TW201202740A - Antireflective films comprising microstructured surface - Google Patents

Abstract

The present invention concerns antireflective films comprising a high refractive index layer and low refractive index layer disposed on the high refractive index layer. The antireflective films have a microstructured surface that can be derived from a microreplicated tool.

Description

201202740 VI. Description of the Invention: [Technical Field] The present invention relates to an antireflection film comprising a high refractive index layer and a low refractive index layer on the high refractive index layer, the antireflection film having a derivable The microstructure surface of the microreplication tool. [Prior Art] Different matt films (also known as anti-glare films) have been described. The matte film can be fabricated to have alternating layers of high and low refractive index. The matte film exhibits low gloss and antireflection. However, in the absence of alternating high and low refractive index layers, the film will exhibit anti-glare properties but will not exhibit anti-reflective properties. As described in paragraph 0039 of US 2007/0286994, matte anti-reflective films are generally It has lower transmittance and higher turbidity than the equivalent gloss film. The turbidity is generally at least 5%, 7%, 8%, 9%, or 1% by weight as measured according to ASTM D1003. For example, according to ASTM D 245'〇3 at 6〇. As measured below, other glossy surfaces typically have a gloss of at least 13 inches, while the non-glossy surface has a gloss of less than 120. There are several ways to obtain a matt film. For example, a matt coating is prepared as described in US 6,778,240. In addition, by adding matt particles

Prepared by providing high and low refractive index layers.

. According to U.S. Patent No. 5,82, 957, 156,113, doc 201202740, "Non-limiting examples of textured materials or surfaces that can be imparted to the antireflective film by any textured material, surface or method include: matt Processed film or microfilm, micro-imprinted film, micro-reproducing tool containing the desired texture pattern or template, sleeve or ribbon, roller (such as metal or rubber roller) or rubber-coated newspaper tube . SUMMARY OF THE INVENTION The present invention is directed to an antireflective film comprising a high refractive index layer and a low refractive index layer on the high refractive index layer. The antireflective film has a microstructured surface that can be derived from a microreplication tool. In certain embodiments, the microstructured surface comprises a plurality of microstructures having a complementary cumulative slope size distribution such that at least 30% of the microstructures have a slope size of at least 0.7 degrees and at least 25% of the microstructures have less than 13 degrees The slope size. In another embodiment, the antireflective film is characterized by a transparency of less than 9% by weight and an average surface roughness (Ra) of at least G.G5 microns and no greater than 〇14 microns. In another embodiment, the antireflective film is characterized by a transparency of less than 9% by weight and an average maximum surface height of at least 0.50 microns and no greater than 微米.μm (Rzp in another embodiment, the antireflective film The transparency is characterized by less than 9% by weight and the microstructured layer comprises a peak having an average equivalent diameter of at least 5 microns and no greater than 30 microns. In certain embodiments, the antireflective film is free of embedded matt particles. In other embodiments, no more than 50% of the microstructures comprise embedded 156113.doc 201202740 glossy particles. The antireflective film generally has at least itit brightness and no more than 10% turbidity.骐 has an average photopic reflectance of less than 2% in the wavelength range of 5 〇〇 (10) to (2) (10). In certain embodiments, at least 3 〇 %, at least 35%, or at least 4 〇 % of the microstructure has less than 1.3. The slope of the degree. In some embodiments, less than 15%, or less than 1%, or less than 5% of the microstructure has a slope size of 4.1 degrees or greater. In addition, at least 7% of the micro The structure has a slope size of at least 〇3 degrees. In embodiments having low "bright spots", the microstructures include peaks having an average equivalent circular diameter (ECD) of at least 5 microns or at least 丨〇 microns. Furthermore, the average ECD of the peaks is generally less than 3 microns or Less than 25 microns. In some embodiments 'the microstructure comprises a peak having an average length of at least 5 microns or at least 10 microns. Further, the average width of the microstructure peaks is typically at least 5 microns. In some embodiments, The average width of the iso peaks is less than 丨5 μm. In other embodiments, high refractive index compositions and low refractive index compositions are described as being capable of producing the antireflective films described herein from the compositions. A matte (i.e., anti-glare) film and an anti-reflective film are described. Referring to Figure 1A, a matte film 1 includes a microstructured high refractive index (e.g., viewing surface) layer 6 generally disposed on a light transmissive (e.g., film) substrate 50. The substrate 5 and the matte or antireflective film generally have a transmittance of at least 85°, or 90°, and in some embodiments at least 91%, 92%, 93% or 156,113. .doc 20120 2740 High Transmittance. The S-transparent substrate can be a film. The thickness of the film substrate is generally dependent on the intended use. For most applications, the substrate thickness is preferably less than about 0.5 mm and more preferably about 〇. 〇2 to about 0 2 mm. Alternatively, the transparent film substrate can be an optical (eg, illumination) display through which tests, graphics or other information can be displayed. The transparent substrate can include any of the types commonly used in different optical devices. Non-polymeric materials (such as glass), or various thermoplastic and cross-linked polymeric materials (such as polyethylene terephthalate (PET), (such as double-looking A) polycarbonate, cellulose acetate, poly(methacrylic acid) And consisting of vinegar) and polyolefins (such as biaxial polypropylene). The antireflective film of Figure 1B additionally includes a low refractive index surface layer 80 on the microstructured high refractive index layer. As shown in Fig. 1B, the exposed low refractive index (observation) surface layer of the antireflective film also includes a microstructured surface formed from the underlying microstructured high refractive index layer. The south refractive index layer has a refractive index of at least about (10). For coatings having a high refractive index inorganic (e.g., yttrium oxide) nanotin t, which is separate from the parent organic material, the maximum refractive index of the high refractive index layer is generally no greater than 1.75. The low refractive index layer has a refractive index smaller than that of the high refractive index layer. % : The difference in refractive index between the rate layer and the low refractive index layer is generally about 15 illusion, \2 or Ο or more. The low refraction (4) has a small square refracting car MW, about Μ5, and even more Usually less than about = radiance. The minimum refractive index of the low refractive index layer is generally at least about the combination of a relatively thick high refractive index durable matte or antireflective film and a relatively thin low refractive index layer. The high refractive index layer typically has an average thickness ("(")) of at least 0.5 microns, preferably at least 丨 microns, and more preferably at least 2 or 3 microns. The high refractive index layer typically has a thickness of no greater than 15 microns and more typically no greater than A thickness of 4 or 5 microns. The low refractive index layer has an optical thickness of about 1/4 wavelength. The thickness is generally less than 〇5 μm, more typically less than about 0.2 μm and often about 90 11 〇 1 to 11 〇 nm. When a durable high refractive index layer is used in combination with a durable low refractive index layer, a durable (e.g., double layer) antireflective sheet can be provided in the absence of other hard coat layers. However, when no matte or anti-wear is required The thickness of the high refractive index layer may be thinner when the reflective film is durable. Λ In some embodiments, the microstructures may be recessed. For example, Figure 8 includes a recessed microstructure 320 or a microstructured aperture. A schematic side view of a structure (e.g., matte) layer 31. The tool surface (from which the microstructured surface is formed) generally includes a plurality of recessed holes. The microstructure of the matte or antireflective film is generally raised. For example, Figure 2 The system contains raised micro knots A schematic side view of a microstructured layer 33A of the structure 34. Figures 8A through 10D depict different microstructured surfaces comprising a plurality of microstructured protrusions. In some embodiments, the microstructures can form a regular pattern. For example, Figure 3 is a schematic top view of a microstructure 4 〇 formed in a regular pattern in the major surface 415. However, in general, the microstructures will form an irregular pattern. For example, 'Figure 3 Β is an microstructure forming an irregular pattern (4) A top view is illustrated. In some cases, the microstructures may form a seemingly random pseudo-random pattern. The features of the microstructure may be analyzed by slope (e.g., discrete). Figure 4 is one of the microstructures (e.g., matte) layer 140. A schematic side view of a portion.Specific 156113.doc 201202740 Figure 4 shows the microstructure in the major surface i2〇 and the opposing T major surface 142. The microstructure 1 60 has a cross-section such as & peach. The slope distribution of the surface of the structure. The slope of the microstructure is at position 510. The slope is θ, where Θ is the normal to the surface of the microstructure perpendicular to the 〇. ) is tangent to the same position 53 of 530 square angle between the surface structure of the helmet wash Μ tangent. The slope Θ is also a tangent υ, and there is no angle between the major surfaces 142 of the first layer. In general, the microstructure of the high refractive index layer and the antireflective film is usually = height distribution. In certain embodiments, the average height of the microstructures (as measured by the test methods described in the Examples) is no greater than about 5 microns, or no greater than about 4 microns, or no greater than about 3 microns, or no greater than about (d) meters, or no more than about 1 micron. The average height is generally at least 〇 or 〇 2 microns. In certain embodiments, the microstructure is substantially free of (e.g., inorganic oxide or polystyrene) matte particles. However, as shown in Fig. Α, the microstructure 7〇 and the high refractive index layer usually contain (for example, oxidized) nanoparticles 3〇 even in the absence of matte particles. The size of the nanoparticles is chosen to avoid significant visible light scattering. It may be desirable to use a mixture of inorganic oxide particle types to optimize optical or material properties and reduce overall combined cost. The surface modified colloidal nanoparticle may be an inorganic oxide particle having a primary particle size or a combined particle size of at least 1 nm or 5 nm (e.g., unrelated). The primary or binding particle size is typically less than 1 〇〇, 75 nm, or 50 nm. The primary or binding particle size is typically less than 4 〇 nm, 3 〇 nm, or 20 nm ^ These nanoparticles are preferably independent. Its measurement can be based on transmission electron microscopy (TEM). The surface modified colloidal nanoparticles can be substantially completely agglomerated. 1561I3.doc 201202740 ^ Condensed nano-particles (except for rare stones) _ generally have greater than training, compared with: And more preferably greater than 70% crystallinity (measured as isolated metal oxide particles). For example, the degree of crystallinity can be raised to about secret or greater. Crystallinity can be determined by X-ray diffraction techniques. The agglomerated crystals (e.g., oxygen = zirconium) nanoparticles have a high refractive index, while the amorphous nanoparticles generally have a lower refractive index. Since the particle size of the nanoparticle is substantially small, the nanoparticle does not form a microstructure. Conversely, the material microstructure contains a plurality of nanoparticles. Although not shown, the low refractive index layer 8G generally also includes (e.g., Mengmi particles. In some embodiments, the partial microstructure of the still refractive index layer may include embedded matte particles. Matte particles - Typically having greater than about 0 a micron (ho nano), or greater than about 0.5 micron, or greater than about 0.75 micron, or greater than about micron, or greater than about 1.25 micron, or greater than about 15 micron, or greater than about 175 micron, Or an average particle size greater than micrometers. For an antireflective film comprising a relatively thin layer of high refractive index, typically less matte particles. However, for embodiments in which the high refractive index layer is thicker, The matte particles can have an average particle size of up to 5 microns or 10 microns. The concentration of matte particles can range from at least 1 or 2% by weight to about 5, 6, 7, 8, 9, or 1 Torr. or greater. Figure 5 is a schematic side view of an optical film 8 (10) comprising a matte layer 86 on a substrate 85. The matte layer 86 includes a first major surface 810 attached to the substrate 85 and a plurality of dispersions. No light in the polymer binder 8 4 〇 PARTICLE .1561I3.doc 201202740 830 and/or a portion of the matte particulate agglomerate beta microstructure 87〇 (such as at least about 50%, or at least about 60%, or at least about 7〇%, or at least about 8〇) %, or at least about 90%) does not contain matte particles 83〇 or matte particle agglomerates 880. Therefore, the microstructures do not contain (e.g., embedded) matte particles. It is inferred that even when such matte Where the presence of particles is insufficient to provide the desired antireflection, clarity and haze properties, the presence of matte particles (e.g., vermiculite or caC〇3) can still provide improved durability, as will be explained below. The particle size of the matte particles is relatively large, so it is difficult to keep the matte particles uniformly dispersed in the coating composition. This causes a change in the concentration of the applied matte particles (especially in the case of screen coating), and further A change in matt properties is caused. For embodiments in which at least a portion of the microstructures comprise embedded matte particles or agglomerated matte particles, the average particle size of the matte particles is generally, average of the microstructures. FIG inch (e.g., at least about 2-fold or more times smaller) and matte particles are sufficient to enable the micro-structure layer of polymerizable resin composition 5

