JP2006003511A - Optical film, its manufacturing method, polarizer and display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical film which is an excellent in slidability, and is improved in anti-blocking property and failure caused by foreign matter even when a wide and thin base material is used, to provide a manufacturing method of the optical film, and to provide a polarizer and a display device using the optical film. <P>SOLUTION: In the manufacturing method of the optical film, ink droplets are stuck on a transparent base material film, thereby, fine convex structures are formed on at least one side surface of substrate surfaces and, resultantly, anti-blocking processing is performed. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an optical film, a polarizing plate, and a display device, and more particularly, an optical film excellent in slipperiness, blocking prevention, and improved foreign matter failure, and a method for producing the same, even for a wide or thin film substrate, and The present invention relates to a polarizing plate and a display device.

  With the improvement in image quality of CRTs and liquid crystal display devices, display devices provided with an optical functional layer such as an antireflection layer are required in order to improve visibility. For example, optical films having an antireflection layer, etc. Is attached to the front surface of the display device. In a display device with a large screen such as a television, an object may come into direct contact with it and is easily damaged. Therefore, an antireflection film with a hard coat layer in which a hard coat layer is usually formed on a transparent long base film for preventing scratches and an antireflection layer is formed thereon is used.

  As an antireflection film, a wide film having a size of 1 m or more and further 1.4 m or more has recently been required due to a large screen. In addition, a thin support having a substrate (support) thickness of 80 μm or less has been used for mobile phones and notebook computers. Therefore, a resin film such as cellulose ester is used for the support, and a hard coat layer, an antireflection layer, and an antifouling layer are formed thereon.

However, when the base becomes wider for increasing the size as described above, or when the thickness of the base is reduced for thinning, after forming the hard coat layer and the antireflection layer, or When winding up the finished antireflection film, if the adhesion is high, blocking will occur, the winding shape will deteriorate, the black band will appear as a black band on the circumference, and in severe cases it will be deformed, yield will be In addition to incurring a decrease in the number of images, it may become impossible to adapt to a display device. For this reason, fine particles are added to the film itself or the back coat layer to give fine irregularities to the film surface, thereby reducing the friction coefficient of the surface and preventing blocking. In particular, various techniques for forming a backcoat layer are disclosed. (For example, see Patent Documents 1 to 3.)
However, in the case of large-sized and thin-films, in order to effectively prevent blocking, the addition of relatively large-sized fine particles, in particular, the formation process of the hard coat layer and antireflection layer, and foreign matter failure due to fine particles after formation There was a case.

Similarly, when fine particles are added to the backcoat layer, coating irregularities and foreign matter are observed when particles having a relatively large particle size are contained in order to effectively reduce the generation of the blocking and black bands. In some cases, foreign matter may fail on the polarizing plate or the display panel.
JP 2001-183528 A JP 2001-64422 A JP 2001-83327 A

  In view of the above problems, an object of the present invention is to provide an optical film with excellent slipperiness, anti-blocking, improved foreign matter failure, and method for producing the same, and polarization using the same, even if the substrate is wide or thin. It is to provide a board and a display device.

  The above object of the present invention is achieved by the following configurations.

(Claim 1)
A method for producing an optical film, comprising: depositing ink droplets on a transparent substrate film to form a fine convex structure on at least one surface of the substrate surface and performing an anti-blocking process.

(Claim 2)
^2. The optical film according to claim 1, wherein the fine convex structure has 1 to 1000 convex portions having a convex portion height a of 0.01 to 0.5 μm per 1000 μm ² . Production method.

(Claim 3)
The method for producing an optical film according to claim 1, wherein the ink droplet contains a thermoplastic resin, an actinic ray curable resin, or a thermosetting resin.

(Claim 4)
The method for producing an optical film according to claim 1, wherein the ink droplet contains fine particles.

(Claim 5)
The width | variety of the said transparent base film is 1.4m-4m, The manufacturing method of the optical film of any one of Claims 1-4 characterized by the above-mentioned.

(Claim 6)
The said transparent base film is a cellulose-ester film or a cycloolefin polymer film, The manufacturing method of the optical film of any one of Claims 1-5 characterized by the above-mentioned.

(Claim 7)
The optical film manufactured by the manufacturing method of the optical film of any one of Claims 1-6.

(Claim 8)
The optical film according to claim 7, wherein a hard coat layer is provided on at least one surface of the optical film.

(Claim 9)
The optical film according to claim 8, further comprising an antireflection layer provided on the hard coat layer.

(Claim 10)
A polarizing plate comprising the optical film according to claim 7.

(Claim 11)
A display device comprising the optical film according to claim 7.

(Claim 12)
A display device comprising the polarizing plate according to claim 10.

  According to the present invention, there are provided an optical film that is excellent in slipperiness even when it is a wide or thin film substrate, has improved blocking prevention, and foreign matter failure, a method for producing the same, and a polarizing plate and a display device using the optical film. I can do it.

  The best mode for carrying out the present invention will be described in detail below, but the present invention is not limited thereto.

  The optical film of the present invention is an optical film characterized by depositing ink droplets on a transparent substrate film, forming a fine convex structure on at least one surface of the substrate surface, and performing anti-blocking processing. Manufactured by a manufacturing method.

  In particular, an ink droplet containing a composition that forms a fine convex structure by an ink jet method is ejected onto a transparent substrate film, and an antiblocking function is provided on the surface of the substrate or a functional layer provided on the substrate. It has been found that an optical film excellent in slipperiness and excellent in an antiblocking effect can be realized by forming a fine convex structure having, and as a result, the present invention has been achieved. Note that the fine convex structure referred to here may be a layer, or may have a state in which fine convex portions formed by ink droplets are scattered on the substrate without having a layer structure.

In the fine convex structure according to the present invention, the fine convex structure preferably has 1 to 1000 convex portions having a height a of 0.01 to 0.5 μm per 1000 μm ² , and the ink droplet composition By using a thermoplastic resin, an actinic ray curable resin, or a thermosetting resin as the product, the extremely fine convex structure defined above can be realized. As the ink droplets by the ink jet method, one type of ink may be used, but two or more types of ink droplets having different compositions may be used, or two or more types of ink droplets having different particle sizes may be used. It may be used. Alternatively, it is preferable to include fine particles in the ink droplet, and it is also preferable to control the solvent content in the ink, the surface energy of the ink, and the surface energy (contact angle) of the ink adhesion surface. The target effect is further exhibited.

  In addition, the optical film of the present invention has a configuration in which the fine convex structure defined above is directly formed on the transparent substrate film, or on the transparent substrate film having one or more functional layers provided in advance. Any of the structures provided with the fine convex structure of the present invention may be used.

  The fine convex structure according to the present invention can be adjusted, for example, to increase the number of convex portions when increasing the anti-blocking property, or to increase the height if the number is the same, or to tighten the convex portion. . Moreover, according to this invention, the number of convex parts can also be easily changed in the width direction of a film. For example, it is possible to increase the number of convex portions at the end and reduce the center of the film and vice versa. Alternatively, the number of convex portions can be changed in the longitudinal direction of the film. For example, the number of protrusions can be increased or the height of the protrusions can be increased at the center of the winding where deformation or blocking failure is likely to occur, and the number and height of the protrusions can be increased toward the outer side of the winding. It becomes possible to change. In particular, when the film width is as wide as 1.4 to 4 m, the conventional method cannot sufficiently cope with it, but the present invention can be remarkably improved. According to the present invention, it is also excellent in that an appropriate anti-blocking process can be additionally easily provided after various processes are performed on the film. In addition, it is easy to change the number of convex portions according to the type of film, and the productivity is remarkably improved. The ink jet method is extremely excellent in that such control can be easily performed.

Convex portions are formed in the present invention, the height a is is preferably convex portion of 0.01~0.5μm is 1 to 1000/1000 .mu.m ^2. If it is 1 or less, the blocking prevention effect may be insufficient, and if it is 1000 or more, there is no problem with the blocking prevention effect, but productivity may be reduced and haze may be deteriorated. The number is preferably 10 to 1000/1000 μm ² .

Moreover, it is preferable that the convex part whose height a is 0.02-0.3 micrometer is 1-1000 piece / 1000 micrometer < ² >, and the convex part of 0.03-0.1 micrometer is 1-1000 piece / 1000 micrometer < ² >. Is more preferable.

  Further, the diameter b of the convex portion is preferably 0.01 to 1 μm, more preferably 0.01 to 0.3 μm. As for the relationship between the height a of the convex part and the diameter b, b / a is preferably 1 to 100, more preferably 1.5 to 30, and particularly preferably 2 to 10. If it is less than 1, the formed convex part may be peeled off, resulting in a foreign matter failure. If it exceeds 100, the anti-blocking property is insufficient, and the base film tends to be deformed.

  FIG. 1 is a schematic view showing an example in which a fine convex structure having an anti-blocking function is provided on a transparent substrate film by an ink jet method.

  1A is a perspective view of a fine convex structure, and FIG. 1B is a cross-sectional view.

  In FIG. 1B, an example of the fine convex structure formed by the ink droplet 3 on the transparent base film 1 by the ink jet method is shown. The height a of the convex portion defined in the present invention is shown in FIG. Is defined as the height (μm) to the top of the convex structure with the surface of the transparent base film as the bottom as the bottom, and similarly the diameter b is defined as the maximum length of the bottom of the convex in contact with the substrate. .

The fine convex portion on the surface can be measured by a commercially available stylus type surface roughness measuring machine or a commercially available optical interference type surface roughness measuring machine. For example, an optical interference type surface roughness measuring device is used to measure two-dimensionally about a range of about 4000 μm ² (55 μm × 75 μm), and the convex portion is color-coded as a contour line from the bottom side and displayed.

Here, the number of protrusions having a height a of 0.01 μm to 0.5 μm with respect to the film surface was counted and indicated by the number per 1000 μm ² area. The measurement is carried out by measuring 10 arbitrary points of the corresponding part of the optical film and obtaining the average value.

  In the present invention, as the shape of the convex structure for the anti-blocking process, FIG. 1B shows an example of the convex portion formed by the ink droplet landed on the Conide type convex portion. The invention is not limited to the convex structure of the above shape.

  FIG. 1C is a schematic view in which a fine convex structure is provided on the functional layer provided in advance by the ink jet method of the present invention. The functional layer is not particularly limited, and examples thereof include a back coat layer, an anti-curl layer, an antistatic layer, an undercoat layer, a light scattering layer, and an adhesive layer.

  FIG. 2 is a cross-sectional view showing an example of another fine convex structure.

