × 1cm in width × 0.56mm in thickness.

[0102] Next, as the first step, the contact 41 (whether wetted or dry) is brought into contact with the surface 3a of the functional layer under a load of 200g. Specifically, the contact 41 is held by the retainer 42 of the automatic tribological analysis device 4, the contact 41 is clamped between the retainer 42 and the surface 3a of the functional layer, and the contact 41 is pressed against the surface 3a of the functional layer under the aforementioned load via the retainer 42.

[0103] Next, as the second step, the contact 41 was moved 50 mm along the long side of the laminate 1 at a speed of 1.7 mm / s while being pressed against the surface 3a of the functional layer, and the static and dynamic friction forces on the surface 3a of the functional layer were measured.

[0104] Next, as the third step, the retainer 42 is moved upward, causing the contact 41 to separate from the surface 3a of the functional layer and return to its initial position before the first step.

[0105] Then, the first, second and third processes are repeated 5 times in sequence. The static friction coefficient μs of the functional layer surface 3a is calculated based on the average static friction force measured in the second process. The dynamic friction coefficient μk of the functional layer surface 3a is calculated based on the average dynamic friction force measured in the second process.

[0106] In addition, the maximum coefficient of friction μk is calculated based on the dynamic friction force on the surface of the functional layer measured in the second process. max and minimum friction coefficient μk min The maximum friction coefficient μk was calculated. max With minimum friction coefficient μk min The difference is μkw.

[0107] In addition, the static friction coefficient μs was calculated when a water-wetted contact was used. ＊水 The static friction coefficient μs relative to the case of using dry contacts ＊无 The ratio, and the coefficient of dynamic friction μk when using water-wetted contacts. ＊水 The coefficient of dynamic friction μk relative to the case where dry contacts are used ＊无 The ratios are shown in Table 1.

[0108] Furthermore, regarding the friction test results (μs, μk, μk...) max μk min (and μkw), showing the case where dry contacts were used. Figure 6 The case of using water-wetted contacts is shown. Figure 7 .

[0109] It should be noted that the environmental conditions for the friction test were 30℃ and 50% RH.

[0110] (2) Surface force test

[0111] like Figure 4 As shown, the laminate 1 obtained in each embodiment and comparative example is placed on the surface force measuring device 5 (manufactured by ELIONIX Corporation, trade name ENT-NEXUS). Specifically, the laminate 1 is horizontally arranged on the stage 52 of the surface force measuring device 5 with the surface 3a of the functional layer as the upper surface. The surface force measuring device 5 includes a probe 51, which has a surface layer 51a formed of polydimethylsiloxane (PDMS). The probe 51 is movable in the vertical direction. A metal ball (SUJ2) with a diameter of 1 mm was ultrasonically cleaned in an organic solvent (acetone) for 10 minutes, then rinsed with pure water, ultrasonically cleaned in a neutral detergent aqueous solution for 10 minutes, and rinsed with pure water. After cleaning in the above order, a one-component solvent-free de-alcoholized silicone adhesive of polydimethylsiloxane (manufactured by Three Bond Corporation, silicone adhesive sealant for electrical / electronic use) was applied to the surface of the metal ball to make the probe 51. The surface layer 51a is elastic, with a tensile strength E′ of 2.2 MPa and a hardness (A hardness tester) F′ of 20. The thickness of the surface layer 51a is 1 μm.

[0112] Next, as Figure 4 As shown in (a), the probe 51 is positioned in the initial position, and the surface 3a of the functional layer contacts the surface layer 51a without applying a load.

[0113] Next, as Figure 4 (b) and Figure 4 As shown in (c), the probe 51 is moved at a speed of 50 μN / s in a direction away from the laminate 1 (specifically upwards), and the absolute value of the surface force is calculated based on the minimum value of the load applied to the probe 51 when the surface layer 51a leaves the surface 3a of the functional layer.

[0114] The surface force test was repeated 3 times (n1 to n3), and the results are shown in Table 2.

[0115] It should be noted that the environmental conditions for the surface force test are 30℃ and 50%RH.

[0116] (3) Quantitative determination of functional groups

[0117] The laminates 1 obtained in each embodiment and comparative example were cut into 10 mm squares, fixed in a scanning X-ray photoelectron spectroscopy apparatus (ULVAC-PHI, trade name Quantum 2000), and a 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 relative to the sample surface, bond energy correction: the peak from the C1s bond in the C1s spectrum was corrected to 285.0 eV, neutralization conditions: a combination of a neutralization gun and an Ar ion gun (neutralization mode)). Qualitative analysis was performed. Additionally, for the elements shown in Table 2, narrow-scan measurements were performed under the same conditions as the wide-scan measurements, and the elemental ratios (atomic %) were calculated.

[0118] The above functional group quantitative determination was repeated twice (n1 and n2), and the results are shown in Table 2.