(or in addition) 'The low refractive index layer can <RTIgt; include matte particles. The surface of the frame can be made by using any suitable manufacturing method. Micro-replication-micro-replication of tools is produced by casting and curing a resin composition with a tool surface (such as the U.S. patents using a polymerizable resin from a tool contact 156113.doc 201202740 5,175,030 (Lu et al. And 5,183,597 (Lu)). The tool can be manufactured by any available manufacturing method, such as by using an engraving or diamond car j. An exemplary diamond turning system and method may include and utilize a rapid tool servo system (FTS) as described in, for example, PCT Publication No. WO 00/48037 and U.S. Patent Nos. 7,350,442 and 7,328,638. This is incorporated herein by reference. Figure 6 is a schematic side view of a cutting tool system for cutting a tool. The tool can be micro-replicated to produce a microstructure 160 and a matte layer 14A. The cutting tool system 1 utilizes a thread cutting lathe turning process and includes a roller 1 能够 that can be rotated about the central axis 1〇2〇 by the driver 1030 and/or along the central axis 1020, and a for cutting The cutter material 1040 of the roller material. The cutter is mounted on the servo system 1〇5〇 and is movable into and/or along the drum by the drive 1060 in the X-direction. In general, cutter 1040 can be mounted perpendicular to the roll and central axis 1020 and into the engraved material of the roll as it rotates about the central axis. The cutter is then moved parallel to the central axis for thread cutting. Cutter 1040 can operate at both high frequencies and low displacements to create features in the roll that create microstructures 16 upon microreplication. The servo system 1050 is a fast tool servo system (FTS) and includes a PBT device (commonly referred to as a PZT stack) that can quickly adjust the position of the cutter 1040. The FTS 1050 allows the cutter 1〇4〇 to move highly accurately and at high speed in the χ_, 丫_ and /戋ζ_ directions or off-axis directions. The feeding system 1050 can be any high-quality 156I13.doc 201202740 mass displacement servo system capable of producing controlled motion (in terms of rest position). In some cases, servo system 1050 can reliably and reproducibly provide displacements ranging from about 1 micron or better to about 2 micrometers. Actuator 1060 can move cutter 1040 in a direction parallel to the center axis 1〇2〇. In some cases, the displacement resolution of the driver 1060 is preferably better than about 0.1 microns, or better than about 0.01 microns. The rotational motion generated by the driver 1〇3〇 is synchronized with the translational motion produced by the driver 1〇6〇 to precisely control the resulting shape of the microstructure 160. The engraving material of the roller 10 10 can be any material that can be engraved by the cutter 〇 4〇. Exemplary roller materials include metals such as copper, various polymers, and various glass materials. Cutter 1040 can be any type of cutter and can have any shape desired in an application. For example, Fig. 7A is a schematic side view of a cutter 111 of a curved cutting insert 1115 having a radius "R". In some cases, the radius R of the cutting insert 1115 is at least about! 〇〇 microns, or at least about 5 〇 micrometers, or at least about 200 microns. In certain embodiments, the cutting insert has a radius Κ of at least about 3 μm, or at least about 400 μm, or at least about 50 μm, or at least about 1 μm, or at least about 15 μm. , or at least about 2 microns micron' or at least about 2500 microns, or at least about 3000 microns. Alternatively, a cutter 1120 having a v-shaped cutting insert 125 as shown in FIG. 7B, a cutter 1130 having a segmented linear cutting insert 1135 as shown in FIG. 7C, or a curved shape as shown in FIG. 7D may be used. The cutter 1140 of the cutting insert 1145 forms the microstructured surface of the tool. In one embodiment, a v-shaped cutting insert having a vertex angle β of at least about 178 degrees or greater is used. 156113.doc -12· 201202740 Return to the township picture Figure 6 'When cutting the barrel material, the core axis (10) is swung to the UH0 and the direction of the cutter is removed. The thread can be defined around the roller. Having a pitch along the central axis through the cutter as it moves in a direction perpendicular to the surface of the roll to cut the roll material. The material width of j varies with the cutting and cutting of the cutter. Reference: For example, Figure 7A 'The maximum penetration depth of the cutter corresponds to the large width P" cut by the cut state - generally, the ratio of deuteration is in the range of about 2 to about 4. Microfabrication of nine different patterned guards to fabricate several microstructured high refractive index layers' to produce a high refractive index matte layer. Microstructures due to the precise replication of the surface of the tool surface of the high refractive index matte layer The description of the high refractive index layer is also described as the surface of the opposite guard. The microstructured surfaces H5 and H5A are made of the same fixture and thus exhibit substantially the same complementary cumulative slope size distribution, F shoulder and peak size characteristics, which will It follows that the microstructured surfaces H10A and H10B also utilize the same tools and therefore exhibit substantially the same complementary cumulative slope size distribution, F shoulder and peak size characteristics. The microstructured surfaces H2A, H2B and H2C also utilize the same tool. 'H2B and H2C have substantially the same cumulative cumulative slope size distribution and peak size characteristics as H2A. Figures 8A through 9D illustrate some examples of surface patterns of exemplary microstructured high refractive index layers. A representative microstructured antireflective film is depicted in 10A through 10D. Surface 156113 of the fabricated sample was fabricated using atomic force microscopy (AFM), confocal microscopy, or phase shifting interferometry according to the test methods described in the examples. .doc • A representative portion of 13-201202740 (which has an area of about 200 microns by 25 〇 microns to about 500 microns by 600 microns) for characterization. Fcc(e) complementary cumulative slope size distribution for slope distribution It is defined by the following equation: ~(θ) = ^—— Σ^σ(^) 9=〇〇The slope of the Fcc system at a certain angle (θ) is greater than or equal to the fraction of θ. The microstructure of the high refractive index layer The structure of the microstructure of Fcc (e) is described in the table below. Table 1 - Microstructure high refractive index layer transparency, turbidity and cumulative slope size characteristics