  FIG. 2A shows an example of a convex structure landed in a spherical shape. The viscosity of the ejected ink droplet, the ink ejection speed, the contact angle between the ink droplet and the ink landing surface, the inkjet head and the base are shown. A convex structure having such a shape can be formed by appropriately adjusting the distance to the material. The distance between the inkjet head and the substrate is preferably 0.2 to 100 mm, and can be changed according to the shape of the convex to be formed. The contact angle between the ink droplet and the ink landing surface is appropriately adjusted in the range of 0 to 180 °. Preferably it is 5-120 degrees. Also, the ink droplets after ejection can be split by increasing the ink ejection speed to form finer convex portions as the ink droplets, or the convex velocity can be controlled by controlling the ejection speed to be larger or convex. Part can be formed. These conditions of the ink jet part can be set with reference to the conditions used in the ink jet printing. Further, it is possible to increase the ink discharge speed and crush the convex portion due to ink droplets by impact of landing.

  The ink discharge speed can be generally controlled in the range of 0.1 to 20 m / s by increasing or decreasing the voltage applied to the piezo element of the piezo-type ink jet device for the ink droplet tip speed V1. Preferably it is the range of 1-20 m / s. Further, the preferable lower limit of the velocity V1 of the ink droplet tip is 5 m / s, and the preferable upper limit is 12 m / s. The velocity V2 at the trailing edge of the ink droplet is smaller than the velocity V1 at the leading edge of the ink droplet, and is generally 0.1 to 10 m / s. The velocity V2 at the trailing edge of the ink droplet is determined by the ink droplet separation state, that is, the surface tension and viscosity of the ink.

  The ejection time t is set to 3 μs to 1 ms according to the control condition of the voltage applied to the piezo element. The control condition of the voltage applied to the piezo element is set according to the waveform control condition, the surface tension, the viscosity, etc. of the ink droplet so that the ink droplet can be stably ejected.

  As will be described later, the liquid droplets are ejected in a columnar shape, and there are cases where the liquid droplets do not divide until they land on the substrate and may divide. When the droplets are not split and become spherical droplets in the air before landing, the droplet leading edge velocity and the trailing edge velocity at landing are almost the same. Since the columnar droplets become spherical, the droplet velocity at the time of landing is strictly different from the droplet leading edge velocity and the trailing edge velocity at the time of ejection, but the difference is small with respect to the droplet velocity. On the other hand, when dividing into several droplets, the leading edge velocity at the time of ejection becomes the velocity of the leading droplet at the time of landing, and the trailing edge velocity at the time of ejection is the velocity of the last droplet at the time of landing. It seems to be speed. Normally, when the droplet tip speed is 3 m / s or less, the droplet often does not break, and when the droplet tip speed is 3 to 20 m / s, the droplet often breaks.

  The method for forming a convex structure by the ink jet method of the present invention can form a convex structure of an arbitrary shape as compared with the conventional method of adding a matting agent to a film or the method of coating a backcoat layer containing fine particles, In particular, it is a great feature that it can have different convex shapes in the width direction and the length direction, and can change the amount of adhesion. Moreover, since the pattern formed during production can be changed, it is possible to respond quickly to various varieties. Also, there is a degree of freedom to add according to the processing of the opposite surface.

  FIG. 2B is a cross-sectional view showing an example of an anti-blocking process having a semicircular convex structure.

  As an example of the arrangement of the above convex structures, the above description shows an example in which the convex portions are landed at intervals. However, as shown in FIG. The structure covered with a convex part may be sufficient. In the present invention, the size and shape of such a convex portion can be changed to vary the fine convex structure.

  The convex portion 3 formed by the ink droplets may have a substantially circular shape or an elliptical shape when viewed from the normal direction of the film. For example, an ellipse with a ratio of aspect ratio x1.01 to x10 may be used. An elliptical convex portion can be formed by carrying out the ink adhesion while carrying the film side or the inkjet head portion at a high speed.

  FIG. 3 is a schematic diagram illustrating an ink discharge angle and a discharge method.

  The angle at which ink is ejected from the inkjet head toward the film shown in FIG. 3A is 90 ° in the normal direction of the film, 0 ° in the direction in which the film with the ink attached is conveyed, If the direction in which the toner is conveyed is 180 °, it can be set in the range of 0 ° to 180 °. Preferably, the angle is 0 ° to 90 °, because the difference between the flying speed of ink and the relative speed of film transport can be reduced, and a desired convex shape can be easily formed. More preferably, it is 5 ° to 85 °.

  FIG. 3B shows a method in which a plurality of inkjet heads having various angles with respect to the film surface are arranged and ink is continuously ejected. At that time, not only the angle but also the height from the film surface can be arbitrarily changed.

  FIG. 3C shows a state in which a plurality of inkjet heads are arranged around the film surface transported by holding the back roll and ink droplets are ejected. Thus, the film surface on which the ink droplets are landed may be either a flat surface or a curved surface.

  Next, the ink jet system according to the present invention will be described.

  FIG. 4 is a cross-sectional view showing an example of an ink jet head that can be used in the ink jet method according to the present invention.

  4A is a cross-sectional view of the inkjet head, and FIG. 4B is an enlarged view taken along line AA in FIG. 4A. In the figure, 11 is a substrate, 12 is a piezoelectric element, 13 is a flow path plate, 13a is an ink flow path, 13b is a wall, 14 is a common liquid chamber constituent member, 14a is a common liquid chamber, 15 is an ink supply pipe, 16 Is a nozzle plate, 16a is a nozzle, 17 is a drive circuit printed board (PCB), 18 is a lead portion, 19 is a drive electrode, 20 is a groove, 21 is a protective plate, 22 is a fluid resistance, 23 and 24 are electrodes, 25 Is an upper partition wall, 26 is a heater, 27 is a heater power supply, 28 is a heat transfer member, and 10 is an inkjet head.

  In the integrated inkjet head 10, the laminated piezoelectric element 12 having the electrodes 23 and 24 is grooved in the direction of the flow path 13a corresponding to the flow path 13a, so that the groove 20 and the driving piezoelectric element 12b. And non-driving piezoelectric element 12a. The groove 20 is filled with a filler. The flow path plate 13 is joined to the piezoelectric element 12 subjected to the groove processing through the upper partition wall 25. In other words, the upper partition 25 is supported by the non-driving piezoelectric element 12a and the wall 13b that separates the adjacent flow path. The width of the driving piezoelectric element 12b is slightly narrower than the width of the flow path 13a. When the driving piezoelectric element 12b selected by the driving circuit on the driving circuit printed board (PCB) is applied with a pulsed signal voltage, the driving piezoelectric element 12b. The element 12b changes in the thickness direction, and the volume of the flow path 13a changes via the upper partition wall 25. As a result, ink droplets are ejected from the nozzles 16a of the nozzle plate 16.

  Heaters 26 are bonded to the flow path plate 13 via heat transfer members 28, respectively. The heat transfer member 28 is provided around the nozzle surface. The heat transfer member 28 is intended to efficiently transfer the heat from the heater 26 to the flow path plate 13, carry the heat from the heater 26 to the vicinity of the nozzle surface, and warm the air in the vicinity of the nozzle surface. A material with good conductivity is used. For example, metals such as aluminum, iron, nickel, copper, and stainless steel, or ceramics such as SiC, BeO, and AlN are preferable materials.

  When the piezoelectric element is driven, the piezoelectric element is displaced in a direction perpendicular to the longitudinal direction of the flow path, and the volume of the flow path is changed. By the change in volume, ink droplets are ejected from the nozzle. The piezoelectric element is given a signal that keeps the flow path volume constantly reduced, and after the displacement of the selected flow path in the direction of increasing the flow volume, the displacement that reduces the flow volume again is applied. By applying a pulse signal to be applied, ink is ejected as ink droplets from a nozzle corresponding to the flow path.

  FIG. 5 is a schematic view showing an example of an inkjet head unit and a nozzle plate that can be used in the present invention.

  5, (a) of FIG. 5 is a cross-sectional view of the head portion, and (b) of FIG. 5 is a plan view of the nozzle plate. In the figure, 1 is a transparent substrate, 31 is an ink droplet, and 32 is a nozzle. The ink droplet 31 ejected from the nozzle 32 flies in the direction of the transparent substrate 1 and adheres. The ink droplets landed on the transparent substrate 1 are formed with convex portions by drying.

  In the present invention, as shown in FIG. 5B, the nozzles of the inkjet head unit are preferably arranged in a staggered manner, and are provided in multiple stages in parallel in the transport direction of the transparent substrate 1. preferable. Further, it is preferable that fine vibrations are applied to the ink jet head portion during ink ejection so that ink droplets land randomly on the transparent substrate. Thereby, generation | occurrence | production of an interference fringe can be suppressed. The fine vibration can be given by a high frequency voltage, a sound wave, an ultrasonic wave, or the like, but is not particularly limited thereto. In addition, the flow of air is controlled so that the ink droplets 31 emitted by the ink jet method are not disturbed and biased by the surrounding air of the transparent substrate 1 that moves and are not unintentionally uneven.

  As the ink jet head, the electrostatic discharge type ink jet head described in Japanese Patent Application Laid-Open No. 2004-58505 can be diverted to the anti-blocking process of the present invention, the liquid discharge head described in Japanese Patent Application Laid-Open No. 2004-58532, and the ink jet described in Japanese Patent Application Laid-Open No. 2004-54271. The patterning device can also be diverted to the anti-blocking process of the present invention, the jet head described in JP-A-2004-55520 can be diverted, and the inkjet head described in registration 3,5000,636 can be diverted, The ink jet recording system described in Registration No. 3,501,583 can also be used for the anti-blocking process of the present invention.

  Further, it is preferable to check whether or not the head is clogged by performing a test discharge before discharging the ink for forming the convex portion. When clogging is confirmed or at the start of production, the head cleaning is performed. It is preferable to implement. The head cleaning may be performed with the ink used or with a cleaning liquid mainly composed of a solvent. A solvent that can be used for the ink is preferably used as the solvent of the cleaning liquid. If necessary, a surfactant (nonionic, fluorine, silicon, etc.) may be contained in an amount of about 0.01 to 1%.

  The ink discharge density for forming the convex portion is preferably adjusted as appropriate. For example, the ink discharge density for forming the small convex portion is increased with respect to the ink discharge density for forming the large convex portion. It is preferable.

  When clogging of a head is detected during production, it is preferable to stop supplying ink to the head. It is also preferable to increase the amount of ink discharged from other heads so that unevenness does not occur in the convex portions formed thereby. When using a multi-stage inkjet head, it is preferable to clean the clogged inkjet head while continuing production. In that case, the ink is discharged so that the cleaning liquid does not adhere to the substrate film to be treated. It is preferable to change the direction or to discharge toward another member that receives the cleaning liquid. During head cleaning, it is preferable to increase the amount of ink discharged from another inkjet head or to continue production using a spare inkjet head.

  In addition, when any abnormality such as clogging of the head is confirmed during production, it is preferable to mark the end portion of the film substrate with an ink jet. The marking is preferably performed with colored ink, and it becomes easy to remove the part from the product later by clarifying the abnormal part.