[0119] (4) C1s spectral waveform analysis

[0120] The C1s spectrum calculated in (3) above was analyzed using the peaks shown in Table 2.

[0121] In the obtained C1s spectra, peaks 1 to 7, shown in Table 2, were identified in the bonding energy range of 280 eV to 300 eV. Based on the bonding energy values, the constituent functional groups corresponding to peaks 1 to 7 were identified as shown in Table 2. Furthermore, Table 2 shows the percentage of area of ​​each peak relative to the sum of the areas of the peaks in the 280 eV to 300 eV range (the sum of the areas of peaks 1 to 7), and the ratio of the area of ​​peak 6 to the area of ​​peak 7.

[0122] (5) Sliding test

[0123] like Figure 5 As shown in (a), the laminate 1 obtained in each embodiment and comparative example after the above friction test is placed in the sliding test apparatus 6 (manufactured by Ogawa Seiki Co., Ltd., trade name 10-pen tester). Specifically, the laminate 1 is horizontally arranged on the stage (not shown) of the sliding test apparatus 6 with the surface 3a of the functional layer as the upper surface. The sliding test apparatus 6 includes a contact 61 (manufactured by Minoan Co., Ltd., trade name RUBBERSTICK, product code 4004005007) made of rubber material and a retainer 62 for retaining the contact 61.

[0124] Next, the surface 3a of the functional layer is moistened with water, and the contact 61 is brought into contact with the surface 3a of the functional layer under a load of 2 kg.

[0125] Next, with the contact 61 pressed against the surface 3a of the functional layer, the contact is moved back and forth 1000 times along the long side of the laminate 1 at a speed of 66.7 mm / s over a range of 50 mm. It should be noted that the environmental conditions for the sliding test are 25°C and 50% RH.

[0126] Next, as Figure 5 As shown in (b), the laminate 1 after the sliding test is placed in the automatic friction and wear analysis device 4, and the contact 41 is brought into contact with the sliding mark 61a. The static friction coefficient μs, dynamic friction coefficient μk, and maximum friction coefficient μk of the surface 3a of the functional layer after the sliding test are calculated in the same manner as in the friction test described above. max and minimum friction coefficient μk min The differences in static friction coefficients (Δμs), dynamic friction coefficients (Δμk), and maximum friction coefficients (Δμk) before and after the sliding test are calculated. max The difference in minimum friction coefficient Δμk min And Δμkw are shown in Table 3.

[0127] In addition, the friction test results (Δμs, Δμk, Δμk) before and after the sliding test will be compared. max Δμk min and Δμkw) are shown in Figure 8 .

[0128] [Example 1]

[0129] <Preparation of Hard Coating Agent A>

[0130] 100 parts by weight of a multifunctional acrylate (manufactured by Aica Kogyo Co., Ltd., trade name Z-850-27ALL) as the base resin, 0.5 parts by weight of a leveling agent (manufactured by DIC Co., Ltd., trade name GRANDIC PC-4100) and 3.9 parts by weight of a photopolymerization initiator (manufactured by Ciba Japan Co., Ltd., trade name IRGACURE 907) were mixed and diluted with methyl isobutyl ketone to achieve a solid content of 40% by weight, thus preparing a hard coating agent A.

[0131] <Preparation of Hard Coating Agent B>

[0132] 100 parts by weight of a multifunctional acrylate (manufactured by Aica Kogyo Co., Ltd., trade name Z-850-16ALL) as the base resin, 0.15 parts by weight of a leveling agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KY-1203) and 3 parts by weight of a photopolymerization initiator (manufactured by Ciba Japan Co., Ltd., trade name IRGACURE 127) were mixed and diluted with methyl isobutyl ketone to achieve a solid content of 50% by weight, thus preparing a hard coating agent B.

[0133] <Creating Layered Bodies>

[0134] A coating layer was formed by applying coating agent A to one side of a transparent polyimide film (manufactured by KOLON, trade name CPITMC_80, thickness 80 μm) as the substrate. The coating layer and the transparent polyimide film were then heated at 120°C for 1 minute. Next, a high-pressure mercury lamp was used to accumulate a light intensity of 200 mJ / cm². 2 The coating layer was irradiated with ultraviolet light, thereby forming a hard coating (HC)A as a functional layer. The thickness of hard coating A is 5 μm.

[0135] Next, coating agent B was applied onto the hard coating layer A to form a coating layer. The coating layer, together with the transparent polyimide film, was heated at 85°C for 1 minute. Next, a high-pressure mercury lamp was used to accumulate a light intensity of 250 mJ / cm². 2 The coating layer was irradiated with ultraviolet light, thereby forming a hard coating layer (HC)B. The thickness of the hard coating layer B is 5 μm.