156113.doc • 14 - 201202740 The optical transparency values disclosed herein were measured using a HaZe-Gard Phls turbidity meter from B YK_Gardiner. As shown in the Table, the optical clarity of the polymeric high refractive index hardcoat microstructure surface is generally at least about 6% or 65%. In certain embodiments, the optical transparency is at least (10) or 8%. In some implementations, the transparency is no more than 9G%, or 89%, or 88/. Or 87/. ‘Or 86%, or 85%. As shown in Table 4 below, the microstructured antireflective film also has such optical transparency. Optical haze is generally defined as the ratio of transmitted light to total transmitted light that is greater than 25 degrees from the normal direction. The optical turbidity values disclosed in the text are also measured according to the procedure described in ASTM Dl 3, to be measured by a pius turbidity meter (available from BYK-Gardiner, Silver Springs, Md). As described in Table 1, the optical turbidity of the microstructured surface of the polymerized ruthenium index hard coat layer is less than 20 /. And preferably less than i 5%. In a preferred embodiment, the optical haze is in the range of from about 1%, or 2% or from 3 Torr/Torr to about 10%. In certain embodiments, the optical turbidity is in the range of about 1%, or 2%, or 3% to about 5%. As shown in Table 4 below, the microstructured antireflective film also has such turbid microstructured surfaces including a plurality of peaks which are characterized by a test method as described in the Examples below. The ruler of the peak is shown in Table 2 below: 156113.doc 15 201202740 Table 2 - Microstructure High Refractive Index Layer Peak Size Characteristics Average ECD Micron Average Length Micron Average Width Micron W/L Average NN Micron Bright Spot Comparative Example H11 3.37 4.10 3.05 0.82 13.24 2 Comparative Example H1 12.35 18.94 9.23 0.55 18.90 1 H5 11.29 14.52 9.53 0.67 17.25 1 H4 23.46 50.70 12.15 0.28 33.44 2 H10A 15.31 20.72 12.42 0.61 22.60 2 H10B 14.7 19.776 11.986 0.619 21.34 2 H6 21.82 28.66 18.18 0.64 29.36 3 H8 24.38 31.63 20.74 0.67 34.37 3 H9 21.55 29.47 17.43 0.60 29.11 3 H3 58.23 74.94 48.69 0.66 76.34 4 H7 30.55 41.44 24.82 0.61 40.37 4 H2A Not determined These dimensional features have been found to be associated with "bright spots" which are matte The image displayed on the surface is visually degraded by the interaction of the matte surface with the pixels of the LCD. The appearance of a bright spot can be described as a plurality of bright spots of a particular color, which superimposes "granularity" on the LCD image to reduce the transparency of the transmitted image. The level or number of bright spots depends on the relative size difference between the microreplicated structure and the LCD pixels (ie, the number of bright spots is display dependent). In general, microreplicated structures need to be much smaller than the LCD pixel size to eliminate bright spots. The number of bright spots is a set of physical acceptance criteria for a white display of a white display obtained by the brand name "Apple iPod Touch" (measured with a microscope, which has a pixel pitch of about 159 μηη) Samples of different spot levels were evaluated for visual comparison. The number is in the range of 1 to 4, where 1 is the lowest number of bright spots and 4 is the highest number. Although Comparative Example H1 had a low bright spot, as indicated in Table 1, the microstructured high refractive index layer had low transparency and high haze. 156113.doc -16· 201202740 Comparative Example H11 is a commercially available matte film in which substantially all of the peaks are formed from matte particles. Therefore, the average equivalent circle diameter (ecd), the average length, and the average width are substantially the same. Other examples (ie, other than H1) show that the combination of low anti-reflection and low speckle can be obtained with an anti-reflection film that is different from the peak size of the m! „fJl. For example, the peak of all other exemplary microstructured surfaces. There is an average ECD that is substantially at least 5 microns higher than the comparative example H11 and typically at least 1 micron. In addition, other examples having bright spots below H3 & H7 have an average ECD of less than 30 microns or less than 25 microns (ie, peaks) The peaks of other exemplary microstructured surfaces have an average length greater than 5 microns (i.e., greater than H11) and generally greater than 1 〇 microns. The average width of the peaks of the exemplary microstructured surface is also at least 5 microns. The peaks have an average length of no greater than about 15 microns, and in some embodiments no greater than 1 〇 microns. The ratio of width to length (ie, W/L) is generally at least!.〇, or 〇9, or 〇8 In some embodiments, the W/L system is at least 〇·6. In another embodiment, the W/L system is less than 〇.5 or 〇·4 and generally at least. The closest neighbor distance ypNN is generally at least ίο. Or 15 microns and no more than 100 microns. In some implementations The NN is in the range of 15 microns to about 20 microns or 25 microns. Except for the case where W/L is less than 0.5, the higher bright spot embodiment typically has a NN of at least about or 40 microns. The rate layer was applied to the microstructured high refractive index layer of Table 2. Using a 81^1^ core with a mechanical arm 1^〇3100 from Shimadzu Co" Japan and Shimadzu Scientific Instruments, (: 〇1111111^, \10 111; ¥-3101PC UN-VIS-NIR scanning spectrophotometer, or in the reflection angle of 380 to 800 nm under the incident angle of 156113.doc •17·201202740' or the measurement of RSIN and RSEX from Hunter Labs The UltaScan XE mode (the RSIN Y-RSEX Y) 'measures the reflection of the microstructured anti-reflective film (ie, the first surface specular reflection). These instruments measure the reflection of the region about 1 cm2. Curve and record the wavelength at which the reflection is minimal. Record the transparency, turbidity, and complementary cumulative slope size distribution of the microstructure surface with the re-measurement of the bright spot not greater than "3" as shown in the following table. Table 3 - Microstructure anti-reflective film surface Characteristics HIHC Lambda Rphot transparent Turbidity Fee (01) Fee (0.3) Fee (0·7) Fee (1.3) Fee (4.1) Comparative Example F11 H11 555 1.11 82.4 4.9 94.9 82.6 54.1 27.2 3.4 Comparative Example F1 H1 487 1.51 37.7 19.5 99.7 99.0 95.8 86.6 22.2 F6 H6 536 1.42 82.1 3.30 96.0 84.7 49.8 11.1 0.0 F8 H8 548 1.32 87.0 1.72 96.4 83.6 44.4 6.7 0.0 F9 H9 559 1.67 71.2 5.04 98.0 92.0 68.9 30.8 0.0 F2A1 H2 558 2.48 80 5.4 95.3 ^84.2 60.4 32.9 0.6 F2A2 H2 530 1.93 78.7 5.5 98.0 92.4 75.2 48.2 7 5 F2B H2B 644 1.33 74.0 8.94 Not determined F2C H2C 473 1.40 72.9 7.84 Not determined _ F4 H4 614 1.57 82 3.37 93.9 78.7 46.7 18.1 0.1 F5 H5 547 1.35 87.6 4.93 94.9 81.3 44.2 8.4 0.0 F10A H10A 518 1.57 79.3 4.07 97.3 89.7 65.2 26.0 0.0 F10B H10B 573 1.26 77.8 3.28 96.4 88.1 63.8 26.1 0.0 ~ The antireflective film shows less than 2% or less than 15% at 550 nm as measured by the spectrophotometer described above Average reflectance (ie Rphot) 0 The values indicated in the Slope Size column are the total number of microstructures with this slope size or greater 156113.doc -18·201202740 Ratio (i.e., the total percentage of the surface microstructure). For example, 'in the case of microstructure surface Η6, 97.3% of the microstructures have a slope of 〇.1 degree or greater; 89.8% of the microstructures have a slope of 〇.3 degrees or greater; 62.6% The microstructure has a slope of 〇.7 degrees or greater; 22.4% of the microstructures have a slope of U degrees or greater; and 〇% of the (none) microstructure (measured area) has 4 · 1 degrees or A larger slope size. Conversely, since 62.6% of the microstructures have a slope of 〇.7 degrees or more, they are 100%-62.6. /. = 37.4% of the microstructure has a slope of less than 〇.7 degrees. In addition, due to 22.4 ° /. The microstructure has a slope of h3 degrees or greater, so a microstructure of 100%-22.4% = 77.6% has a slope size less than i3 degrees. As shown in Tables 1 and 3 and Figure 11, at least or more of the microstructures of each microstructure surface have a slope size of at least 0.1 degrees or greater. In addition, at least 75% of the microstructures have a slope size of at least 0 J degrees. The preferred high-refractive-index hard coating with high transparency and low haze and the cumulative slope characteristics of the eight-foot microstructured surface are different from H1 and F1. In the case of ρ 1 , at least 95.8% of the microstructures have a slope size of at least 0.7 degrees. Therefore, only 4.2% of the microstructures have a slope size less than 〇·7 degrees. For other microstructured surfaces, at least 30% or 35% or 40% and in certain embodiments at least 45% or 50%/〇 or 55%, or 6〇〇/0 or 65% or 70〇/〇 Or 75% of the microstructures have a slope size of at least 0.7 degrees. Therefore, at least 25%, or 30%, or 35%, or 403⁄4, or 45. /. , or 50%, or 55%, or 60%, or 65. /. , or 70. /. The microstructure has a slope greater than 〇7 degrees. I561J3.doc •19·201202740 or (or in addition), the preferred anti-reflective microstructure surface and ? The difference between 1 may be that for F1, at least 86.6% of the microstructures have a slope size of at least 丨3 degrees. Therefore, only 13.4% has a slope size less than 丨3 degrees. For other microstructured surfaces and t, at least 25% of the microstructures have a slope size of less than 13 degrees. In an embodiment t, at least 3%, or 35%, or 4%, or 45. /. The microstructure has a slope size of at least h3 degrees. Thus, 55% or 60% or 65% or 70% of the microstructures have a slope greater than 〖3 degrees. In other embodiments, at least 5% or 10% or 15% or 2% of the microstructures have at least 1.3. The slope of the degree. Thus, 8〇% or 85% or 9〇% or 95% of the microstructures have a slope size of less than 13 degrees. Alternatively (or in addition), the anti-reflective microstructure surface may differ from F1 in that: for F1, at least about 22.2% of the microstructures have a slope of at least 4" degrees, and in the case of a preferred structure surface, Less than 20% or 15% or 10% of the microstructure has a slope size of 4.1 degrees or greater. Therefore, 8〇% or 85% or 90% has a slope size of less than 4.1 degrees. In one embodiment, 5 to 10% of the microstructures have a slope size of 4.1 degrees or greater. In most embodiments, less than 5% or 4. /. Or a 3% or 2% or 1% microstructure has a slope size of 41 degrees or greater. Applying the low refractive index layer to the microstructured high refractive index layer as described above reduces the transparency by up to about 10%, with the proviso that the transparency of the antireflective film is within the target range. In certain embodiments, the difference in transparency between the microstructured high refractive index layer and the antireflective film is no greater than about 3%, or 2% or 1%. Further, applying a low refractive index layer to the microstructured high refractive index layer can increase the turbidity by up to 5%. In certain embodiments, the microstructure height 156113.doc -20 201202740 is no greater than 3%, or 2% or 1% of the difference in turbidity between the refractive index layer and the antireflective film. Applying a low refractive index layer to the microstructured high refractive index layer generally changes the complementary cumulative slope size distribution of the microstructured surface. Referring to the figure 丨丨, the complementary cumulative slope of the microstructure antireflection film of the low refractive index layer is additionally included: the cloth tends to be slightly lower 'however, generally has a high refractive index layer corresponding to the microstructure: a complementary cumulative slope size distribution curve. Although the complementary cumulative slope size distribution of the microstructured low refractive index layer is low, the complementary cumulative slope size distribution and ♦ size characteristics are within the same target range as previously described for the microstructured high refractive index layer. In certain embodiments, the change in the percentage of microstructures having a slope size of at least 〇7 degrees or at least 1.3 degrees (ie, hif12=value) is less than 5%, 4%, 3%, 2%, or 1°. /0. In other embodiments, the percentage of microstructures having a slope of 〇.7 degrees or greater and the percentage of microstructures having a slope of at least i.3 degrees may be increased by up to 1%. It is speculated that a high refractive index microstructure layer having a slope size greater than that required above can be fabricated. After applying the low refractive index layer, the slope is reduced by applying a low refractive index layer to the microstructured high refractive index layer. Slightly change the size of the peak structure. For example, the average variation in mean equivalent circle diameter (ECD) and/or average length 'and/or average width is less than 15 or 丨 microns. In certain embodiments, the average ECD change is no greater than 〇 5, 〇 4, 〇 3, or 0.2 microns. The average change in average W/L is no greater than 〇 5. The distance between the closest peak structures (i.e., the two most adjacent peak structures) can vary by 0.5 micrometers' but is generally no greater than 2.5 or 3 microns. 156113.doc -21- 201202740 For the 7 Γ lGi 14-relevant refractive microstructure layer and the AR film, the micro-structures substantially cover the Tiga## _ surface. However, without being bound by theory, it is believed that a microstructure with a slope of at least 度7 degrees can provide the desired matt properties. Therefore, a microstructure with a slope of at least 度7 degrees can be covered. 40/〇' or at least about 45%, or at least about 5%, or at least about, or up to eight tablespoons 60/. 'or at least about 65%, or at least about the major surface, yet still provide the desired high clarity and low haze and sufficient anti-reflective properties. The characteristics of the complex peaks of the microstructure surface can also be analyzed for average southness, average roughness (Ra), and average maximum surface height (4). Table 4. Average Height and Roughness Average Height (μm) Ra (μm) Rz (μm) Comparative Example F11 Comparative Example ϊ F ~F6 -0357_ 0.678 0.148 ΟΪ68 2.462 1.297 _ 0.441 0.101 0.785 VO τ?〇-- 0.387 0.085 0.727 ry 0.549 0.137 1.067 F2A1 0.290 Divided F2A2 Ί?Α -- 0.352 Determination T?c — 0.371 0.081 0.687 r5 0.257 0.058 0.503 r ( l/ΜΒΙ* spot, 171 Λ A 0.375 0.097 0.727 rlUA i?mr> 0.381 0.089 0.714 JP lUo 0.660 0.090 0.790 The average surface roughness (i.e., Ra) is generally less than 2 〇 2 μm. A preferred embodiment with high transparency and sufficient turbidity exhibits Ra of not more than 〇 5 μm » In some embodiments 'Ra is less than 〇14, or 〇13, or 〇12, or 0·11' or 0.10 microns. Ra is generally at least 0 04 or 0 05 microns. The average maximum surface height (ie RZ) is generally less than 3 microns. Or less than 2.5 micro 156113.doc -22-201202740 m. A preferred embodiment with high transparency and sufficient turbidity exhibits an Rz of no more than 1.2 〇 microns. In some embodiments, the RZ system is less than i 1 〇 or 1 〇. 〇micron. Rz is generally at least 40 or 〇 5 〇 micron. The high refractive index layer of the matte or antireflective film generally comprises a polymeric substance, such as a reaction product of a polymerizable resin having a refractive index of at least 16 Å. The polymerizable resin preferably comprises a surface modified Nanoparticles (preferably having a refractive index of at least 16 Å). Various (e.g., non-fluorinated) radical polymerizable monomers, oligomers, polymers, and mixtures thereof can be used in the organic material of the high refractive index layer. Various high refractive index particles are known, including, for example, zirconia alone ("Zr02"), titanium dioxide ("Ti〇2"), cerium oxide, aluminum oxide, tin oxide, or combinations thereof. Mixed metal oxidation may also be used. Oxidation error for high refractive index layer can be trademarked; g "Nalc〇〇〇ss〇〇8" is available from (7) Chemical Co. and under the trade name "Buhler zirc〇nia zw〇 from Buhler AG Uzwil, Switzerland The cerium oxide nanoparticles can also be prepared as described in U.S. Patent No. 7,24 M37 and U.S. Patent No. 6,376,59. The low refractive index surface layer comprises the reaction product of a polymerizable low refractive index composition. Preferably, the low refractive index compositions comprise - or a plurality of fluorinated free radical polymerizable materials and surface modified inorganic nanoparticles. Preferably, the surface modified particles having a low refractive index (e.g., less than 1.50) are dispersed in the free radically polymerized fluorinated organic material described herein. A variety of low refractive index inorganic particles such as metal oxides, metal nitrides, and gold halides (10) such as fluorides are known. The low refractive index particles include colloidal stone, fluorinated town, and fluoroquinone. For the low-refractive-index composition, the stone stone can be used as the brand name l56U3.doc •23- 201202740

Nalco Collodial Silicas" was purchased from Nalco Chemical c〇

Naperville, II Bu products such as 1040, 1042, 1050, 1060, 2327 and 2329. Suitable smoky stones include, for example, those available under the trade designation "Aer〇su Series OX-50" and Product Nos. 130, 150, and 200 from DeGussa AG (Hanau, Germany). The smoky stone can also be sold under the trade names "CAB-O-SPERSE 2095", "CAB-O-SPERSE A105", and "CAB-O-SIL M5" from Cabot Corp., Tuscola, 111. » This low refraction The concentration of the (eg, inorganic) nanoparticles in the rate layer and/or the high refractive index layer is generally at least 25% by weight or 30% by weight. The low refractive index layer generally comprises no more than 50% by weight or 40% by weight of the inorganic oxide nanoparticles. The concentration of the inorganic nanoparticles in the high refractive index layer is generally at least 4 Å by weight/◦ and not more than about 60% by weight or 70% by weight. The inorganic nanoparticles of shai are preferably treated with a surface treatment agent. For Shi Xishi, it is better to use decane; for enamel filler, it is better for other substances. For metal oxides such as cerium oxide, decane and carboxylic acid are preferred. A variety of surface treatment agents are known, some of which are described in us 2007/0286994. The high refractive index (e.g., zirconia) nanoparticle can be surface treated with a surface treatment agent comprising a compound comprising a carboxylic acid end group and a CyC8 ester repeating unit or at least one C6_CM ester unit, such as PCT Application No. 0 0 2010/074862 'The case is incorporated herein by reference. This compound usually has the following general formula: 156113.doc -24- 201202740

Υ——L2 — ζ Jn , or L2 — Υ--- 7 Jn I where n has an average value of 1.1 to 6; L1 is (VC8 alkyl, aralkyl, or aryl, which may be passed through one or more Substituted by an oxygen atom or an ester group; L2 is C^C: 8 ortho, aralkyl, or aryl, which may be substituted by one or more oxygen atoms as needed;