  The fine convex structure forming method used in the present invention is preferably an ink jet method in which small droplets of ink are ejected from multiple nozzles. FIG. 6 shows an example of an ink jet method that can be preferably used in the present invention. Indicates.

  6, a) in FIG. 6 is a method in which the inkjet head 10 is arranged in the width direction of the transparent substrate 1 and a fine convex structure is formed on the surface of the transparent substrate 1 while being conveyed (line head method). 6b) shows a method (flat head method) in which the inkjet head 10 moves in the sub-scanning direction while forming a fine convex structure on the surface thereof, and FIG. 6c) shows that the inkjet head 10 is transparent. This is a method of forming a fine convex structure on the surface of the substrate 1 while scanning the width direction (capstan method), and any method can be used. In the present invention, from the viewpoint of productivity. A line head system is preferred. By using such an inkjet head, it is possible to easily form a convex portion having an arbitrary pattern at an arbitrary position on the transparent substrate. For this reason, the ink jet method has a high degree of freedom and is superior to the conventional matting agent addition method.

  Reference numeral 29 in FIGS. 6A to 6C denotes an actinic ray irradiating unit used when an actinic ray curable resin described later is used as the ink. When a thermoplastic resin is used for the ink, 29 is unnecessary.

  Moreover, in this invention, you may provide another actinic ray irradiation part in the downstream of the conveyance direction of the transparent base material of a) of FIG. 6, b), and c). The distance between the ink jet head part and the actinic ray irradiation part is preferably about 0.1 to 20 m and set appropriately. Moreover, it is preferable that the installation position can be changed or adjusted as necessary.

  In the present invention, in order to form fine convex portions, the ink droplet is preferably 0.01 to 100 pl, more preferably 0.1 to 50 pl, and particularly preferably 0.1 to 10 pl. By ejecting ink droplets under the above conditions, an optical film having fine convex portions excellent in haze can be obtained.

  In the present invention, the ink ejected from the ink jet head may be deposited on the convex forming surface before being separated from the ink jet head in a columnar state in which the ink extends following the tip of the ink. Is preferably attached as ink droplets after the ink has been separated from the inkjet head. It is preferable that the ink droplets ejected from the head adhere to the projection forming surface without splitting, or the ink droplets are made minute by applying ejection conditions that intentionally split. Thus, it is preferable to form a finer convex portion, which can be appropriately adjusted according to the shape of the convex portion to be formed.

  Further, the viscosity of the ink droplet is preferably 25 mPa · s or less, and more preferably 10 mPa · s or less. The ink viscosity upon landing is preferably higher than the ink viscosity upon ejection, preferably 15 mPa · s or more, and more preferably 25 mPa · s or more. The higher the viscosity at the time of landing, the easier it is to form a convex part with a large Ra, and it is preferable to adjust the viscosity appropriately in order to form a desired convex part shape.

  Next, the ink used in the ink jet system for forming the fine convex structure according to the present invention will be described.

  The ink according to the present invention is characterized in that it contains a composition that forms a fine convex structure by an ink jet method, and the composition includes a thermoplastic resin, an actinic ray curable resin, or a thermosetting resin. It is preferable that

  First, the thermoplastic resin used in the present invention will be described.

The thermoplastic resin according to the present invention is not particularly limited, but preferred examples include, but are not limited to, cellulose esters, polycarbonates, acrylic resins, cycloolefin polymers, polyesters, and polyvinyl alcohols. The thermoplastic resin used in the ink is preferably mainly composed of cellulose ester, and cellulose ester used in the transparent substrate film described later is preferably used. That is, cellulose acetates such as cellulose acetate, cellulose diacetate, cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate phthalate, cellulose triacetate, and cellulose nitrate are preferable, and cellulose acetate, cellulose diacetate, and cellulose acetate propio are particularly preferable. Nate is preferred. A cellulose ester having a total acyl group substitution degree of 2.0 to 3.0 is preferably used. When a cellulose ester is used for the transparent substrate film, a cellulose ester having a substitution degree equal to or lower than that of the cellulose ester is preferably used. In particular, the cellulose ester is preferably used when the convex forming surface is subjected to alkali saponification treatment to bond a polarizer. The cellulose ester can be dissolved in an organic solvent described later and used as an ink composition.

  Next, the actinic ray curable resin used in the present invention will be described.

  Typical examples of the actinic radiation curable resin include an ultraviolet curable resin, an electron beam curable resin, and the like, but a resin that is cured by irradiation with active rays other than ultraviolet rays and electron beams may also be used.

  Examples of the ultraviolet curable resin include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. I can do it.

  Specific examples include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, and the like.

  In general, UV-curable acrylic urethane resins include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylate) in addition to products obtained by reacting polyester polyols with isocyanate monomers or prepolymers. And acrylate only), and those easily formed by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate, as described in JP-A-59-151110 Can be used.

  Examples of UV curable polyester acrylate resins include those that are easily formed by reacting polyester polyols with 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers, as disclosed in JP-A-59-151112. Those described can be used.

  Specific examples of the ultraviolet curable epoxy acrylate resin include an epoxy acrylate as an oligomer, a reactive diluent and a photoreaction initiator added thereto, and reacted to form an oligomer. The thing as described in 105738 can be used.

  Specific examples of these photoinitiators include benzoin and derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. You may use with a photosensitizer.

  The above photoinitiator can also be used as a photosensitizer. Further, when using an epoxy acrylate photoreactant, a sensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used.

  Examples of the resin monomer include general monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate, and styrene as monomers having one unsaturated double bond. In addition, monomers having two or more unsaturated double bonds include ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, and the above trimethylolpropane. Examples thereof include triacrylate and pentaerythritol tetraacryl ester.

  Examples of commercially available UV curable resins that can be used in the present invention include ADEKA OPTMER KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (Asahi Denka ( Co., Ltd.); Koeihard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS -101, FT-102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Co., Ltd.); Seika Beam PHC2210 (S), PHCX-9 (K-3), PHC2213, DP- 10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (manufactured by Dainichi Seika Kogyo Co., Ltd.) KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (manufactured by Daicel UCB); RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102, RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (Dainippon Ink Chemical Co., Ltd.); 340 clear (manufactured by China Paint Co., Ltd.); Sunrad H-601, RC700, RC750 (manufactured by Sanyo Chemical Industries); SP-1509, SP-1507 (manufactured by Showa Polymer Co., Ltd.); RCC-15C ( Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (Toagosei Co., Ltd.) and the like can be appropriately selected and used.

  These actinic radiation curable resins can be cured by a known method.

As a light source for curing the ultraviolet curable resin by a photocuring reaction, any light source that generates ultraviolet light can be used without limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. The irradiation conditions vary depending on individual lamps, but the amount of light irradiated may be any degree 20~10000mJ / cm ^2, preferably from 50~2000mJ / cm ^2. By using a sensitizer having an absorption maximum in the near ultraviolet region to the visible light region, it can be efficiently formed.

  The organic solvent used in the ink containing the ultraviolet curable resin is appropriately selected from, for example, hydrocarbons, alcohols, ketones, esters, glycol ethers, and other organic solvents, or a mixture thereof. Available. For example, propylene glycol monoalkyl ether (1 to 4 carbon atoms of the alkyl group) or propylene glycol monoalkyl ether acetate (1 to 4 carbon atoms of the alkyl group) is 5% by mass or more, more preferably 5%. It is preferable to use the organic solvent containing from mass% to 80 mass% or more.

  In addition, a surfactant such as a fluorine-based surfactant, a silicon-based surfactant, or a nonionic surfactant can be added to the ink in an amount of about 0.01 to 5.0%.

  Next, the thermosetting resin used in the present invention will be described.

  Examples of the thermosetting resin that can be used in the present invention include unsaturated polyester resins, epoxy resins, vinyl ester resins, phenol resins, thermosetting polyimide resins, thermosetting polyamide imides, and the like.

As the unsaturated polyester resin, for example, orthophthalic acid resin, isophthalic acid resin, terephthalic acid resin, bisphenol resin, propylene glycol-maleic acid resin, dicyclopentadiene or derivatives thereof are introduced into the unsaturated polyester composition. Low styrene volatile resin with low molecular weight or added film-forming wax compound, low shrinkage with thermoplastic resin (polyvinyl acetate resin, styrene / butadiene copolymer, polystyrene, saturated polyester, etc.) Resin, unsaturated polyester brominated directly with Br ₂ , or reactive type such as copolymerization of het acid or dibromoneopentyl glycol, halides such as chlorinated paraffin, tetrabromobisphenol and antimony trioxide, phosphorus Compound combinations Additive-type flame retardant resin that uses sesame or aluminum hydroxide as an additive, toughness resin that is hybridized with polyurethane or silicone, or toughened with IPN (high strength, high elastic modulus, high elongation), etc. is there.

  Examples of the epoxy resin include glycidyl ether type epoxy resins including bisphenol A type, novolak phenol type, bisphenol F type and brominated bisphenol A type, glycidyl amine type, glycidyl ester type, cyclic aliphatic type, and heterocyclic epoxy type. Special epoxy resins containing

  As the vinyl ester resin, for example, an oligomer obtained by ring-opening addition reaction of an ordinary epoxy resin and an unsaturated monobasic acid such as methacrylic acid is dissolved in a monomer such as styrene. There are also special types such as vinyl monomers having vinyl groups at the molecular ends and side chains. Examples of vinyl ester resins of glycidyl ether type epoxy resins include bisphenol type, novolak type, brominated bisphenol type, etc., and special vinyl ester resins include vinyl ester urethane type, isocyanuric acid vinyl type, side chain vinyl ester type, etc. There is.

  The phenol resin is obtained by polycondensation using phenols and formaldehyde as raw materials, and there are a resol type and a novolac type.

  Examples of thermosetting polyimide resins include maleic acid-based polyimides such as polymaleimide amine, polyamino bismaleimide, bismaleimide / O, O'-diallyl bisphenol-A resin, bismaleimide / triazine resin, and nadic acid-modified polyimide. And acetylene-terminated polyimide.

  A part of the actinic ray curable resin described above can also be used as a thermosetting resin.

  In addition, antioxidants and ultraviolet absorbers may be used as appropriate for the ink made of the thermosetting resin according to the present invention.

  In the present invention, when the convex portion formed by the ink jet method contains a thermosetting resin, it is preferable to perform the heat treatment immediately after the ink droplets have landed on the transparent substrate.

  The term “immediately after the ink droplets have landed on the transparent substrate” as used in the present invention specifically means that the heating of the ink droplets is preferably started simultaneously with the landing or within 5 seconds. Can be raised. For example, a transparent substrate can be wound on a heat roll, and ink droplets can be landed on it, more preferably at the same time as landing or for 2.0 seconds. In addition, if the distance between the nozzle part and the heating part is too close and heat is transferred to the head part, the nozzle part is clogged due to curing at the nozzle part, so care must be taken. Further, if the heating interval exceeds 5.0 seconds as necessary, a gentle convex structure can be obtained by flowing and deforming the landed ink droplets.