[0136] Through the above operations, a laminate containing a transparent polyimide film (substrate) and hard coatings A and B was produced.

[0137] [Example 2]

[0138] <Creating Layered Bodies>

[0139] A coating was formed by applying a hard coating agent A to one side of a polyethylene terephthalate (PET) film (manufactured by Toray Industries, Inc., trade name 50U48, thickness 50 μm) as the substrate. Next, the coating was dried by heating and then cured by ultraviolet (UV) irradiation. The heating temperature was set to 90°C and the heating time was set to 60 seconds. For UV irradiation, a high-pressure mercury lamp was used as the light source, and UV light with a wavelength of 365 nm was used, with a cumulative irradiation dose set to 300 mJ / cm². 2 This resulted in a 5μm thick hard coating (HC) being formed on the PET film.

[0140] Next, the surface of the HC layer of the PET film with the HC layer was subjected to plasma treatment in a vacuum atmosphere of 1.0 Pa using a roll-to-roll plasma treatment apparatus. In this plasma treatment, argon gas, which is an inert gas, was used, and the discharge power was set to 780 W.

[0141] Next, an anti-reflective layer was formed on the HC layer of the plasma-treated PET film. Specifically, using a roll-to-roll sputtering apparatus, a 2.0 nm thick indium tin oxide (ITO) layer as an adhesive layer and a 165 nm thick SiO2 layer as an inorganic oxide substrate were sequentially formed on the HC layer of the PET film with the HC layer. For the adhesive layer formation, an ITO target was used, along with argon as an inert gas and 10 parts by volume of oxygen as a reactive gas relative to 100 parts by volume of argon. The discharge voltage was set to 350 V, and the gas pressure in the deposition chamber (deposition pressure) was set to 0.4 Pa. The ITO layer was formed by MFAC sputtering. For the inorganic oxide substrate layer formation, a Si target was used, along with 100 parts by volume of argon and 30 parts by volume of oxygen. The discharge voltage was set to 350 V, and the deposition pressure was set to 0.3 Pa. The SiO2 layer was formed by MFAC sputtering.

[0142] Next, an anti-fingerprint layer was formed on the anti-reflective layer. Specifically, a 6 nm thick anti-fingerprint layer was formed on an inorganic oxide substrate using a vacuum evaporation method with a perfluoropolyether-based alkoxysilane compound as the evaporation source. The evaporation source was a solid component obtained by drying "KY1903-1" (containing a perfluoropolyether-based alkoxysilane compound, with a solid content concentration of 20% by mass) manufactured by Shin-Etsu Chemical Industry Co., Ltd. Furthermore, the heating temperature of the evaporation source in the vacuum evaporation method was set to 260°C.

[0143] Through the above operations, a laminate containing a PET film (substrate), a hard coating, an anti-reflective layer (sealing layer and inorganic oxide base layer) and an anti-fingerprint layer was produced.

[0144] [Comparative Example 1]

[0145] <Preparation of Hard Coating Agent C>

[0146] In a resin solution (DIC Corporation, trade name UNIDIC 17-806, solids concentration 80% by mass) obtained by dissolving a mixture of UV-curable resin monomers and oligomers with urethane acrylate as the main component in butyl acetate, 5 parts by mass of a photopolymerization initiator (BASF Corporation, trade name IRGACURE 906) and 0.01 parts by mass of a leveling agent (DIC Corporation, trade name GRANDIC PC4100) were added relative to 100 parts by mass of the solids content of the solution. Cyclopentanone and propylene glycol monomethyl ether were added to the above compound solution at a ratio of 45:55, so that the solids concentration of the above solution reached 36% by mass. This produced a hard coating agent C.

[0147] <Creating Layered Bodies>

[0148] Next, a hard coating agent C was applied to a transparent plastic film substrate (cellulose triacetate film, manufactured by Konica Minolta Advanced Layer Co., Ltd., trade name KC4UY, thickness 40 μm, refractive index 1.48) to form a coating film, resulting in a cured hard coating layer (HC) thickness of 7.8 μm. The film was then dried at 90°C for 1 minute, followed by irradiation with a high-pressure mercury lamp accumulating a light intensity of 300 mJ / cm². 2 The coating was cured by ultraviolet light.

[0149] Through the above operations, a laminate containing a cellulose triacetate film (substrate) and a hard coating was produced.