And Y is a lanthanide terminal group which includes c:rC8 alkyl, ether, ester, alkoxy, (meth) acrylate, or a combination thereof. In certain embodiments, L2 comprises Ce-C:8 alkyl and the average of η is from 15 to 2.5. Ζ preferably includes a CrC8 alkyl group. The ruthenium preferably includes a (fluorenyl) acrylate end group. The surface modifier containing a carboxylic acid end group and a C3-C8 ester repeating unit is derived from the reaction of a perylene polycaprolactone such as hydroxypolycaprolactone (mercapto) acrylate with an aliphatic or aromatic acid anhydride. The hydroxypolycaprolactone compound is usually obtained as a polymerization mixture having a molecular distribution. At least a portion of the molecule has a C3_CS ester repeat unit, i.e., η is at least two. However, since the mixture also includes a molecule in which η is 1, the η average of the hydroxypolycaprolactone compound mixture 156113.doc -25·201202740 may be L1, 1, > 3, i 4 or 丨5. In certain embodiments, the average value of 11 is 2. 〇, 2.1, 2.2, 2.3, 2.4, or 2.5. Suitable trans-polycaprolactone (meth) acrylate compounds are commercially available under the trade designation "Pemcure 12A" from Cognis and under the trade designation "SR495" from Sartomer (it is said to have a molecular weight of 344 g/mole). Suitable aliphatic acid anhydrides include, for example, maleic anhydride, succinic anhydride, octane anhydride, and glutaric anhydride. In certain embodiments, the aliphatic anhydride is preferably succinic anhydride. The aromatic anhydride has a relatively high refractive index (e.g., a illusion of at least 〇5 )). The surface treatment compound containing, for example, those derived from an aromatic acid anhydride can increase the refractive index of the entire polymerizable resin composition. Suitable aromatic anhydrides include, for example, phthalic anhydride. Alternatively (or in addition), the surface treatment agent may comprise a (meth) acrylate functional compound prepared by the reaction of the aforementioned aliphatic or aromatic acid anhydride with a hydroxy (meth) acrylate (eg, C^C8) alkyl ester. . Examples of surface modifying agents of this type are succinic acid mono-(2-propenyloxy-ethyl) ester, maleic acid mono-(2-propenyloxyethyl) ester, and glutaric acid 2 · (2-propenyloxy-ethyl) ester, maleic acid mono-(4-propyleneoxy-butyl) ester, succinic acid mono-(4-propenyloxy-butyl) ester, and Glutaric acid monopropenyloxy-butyl) is brewed. Such species are shown in w〇 2〇〇8/i2i465, which is incorporated herein by reference. In the embodiment, the low refractive index composition comprises a radical polymerizable gas-containing polymer. A class of fluoropolymers are known as tetrafluoroethylene ("TFE"), hexafluoropropylene 156113.doc • 26 - 201202740 olefin ("HFP"), and vinylidene fluoride ("VDF", "VF2") Monomer formation. The fluoropolymer preferably comprises at least two of the constituent monomers (HFP and VDF) of different molar contents, and more preferably all three of the constituent monomers. The fluoropolymer contains a radical polymerizable group. This can be accomplished by including a halogen-containing cure site monomer ("CSM") and/or a halogenated end group. Or (or in addition) 'dehydrofluorination can be carried out by any method which will provide sufficient (0.5 to 6 moles per mole) of carbon-carbon unsaturated bonds of the fluoropolymer to render the fluoropolymer Reactive. The halogen cure site can be introduced into the polymer microstructure via the use of a halogenated chain transfer agent which produces a fluoropolymer chain end containing reactive halogen end groups. Such chain transfer agents ("CTA") are well known in the literature and are typical examples: Br-CF2CF2-Br 'CF2Br2, CF2I2, CH2I2 » Other typical examples can be found in U.S. Patent No. 4,0, issued to Weisgerber. , No. 356. One of the advantages of using a cure site monomer in forming a co-crosslinked network is (as opposed to a de-fluidization process): does not impair the optical transparency of the formed polymer layer 'because of the reaction of the acrylate with the fluoropolymer Does not depend on the unsaturated bond in the polymer backbone to react. Further fluoropolymers include those having a high degree of branched chain structure as described in U.S. Patent No. 7,615,283, incorporated herein by reference. The polymer comprises the reaction product of i) at least one polyfunctional free radical polymerizable material having a fluorine content of at least 25 and 3:3%, and π) optionally having a fluorine content in the range of from 〇 to less than 25% by weight. At least one polyglycolically free radical polymerizable material, wherein the total content of the polyfunctional material is 156113.doc -27-201202740, which accounts for at least about 9% by weight of the solids by weight of the polymerizable organic composition. It is presumed that the fluorine (meth) acrylate polymer intermediate solution includes a mixture of unreacted 2 radical polymerizable starting materials, oligomer species, and polymer species having a high branching bond structure. A highly branched polymer is defined as a polymer having a linker of greater than 2; this definition can be extended to highly crosslinked polymers in which macrocycles are present, but non-trapezoidal and spiropolymerization The low refractive index composition is prepared by a two-step process. The first (eg, solution) polymerization utilizes diluted organic solvent conditions to form a highly branched chain fluoroacrylate polymer (eg, nanogel) followed by The high-branched chain fluoroacrylate is used as a reactant in a second (eg, photo) polymerization reaction under substantially 1% solids conditions to form a fluorinated crosslinking system, which is presumed to be Interpenetrating network of polymers in crosslinked (meth) acrylate matrices. A variety of fluorinated mono- and polyfunctional free radical polymerizable monomers, oligomers, and polymers can be used to prepare the low refraction Rate layer. These materials generally include a radical polymerizable moiety, and a (per)fluoropolyether moiety, a (per)fluoroalkyl moiety, and a (per)fluoroalkyl moiety. Has a high fluorine content (for example, to 20% by weight) as much as functional species belonging to such class-based. Other species in each of the categories having a fluorine content of less than 25% by weight can be used as the auxiliary component. In certain embodiments, the auxiliary fluorinated (meth) acrylate monomers can aid in the compatibility of low refractive index or other fluorinated materials present in the reaction mixture. Low refractive index layers and fluoro(fluorenyl) acrylate polymers can be prepared from a variety of (per)fluoropolyether (fluorenyl) acrylate compounds. A suitable high dry matter 156113.doc -28-201202740 is a (for example, perfluoropolyether) acrylate oligomer having a refractive index of 1.341 according to the supplier and is commercially available under the trade designation "CN4000" from Sartomer. In terms of low refractive index, it is believed that the fluorine content of the material is at least about 50% by weight. According to NMR analysis, the molecular weight (??) of CN4000 was about 1300 g/mol' and consisted mainly of perfluoropolyether of the following formula:

R-0-[CF2-0]w.[CF2CF20]x-[CF2CF2CF2-0]y-[CF2CF2CF2CF2-0]zR wherein -[CF2_0]w- and -[cf2cf2o]x-repeat units are the perfluoropolymer The main repeating unit of the main chain in the ether suture, and the R terminal group is mainly H2C=CH-CO- 0-(CH2CH2-〇)x-CH2CF2-. The fluoropolymer-containing low refractive index composition described herein preferably comprises at least one amino-based organodecyl ester coupling agent or a condensation product thereof (as described in U.S. 7,323,514). Suitable amine organodecyl ester coupling agents include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, (aminoethylaminomercapto)phenethyltrimethoxyloxy Decane, (aminoethylaminomethyl) phenethyltriethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxyoxydecane, N-(2 -aminoethyl)-3-aminopropyl decyl diethoxy oxime, N-(2-aminoethyl)-3-aminopropyltrimethoxy decane, N_(2-amine Benzyl)-3-aminopropyltriethoxydecane, 4-aminobutyltrimethoxy decane, 4-aminobutyltriethoxydecane, 3-aminopropylmethyldi Ethoxylate, 3-aminopropylmethyldimethoxydecane, 3-aminopropyldimethoxymethoxydecane, 3-aminopropyldimethylethoxydecane, 2, 2-dimethoxy-1-aza-2-indolecyclopentanylamine, 2,2-diethoxy-indole_aza_2_indolecyclopentan-1-ethylamine, 2,2 -diethoxy-1-aza_2_矽cyclopentane, 2,2_2 156113.doc 29- 201202740 曱oxy·1-aza-2-indolecyclopentane, 4-aminobenzene Trimethoxy decane, and 3-phenylaminopropyl trimethyl Oxydecane. A suitable amine-based organodecyl ester coupling agent is commercially available under the trade designation "All06". Without being bound by theory, it is presumed that the amine-based organodecyl ester coupling agent increases the viscosity of the low refractive index coating composition, thereby preventing flow. When the low refractive index coating composition flows from the peak of the microstructured high refractive index layer to the valley or planar layer between the peaks, the reflection increases. The fumed vermiculite similarly increases the viscosity of the low refractive index composition. The high molecular weight resin and the low boiling point solvent also increase the resistance to excessive flow of the low refractive index coating composition. The low refractive index and organic high refractive index polymerizable composition generally comprises at least 5 weight percent / 10% or 10% by weight of a crosslinking agent (i.e., a monomer having at least three (fluorenyl) acrylic acid-forming groups). The concentration of the crosslinking agent in the low refractive index composition is generally not more than about 30% by weight, or 25% by weight, or 20% by weight. The concentration of the crosslinker in the high refractive index composition is generally no greater than about 15% by weight. Suitable parenteral monomers include, for example, tris-methylpropane triacrylate (sold under the trade designation "SR351" from Sartomer Company, Exton, pa.), ethoxylated trimethylolpropane III Acrylate (sold under the trade designation "SR454" from Sartomer Company, Exton, Pa.), pentaerythritol tetrapropanate, pentaerythritol triacrylate (sold under the trade designation "SR444" from Sartomer), dipentaerythritol pentaacrylate (sold under the trade designation "SR399" from Sartomer), ethoxylated pentaerythritol tetraacrylate 酉θ, ethoxylated pentaerythritol triacrylate (sold under the trade name "" from Sartomer), dipentaerythritol hexaacrylate, and Bismuth (2-hydroxyethyl) isocyanurate triacrylate (trade name "SR368" from 156113.doc •30· 201202740

Sartomer). In some aspects, a poly-(meth) acrylate compound containing an intramethylene ureido group as described in U.S. Patent No. 4,262,072 (Wendling et al.) is used. The high refractive index polymerizable composition generally comprises at least one aromatic (fluorenyl) acrylate monomer (i.e., bis(indenyl) acrylate monomer) having two (meth) acrylate groups. In certain embodiments, the bis(indenyl) acrylate monolith system is derived from bisphenol A. An exemplary bisphenol-A ethoxylated diacrylate monoester was purchased from Sartomer under the trade designation "SR602" (it is said to have a viscosity of 610 cps at 20 ° C and a Tg of 2 ° C). Another exemplary bisphenol A ethoxylated diacrylate monoester is available from Sartomer under the trade designation "SR601" (it is said to have a viscosity of 1080 cps at 20 ° C and a Tg of 60 t). Other various bisphenol A monomers are described in the related art, such as those described in U.S. Patent No. 7,282,272. In other embodiments, the high refractive index layer and the AR film are free of monomers derived from bisphenol A. a bifunctional aryl (meth) acrylate monoester system described in 2008/0221291, a biphenyl bis(indenyl) acrylate monomer, which is incorporated herein by reference. . The biphenyl di(meth)acrylic acid vinegar monomer may have the following general structure:

I56113.doc 201202740 wherein each R1 is independently hydrazine or methyl; each R2 is independently Br; m is in the range of 0 to 4; each Q is independently 〇 or S; η is in 〇 to 1 In the range of hydrazine; L is preferably a C2 to C12 alkyl group substituted with one or more hydroxy groups; hydrazine is an aromatic ring; and t is independently hydrazine or 1. At least one and preferably two -Q[L-0]n C(0)C(R1)=CH2 groups are substituted in the ortho or meta position to render the monomer liquid at 25 °C. The bis(indenyl) acrylate monomer can be used alone or in combination with a triphenyl tri(meth) acrylate monomer such as described in WO 2008/1 12452, which is incorporated by reference. Into this article. WO 2008/112452 also describes trisyl mono(mercapto) acrylates and bis(indenyl) acrylates, which are also presumed to be suitable components for the high refractive index layer. In certain embodiments, the difunctional aromatic (fluorenyl) acrylate monosystem has a molecular weight of less than 450 g/mole and a refractive index of at least 丨5〇, 丨51, 1.52, 1.53, 1.54, An aromatic mono(meth)acrylate monomer combination of us, I%, i57 or i58. These reactive diluents generally include phenyl, biphenyl or naphthyl. Other such reactive diluents may be either patterned or non-halogenated (e.g., non-brominated). The inclusion of a reactive diluent such as a biphenyl mono(meth)acrylate monomer can improve the refractive index of the organic component and improve the processability of the polymerizable composition by lowering the viscosity. The concentration of the aromatic mono(indenyl) acrylate reactive diluent is generally in the range of 156113.doc • 32·201202740% by weight or 2% by weight to about 10% by weight. In certain embodiments, the high refractive index layer comprises no more than 9, 8, 7, 6, or 5% by weight of reactive diluent "High refractive index layer and anti-reflection when excess reactive diluent is used The film will exhibit a reduced pencil hardness, for example, when the monofunctional reactive diluent amounts to no more than about 7% by weight, the pencil hardness will generally be from about 3H to 4H. However, when the monofunctional diluent amounts to more than 7% by weight in total, the pencil hardness is lowered to 2H or lower. Suitable reactive diluents include, for example: (phenoxy)phenoxyethyl acrylate; phenoxy-2-methylethyl (meth)acrylate; phenoxyethoxyethyl (meth) acrylate , (meth)acrylic acid 3-hydroxy-2-hydroxypropyl ester; (meth) benzyl acrylate; ethyl phenyl thioacrylate; 2 - naphthyl thioethyl acrylate; 1-naphthyl thio acrylate Ester; 2,4,6-tribromophenoxyethyl acrylate; 2,4-dibromophenoxyethyl acrylate; 2-bromophenoxyethyl acrylate; 丨-naphthyloxyethyl acrylate; Ethyl naphthylacetate; 2-methylethyl phenoxyacrylate; phenoxyethoxyethyl acrylate; 3-phenoxy-2-propyl propyl acrylate; 2,4-dibromo-6- Second butyl phenyl acrylate; 2,4-dibromo-6-isopropyl phenyl acrylate; benzyl acrylate; phenyl acrylate; 2,4,6-tribromophenyl acrylate. Other high refractive index monomers such as pentabromobenzyl acrylate and pentabromophenyl acrylate can also be used. A suitable diluent is phenoxyethyl acrylate (pEA). Phenyloxyethyl acrylate is commercially available from more than one commercial source and is commercially available under the trade designation "SR339" from Sartomer; under the trade name r Etermer 21" from Eternal Chemical Co. Ltd.; and under the trade name "丁〇_ 1166" Lin from Toagosei Co. Ltd. Benzyl acrylate was purchased from Alfa Aeser corp, 156113.doc -33- 201202740