  In order to prevent heat from being transferred to the nozzle portion during the heating, in the ink jet system of the present invention, it is preferable to dispose the heating portion at a position that does not directly act on the nozzle portion of the ink jet head.

  The heating method is not particularly limited, but it is preferable to use a heat plate, a heat roll, a thermal head, or a method of spraying hot air on the landed ink surface. Further, the back roll provided on the opposite side of the transparent support of the ink jet emitting portion may be continuously heated as a heat roll. The heating temperature cannot be generally defined by the type of thermosetting resin to be used, but is preferably in a temperature range that does not affect the heat deformation of the transparent substrate, preferably 30 to 200 ° C, Furthermore, 50-120 degreeC is preferable, Especially preferably, it is 70-100 degreeC.

  In the ink according to the present invention, any of the above-described thermoplastic resin, actinic ray curable resin, or thermosetting resin can be used as the composition, and it is preferable to use a thermoplastic resin.

  The ink according to the present invention may contain 0 to 99.9% by mass of a solvent as required. For example, the thermoplastic resin component, the actinic ray curable resin monomer component, or the thermosetting resin monomer component may be dissolved or dispersed in an aqueous solvent, or an organic solvent may be used. An organic solvent having a low boiling point or a high boiling point can be appropriately selected and used, and the addition amount, type, and composition of these solvents are preferably adjusted appropriately in order to adjust the viscosity of the ink.

  Examples of the solvent that can be used in the ink according to the present invention include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, and butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Ketone alcohols such as alcohol; aromatic hydrocarbons such as benzene, toluene and xylene; glycols such as ethylene glycol, propylene glycol and hexylene glycol; ethyl cellosolve, butylcellosolve, ethylcarbitol, butylcarbitol, Glycol ethers such as diethyl cellosolve, diethyl carbitol, propylene glycol monomethyl ether; N-methylpyrrolidone, dimethylformamide, methyl lactate, ethyl lactate, methyl acetate , Ethyl acetate, esters such as amyl acetate; dimethyl ether, and diethyl ether, water and the like, they alone or as a mixture of two or more thereof can be used. Further, those having an ether bond in the molecule are particularly preferred, and glycol ethers are also preferably used.

  Specific examples of glycol ethers include, but are not limited to, the following solvents. Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether Ac, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether Ac, ethylene glycol Examples thereof include diethyl ether, and Ac represents acetate. In the ink according to the present invention, among the above solvents, a solvent having a boiling point of less than 100 ° C. is preferably used. It is desirable that these solvents are volatilized immediately after being ejected from the ink jet head, and are volatilized and dried as quickly as possible so that a desired convex shape is maintained even after landing. Alternatively, the convex shape can be controlled by mixing different volatile solvents and changing the ratio.

  The solvent used in the ink is preferably used by mixing a solvent that dissolves the base film and a solvent that does not dissolve, and the mixing ratio is preferably 1: 9 to 9: 1, and the ratio is appropriately adjusted.

  Next, a preferred embodiment for forming a fine convex structure by the ink jet method in the present invention will be described.

  As a method for forming a fine convex structure in the present invention, two or more ink droplets having different particle diameters can be emitted and formed. Furthermore, after forming a fine convex structure on a transparent substrate with ink droplets having a large particle size, it is also possible to form a finer convex structure with ink droplets having a smaller particle size than the ink droplet.

  FIG. 7 shows an example in which a fine convex structure 71 is formed with ink droplets having a larger particle diameter and then a fine convex structure 72 is formed with ink droplets having a smaller particle diameter by an ink jet method on a transparent substrate. It is a schematic diagram showing.

  FIG. 7A is an example in which a Conide-type convex portion 71 is provided using a relatively low viscosity ink, and then a minute convex portion 72 is provided on the surface and the non-landing portion. (B) is an example in which the contact angle between the ink droplet and the substrate surface is controlled, and a spherical convex portion 71 ′ is provided, and then a minute convex portion 72 is provided by the surface and the non-landing portion. is there.

  In this case as well, the height, diameter, and number of formed protrusions formed by droplets having a large particle size must be controlled within the scope of the present invention.

  In this way, by forming ink droplets having different particle diameters as the ink for forming the convex structure, it is possible to form fine convex portions having an excellent anti-blocking effect. Each ink droplet is preferably 0.01 to 100 pl, more preferably 0.1 to 50 pl, and particularly preferably 0.1 to 10 pl. When two or more kinds of ink droplets having different sizes are used, the volume of the ink droplets having the smallest average particle size relative to the ink droplets having the largest average particle size is 0.1. It is preferable that it is -80 volume%, More preferably, it is 1-60 volume%, Most preferably, it is 3-50 volume%. Further, it is a more preferable aspect that three or more kinds of ink droplets having different capacities are combined.

  When two or more ink droplets are used, each ink droplet having a different solid content concentration can be used. For example, finer convex portions can be formed by setting the solid content concentration of fine droplets low and volatilizing the solvent while the ink is flying or after landing. By appropriately adjusting the solid content concentration of each ink droplet, it is possible to easily control the formation and shape of a fine convex structure.

  Furthermore, in the present invention, when a convex structure is formed by combining ink droplets having different capacities, after a large ink droplet is landed on the transparent substrate, a finer ink droplet is landed thereon. Is preferred.

  As another preferable example of the fine convex structure in the present invention, it is also preferable that the ink droplet contains fine particles.

  FIG. 8 is a cross-sectional view showing an example of a convex portion in which fine particles are contained in an ink droplet.

  In the thermoplastic resin, the actinic ray curable resin or the thermosetting resin, fine particles 4 described later are included, and if the fine particles can form convex portions having a preferable size of the present invention, the size and shape are not limited. Absent. There are cases in which only relatively large particles (a), only small particles (b), and large and small particles are mixed (c). Moreover, the convex part of each structure may be mixed (d).

  In the present invention, examples of the fine particles that can be contained in the ink droplet include inorganic fine particles and organic fine particles.

  Examples of inorganic fine particles include silicon-containing compounds, silicon dioxide, aluminum oxide, zirconium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and Calcium phosphate and the like are preferable, and an inorganic compound containing silicon and zirconium oxide are more preferable, and silicon dioxide is particularly preferably used. These include particles having a shape such as a spherical shape, a flat plate shape, and an amorphous shape.

  As the silicon dioxide fine particles, for example, commercially available products such as Aerosil R972, R972V, R972CF, R974, R812, 50, 200, 200V, 300, R202, OX50, TT600, MOX170 (manufactured by Nippon Aerosil Co., Ltd.) are used. I can do it.

  As the fine particles of zirconium oxide, commercially available products such as Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) can be used.

  The organic fine particles include polymethacrylate methyl acrylate resin fine particles, acrylic styrene resin fine particles, polymethyl methacrylate resin fine particles, silicon resin fine particles, polystyrene resin fine particles, polycarbonate resin fine particles, benzoguanamine resin fine particles, and melamine resin. Examples thereof include fine particles, polyolefin resin fine particles, polyester resin fine particles, polyamide resin fine particles, polyimide resin fine particles, polyfluoroethylene resin fine particles, and cellulose ester resin. For example, MS-300K and MS-300X (particle size: 0.1 μm) are preferably used as the polymethyl methacrylate crosslinked particles, and MP1451 (all manufactured by Soken Chemical Co., Ltd.) is used as the acrylic monodisperse particles.

  The average particle size of the fine particles used in the present invention is preferably 0.001 to 0.5 μm, more preferably 0.005 to 0.5 μm, and particularly preferably 0.01 to 0.3 μm. You may contain 2 or more types of microparticles | fine-particles from which a particle size and refractive index differ. For example, by using monodispersed particles having a particle size of 0.03 to 0.3 μm, it is possible to efficiently form convex portions having the same convex portion height. Preferably, the refractive index difference between the resin and fine particles contained in the ink is within ± 0.02, and the refractive index difference between the resin contained in the ink and the base film is also within ± 0.02.

  The ratio of the resin and fine particles contained in the ink is preferably 1 to 99% of the total solid content, preferably 5 to 95%, preferably 20 to 90%. .

  Subsequently, the manufacturing method of the optical film of this invention is demonstrated.

  FIG. 9 is a schematic diagram showing a flow in which a step of providing a fine convex structure by an ink jet method is added to the step of manufacturing a transparent substrate by solution casting.

  In FIG. 9, reference numeral 11 denotes a support that runs endlessly. A mirror band metal is used as the support. Reference numeral 12 denotes a die for casting a dope obtained by dissolving a transparent substrate forming resin in a solvent onto the support 11. 13 shows a peeling roll which peels off the film | membrane which the dope cast | casted by the support body 11 solidified, 14 shows the peeled film. 5 indicates a tenter conveying / drying process, 51 indicates an exhaust port, and 52 indicates a dry air intake port. The exhaust port 51 and the dry air intake port 52 may be reversed. Reference numeral 6 denotes a tension cutting means. Examples of the tension cutting means include a nip roll and a suction roll. The tension cutting means may be provided between each process.

  8 represents a roll conveying / drying process, 81 represents a drying box, 82 represents an exhaust port, and 83 represents a dry air intake. The exhaust port 82 and the dry air intake port 83 may be reversed. Reference numeral 84 denotes an upper conveyance roll, and 85 denotes a lower conveyance roll. The transport rolls 84 and 85 are a set of upper and lower, and are composed of a plurality of sets. 7 shows the roll-shaped film wound up.

  The ink jet head unit 10 for emitting ink droplets according to the present invention may be installed at any position in the dope casting unit, between the peeling unit and the tenter unit, between the tenter unit and the drying unit, or in the drying box. Can be provided at positions 10A to H in the figure. In that case, you may provide an inkjet head part in any one side of a film surface, or both sides. There are no particular restrictions on the number of ink jet head units 10 installed, and one or a plurality of ink jet head units 10 may be provided, but a plurality of ink jet head units are preferably installed.

  FIG. 10 is a schematic diagram showing a flow in which a step of providing a fine convex structure by an ink jet method is added to the step of manufacturing a transparent substrate by melt casting.

  In FIG. 10, reference numeral 21 denotes a die for melt casting, from which a melted polymer, which will be described later, is extruded and becomes a film F through a film forming roll 22. Subsequently, the film is stretched by the tenter conveyance / drying step 5 and wound up through a roll to form a roll-shaped film 7.

  The inkjet head unit 10 for emitting ink droplets according to the present invention can be provided at positions 10I to K in the drawing. In that case, you may provide an inkjet head part in any one side of a film surface, or both sides. There are no particular restrictions on the number of ink jet head units 10 installed, and one or a plurality of ink jet head units 10 may be provided, but a plurality of ink jet head units are preferably installed.