[0150] [Comparative Example 2]

[0151] <Preparation of Anti-glare Layer Forming Material>

[0152] As the resin contained in the anti-glare layer forming material, 100 parts by weight of UV-curable urethane acrylate resin (manufactured by DIC Corporation, trade name UNIDIC 17-806, solid content 80% by mass) were prepared. Relative to the resin solid content of 100 parts by mass of the above resin, 14 parts by mass of styrene crosslinked particles (manufactured by Soken Chemical Co., Ltd., trade name MX-350H, weight average particle size 3.5 μm, refractive index 1.59) as anti-glare layer forming particles were mixed in; 2.5 parts by mass of synthetic montmorillonite (manufactured by Kunimine Industries CO.,LTD., trade name Smekton SAN) as a thixotropic agent; 5 parts by weight of a photopolymerization initiator (manufactured by BASF Corporation, trade name OMNIRAD907); and 0.5 parts by weight of a leveling agent (manufactured by DIC Corporation, trade name Megafac F-556, solid content 100% by mass). The mixture was diluted with a toluene / ethyl acetate mixed solvent (weight ratio 90 / 10) to achieve a solid component concentration of 30% by mass, thus preparing an anti-glare layer forming material (coating solution).

[0153] <Creating Layered Bodies>

[0154] Next, a transparent plastic film substrate (TAC film, manufactured by Fujifilm Corporation, trade name TG60UL, thickness 60μm) was prepared as the base material. An anti-glare coating material (coating liquid) was applied to one side of the transparent plastic film substrate using a bar coater. The transparent plastic film substrate with this coating was then transported to a drying process. In the drying process, the coating was dried by heating at 110°C for 1 minute. Then, it was irradiated with a high-pressure mercury lamp with a cumulative light intensity of 300 mJ / cm². 2The coating is cured by ultraviolet light, forming an anti-glare layer with a thickness of 5.0 μm.

[0155] Through the above operations, a laminate containing a TAC film (substrate) and an anti-glare layer was produced.

[0156] [Table 1]

[0157]

[0158] [Table 2]

[0159]

[0160] [Table 3]

[0161]

[0162] Industrial applicability

[0163] The laminate of the present invention can be suitably used in optical components and image display devices (representatively liquid crystal display devices and organic EL display devices) with laminates.

Claims

1. A laminated body, comprising: Substrate, and A functional layer disposed on one side of the substrate in the thickness direction. The carbon content on the surface of the functional layer is less than 50 atomic percent. The fluorine content on the surface of the functional layer is above 30 atomic% and below 41.8 atomic%. In the following friction test based on Bowden's method for surface contact, the static and dynamic coefficients of friction of the functional layer surface, measured using a water-wetted contact, were both below 0.

13. Friction test: The laminated body is placed in an automatic friction and wear analysis device; As a first step, the contactor is brought into contact with the surface of the functional layer under a load of 200g; As a second step, the contact is moved 50 mm at a speed of 1.7 mm / s, and the static and dynamic friction forces on the surface of the functional layer are measured. As a third step, the contact is separated from the surface of the functional layer and returned to its initial position; The first, second, and third steps are repeated five times in sequence. The static friction coefficient of the functional layer surface is calculated based on the static friction force, and the dynamic friction coefficient of the functional layer surface is calculated based on the dynamic friction force.

2. The laminated body according to claim 1, wherein, The absolute value of the surface force of the laminate, as measured by the following surface force test, is less than 110 μN. Surface force test: The laminate is disposed on a surface force measuring device having a probe, the probe having a surface layer formed of polydimethylsiloxane; The probe is positioned at an initial position so that the surface of the functional layer contacts the surface layer; Next, the probe is moved away from the stack, and the absolute value of the surface force of the stack is calculated based on the minimum load applied to the probe when the surface layer leaves the surface of the functional layer.

3. The laminated body according to claim 1, wherein, In the C1s spectrum obtained by measuring the surface of the functional layer using X-ray photoelectron spectroscopy analysis. The total area of ​​peaks located in the 293eV~295eV range is more than 30% of the total area of ​​peaks located in the 280eV~300eV range. The area of ​​the peak located in the 293eV~294eV range is greater than 1.5 and less than 2.5 compared to the area of ​​the peak located in the 294eV~295eV range.

4. The laminate according to any one of claims 1 to 3, wherein, The absolute values ​​of the differences in static friction coefficients before and after the following sliding tests, and the absolute values ​​of the differences in kinetic friction coefficients before and after the following sliding tests, are both less than 0.

03. Sliding test: The laminate is placed in the sliding test device; Wet the surface of the functional layer with water, and apply a 2kg load to bring a contact made of rubber material into contact with the surface of the functional layer. Next, the contact is moved back and forth 1000 times within a 50mm range at a speed of 66.7mm / s.

5. The laminated body according to claim 4, wherein, The coefficient of dynamic friction before the sliding test is greater than the coefficient of dynamic friction after the sliding test.

6. The laminate according to any one of claims 1 to 3, wherein, The functional layer includes an anti-fingerprint layer located on the outermost surface of the functional layer. The anti-fingerprint layer is formed by vapor deposition of a fluorinated silane compound.

7. An optical component with a stacked body, comprising: The laminate according to any one of claims 1 to 6, and An optical component disposed on the side of the substrate opposite to the functional layer.

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

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