Ward Hill, 方法 方法 A method of forming an anti-reflective coating on an optical display or an anti-reflective film for an optical display can include providing a light transmissive substrate layer; providing a microstructured high refractive index material on the substrate layer; The low refractive index layer bonded to the high refractive index layer is described. The low refractive index layer can be provided by applying the low refractive index material layer to the (e.g., cured) layer of the high refractive index material and irradiating with sufficient ultraviolet radiation to crosslink. Alternatively, the low refractive index coating can be applied to a release liner, at least partially cured, and transferred to a coating. Alternatively, the antireflective material can be applied directly onto the substrate or onto the release layer of the transferable antireflective film and subsequently transferred from the release layer to the substrate using a thermal or radiation induced transfer method. A suitable method of transfer is described in U.S. Published Application No. 2006/0147614. The low refractive index composition and the high refractive index composition can be applied directly to the film or display surface substrate using conventional film coating techniques. Advantageously, a combination of low reflectance and good durability can be obtained with a single low refractive index layer provided on a single high refractive index layer. The film can be coated using a variety of techniques including dip coating, roll and reverse roll coating, wire wound coating, and die coating. The mode coater includes, in particular, a knife coater, a slit coater, a slide coater, a liquid bearing coater, a curtain coater, a forging die coater, and an extrusion coater. . Many types of mode coaters are described in the literature (eg Edward Cohen and Edgar Gutoff, Modern Coating and Drying Technology, VCH Press, NY 1992, ISBN 3-527-28246-7, and Gutoff and Cohen, Coating and Drying). Defects: Troubleshooting Operating Problems, 156113.doc • 34- 201202740

Wiley Interscience, NY ISBN 0-471-59810-0). Such low refractive index coatings are typically applied from a solvent, and the high refractive index coating is generally substantially free of solvent. Alternatively, an inorganic low refractive index coating such as SiO 2 can be applied by vapor deposition. The low refractive index coating composition is typically dried in an oven to remove the solvent, and then by, for example, using an H-bulb or other lamp at a desired wavelength (preferably in an inert atmosphere (less than 50 parts / Each million parts of oxygen) is cured by exposure to ultraviolet radiation. This reaction mechanism causes cross-linking of the radical polymerizable material. The microstructured high refractive index layer can be exposed to ultraviolet radiation by, for example, using an h_bulb or other lamp at a desired wavelength (preferably in an inert atmosphere (less than 5 parts per million oxygen)) Cured. This reaction mechanism causes crosslinking of the free radical polymerizable material. The cured microstructure layer can be dried in an oven to remove photoinitiator by-products or traces of solvent, if any. Alternatively, the polymerizable composition comprising a higher straight solvent is drawn onto the web, dried and subsequently microreplicated and cured. While the substrate is generally conveniently in the form of a web of continuous web, the coating can be applied to individual sheets. The substrate can be treated to improve adhesion of the substrate to adjacent layers, such as chemical processing, corona treatment (such as air or nitrogen corona), plasma treatment, flame treatment, or actinic radiation. If necessary, a bonding layer or primer may be applied to the substrate and/or hard coat layer as needed to increase interlayer adhesion. Or (or in addition), a primer may be applied to reduce the interference band or provide antistatic properties. 1561J3.doc • 35- 201202740 Different permanent and removable grade adhesive compositions can be provided on the reverse side of the film substrate. For embodiments utilizing pressure sensitive adhesives, the antireflective film article typically includes a removable release liner. The release liner is removed during application to the surface of the display such that the anti-reflective film article can adhere to the surface of the display. In certain embodiments, the antireflective films described herein are durable. In one aspect, the durable anti-reflective film is scratch resistant after repeated contact with an abrasive material such as steel wool. The presence of significant scratches increases the turbidity of the antireflective film. In one embodiment, the anti-reflective tweezers are wiped using a 3.2 cm mandrel and a 2 〇〇g quality steel wool according to a Steel Wool Durability Test as further described in the Examples. 5, 1 1 5 After 2 or 25 times, its turbidity increase is less than 1.0%. Surface layers that are resistant to visible scratches do not necessarily retain their low surface energy. The anti-reflective film retains low surface energy after repeated contact with abrasive materials such as steel wool. According to the steel wool durability test, the anti-reflective film can exhibit at least 45 degrees with hexadecane after being wiped for 5, 10, 15, 20 or 25 times with a 3.2 cm diameter mandrel and 1 gram of steel wool. Enter the contact angle before 50 degrees or 60 degrees. After using a 3.2 cm diameter mandrel and 2 g g of steel wool to wipe 10-man 50 times, 1 time, 200 times or even 300 times, the anti-reflective film generally shows at least 90 degrees with water. 95 degree, or 100 degree static contact angle. Example: Microstructure surface features The following methods are used to determine and characterize peak regions and height distributions of interest, 156113.doc -36· 201202740 by atomic force microscopy (AFM), confocal scanning laser microscopy ( CSLM), or phase-shifting interferometry (psi) utilizes the contrast of the objective lens. The surface profiler is obtained from an area of about 2 Å to 2 μm to about 10 μm. The method utilizes curvature thresholds and iterative algorithms to optimize selection. Using a curvature instead of a simple height threshold helps to pick out the relevant peaks at the trough. In some cases, this also helps to avoid the choice of a single continuous mesh. Use a median waver to reduce the arpeggio before analyzing the height distribution. Then for each point in the height distribution, calculate the curvature parallel to the steepest slope (along the gradient vector). The curvature perpendicular to this direction is also calculated. The curvature is calculated using three points and is described in the following sections. The peak region determines that the negative value of the curvature of the eight directions is not excessive by confirming the region having positive curvature in at least one of the two directions. To accomplish this, a binary image is produced by using the thresholds of the two curvatures. Apply some standard image processing functions to the binary image to clean it up. Also, remove the shallow peak area. The size of the median filter and the distance between the points used for curvature calculation are important. If it is too small, the main peak may split into smaller light areas due to defects on the peak. If it is too large, it may It is not possible to determine the correlation peak. These dimensions π are set to be proportional to the width of the peak region or the width of the valley region between the peaks. 'Whether it is smaller than 1', the size of these regions depends on the size of the chopper and The distance between the points used for curvature calculation. Therefore, the most recent process is determined to satisfy a certain (four) good peak identification ship condition: interval. 156113.doc •37- 201202740 Slope and curvature analysis surface type data is obtained by x&amp The y position is the surface height of the function. This data is represented as a function H(x, y). The x direction of the image is the horizontal direction of the image. The y direction of the image is the vertical direction of the image. Use MATLAB to calculate the following: Gradient vector

'Η(χ + Αχ^)-Η(χ~Αχ,ν)λ 2 "Ugly (yes, y + Ay) - "(jc, y - know)丫1 2Αχ ) + l 2Ay J 2_slope ( In degrees _ng(q) 0 = arctan ()▽//(' 丨)丨)=arctan 3. Fcc(0)-the complementary cumulative distribution of the slope distribution χχω

FcCS- ΣΝ〇^) g=0

The FccW is supplemented by the cumulative slope distribution and gives a slope greater than or equal to the fraction. 4. g-curvature, curvature of the direction of the gradient vector (reciprocal micrometer) 5. t-curvature 'curvature perpendicular to the direction of the gradient vector (increases the micrometer) The curvature is as described in Figure 12. The needle is measured at two points and the center point to calculate the curvature at a certain point. For ±, this, ^, 匕 析 'defines the curvature as 1 divided by the radius of the circle formed by the two points formed by the two points. Curvature = ± l / R = ± 2 * sin (0) / d 156113. doc 38 - 201202740 where θ is the diagonal of the hypotenuse, and d is the length of the hypotenuse of the triangle. If the curve is concave upward, the curvature is negative, and if it is concave downward, the curvature is positive. The curvature is measured along the gradient vector direction (i.e., g_curvature) and in a direction perpendicular to the gradient vector (i.e., t-curvature). Use the interpolation method to get two endpoints. Peak Size Measurement Use the curvature distribution to obtain the size statistics for the peaks on the surface of the sample. The threshold of the curvature distribution is utilized to generate a binary image for determining the peak. Using MATLAB, the following threshold is applied at each pixel to produce a binary image for determining the peak: max(g-curvature, t_curvature)>e〇lnax min(g·curvature, t·curvature)>c〇 Min where cOmax and c0min are the values of curvature. In general, c〇max& c〇min is assigned as follows: cOmax=2sin(q〇)N〇/f〇v (q〇 and N〇 fixed parameters) cOmin=-c〇max q〇 should be the minimum slope ( Estimated by degree (very important). It should be an estimate of the minimum number of peak regions that can be expected to have the longest dimension across the field of view. Fov is the length of the longest dimension of the field of view. The height distribution was analyzed using MATLAB with an image processing toolbox and the peak data was obtained. The following sequence outlines the steps in the MATLAB code for analyzing peak region characteristics. The number of L right pixels >=1〇〇1*1〇〇1 , then subtract the number of pixels • Count nskip=fix(na*nb/1〇〇1/1〇〇1)+1 *The original image has The size of the naXnb pixel 156113.doc •39· 201202740 - If nskip>l, then (2*fix(nskip/2)+l) X (2*fix(nskip/2)+1) The median average fix is rounded off Is a function of the nearest integer. - Generate new images that hold each nskip pixel in each direction (for example, if nskip = 3 ', keep the column and rows 1, 4, 8, 11 ...) 2. r = round (Ax / pix) - Δχ Step size in the slope calculation - pix system pixel size - r is rounded to the nearest number of pixels Δ χ - the initial value of the selected Δ 等于 is equal to ffov * f () v. Ffov is the parameter selected by the user before running this program. 3. The median average of the window size of the round (fMX*r) X round (fMY*r) pixel. - If the area is oriented, a median average is performed with a window processing having an aspect ratio (W/L) close to the typical area defined below. The aspect ratio of the window is not allowed to be lower than the predetermined value rm__aspect_min. It should be noted that if the area is oriented, the height distribution should be analyzed using samples aligned to have this direction along the X or y axis. - For this analysis, the areas are considered to be oriented if: The average orientation angle of the areas (weighted by area area) is less than 15 degrees or greater than 75 degrees. 1. The directional angle system is defined as the angle formed by the intersection of the major axis of the ellipse and the region where the axis is generated. 156113.doc •40· 201202740 The standard deviation of this orientation angle is less than 25 degrees coverage is greater than 10% - if the first round or the area is not oriented, set f*MX and fMY equal to [M • if the orientation Y-axis fMx=r〇und(fM*r*sqrt(aspect)); fMY=round(fM*r/sqrt(aspect)); if the orientation is along the x-axis fMX=r〇und( fM*r/sqrt(aspect)); fMY=round(fM*r*sqrt(aspect)); -aspect=If the average aspect ratio weighted by the area is less than rm_aspect-min, set it to rm_aspect_min 〇• fM is the fixed parameter selected before running the program. 4 · Remove the bevel. - Effectively make the average slope in all directions of the entire curve distribution equal to zero. 5. Calculate the slope distribution as previously described. 6. The juice is parallel to the direction of the gradient vector (g_curvature) and the curvature distribution perpendicular to the direction of the gradient vector (t-curvature). 7. Use the above curvature threshold to form a binary image. 8. Corrode the binary image. - Set the number of times the image has been etched equal to r〇und(r*fE) -fE is the fixed parameter selected before running the program (generally £1) 156113.doc -41- 201202740 • This helps to separate The different areas are connected by narrow lines and the area that is too small is eliminated. 9. The image is enlarged. - The number of times the image is enlarged is generally selected to be the same as the number of times the image is etched. 10. The image is further enlarged. - In this round, the image is magnified before being corroded - to help remove cul-de-sacs, to round the edges, and to bring together extremely close areas. 11 · Corrode the image. - The number of times the image is corrupted is generally selected to be the same as the number of times the image is enlarged in the last step. 12. The area that is too close to the edge of the image is removed. - In general, if any part of the area is within the edge (ner〇de +2) ' it is considered too close, where the ner〇de is the number of times the image is pasted in the step 9 - this eliminates only part of Areas within the field of view 13. Fill any holes in each area. 14. Eliminate the area of ECD (equivalent circle diameter) < 2sin(q〇)N0/fov. -q〇 and N〇 are parameters used to calculate the curvature intercept value - this eliminates regions smaller than the hemisphere with radius R - these regions may have slope variations in the range less than q〇 - to be considered to replace this filter Another filter is to eliminate the area where the slope standard deviation is less than the intercept value. 156113.doc -42 - 201202740 15. Then calculate the new r value. - If it is determined that the number of peaks is equal to zero, then ^2 is taken and the integer is taken. Step 4 - New r = round(fw*L〇) fw is the fixed parameter selected before starting the program (general ^1) Length defined in Table A1 - If the new r is less than rMIN, set it equal to Γμιν - if the new r is greater than rMAX, set it equal to ΓΜΑχ - if r does not change or repeat, then the system selects] *value. Run step 17 _ If the coverage is reduced by Kc times or more, or if the number of areas is increased by Kn times or more, select the previous [value. Run step 17 • If the value of r is not selected, run step 4 16. For the selected r, calculate the following dimensions for each defined area: -ECD, L, W and aspect ratio. 17. Calculate the average and standard deviation of each size. 18. Calculate coverage and NN (Table A2). Table A1. Definition of parameters △X r Rounded to the nearest number of silly Δχ fw The distance between the new “round(fw*L0) L〇^the length of the general size of the table area' area, and the radius of the area The smallest one is 0 L〇=niinfW〇, Wi,D〇) 〇W〇W〇=fw〇*W+(l-fwo^I — Wj Wi-WoY coverage 156113.doc -43· 201202740 D〇 curvature diameter distribution 10th percentile (10% is less than this) fwo is used to calculate the parameter of W〇 ίε The number of times the binary image is corrupted = round(r*fE) fM The parameter rrn aspect that affects the window size used for the median average The lower limit of the width-to-length ratio of the mean median window fov The length of the longest dimension of the field of view ffov △X is initially selected by the user or set equal to ffov * f〇v ffov is generally 0.01 and 0.015 cOmax cOmax=2sm(q0) N0/fov max (g-curvature, t-curvature) oil eye dryness cOmin c0min=-c0max min (g-curvature, t-curvature) curvature of the eye 佶N〇 can have the longest dimension across the field of view The peak area of the suspension of the small Xie Xi Xi Shi q〇 important minimum slope (in degrees) of the valuation ΓΜΙΝ r not allowed below this value γ α χ r does not allow this value Kc if (new coverage) < (previous coverage) / Kc, then stop and keep the previous his Kn (new number of regions) > (previous region number) * Kn, then stop And maintaining the previous r value table A2 region size definition ECD region equivalent circle diameter (ECD) L has the same freshened second towel core moment as the ϋ domain of the long axis W aspect ratio with the ϋ The same standardized second central moment of the domain (4) Kunming epidemic W/L-- the square root of NN f. The partial zone _ is included in this calculation, and this is equal to the nearest neighbor coverage domain between the regional centers. Divided by the total area divided by the total area of the image. The partial dip system consists of the average of two height distributions in a size range of ------- shai. The general parameters are as follows: ffov 0.015 fw 1/3 fM 2/3 f^E 0.3 fwo 3/4 156113.doc 201202740