  FIG. 11 is a schematic view showing a flow of another process for providing a fine convex structure on a transparent substrate by an ink jet method. Specifically, after a functional layer such as an ultraviolet curable resin layer or an antireflection layer is coated on a transparent substrate by a coating method, a flow for forming a fine convex structure on the back surface side by an inkjet method is shown.

  In FIG. 11, the transparent base material 502 fed out from the roll 501 is conveyed, and a functional layer is applied by the first coater 503 at the first coater station A. At this time, the functional layer may be a single layer structure or a layer composed of a plurality of layers. The transparent substrate 502 on which the functional layer is applied is then dried in the drying zone 505A. Drying is performed from both surfaces of the transparent substrate 502 by warm air with controlled temperature and humidity.

  Subsequently, it is conveyed to the 2nd coater station B which provides the fine convex structure using an inkjet system. An ink supply tank 508 is connected to the ink jet emitting unit 509, and ink liquid is supplied therefrom. The ink jet emitting unit 509 arranges a plurality of ink jet nozzles as shown in FIG. 5B in a zigzag manner over the entire width of the transparent base material, emits ink droplets onto the functional layer, and is applied to the surface. A convex structure is formed. Also, when ejecting two or more types of ink droplets, each ink droplet may be ejected from two or more rows of inkjet nozzles, or randomly from any inkjet nozzle. It may be emitted. Further, a plurality of ink jet emitting portions may be arranged, and different ink droplets may be emitted from each ink emitting portion. In the present invention, since fine droplets of 0.01 to 100 pl, preferably 0.01 to 10 pl, are emitted, the flying properties of the ink droplets are easily affected by the airflow of the outside air. It is preferable to cover the entire coater station B with a partition wall or the like to prevent atmospheric pressure disturbance. In addition, in order to fly extremely fine droplets of 1 pl or less with high accuracy, a voltage is applied between the ink jet emitting unit 509 and the transparent base material 502 or the back roll 504B to give an electric charge to the ink droplets to electrically inject the ink liquid. A method of assisting droplet flight stability is also preferred. Alternatively, it is preferable to take measures for static elimination such as providing a static elimination bar in order to prevent charging associated with the conveyance of the film throughout the entire process so as not to cause unevenness due to charging of the film. In order to prevent deformation of the landed ink droplets, it is also preferable to use a method in which the transparent substrate is cooled to quickly reduce the flow of the ink droplets after landing. Alternatively, it is possible to volatilize the solvent contained during the flight from when the ink droplets are ejected until they land, and to land with the amount of the solvent contained in the ink droplets decreasing, thereby forming a finer convex structure. Preferred above. Therefore, a method of increasing the temperature of the ink flying space or controlling the atmospheric pressure to 1 atm or lower, for example, 20 to 100 kPa is also preferable. For example, the amount of the solvent contained in the ink droplet can be decreased to be 1/100 to 99/100 with respect to the solvent content at the time of emission and landed.

  In addition, it is also preferable that the shape of the convex portion is greatly deformed by impact due to landing or is landed gently so as not to be crushed.For example, the distance between the ink emitting portion and the landing portion is increased, or the light is emitted against gravity or electric charge. It is also preferable to soften the impact of landing. Alternatively, it is also preferable that the ink droplets are deposited on the film by discharging the ink droplets in an airflow flowing toward the film and disposing the film in a space having the ink droplets.

  When the ink droplet uses a thermosetting resin, a method of heating the back roll 504B as a heat roll is also preferable.

  The transparent substrate 502 that has been cured to such an extent that the convex structure formed by the landed ink droplets can be maintained evaporates unnecessary organic solvent and the like in the drying zone 505B to complete the curing.

  The method of forming the anti-blocking processed part by adhering the ink droplets of the present invention is preferably formed while transferring the film substrate at 1 to 200 m / min, preferably 3 to 100 m / min.

  The substrate film upon landing of the ink preferably has no unevenness in charging, and is preferably charged immediately before, or may be charged uniformly.

  In addition, by measuring the physical properties such as haze and transmission sharpness of the convex part formed by landing the ink, confirm that it is a predetermined value, and if deviation or fluctuation is confirmed, the result is fed back to the ink It is preferable to control by changing the discharge conditions and curing conditions. The measurement is preferably performed after all the convex portions are formed and the resin is cured, and may be performed during the formation of the convex portions. For example, more appropriate feedback control can be performed by performing measurement after forming a relatively large unevenness and after forming a finer convex portion thereafter.

  In the present invention, the ink jet recording apparatus and the image forming method described above are not limited, and it is also preferable to use the ink discharge amount measuring method and the apparatus described in JP-A-9-118024, in a wide range. A uniform convex portion can be formed. It is also preferable to use the ink jet head and the warp adjustment method described in JP-A-10-151748. It is also preferable to divert the image forming apparatus and the image forming method using the ink jet recording head described in JP-A-2001-260368. It is also preferable to use the ink jet printer and the ink jet recording method described in JP-A No. 2003-136740. It is also preferable to use an ink jet recording apparatus provided with a cleaning mechanism described in JP-A No. 2003-154671. JP-A-2003-165232, JP-A-2003-182092, JP-A-2003-182093, JP-A-2003-182097, JP-A-2003-182098, JP-A-2003-182211, JP-A-2003-191478, JP-A-2003-191479, etc. It is also preferable to use the inkjet recording apparatus that has been used.

  Furthermore, it is preferable to use the image forming method, ink, and recording apparatus described in JP-A No. 2003-191594. In particular, a recording head having a plurality of nozzles capable of selectively controlling the ejection of ink droplets is irradiated with actinic rays. In the image forming method for ejecting the ink to be cured, it is also preferable to apply the image forming method characterized by changing the actinic ray irradiation conditions after ink landing depending on the type of the recording material. Alternatively, it is also preferable to use the ink jet recording method and the ink jet recording apparatus described in JP-A No. 2003-211651 in the present invention.

  Alternatively, it is also preferable to apply the radiation curable inkjet ink and inkjet recording method described in JP-A No. 2003-213183 to the present invention. Alternatively, it is also preferable to use the ink jet recording apparatus and the ink jet recording method described in JP-A No. 2003-231267 in the present invention. Alternatively, it is also preferable to use the image forming method, ink, and recording apparatus described in JP-A-2003-237061 in the present invention. Alternatively, it is also preferable to apply the image forming method described in JP-A No. 2003-251796 to the present invention. Alternatively, it is also preferable to apply the actinic ray curable ink described in JP-A No. 2003-261799 and an ink jet recording method using the ink to the present invention. Alternatively, it is also preferable to use the image forming method and recording apparatus described in JP-A-2003-260790 in the present invention. Alternatively, it is also preferable to use the image forming method, recording apparatus, and ink described in JP-A No. 2003-276175 in the present invention. Alternatively, the image forming method, ink, and image forming apparatus described in JP-A-2003-276256 are also preferably used in the present invention. Alternatively, it is also preferable to use the image forming method, printed matter, and recording apparatus described in JP-A-2003-277654 in the present invention. Alternatively, it is also preferable to use the ink-jet ink and image forming method described in JP-A-2003-292837 in the present invention. Alternatively, it is also preferable to use the image forming method, ink, and recording apparatus described in JP-A-2003-305839 in the present invention. Alternatively, it is also preferable to use the image forming method and recording apparatus described in JP-A-2003-312120 in the present invention. Alternatively, it is also preferable to use the image forming method and recording apparatus described in JP-A-2003-313464 in the present invention. Alternatively, the image forming method and recording apparatus described in JP-A-2003-327875 are also preferably used in the present invention. Alternatively, it is also preferable to apply the actinic ray curable ink jet recording method described in JP-A-2004-9360 to the present invention. Alternatively, the image forming method described in JP-A-2004-25480 and the ink jet recording apparatus used therefor are also preferably used in the present invention. Alternatively, it is also preferable to use the ink jet printer described in JP-A-2004-34543 in the present invention. Alternatively, it is also preferable to use the ink jet recording method, ink and ink jet printer described in JP-A-2004-34545 in the present invention. Alternatively, it is also preferable to use the image forming method, printed matter, and recording apparatus described in JP-A-2004-51656 in the present invention. Alternatively, the actinic ray curable ink, the image forming method, and the recording apparatus described in JP-A-2004-51922 are also preferably used in the present invention. Alternatively, the actinic ray curable ink, the image forming method, and the recording apparatus described in JP-A-2004-51923 are also preferably used in the present invention. Alternatively, it is also preferable to apply the ink-jet recording ink storage method and image forming method described in JP-A-2004-51924 to the present invention. Alternatively, it is also preferable to apply the ink jet conditions and ink discharge conditions described in JP-A-2004-37855 to the present invention.

  Next, the transparent base material of the optical film according to the present invention will be described.

  In the present invention, it is preferable to use a thermoplastic resin film as the transparent substrate of the optical film.

  Although it does not specifically limit as a thermoplastic resin used for this invention, Although a cellulose ester, a polycarbonate, an acrylic resin, a cycloolefin polymer, polyester etc. are mentioned as a preferable example, it is not limited only to these. These are preferably used regardless of whether they are a film produced by solution casting or a film produced by melt casting.

  For example, a cellulose ester film such as Konica Minoltak KC8UX, KC8UY, LC4UX, KC4UY, KC8UCR3, KC8UCR4, KC8UX-H (manufactured by Konica Minolta Co., Ltd.) is used.

  The thermoplastic resin film used in the present invention preferably contains a cellulose ester or a cycloolefin polymer as a main component. These films are preferably polarizing plate protective films or retardation films.

<Cellulose ester>
The ratio Mw / Mn of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the cellulose ester used in the present invention is preferably 1.4 to 3.0. In the present invention, the cellulose ester film may contain, as a material, a cellulose ester having a Mw / Mn value of 1.4 to 3.0, but the cellulose ester contained in the film (preferably cellulose triacetate). Or the value of Mw / Mn of cellulose acetate propionate) is more preferably in the range of 1.4 to 3.0. In the synthesis process of cellulose ester, it is difficult to make it less than 1.4, and cellulose ester having a uniform molecular weight can be obtained by fractionation by gel filtration or the like. However, this method is very expensive. Moreover, it is preferable that it is 3.0 or less because the flatness is easily maintained. In addition, More preferably, it is 1.7-2.2.

  The molecular weight of the cellulose ester used in the present invention is preferably a number average molecular weight (Mn) of 80,000 to 200,000. More preferred are 100,000 to 200,000, particularly preferably 150,000 to 200,000.

  The average molecular weight and molecular weight distribution of the cellulose ester can be measured by a known method using high performance liquid chromatography. Using this, the number average molecular weight and the weight average molecular weight can be calculated, and the ratio (Mw / Mn) can be calculated.