Kc 1/2 Kn 2-4 rmin 2 rmax 50 rm aspect min 1/3 N〇 4 q〇 1/3-1/2 Adjust these parameter settings to ensure that the main features (not minor features) can be determined. Height Frequency Distribution Subtracts the minimum height value from the height data so that the minimum height is zero. A high frequency distribution is produced by drawing a histogram. The average of this distribution is called the average height. Roughness measurement

Ra- calculates the average roughness of the entire measurement array. 1 Μ Ν

Ra = -L-y y\z

MNh U where Zjk = the height of each pixel after subtracting the zero mean.

The average maximum surface of the ten largest peak-to-valley spacings in the Rz evaluation area is = [+ + 2+·" + Ζι.)] where Η is the peak height and the L-system valley height, and Hik, one has The common reference slope and roughness are all indicated for the complementary cumulative slope distribution, peak size I56113.doc •45·201202740 are based on the average of the two regions. For larger membranes, such as a typical 17 computer monitor, The average of 5 to 1 randomly selected regions is generally used. The synthesis of high refractive index hard coating composition biphenyl diacrylate 2,2,-diethoxybiphenyl diacrylate (DEBPDA) will 2, 2, - double age (1415 g, 7.6 m, υ equivalent), fluorinated clock (1) 8 §, 0.2 mol, 0.027 equivalent), ethyl carbonate (1415 g, 161 mol, 2.11 equivalent) was added to It was equipped with a 12000 ml 4-neck resin head round bottom flask equipped with a temperature detector, a nitrogen purge tube, an overhead stirrer and a heating mantle and heated to 155 C ^. After 4.5 hours, GC analysis showed 0% starting material, 0 / 〇 monoethoxylate and 94% of the product. Cool to § 〇. 匸, add $ 4 liters Stupid, add 2 · 5 liters of deionized water, mix for 5 minutes and phase separation. Remove water and rinse again with 2.5 liters of deionized water, phase separation, remove water and distill the solution to remove residual water and about 1.8 Toluene was added. The solution was cooled to 50 ° C and 1.8 liters of cyclohexane was added, and the 4-hydroxy-2,2,6,6-tetramethyl butyl base was purchased from CIBA Specialty Chemicals under the trade name Pr〇stab 5198. Oxygen (commonly known as 4-hydroxyindole) (〇·52 g, 〇.003 mol, 0.00044 eq.), phenothiazine (0.52 g, 0.0026 mol, 0.00〇38 equivalent), acrylic acid (1089.4 g, ι 5·) 12 moles, 22 equivalents), hydrazine sulfonic acid (36.3 g, 0.38 moles, 0.055 equivalents) and heated to reflux (pot temperature 92 to 95. 〇. Dean-Stark separator was placed on the flask for collection After 18 hours, GC analysis showed a mono- acrylate intermediate of 8 〇 / 0. Additional 8 g of acrylic acid was added and refluxed for a further 6 hours for a total of 24 hours. After 24 156113.doc • 46 · 201202740 hours, GC Analysis showed 3% monoacrylate intermediate. Cool the reaction to 50 ° C and use 2356 ml 7% sodium carbonate Rinse for 3 minutes, phase separation 'removal water' rinse again with 2356 ml DI water, phase separate and remove water. 4-hydroxyindole (〇·52 g, 0.003 mol, 0.00044 equiv), pheno Thiazide (0.52 g ' 0.0026 mol, 0.00038 equiv), N_subwall phenylhydroxylamine aluminum (0.52 g, 0.0012 mol, 〇_〇〇〇 17 equivalent) added to (pink_red) toluene/ring Concentrate in hexane to about 5000 such as a solution in vacuo. The filtrate was concentrated in vacuo by air-purging at 50 ° C and 12 torr vacuum for 3 hours. The resulting yellow to brown oil was further purified by steaming on a roll film evaporator. The distillation conditions were a condenser heated at 15 ° C, a condenser at 50 ° C and 1 to 5 mtorr. The recovered yield was 2467 g (85% of theory) and the purity was about 90 ° / 〇 DEBPDA. Synthesis of triphenyltriacrylate 1,1,1-anthracene (4-propenyloxyethoxyphenyl)ethane (TAEPE) 叁(4-hydroxyphenyl)ethane (200 g, 0.65 Mo) Ear, 1.0 equivalent), potassium fluoride (0.5 g, 0.0086 m, 0.013 equivalent), ethyl carbonate (175 g '2.0 mol, 3.05 eq) added to a temperature probe, overhead stirrer and heating A 1000 ml 3-neck round bottom flask was placed and heated to 165 °C. After 5 hours' GC analysis showed 〇% starting material, 〇% monoethoxylate, 2% diethoxylate, and 95% product. After cooling to 100 ° C, 750 ml of toluene was added and transferred to a 3000 ml 3-neck round bottom flask with an additional 750 ml of toluene. The solution was cooled to 50 ° C and added 4-hydroxy TEMPO (0.2 g, 0.00116 moles, 0.00178 equivalents), acrylic acid (155 g, 2.15 moles, 3.3 equivalents), methanesulfonic acid (10.2 g, 0.1 mol, 156113 .doc •47· 201202740 0_ 162 eq.) and heated to reflux. A Dean-Stark separator was placed on the flask to collect water. After 6 hours, GC analysis showed 7% of the diacrylic acid blended intermediate and 85% of the product. The reaction was cooled to 5 Torr. (: and treated with 400 ml of 7% sodium carbonate, stirred for 30 minutes, phase separated, water removed, rinsed again with 4 〇〇ml of 20 ° / 〇 gasified sodium water 'phase separation and remove water. With 4000 mi The organic phase was diluted with methanol, filtered through a pad of EtOAc (yield: 250 to 400 mesh), and the filtrate was concentrated in vacuo for 3 hours under vacuum at 50 ° C and 12 torr vacuum. g (85% of theory) of brown oil and purity of about 85% TAEPE. Preparation of zirconia sol The Zr〇2 sol used in the examples has the following properties (measured according to the method described in U.S. Patent No. 7,241,437) Relative) Apparent crystallite size (nm) Cuboid / Square monoclinic (C, T) (111) Μ (-111) Μ (111) Average 尺寸 Size % C / T Weighted average XRD size 100 6-12 7.0-8.5 3.0-6.0 4.0-11.0 4.5-8.3 89%-94% 7.0-8.4 °/〇C/T=Primary particle size preparation of HEAS/DCLA surface modifier in three-neck round bottom flask Detector, mechanical stirrer and condenser. The following reactants were charged to the flask: 83.5 g succinic anhydride, 0.04 g Prostab 5 198 inhibitor, 0.5 g triethylamine, 87.2 g 2-hydroxyethyl acrylate, and 28.7 g of the base-polycaprolactone acrylate from Sartomer under the trade name "SR495" (average η of about 2). Stirring with moderate The flask was mixed and heated to 80 ° C for ~6 hours. After cooling to 4 ° C, 200 g of dipoxy-2-propanol was added and the flask was mixed for a few hours. According to the infrared and gas phase layers 156113.doc •48-201202740 The reaction mixture was determined to be the reaction product of succinic anhydride with 2-ethyl acrylate (ie HEAS) and succinic anhydride with hydroxy-polycaprolactone acrylate. A mixture of (ie, DCLA) in a weight ratio of 81.5/18.5. HE AS surface modifier - prepared by reacting a benzoic acid needle with acrylic acid 2-ethyl ester. Preparation of HIHC 1 will oxidize The wrong sol (1000 g @ 45.3% solids) and 476.4 g of 1-decyloxy-2-propanol were placed in a 5 L round bottom flask. The flask was set up for vacuum evaporation and mounted on an overhead stirrer, temperature Detector, heating jacket attached to temperature monitoring controller. Heat zirconia sol and decyloxypropanol to 5〇»c. HEAS/DCLA Surface modifier (233.5 g @ 50% solids in decyloxy-2-propanol, 81.5/18.5 by weight of HEAS/DCLA), DEBPDA (120.5 g), gambling from Toagosei Co. Ltd. of Japan Phenyl 2-phenylacrylate (HBPA) (5 0.2 g @ 46% solids in ethyl acetate) under the trade name "SR 351 LV" (85.3 g) and the trade name "pr〇stab 5198" (〇· 17 g) Low viscosity trimethylolpropane triacrylate from Sartomer was charged into the flask with stirring. Set the temperature monitoring to 8 〇 and 8 〇. /0 power. The water and solvent are removed via a vacuum evaporation chamber until the batch temperature is reached. This process was repeated six times and all six batches of material were subsequently combined into vacuum distillation and equipped with a heating jacket, temperature probe/thermocouple, temperature control benefit, overhead mixer and water vapor The 12 L round bottom flask was placed in the steel tube of the liquid composition. The liquid composition was heated to 8 ° C, at which time a stream of water vapor was introduced into the liquid composition at a rate of 8 liters per hour under vacuum. Continuous vacuum distillation for 6 hours by vapor flow followed by a vaginal flow of 156113.doc -49 - 201202740. The batch was distilled again at 8 ° C for 60 minutes. The vacuum is then destroyed by air cleaning. Charged with photoinitiator (17 7 g rDarocure 4265), biphenyl (2,4,6-trimethylbenzylidene)-phosphine oxide and 2-hydroxyl_2_methyl_ι_phenyl-1- A 50:50 mixture of acetone) and mix for 3 minutes. The resulting product was about 68% surface modified oxides contained in acrylate monomers having a refractive index of 1.6288. Preparation of HIHC 2 A zirconia sol (5000 g @ 45·30/〇 solid) and 2433 g of 1-decyloxy-2-propanol were charged into a 12 L round bottom flask. The flask was set for vacuum distillation. A heating jacket, a temperature probe/thermocouple, a temperature controller, an overhead stirrer, and a steel tube for incorporating water vapor into the liquid composition are installed. The oxidized sol and the decyloxypropanol were heated to 5 °C. HEAS surface modifier (1056 g @ 50% solids in 1-methoxy-2-propanol), DEBPDA (454.5 g), HBPA (197 g @ 46% solids in ethyl acetate), SR 351 LV (317.1 g) and ProStab 5198 (0.69 g) were separately charged into the flask. Set the temperature controller to 8 °C. The water and solvent were removed via vacuum distillation until the batch temperature reached 80 ° C, at which time a stream of water vapor was introduced into the liquid composition at a rate of 800 ml per hour under vacuum. The vacuum stream was continuously vacuum distilled for 6 hours, after which the vapor stream was stopped and the batch was further distilled at 80 ° C for 60 minutes. The air is then used to destroy the vacuum. A photoinitiator (87.3 g Darocure 4265) was charged and mixed for 30 minutes. The resulting product was about 73% surface-modified cerium oxide contained in the acrylate monomer, which had the following characteristics. A high refractive index hard coat 156113.doc -50·201202740 layer coating composition 3 to 9 was prepared in the same manner as HIHC 1 and HIHC 2 . The components (% by weight solids) of the high refractive index hard coat layer are as follows. HIHC1 HIHC2 HIHC3 HIHC4 HIHC5 Zr02 w/HEAS and DCLA 68 70.9 68 68 Zr02wHEAS 73* DEBPDA 15.6 12.9 16.3 15.6 15.6 HBPA 3 2.6 3.1 3 3 SR351 LV 11.1 9 7.3 11.1 11.1 Darocure 1173 2.4 2.3 Darocure 4265 2.3 2.5 2.3 Total 100 100 100 100 100 Viscosity ** @60°C 0.77 1.73 4.06 1.44 1.88 Viscosity @70°C 0.47 0.91 2.35 0.86 1.1 Viscosity @80°C 0.54 Refractive index @25°C 1.6288 1.645 1.6378 1.6244 1.6288 * 73% by weight surface modification Zr02 comprises about 58% by weight of B<2>> and 15% by weight of surface modifying agent. **Measured on a TA instrument AR2000 with a 60 mm 2 degree cone, the temperature was lowered from 80 °C to 45 °C at 2 °C/min, and the shear rate was Ι/s. The viscosity unit is Pascal-second. HIHC6 HIHC7 HIHC8 HIHC9 Zr02 w/HEAS and DCLA 68 73 Zr〇2 w/HEAS 73 only 71.54 DEBPDA 12.9 12.6 TAEPE 6 0 SR601 15.6 12.9 0 HBPA 3 2.6 2.6 4.6 SR351 LV 11.1 9 8.8 SR339 3 0 Darocure 1173 2.5 0 Darocure 4265 2.3 2.5 2.5 Total 100 100 100 100 Viscosity @60°C 3.07 3.39 3.59 1.18 Viscosity @70°C 1.61 1.96 1.69 0.64 Viscosity @80°C 0.95 0.95 0.39 Refractive index @25°C 1.6198 1.6252 1.6676 1.6439 SR601-(bisphenol- A brand name of ethoxylated diacrylate monomer is purchased from Sartomer (it is said to have a viscosity of 1080 cps at 20 ° C and a Tg of 60 ° C) 〇

Darocure 1173-(2-Phenyl-2-indenyl-1-phenyl-propan-1-one photoinitiator) 156113.doc -51 - 201202740 available from Ciba Specialty Chemicals. SR399-(trade name for dipentaerythritol pentaacrylate) is purchased from Sartomer(R) microstructured high refractive index hardcoat: Example HI, H2, H3, H2B, H2C- rectangular rectangular replication tool (4 inches wide and 24 inches long) was preheated on a 160 °F hot plate and used to make a Handspread coating. The "Catena 35" laminator from the General Binding Corporation (GBC) of Northbrook, IL, USA was heatd to 160 °F (set speed 5, lamination pressure "large gauge"). The high refractive index hardcoat was preheated in an oven at 60 °C and the Fusion Systems UV processor was started and preheated (60 fpm, 100% power, 600 watts/inch D-lamp, dichroic mirror). A sample of the polyester film was cut into the length of the tool (~2 feet). A high refractive index hardcoat is applied to the end of the tool using a plastic disposable straw, and 4 mil (Mitsubishi 0321E100W76) primed polyester is placed on top of the bead and tool and has a polyester The tool passes through the laminator whereby the coating is substantially distributed over the tool such that the depression of the tool is filled with the high refractive index hardcoat composition. The samples were placed on a UV processor tape and cured via UV polymerization. The resulting cured coating is about 3 to 6 microns thick. HIHC formulation H1 HIHC3 H2A HIHC4 H3 HIHC1 H2B HIHC9 H2C HIHC8 156113.doc -52- 201202740 Other high refractive index hardcoats (18 inches wide) were applied to a 4 mil PET substrate using a screen coater. Apply high-refractive-index hardcoats other than H10A and H10B to a tool temperature of 170°F, a mold temperature of 160°F, and a high refractive index hardcoat temperature of 160°F to the brand name “4 mil Polyester Film 0321 E100W76" was purchased from Mitsubishi's primed PET. High refractive index hard coat H10A at a tool temperature of 180 °F, a mold temperature of 170 °F (for H10A) and 180 °F (for HI 0B) and a high refractive index hard coat temperature of 180 °F H10B was applied to a 3M unprimed 4 mil polyester film (corona treated at 0.75 MJ/cm2) under the trade designation "ScotchPar". The substrate was also heated by an IR heater set to about 150-180 °F prior to coating. The high refractive index hard coat layer is overcoated by a rolling stack of resin between the tool and the interlayer. The coatings are UV cured with a D lamp and a dichroic mirror at 50 to 100% power. The resulting cured coating is about 3 to 6 microns thick. Other processing conditions are included in the table below. HIHC Coating Swing Pressure (psi) Tool Temperature (°F) Screen Speed (fpm) Resin Temperature (T) UV Setting (Power %) *Thickness (um) IR Heater (T) H6 HIHC5 80 170 40 160 100 4 to 5 160 H8 HIHC5 80 170 40 160 100 4 to 5 160 H9 HIHC5 80 170 40 160 100 4 to 5 160 H4 HIHC 1 80 170 40 160 50 3 to 5 160 H5 HIHC5 80 170 40 160 100 4 to 5 160 H5A HIHC 7 80 170 40 160 100 4 to 5 160 H6 HIHC 5 80 170 40 160 100 4 to 5 160 H7 HIHC 5 80 170 40 160 100 4 to 5 160 H10A HIHC 6 80 180 25 146 100 3 to 5 180 H10B HIHC 2 80 180 25 180 100 4 to 5 180 * Approximate thickness As described in Table 1 above, the transparency, turbidity, and complementary cumulative slope distribution of the microstructured high refractive index hard coat sample 156I13.doc -53 - 201202740 Characteristics. The peak size of the microstructured surface was also characterized as described in Table 2. Low refractive index composition Surface modified SiO 2 nanoparticle (HMDS/A174) vermiculite was prepared as described in paragraph 0117 of US 2007/02 86994 A1. The "L1 component" is prepared by radically polymerizable amorphous trimer of tetrafluoroethylene (TFE), vinylidene fluoride (VDF) and hexafluoropropylene (HFP) by stirring, And a monomer containing Br- and I-curing sites of 70% by weight of fluorine ("Dyneon FPO3740" from Dyneon LLC of Oakdale, MN) (39.41% by weight solids) was added to a certain amount of MEK to obtain 5 wt% solution. Subsequently, additional MEK was added with stirring to further dilute the concentration of FPO3740 to 3%. Next, a 19.9% by weight blend of HMDS/A174 vermiculite (34.38 wt% solids) in MEK was added to the FPO3740/MEK blend with stirring. Next, a 20 ° / 〇 (by weight) solution of dipentaerythritol pentaacrylate ("SR3 99" available from Sartomer) mixed with MEK was added to the FPO/MEK/HMDS vermiculite mixture. Finally, another portion of MEK was added to dilute the total solids to 7% by weight. A biphenyl dimethyl ketal photoinitiator (available under the trade name "Esacure KB1" (Gallarate, Italy)) (1.48 wt% solids) pre-diluted to 1 〇% by weight in MEK Add to the solution. Additional MEK was added to further reduce the percent solids to 4%. High-strand branched fluoroacrylate (FPA) was prepared using the following components as described in WO 2007/146509 A1. 156N3.doc -54· 201202740 Substance description function (ie, monomer, solvent, initiator, etc.) _ Typical input percentage 2,3,3,3,4,4,5,5,-octafluoro-1,6· Hexane diacrylate monomer 3.91 CN-4000 acrylate monomer-1.08 VAZO 52 Initiating plastic __ 0.35 thioglycolic acid isooctyl ester chain transfer agent 0.00005 ethyl acetate solvent ___ 37.61 methyl ethyl ketone solvent 75.05 The preparation of the Tri 8F HDDA Michael adduct 2 ° L2 component described in WO 2007/146509 A1, page 4, line 10 is prepared as follows: pre-dissolved in ethyl acetate in an amount of 1% by weight The Sartomer CN4000 is added to the mixing vessel. Subsequently, the following components (pre-dissolved in 5% by weight of high-branched fluoroacrylate (FPA) in ethyl acetate, 10% by weight of Sartomer SR399 pre-dissolved in MEK, at 5% ( The weight) trl_8F HDDA) pre-dissolved in butyl acetate was added to the mixing vessel. Next, HMDS/A174 vermiculite (30.5 wt. 0 / 〇 solid) pre-dispersed in methyl isobutyl ketone at 33.5% by weight was added. The photoinitiator (acquired hydroxy-2-mercapto-l-[4-(l-methylvinyl)phenyl]acetone' can be purchased from "Lamberti Esacure One") (pre-dissolved in MEK at 10%) 3 wt% solids) was added to the mixing vessel. Finally, an additional solvent was added to the formulation to make it contain 4% solids. The weight percent solids of the (i.e., cured) composition and the solvent utilized in the coating composition are described in the following table. As described in the following table, various blends were prepared from LI, L2, A1106, and fluorite obtained from "Cab-O-Sil TS530".