The measurement conditions are as follows.
Solvent: Methylene chloride column: Shodex K806, K805, K803G (used by connecting 3 products manufactured by Showa Denko KK)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (manufactured by GL Sciences)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corp.) Mw = 100000-500 calibration curves with 13 samples were used. It is preferable to obtain 13 samples at approximately equal intervals.

  The cellulose ester used in the present invention is preferably an aliphatic carboxylic acid ester having about 2 to 22 carbon atoms, an aromatic carboxylic acid ester, or a mixed ester of an aliphatic carboxylic acid ester and an aromatic carboxylic acid ester. A lower fatty acid ester is preferred. The lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms. Specifically, it is described in cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate phthalate and the like, JP-A-10-45804, 8-2311761, U.S. Pat. No. 2,319,052, and the like. Mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate can be used. Among the above descriptions, the lower fatty acid esters of cellulose particularly preferably used are cellulose triacetate and cellulose acetate propionate. These cellulose esters can be used as a mixture.

  In the case of cellulose triacetate, those having a total acyl group substitution degree (acetyl group substitution degree) of 2.6 to 2.9 are preferably used.

  A preferred cellulose ester other than cellulose triacetate has an acyl group having 2 to 22 carbon atoms as a substituent, the substitution degree of the acetyl group is X, and the substitution degree of the acyl group of 3 to 22 carbon atoms is Y. Sometimes, it is a cellulose ester that simultaneously satisfies the following formulas (I) and (II).

Formula (I) 2.6 ≦ X + Y ≦ 2.9
Formula (II) 0 ≦ X ≦ 2.5
Among them, cellulose acetate propionate (total acyl group substitution degree = X + Y) satisfying 1.9 ≦ X ≦ 2.5 and 0.1 ≦ Y ≦ 1.0 is preferable. The portion not substituted with an acyl group usually exists as a hydroxyl group. These can be synthesized by known methods.

  These acyl group substitution degrees can be measured according to the method prescribed in ASTM-D817-96.

  As the cellulose ester, cellulose ester synthesized from cotton linter, wood pulp, kenaf or the like as a raw material can be used alone or in combination. In particular, it is preferable to use a cotton linter (hereinafter sometimes simply referred to as a linter) or a cellulose ester synthesized from wood pulp alone or in combination.

  Moreover, the cellulose ester obtained from these can be mixed and used in arbitrary ratios, respectively. These cellulose esters are prepared by using an organic acid such as acetic acid or an organic solvent such as methylene chloride when sulfuric acid is used as the acylating agent (acetic anhydride, propionic anhydride, butyric anhydride). It can obtain by making it react by a conventional method using a protic catalyst like.

  In the case of acetylcellulose, it is necessary to extend the time for the acetylation reaction in order to increase the acetylation rate. However, if the reaction time is too long, the decomposition proceeds at the same time, and the polymer chain is broken and the acetyl group is decomposed, resulting in undesirable results. Therefore, it is necessary to set the reaction time within a certain range in order to increase the degree of acetylation and suppress decomposition to some extent. It is not appropriate to define the reaction time because the reaction conditions are various and greatly change depending on the reaction apparatus, equipment and other conditions. As the decomposition of the polymer progresses, the molecular weight distribution becomes wider. Therefore, in the case of cellulose ester, the degree of decomposition can be defined by the value of weight average molecular weight (Mw) / number average molecular weight (Mn) that is usually used. That is, in the process of acetylation of cellulose triacetate, the weight average molecular weight is used as one index of the reaction degree for allowing the acetylation reaction to be carried out for a sufficient time for acetylation without being too long and being decomposed too much. The value of (Mw) / number average molecular weight (Mn) can be used.

  An example of a method for producing a cellulose ester is shown below: 100 parts by mass of a flocculent linter was crushed as a cellulose raw material, 40 parts by mass of acetic acid was added, and pretreatment activation was performed at 36 ° C. for 20 minutes. Thereafter, 8 parts by mass of sulfuric acid, 260 parts by mass of acetic anhydride and 350 parts by mass of acetic acid were added, and esterification was performed at 36 ° C. for 120 minutes. After neutralization with 11 parts by mass of a 24% magnesium acetate aqueous solution, saponification aging was carried out at 63 ° C. for 35 minutes to obtain acetylcellulose. This was stirred for 160 minutes at room temperature using a 10-fold acetic acid aqueous solution (acetic acid: water = 1: 1 (mass ratio)), then filtered and dried to obtain purified acetylcellulose having an acetyl substitution degree of 2.75. . This acetylcellulose had Mn of 92000, Mw of 156000, and Mw / Mn of 1.7. Similarly, cellulose esters having different degrees of substitution and Mw / Mn ratios can be synthesized by adjusting the esterification conditions (temperature, time, stirring) and hydrolysis conditions of the cellulose ester.

  The synthesized cellulose ester is preferably purified to remove low molecular weight components or to remove unacetylated or low acetylated components by filtration.

  In the case of mixed acid cellulose ester, it can be obtained by the method described in JP-A-10-45804. The measuring method of the substitution degree of an acyl group can be measured according to the provisions of ASTM-D817-96.

  Cellulose esters are also affected by trace metal components in cellulose esters. These are considered to be related to water used in the production process, but it is preferable that there are few components that can become insoluble nuclei, and metal ions such as iron, calcium, and magnesium contain organic acidic groups. Insoluble matter may be formed by salt formation with a polymer degradation product or the like that may be present, and it is preferable that the amount is small. The iron (Fe) component is preferably 1 ppm or less. About calcium (Ca) component, it is contained in a lot of ground water and river water, etc., and it becomes hard water, and it is unsuitable as drinking water. Coordination compounds with ligands, that is, complexes are easily formed, and scum (insoluble starch, turbidity) derived from many insoluble calcium is formed.

  The calcium (Ca) component is 60 ppm or less, preferably 0 to 30 ppm. The magnesium (Mg) component is preferably in the range of 0 to 70 ppm, particularly preferably 0 to 20 ppm, since too much will cause insoluble matter. Metal components such as iron (Fe) content, calcium (Ca) content, magnesium (Mg) content, etc. are pre-processed by completely digesting cellulose ester with micro digest wet cracking equipment (sulfuric acid decomposition) and alkali melting. After performing, it can obtain | require by performing an analysis using ICP-AES (inductively coupled plasma emission spectroscopy analyzer).

  The cellulose ester film used in the present invention preferably has a refractive index of 1.45 to 1.60 at 550 nm. As a method for measuring the refractive index of the film, an Abbe refractometer is used, and measurement is performed based on Japanese Industrial Standard JIS K 7105. Further, the refractive index of each layer of the antireflection layer described later is calculated from the reflection spectrum of 5 ° regular reflection of the thin film applied to each layer. The cellulose ester film can contain additives such as a plasticizer, an ultraviolet absorber, an antioxidant, and a matting agent.

<Plasticizer>
The plasticizer is not particularly limited, but is selected from polyhydric alcohol ester plasticizers, phosphate ester plasticizers, phthalic acid esters, citric acid esters, fatty acid esters, glycolate plasticizers, polycarboxylic acid esters, and the like. It is preferable to include at least one plasticizer. Of these, at least one is preferably a polyhydric alcohol ester plasticizer.

  The polyhydric alcohol ester plasticizer is a plasticizer comprising an ester of a dihydric or higher aliphatic polyhydric alcohol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule. Preferably it is a 2-20 valent aliphatic polyhydric alcohol ester.

  The polyhydric alcohol used in the present invention is represented by the following general formula (1).

Formula (1) R _1- (OH) _n
However, R ₁ represents an n-valent organic group, n represents a positive integer of 2 or more, and the OH group represents an alcoholic and / or phenolic hydroxyl group.

  Examples of preferred polyhydric alcohols include the following, but the present invention is not limited to these. Adonitol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, galactitol, mannitol, 3-methylpentane- Examples include 1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, and xylitol. In particular, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol are preferable.

  There is no restriction | limiting in particular as monocarboxylic acid used for the polyhydric alcohol ester of this invention, Well-known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid, etc. can be used. Use of an alicyclic monocarboxylic acid or aromatic monocarboxylic acid is preferred in terms of improving moisture permeability and retention.

  Examples of preferred monocarboxylic acids include the following, but the present invention is not limited thereto.

  As the aliphatic monocarboxylic acid, a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used. The number of carbon atoms is more preferably 1-20, and particularly preferably 1-10. When acetic acid is contained, the compatibility with the cellulose ester is increased, and it is also preferable to use a mixture of acetic acid and another monocarboxylic acid.

  Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanoic acid, undecylic acid, lauric acid, tridecylic acid, Saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, laccelic acid, undecylenic acid, olein Examples thereof include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid.

  Examples of preferable alicyclic monocarboxylic acids include cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, and derivatives thereof.

  Examples of preferred aromatic monocarboxylic acids include those in which an alkyl group is introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, and two or more benzene rings such as biphenylcarboxylic acid, naphthalenecarboxylic acid, and tetralincarboxylic acid. The aromatic monocarboxylic acid which has, or those derivatives can be mentioned. Benzoic acid is particularly preferable.

  The molecular weight of the polyhydric alcohol ester is not particularly limited, but is preferably 300 to 1500, and more preferably 350 to 750. A higher molecular weight is preferred because it is less likely to volatilize, and a smaller one is preferred in terms of moisture permeability and compatibility with cellulose ester.

  The carboxylic acid used for the polyhydric alcohol ester may be one kind or a mixture of two or more kinds. Moreover, all the OH groups in the polyhydric alcohol may be esterified, or a part of the OH groups may be left as they are.

  Below, the specific compound of a polyhydric alcohol ester is illustrated.

  The glycolate plasticizer is not particularly limited, but alkylphthalylalkyl glycolates can be preferably used. Examples of alkyl phthalyl alkyl glycolates include methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate, methyl phthalyl ethyl Glycolate, ethyl phthalyl methyl glycolate, ethyl phthalyl propyl glycolate, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl phthalyl methyl glycolate, butyl phthalyl ethyl glycolate, propyl phthalyl butyl glycol Butyl phthalyl propyl glycolate, methyl phthalyl octyl glycolate, ethyl phthalyl octyl glycolate, octyl phthalyl methyl glycolate, octyl phthalate Ethyl glycolate, and the like.

  Examples of the phthalate ester plasticizer include diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, and dicyclohexyl terephthalate.

  Examples of the citrate plasticizer include acetyl trimethyl citrate, acetyl triethyl citrate, and acetyl tributyl citrate.

  Examples of fatty acid ester plasticizers include butyl oleate, methylacetyl ricinoleate, and dibutyl sebacate.

  Polycarboxylic acid ester plasticizers can also be preferably used. Specifically, it is preferable to add the polyvalent carboxylic acid ester described in paragraphs [0015] to [0020] of JP-A No. 2002-265639 as one of the plasticizers.

  Examples of the phosphate ester plasticizer include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate and the like.