L8 and L9 were prepared by adding Dyneon FPO3740 pre-dissolved in MEK at a concentration of 10% by weight to a mixing vessel. Subsequently, the FPO 3740 was further diluted with MEK 156113.doc -55 - 201202740 and MIBK. Sartomer CN4000 pre-dissolved in ethyl acetate at 10% by weight and FPA37 pre-dissolved in ethyl acetate at 5% by weight were added to the mixture. Next, HMDS/A174 vermiculite preliminarily dispersed in methyl isobutyl ketone at 33.5% by weight and pure Sartomer SR494 were added to the mixing vessel. Finally, Lamberti Esacure One, which was pre-dissolved in MEK at 1% by weight, was added to the mixing vessel. The components listed for L8 and L9 were added in the order described and in the concentrations in the table below. When the low refractive index composition also contains an oligomeric product of gamma-aminopropyltrimethoxy decane (available under the trade designation "Α1106" from Momentive Performance Materials, Wilton, CT), either immediately before coating or At least 24 hours before coating, the component pre-diluted in sterol at 25% by weight was slowly added to the formulation with stirring. Add additional MEK to place the solid. /〇 Reduced to 4% to prepare for coating. For each low refractive index coating composition, additional MEK was added to make each coating composition 4% by weight solids. Component L2 L3 L4 L5 Dyneon FPO3740 0 27.61 27.65 CN400❶ 15.25 14.56 4.59 4.37 FPA 15.25 14.56 4.59 4.37 A1106 4.77 3.43 5 HMDS/A174 30.5 29.12 33.3 32.9 SR399 15.25 14.56 18.38 18.19 Tri8FHDDA 20.5 19.57 6.15 5.86 KB1 0 1.04 1.04 Esacure 1 3.0 2.86 0.9 0.86 Total 100 99.99 100.24 MEK 63.65 63.29 89 88.5 EtOAc 12.11 12.04 3.63 3.61 MeOH 0.57 0.09 0.6 MIBK 2.98 2.96 0.89 0.88 CHO 5.09 5.06 1.53 1.52 BuOAC 16.156 16.06 4.85 4.82 Total 99.99 99.98 99.99 99.93 156113.doc •56- 201202740 Component L6 L7 L8 L9 Dyneon FPO3740 19.71 28.46 30 30.77 CN4000 7.65 4.5 5 10.69 FPA 7.65 4.5 10 10.69 A1106 2.47 0 5 1.99 HMDS/A174 32.49 33.87 33.5 28.84 SR494 0 15 15.41 SR399 17.48 18.72 0 0 Tri 8F HDDA 10.25 6.03 0 0 KB1 0.74 1.07 0 0 Esacure 1 1.5 0.88 1.5 1.59 Cab-O-Sil TS530 2 0 0 Solvent % in coating solution Total 99.94 100.03 100 99.98 MEK 81.58 89 86.8 76.53 EtOAc 6.04 3.63 9.8 12.47 MeOH 0.3 0 0.6 0.25 MIBK 1.49 0.89 2.8 10.75 CHO 2.54 1.53 0 0 BuOAC 8 .06 4.85 0 0 Total 100.01 99.9 100 100 Application of a low refractive index composition to a microstructured high refractive index hard coat layer: Preparation of each antireflection layer "F" from a microstructured high refractive index layer "Η" having the same numerical designation . Therefore, F1 is produced from Η1, which additionally includes a low refractive index layer. Similarly, F11 was produced from Η11, which additionally included a low refractive index layer. FI, F2A1, F2A2, F3, F10A, F2B, and F2C-by applying a drop of low refractive index coating to a 6 inch multiplication of each previously prepared and cured microreplicated high refractive index hardcoat using a disposable pipette A Handspread coating (4 inches wide) was fabricated on one end of a 12 inch sample and a Webster 4 wire mayer bar was pulled through the beads to the length of the film to the microstructure A uniform wet coating is formed on the high refractive index hard coat layer. All low refractive index formulations were dried in an oven (1 min, 60 ° C) and cured in a Fusion Systems UV processor at 30 fpm (bidirectional) (nitrogen purge, 156113.doc -57 - 201202740 600 watts / eng Helium bulb, 100% power), which produces a dry low refractive index coating of approximately 100 nm. LI solution F1 L6 F2A1 L2 F2A2 L3 F2 L5 F10A L7 F2B L9 F2C L9 Other low refractive index formulations were applied using a syringe coater or pressure jar at a screen speed of 30 ft/min using a screen coater. When using a pressure tank, the solution was passed through a filter (0.5 micron) before passing through the mold. These coatings were then applied to the cured high refractive index coating on the polyester substrate and dried by passing through an oven set at about 120 F for about 1 minute. The coatings were then cured using a UV system with a xenon bulb, an aluminum reflector and 100% power under nitrogen (oxygen < 50 ppm). Other process conditions are included in the table below. LI solution pump type flow rate (ml/min) caliper (nm) coating width (in.) F6 L4 syringe 4.6 536 4 F8 L4 syringe 4.6 548 4 F9 L4 syringe 4.6 559 4 F4 L4 syringe 5 614 4 F5 L4 syringe 4.6 547 4 F10B L8 Pressure Tank 12.3 537 8 The resulting cured low refractive index layer is about 90 to 100 nanometers thick. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic side view of a matte film; 156113.doc -58-201202740 Fig. 1B is a schematic side view of an antireflection film; Fig. 2A is a schematic side view of a microstructured recess; Fig. 2B is a micro Figure 3A is a schematic plan view of a regularly arranged microstructure; Figure 3B is a schematic plan view of an irregularly arranged microstructure; Figure 4 is a schematic side view of the microstructure; Figure 5 includes a Inclusion: Man #II: In, a schematic side view of the optical film of the microstructure of the three people without the zirconia particles; Figure 6 is a schematic side view of the cutting tool system; Figures 7A to 7D are schematic diagrams of different cutters Figure 8 is a two-dimensional surface profile of an exemplary microstructured surface (i.e., microstructured high refractive index layer H丨); Figure 8 is a three-dimensional surface profile of the exemplary microstructured surface of Figure 8A; Figure 8C 8D is a cross-sectional profile of the {_ and 7 directions of the microstructure surface of FIG. 8Α, respectively; FIG. 9 is a two-dimensional surface profile of another exemplary microstructured surface (ie, the microstructured high refractive index layer Η4); 9Β is the third of the exemplary microstructure surface of Figure 9Α Figure 9C to 9D are cross-sectional profiles of the microstructure surface of Figure 9A along the x- and y-directions, respectively; Figure 10A is another exemplary microstructure surface (i.e., anti-reflection film example F10B) Fig. 10B is a three-dimensional surface pattern of the exemplary microstructure surface of Fig. 1A; Figs. 10C to 10D are respectively 156113.doc of the microstructure surface of Fig. 10A along the x_ and y_ directions. 201202740 Cross-sectional profile; Figure 11 is a diagram depicting the cumulative cumulative slope of various exemplary microstructured surfaces; and Figure 12 depicts a method for calculating curvature [Major component notation] 30 Nanoparticles 50 Substrate 60 咼 Refractive index Microstructured Surface Layer 70 Microstructure 80 Low Refractive Index Layer 100 Matte Film 120 Main Surface 140 Matte Layer 142 Main Surface 160 Microstructure 310 Contains recessed microstructures 32 〇 or 320 recessed microstructures 330 Contains raised microstructures 34〇 { 340 raised microstructure 410 regular pattern microstructure 415 main surface 420 irregular pattern microstructure 510 position 520 normal 156113.doc 201202740 530 800 810 830 840 850 860 870 880 1000 1010 1020 1030 1040 1050 1060 1110 1115 1120 1125 1130 1135 1140 1145 Tangential optical film first main surface matt particle polymeric adhesive substrate matt layer microstructure matt particle agglomerate cutting tool system Xingkun cylinder central axis drive cutter Servo system drive cutter curved cutting blade cutter V-shaped cutting blade cutter segmental linear cutting blade cutter curved cutting blade 156113.doc •61-

Claims (1)

201202740 VII. Patent application scope: 1. An antireflection film comprising a high refractive index layer and a low refractive index surface layer on the high refractive layer #_, wherein the low refractive index layer comprises a plurality of complementary cumulative slopes Distributing the microstructure such that at least 30% of the micro-portions have a slope of at least 107 degrees, at least "the microstructure of the 乂 has a slope of less than 1.3 degrees, and the anti-reflective film does not contain a matte particle. 2. An antireflective film comprising a high refractive index layer and a low refractive index surface layer on the high refractive index layer, wherein the low refractive index layer comprises a plurality of microscopically having a cumulative cumulative slope size distribution Structure, such that at least the micro, s., has a slope size of at least 度7 degrees, at least a microstructure ', has a slope size of less than 1.3 degrees, and no more than 5 (%) of the microstructures comprise embedded Matte granules. 3. A matte film such as Kiss 1, wherein at least 30% of the microstructure has a slope of less than 3.4 degrees. 4. A matte film such as Kiss 1, of which at least 35% Microstructure has A slope size of less than 1.3 degrees 5. A matte film of the same as in claim 1, wherein the microstructure of at least 40°/❶ has a slope size of less than 1.3 degrees. 6. The stroke of any one of items 1 to 5 An antireflection film in which a microstructure having less than 1 has a slope size of 4.1 degrees or more, and an antireflection film according to any one of claims 1 to 5, wherein a microstructure of less than 5 Å has a degree of 4.1 degrees. Or a larger slope size. 8. The antireflection film of any one of the items 1 to 5, wherein at least μ% of the 156113.doc 201202740 microstructure has a slope size of at least 0.3 degrees β 9 · as requested The antireflection film of any one of 5, wherein the surface layer comprises an average equivalent circle diameter of at least 5 μm. 1 〇. The antireflection film of claim 9, wherein the average equivalent circle diameter is 11. The antireflection film of claim 9, wherein the average equivalent circular diameter is less than 30 microns. 12. The antireflective film of claim 9, wherein the average equivalent circular diameter is less than 25 microns. 13. The antireflection film of any one of clauses 5 to 5, wherein the microjunction The surface comprises an average length of at least 5 micrometers. 14. The antireflective film of claim 13, wherein the peaks have an average length of at least 1 micron. 1 5. The anti-resistance of any one of claims 1 to 5. A reflective film, wherein the microstructured surface comprises a peak having an average width of at least 5 microns. 16. The antireflective film of claim 15, wherein the peaks have an average width of less than 15 microns. 17. as claimed in item 5 The antireflection film of any one of the present invention, wherein the film has an average roughness (Ra) of less than 0.14 μm. The antireflection film of any one of claim 5, wherein the film has an average maximum of less than 1.20 μm. Surface height (RZ). The antireflection film of any one of claims 5 to wherein the antireflective film has a transparency of at least 70%. The antireflection film according to any one of claims 1 to 5, wherein the antireflection film 156113.doc 201202740 film has a haze of not more than 1%. 21. An antireflective film comprising: a microstructured high refractive index layer and a low refractive index layer on the high refractive index layer, wherein the antireflective film has a transparency of no more than 90%, at least 微米5 microns and no An average surface roughness greater than 〇 14 microns, and the antireflective film does not contain embedded matt particles. 22. An antireflective film comprising: a microstructured high refractive index layer and a low refractive index layer on the high refractive index layer, wherein the antireflective film has a transparency of no more than 90%, at least 〇5 〇 microns and not An average maximum surface height greater than 12 μm, and the antireflective film does not contain embedded matt particles. The antireflective film comprises a microstructured high refractive index layer and a low refractive index on the high refractive index layer. a layer, wherein the antireflective film has a transparency of not more than 90%, and the microstructure layer comprises a peak having an average equivalent diameter of at least 5 microns and not more than 3 Å, and no more than 5% of the microstructure including embedding Matte particles. The antireflection film of any one of claims 1 to 5 and 21 to 23, wherein the antireflection film has an average reflectance reflectance of less than 2% at a wavelength of 550 nm. 25. The antireflection film according to any one of claims 1 to 10, wherein the high refractive index layer comprises a reaction product of a polymerizable resin composition having a refractive index of at least 16 (). A reflective film, wherein the polymeric resin composition comprises nanoparticle having a refractive index of at least about 1.60. 27. The antireflective film of claim 26, wherein the nanoparticles comprise an oxide 156113.doc 201202740 knot. 28. The matte film of claim 26 to 27, wherein the nanoparticles are surface modified with a compound comprising a few acid end groups. 29. The antireflection film of claim 26, wherein the compound comprises a vinegar repeating unit or at least one (: 6-(: 16 ester unit. 30. The antireflective film of claim 29, wherein the surface treating agent comprises the following The reaction product of the substance: i) at least one aliphatic acid anhydride, and ii) at least one hydroxypolycaprolactone (meth) acrylate. 31. The antireflective film of claim 29 or 30, wherein the nanoparticles are surface modified by a reaction of an aliphatic acid anhydride with a hydroxy CrC8 alkyl (meth)acrylate. The antireflection film of claim 25, wherein the polymerizable resin composition comprises one or more aromatic di(meth)propionate monomers in an amount ranging from about 10 to about 20% by weight. 33. The antireflective film of claim 25, wherein the polymerizable resin composition comprises from about 5 to about 15% by weight of a crosslinking agent comprising at least three (meth) acrylate groups. 34. The antireflective film of claim 25, wherein the polymerizable resin composition comprises up to about 10% by weight of an aromatic mono(indenyl) acrylate monomer. The antireflection film of any one of claims 1 to 5 and 21 to 23, wherein the low refractive index layer comprises a radical polymerizable fluorinated polymer. 36. The antireflective film of claim 35, wherein the radical polymerizable fluorinated polymer comprises a polymer species having a high branched structure. The antireflection film of claim 36, wherein the radical polymerizable fluorinated polymer comprises a reaction product of: i) at least one polyfunctional free having a fluorine content of at least 25% by weight a base polymerizable substance, and H) optionally at least one polyvalent monthly b-radical polymerizable substance having a fluorine content in the range of 0 to less than 25% by weight, wherein the total content of the polyfunctional substance accounts for the polymerizable The solid weight of the organic composition. /. At least about 25 wt%. 38. The antireflective film of claim 35, wherein the radical polymerizable fluorinated polymer comprises at least two constituent monomers selected from the group consisting of TFE, VDF, and HFP, and having at least one functional element-containing curing site A reactive functional group of a monomer. 39. The antireflective film of claim 35, wherein the low refractive index layer comprises at least one fluorinated free radical polymerizable monomer having a fluorine content of at least about 25% by weight. 40. The antireflective film of claim 35 wherein the low refractive index layer additionally comprises an amino decane coupling agent. 41. The antireflective film of claim 35, wherein the low refractive index layer additionally comprises fumed vermiculite. 42. A high refractive index polymerizable resin composition comprising: 40% by weight to 70% by weight of a surface-modified oxidation of a compound containing a carboxylic acid end group and a c3_C8 ester repeating unit or at least one Ce-Cw ester unit鍅 Nanoparticles; containing from about 10 to about 20% by weight of one or more aromatic di(meth)acrylic acid vinegar monomers; from 1% by weight to 15% by weight of at least three (fluorenyl) acrylic acid a crosslinker of ester group 156113.doc 201202740; and up to 5% by weight of an aromatic mono(meth)acrylate monomer. 43. The high refractive index polymerizable resin composition of claim 42, wherein the aromatic mono(indenyl) acrylate single system biphenyl monomer. 44. A low refractive index polymerizable composition, comprising: a first radical polymerizable fluorinated polymer comprising a polymer species having a high branched chain structure; and a second radical polymerizable fluorinated polymer, It comprises at least two constituent monomers selected from the group consisting of Tfe, VDF, and HFP, and has a reactive functional group derived from at least one of the functional group-containing curing site monomers. 45. The low refractive index polymerizable composition of claim 44, wherein the first free radical polymerizable fluorinated polymer comprises a reaction product of a rhodium fluoride content of at least 25 weight percent. /. At least one polyfunctional radical polymerizable substance, and 11) optionally at least one polyfunctional radical polymerizable substance having a fluorine content in the range of 〇 to less than 25% by weight, wherein the total content of the polyfunctional substance It is at least about 25% by weight of the solids by weight of the polymerizable organic composition. The low refractive index polymerizable composition of any one of claims 44 to 45, wherein the low refractive index layer additionally comprises at least one fluorinated free radical polymerizable monomer having a fluorine content of at least about 25% by weight. The low refractive index polymerizable composition according to any one of claims 44 to 45, wherein the low refractive index layer additionally comprises an amine based lanthanum coupling agent. The low refractive index polymerizable composition according to any one of claims 44 to 45, wherein the low refractive index layer additionally comprises a surface modified stone. 156113.doc