  The cellulose ester film used in the present invention preferably contains at least two kinds of plasticizers.

  By including two or more plasticizers, elution of the plasticizer can be reduced. The reason is not clear, but it seems that elution is suppressed by the ability to reduce the amount added per type and the interaction between the two plasticizers and the cellulose ester.

  The total content of the plasticizer in the cellulose ester film is preferably 5 to 30% by mass with respect to the total solid content. Furthermore, 5-20 mass% is preferable, 6-16 mass% is more preferable, Especially preferably, it is 8-13 mass%. The contents of the two kinds of plasticizers are each at least 1% by mass, preferably 2% by mass or more.

<Ultraviolet absorber>
The cellulose ester film according to the present invention preferably contains an ultraviolet absorber. The ultraviolet absorber is intended to improve durability by absorbing ultraviolet rays of 400 nm or less, and is particularly preferably added so that the transmittance at a wavelength of 370 nm is 10% or less. Is 5% or less, more preferably 2% or less.

  Although the ultraviolet absorber used in the present invention is not particularly limited, for example, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex compounds, inorganic powders Examples include the body.

  For example, 5-chloro-2- (3,5-di-sec-butyl-2-hydroxylphenyl) -2H-benzotriazole, (2-2H-benzotriazol-2-yl) -6- (linear and side Chain dodecyl) -4-methylphenol, 2-hydroxy-4-benzyloxybenzophenone, 2,4-benzyloxybenzophenone, etc., and tinuvin 109, tinuvin 171, tinuvin 234, tinuvin 326, tinuvin 327, tinuvin 328, etc. These are commercially available products manufactured by Ciba Specialty Chemicals and can be preferably used.

  For example, as the benzotriazole ultraviolet absorber, a compound represented by the following general formula (1) is preferably used.

In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be the same or different, and are a hydrogen atom, halogen atom, nitro group, hydroxyl group, alkyl group, alkenyl group, aryl group, alkoxy group, acyloxy Represents a group, aryloxy group, alkylthio group, arylthio group, mono- or dialkylamino group, acylamino group or 5- to 6-membered heterocyclic group, and R ₄ and R ₅ are closed to form a 5- to 6-membered carbocyclic ring May be.

Specific examples of the ultraviolet absorbent useful in the present invention are listed below, but the present invention is not limited thereto.
UV-1: 2- (2'-hydroxy-5'-methylphenyl) benzotriazole UV-2: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole UV-3 : 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole UV-4: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl)- 5-Chlorobenzotriazole UV-5: 2- (2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole UV-6: 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol)
UV-7: 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole A benzophenone-based ultraviolet absorber that is one of the ultraviolet absorbers useful in the present invention Is preferably a compound represented by the following general formula (2).

  In the formula, Y represents a hydrogen atom, a halogen atom or an alkyl group, an alkenyl group, an alkoxy group, and a phenyl group, and these alkyl group, alkenyl group, and phenyl group may have a substituent. A represents a hydrogen atom, an alkyl group, an alkenyl group, a phenyl group, a cycloalkyl group, an alkylcarbonyl group, an alkylsulfonyl group or a —CO (NH) n-1-D group, and D represents an alkyl group, an alkenyl group or a substituent. Represents a phenyl group which may have m and n represent 1 or 2.

  In the above, the alkyl group represents, for example, a linear or branched aliphatic group having up to 24 carbon atoms, the alkoxy group has, for example, an alkoxy group having up to 18 carbon atoms, and the alkenyl group has, for example, up to 16 carbon atoms. Represents an allyl group, a 2-butenyl group, or the like. In addition, as substituents for alkyl groups, alkenyl groups, and phenyl groups, halogen atoms such as chloro, bromo, and fluorine atoms, hydroxy groups, phenyl groups, (this phenyl group is substituted with alkyl groups or halogen atoms, etc. May be included).

Specific examples of the benzophenone-based compound represented by the general formula (2) are shown below, but the present invention is not limited thereto.
UV-8: 2,4-dihydroxybenzophenone UV-9: 2,2'-dihydroxy-4-methoxybenzophenone UV-10: 2-hydroxy-4-methoxy-5-sulfobenzophenone UV-11: bis (2-methoxy -4-hydroxy-5-benzoylphenylmethane)
Further, as the triazine-based ultraviolet absorber, a compound having a 1,3,5-triazine ring is preferably used.

  Moreover, you may use together the compound which has a 2 or more types of 1,3,5- triazine ring. Two or more kinds of discotic compounds (for example, a compound having a 1,3,5-triazine ring and a compound having a porphyrin skeleton) may be used in combination.

  These additives are preferably contained in an amount of 0.2 to 30% by mass, particularly preferably 1 to 20% by mass with respect to the cellulose ester film.

  Moreover, the triazine type compound shown by the general formula (I) of Unexamined-Japanese-Patent No. 2001-235621 is also preferably used for the cellulose ester film which concerns on this invention.

  The cellulose ester film according to the present invention preferably contains two or more ultraviolet absorbers.

  As the UV absorber, a polymer UV absorber can be preferably used, and in particular, a polymer type UV absorber described in JP-A-6-148430 is preferably used.

  The method for adding the UV absorber is to add the UV absorber to the dope after dissolving the UV absorber in an alcohol such as methanol, ethanol or butanol, an organic solvent such as methylene chloride, methyl acetate, acetone or dioxolane, or a mixed solvent thereof. Or you may add directly in dope composition. For an inorganic powder that does not dissolve in an organic solvent, a dissolver or a sand mill is used in the organic solvent and cellulose ester to disperse and then added to the dope.

  The amount of the UV absorber used is not uniform depending on the type of UV absorber, usage conditions, etc., but when the dry film thickness of the cellulose ester film is 30 to 200 μm, it is 0.5 to 10 with respect to the cellulose ester film. % By mass is preferred, 0.5-4% by mass is more preferred, and 0.6-2% by mass is particularly preferred.

<Fine particles>
The cellulose ester film used in the present invention can contain fine particles.

  As fine particles used in the present invention, as examples of inorganic compounds, silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, tin oxide, indium oxide, zinc oxide, ITO, oxidation Mention may be made of antimony or composite oxides thereof, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. Fine particles containing silicon are preferable in terms of low turbidity, and silicon dioxide is particularly preferable.

  The average primary particle diameter of the fine particles is preferably 5 nm to 1 μm, and more preferably 5 to 50 nm. These are mainly contained as primary particles or secondary aggregates having a particle size of 0.05 to 1 μm, preferably 0.05 to 0.3 μm. The content of these fine particles in the cellulose ester film is preferably 0.001 to 1% by mass, and particularly preferably 0.01 to 0.1% by mass. In the case of a cellulose ester film having a multilayer structure by the co-casting method, it is preferable that these fine particles are contained in the surface layer.

  By forming convex portions by the method of the present invention, the amount of fine particles added to the film can be reduced. As a result, it is possible to provide a film having excellent transparency and excellent handleability.

  Silicon dioxide fine particles are commercially available, for example, under the trade names Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (above Nippon Aerosil Co., Ltd.). I can do it.

  Zirconium oxide fine particles are commercially available under the trade names of Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) and can be used.

  Examples of the polymer include silicone resin, fluororesin, cross-linked acrylic resin, and cross-linked polystyrene resin. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120, and 240 (manufactured by Toshiba Silicone Co., Ltd.) It is marketed by name and can be used.

  Among these, Aerosil 200V and Aerosil R972V are particularly preferably used because they have a large effect of reducing the friction coefficient while keeping the turbidity of the cellulose ester film low. In the cellulose ester film used in the present invention, the dynamic friction coefficient on the back side of the actinic radiation curable resin layer is preferably 1.0 or less, and more preferably 0.1 to 0.8. Moreover, it is preferable that the dynamic friction coefficient of the surface which provides an active ray cured resin layer is 1.0 or less.

<dye>
A dye may be added to the cellulose ester film used in the present invention to adjust the color. For example, a blue dye may be added to suppress the yellowness of the film. Preferred examples of the dye include anthraquinone dyes.

  The anthraquinone dye may have an arbitrary substituent at an arbitrary position from the 1st position to the 8th position of the anthraquinone. Preferred substituents include an anilino group, hydroxyl group, amino group, nitro group, or hydrogen atom. In particular, it is preferable to contain a blue dye described in paragraphs [0034] to [0037] of JP-A No. 2001-154017, particularly an anthraquinone dye. Further, it preferably contains an infrared absorbing dye, and in particular, any one of thiopyrylium squarylium dye, thiopyrylium croconium dye, pyrylium squarylium dye, and pyrylium croconium dye disclosed in JP-A-2001-154017. It is preferable that Specifically, an infrared absorbing dye represented by the general formula (1) or the general formula (2) of the publication can be preferably added.

  Various additives may be batch-added to a dope that is a cellulose ester-containing solution before film formation, or an additive solution may be separately prepared and added in-line. In particular, it is preferable to add a part or all of the fine particles in-line in order to reduce the load on the filter medium.

  When the additive solution is added in-line, it is preferable to dissolve a small amount of cellulose ester in order to improve mixing with the dope. The amount of the cellulose ester is preferably 1 to 10 parts by mass, more preferably 3 to 5 parts by mass with respect to 100 parts by mass of the solvent.

  In order to perform in-line addition and mixing in the present invention, for example, an in-line mixer such as a static mixer (manufactured by Toray Engineering), SWJ (Toray static type in-tube mixer Hi-Mixer) or the like is preferably used.

<Method for producing cellulose ester film>
Next, the manufacturing method of the cellulose ester film used for this invention is demonstrated.

  The cellulose ester film used in the present invention was produced by dissolving a cellulose ester and an additive in a solvent to prepare a dope, casting a dope on a belt-shaped or drum-shaped metal support, and casting. It is performed by a step of drying the dope as a web, a step of peeling from the metal support, a step of stretching or maintaining the width, a step of further drying, and a step of winding up the finished film.

  The process for preparing the dope will be described. The concentration of cellulose ester in the dope is preferably higher because the drying load after casting on the metal support can be reduced. However, if the concentration of cellulose ester is too high, the load during filtration increases and the filtration accuracy increases. Becomes worse. As a density | concentration which makes these compatible, 10-35 mass% is preferable, More preferably, it is 15-25 mass%.

  The solvent used in the dope of the present invention may be used alone or in combination of two or more. However, it is preferable from the viewpoint of production efficiency that a good solvent and a poor solvent of cellulose ester are mixed and used. The more solvent is preferable from the viewpoint of solubility of the cellulose ester. The preferable range of the mixing ratio of the good solvent and the poor solvent is 70 to 98% by mass for the good solvent and 2 to 30% by mass for the poor solvent. With a good solvent and a poor solvent, what dissolve | melts the cellulose ester to be used independently is defined as a good solvent, and what poorly swells or does not melt | dissolve is defined as a poor solvent. Therefore, depending on the acyl group substitution degree of the cellulose ester, the good solvent and the poor solvent change. For example, when acetone is used as the solvent, the cellulose ester acetate ester (acetyl group substitution degree 2.4), cellulose acetate propionate It becomes a good solvent, and becomes a poor solvent for cellulose acetate (acetyl group substitution degree 2.8).

  Although the good solvent used for this invention is not specifically limited, Organic halogen compounds, such as a methylene chloride, dioxolanes, acetone, methyl acetate, methyl acetoacetate, etc. are mentioned. Particularly preferred is methylene chloride or methyl acetate.

  Moreover, although the poor solvent used for this invention is not specifically limited, For example, methanol, ethanol, n-butanol, cyclohexane, cyclohexanone, etc. are used preferably. Moreover, it is preferable that 0.01-2 mass% of water contains in dope.

  A general method can be used as a method of dissolving the cellulose ester when preparing the dope described above. When heating and pressurization are combined, it is possible to heat above the boiling point at normal pressure. It is preferable to stir and dissolve while heating at a temperature that is equal to or higher than the boiling point of the solvent at normal pressure and that the solvent does not boil under pressure, in order to prevent the generation of massive undissolved materials called gels and mamacos. Moreover, after mixing a cellulose ester with a poor solvent and making it wet or swell, the method of adding a good solvent and melt | dissolving is also used preferably.

  The pressurization may be performed by a method of injecting an inert gas such as nitrogen gas or a method of increasing the vapor pressure of the solvent by heating. Heating is preferably performed from the outside. For example, a jacket type is preferable because temperature control is easy.

  The heating temperature with the addition of a solvent is preferably higher from the viewpoint of the solubility of the cellulose ester, but if the heating temperature is too high, the required pressure increases and the productivity deteriorates. A preferable heating temperature is 45 to 120 ° C, more preferably 60 to 110 ° C, and still more preferably 70 ° C to 105 ° C. The pressure is adjusted so that the solvent does not boil at the set temperature.

  Alternatively, a cooling dissolution method is also preferably used, whereby the cellulose ester can be dissolved in a solvent such as methyl acetate.

  Next, this cellulose ester solution is filtered using a suitable filter medium such as filter paper. As the filter medium, it is preferable that the absolute filtration accuracy is small in order to remove insoluble matters and the like, but there is a problem that the filter medium is likely to be clogged if the absolute filtration accuracy is too small. For this reason, a filter medium with an absolute filtration accuracy of 0.008 mm or less is preferable, a filter medium with 0.001 to 0.008 mm is more preferable, and a filter medium with 0.003 to 0.006 mm is still more preferable.

  There are no particular restrictions on the material of the filter medium, and ordinary filter media can be used. However, plastic filter media such as polypropylene and Teflon (registered trademark), and metal filter media such as stainless steel do not drop off fibers. preferable. It is preferable to remove and reduce impurities, particularly bright spot foreign matter, contained in the raw material cellulose ester by filtration.

A bright spot foreign substance is when two polarizing plates are placed in a crossed Nicol state, a cellulose ester film is placed between them, light is applied from the side of one polarizing plate, and observed from the side of the other polarizing plate. It is a point (foreign matter) where light from the opposite side appears to leak, and the number of bright spots having a diameter of 0.01 mm or more is preferably 200 / cm ² or less. More preferably, it is 100 pieces / cm < ² > or less, More preferably, it is 50 pieces / m < ² > or less, More preferably, it is 0-10 pieces / cm < ² > or less. Further, it is preferable that the number of bright spots of 0.01 mm or less is small.

  The dope can be filtered by an ordinary method, but the method of filtering while heating at a temperature not lower than the boiling point of the solvent at normal pressure and in a range where the solvent does not boil under pressure is the filtration pressure before and after filtration. The increase in the difference (referred to as differential pressure) is small and preferable. A preferred temperature is 45 to 120 ° C, more preferably 45 to 70 ° C, and still more preferably 45 to 55 ° C.

  A smaller filtration pressure is preferred. The filtration pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, and further preferably 1.0 MPa or less.

  Here, the dope casting will be described.

  The metal support in the casting (casting) step preferably has a mirror-finished surface, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used as the metal support. The cast width can be 1 to 4 m. The surface temperature of the metal support in the casting step is set to −50 ° C. to a temperature at which the solvent boils and does not foam. A higher temperature is preferable because the web can be dried faster, but if it is too high, the web may foam or flatness may deteriorate. The preferable support temperature is appropriately determined at 0 to 100 ° C, and more preferably 5 to 30 ° C. Alternatively, it is also a preferable method that the web is gelled by cooling and peeled from the drum in a state containing a large amount of residual solvent. The method for controlling the temperature of the metal support is not particularly limited, and there are a method of blowing hot air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use warm water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short. When using warm air, considering the temperature drop of the web due to the latent heat of vaporization of the solvent, while using warm air above the boiling point of the solvent, there may be cases where wind at a temperature higher than the target temperature is used while preventing foaming. . In particular, it is preferable to perform drying efficiently by changing the temperature of the support and the temperature of the drying air during the period from casting to peeling.

  In order for the cellulose ester film to exhibit good flatness, the residual solvent amount when peeling the web from the metal support is preferably 10 to 150% by mass, more preferably 20 to 40% by mass or 60 to 130% by mass. Especially preferably, it is 20-30 mass% or 70-120 mass%.

  In the present invention, the amount of residual solvent is defined by the following formula.

Residual solvent amount (% by mass) = {(MN) / N} × 100
M is the mass of a sample collected during or after the production of the web or film, and N is the mass after heating M at 115 ° C. for 1 hour.

  Further, in the drying step of the cellulose ester film, the web is peeled off from the metal support, and further dried, and the residual solvent amount is preferably 1% by mass or less, more preferably 0.1% by mass or less, Especially preferably, it is 0-0.01 mass% or less.

  In the film drying process, generally, a roll drying method (a method in which a plurality of rolls arranged on the upper and lower sides are alternately passed through and dried) or a method of drying while transporting the web by a tenter method is adopted.

  In order to produce the cellulose ester film for the optical film of the present invention, the web is stretched in the transport direction (MD stretching) where the residual solvent amount of the web is large immediately after peeling from the metal support, and both ends of the web are clipped. It is preferable to perform stretching in the width direction by a tenter method gripped by. The preferred draw ratio in both the machine direction and the transverse direction is 1.05 to 1.3 times, and more preferably 1.05 to 1.15 times. It is preferable that the area is 1.12 times to 1.44 times, and preferably 1.15 times to 1.32 times due to longitudinal and lateral stretching. This can be determined by the draw ratio in the longitudinal direction × the draw ratio in the transverse direction.

  In order to stretch in the machine direction immediately after peeling, it is preferable to stretch by peeling tension and subsequent transport tension. For example, it is preferable to peel at a peeling tension of 210 N / m or more, and particularly preferably 220 to 300 N / m.

  The means for drying the web is not particularly limited, and can be generally performed with hot air, infrared rays, a heating roll, microwave, or the like, but it is preferably performed with hot air in terms of simplicity.

  The drying temperature in the web drying step is preferably increased stepwise from 30 to 180 ° C, and more preferably from 50 to 140 ° C in order to improve dimensional stability.

  Although the film thickness of a cellulose-ester film is not specifically limited, 10-200 micrometers is used preferably.

  The variation of the film thickness of the cellulose ester film is preferably within ± 3% in both the width direction and the longitudinal direction, more preferably within ± 2%, and particularly preferably within ± 0.5%.

  The optical film of the present invention preferably has a width of 1 to 4 m. According to the present invention, the handleability of a wide film having a width of 1.4 to 4 m can be remarkably improved.

<Physical properties>
The moisture permeability of the cellulose ester film used in the present invention, 40 ° C., or less 850g / m ² · 24h at 90% RH, preferably ^{20~800g / m 2 · 24h, 20~750g} / m 2 · 24 h is particularly preferable. The moisture permeability can be measured according to the method described in JIS Z0208.

  The cellulose ester film used in the present invention has a breaking elongation measured by the following measurement of preferably 10 to 80%, more preferably 20 to 50%.

(Measurement of elongation at break)
A film containing an arbitrary residual solvent is cut into a sample width of 10 mm and a length of 130 mm, and a sample stored for 24 hours at 23 ° C. and 55% RH is obtained by performing a tensile test at a pulling speed of 100 mm / min with a distance between chucks of 100 mm. I can do it.

  The visible light transmittance of the cellulose ester film used in the present invention as measured by the following measurement is preferably 90% or more, and more preferably 93% or more.

(Measurement of transmittance)
The transmittance T is 380, 400, 500 nm from the spectral transmittance τ (λ) obtained every 10 nm in the wavelength region of 350-700 nm using a spectral altimeter U-3400 (Hitachi, Ltd.). Transmittance can be calculated.

  The haze of the cellulose ester film used in the present invention is preferably less than 1%, more preferably less than 0.5%, and particularly preferably 0 to 0.1%. The visible light transmittance is preferably 90% or more, more preferably 92% or more, and further preferably 94% or more.

(Haze value)
According to JIS K7105, it can be measured using a haze meter (1001DP type, manufactured by Nippon Denshoku Industries Co., Ltd.) and can be used as an index of transparency.

  The in-plane retardation value (Ro) of the cellulose ester film used in the present invention is preferably 0 to 70 nm or less. More preferably, it is 0-30 nm or less, More preferably, it is 0-10 nm or less. The retardation value (Rt) in the film thickness direction is preferably 0 to 400 nm, preferably 10 to 200 nm, and more preferably 30 to 150 nm.

  The retardation value (Ro) (Rt) can be obtained by the following equation.

Ro = (nx−ny) × d
Rt = ((nx + ny) / 2−nz) × d
Here, d is the thickness (nm) of the film, the refractive index nx (also referred to as the maximum refractive index in the plane of the film, the refractive index in the slow axis direction), ny (in the direction perpendicular to the slow axis in the film plane). ) (Refractive index of the film in the thickness direction).

  The retardation values (Ro) and (Rt) and the slow axis angle can be measured using an automatic birefringence meter. For example, the wavelength can be obtained at 590 nm in an environment of 23 ° C. and 55% RH using KOBRA-21ADH (Oji Scientific Instruments).

  The slow axis is preferably in the width direction ± 1 ° of the film or in the longitudinal direction ± 1 °.

  In the present invention, a thermoplastic resin film having a multilayer structure of two or more layers by co-casting or sequential casting or coating may be used.

  Moreover, the cellulose-ester film of Unexamined-Japanese-Patent No. 2000-352620 paragraph number [0036]-[0105] description can also be used preferably. Alternatively, cellulose ester films described in JP-A-2004-29199, paragraph numbers [0013] to [0124] are also preferably used.

<Cycloolefin polymer>
Next, the cycloolefin polymer film preferably used in the present invention will be described.

  The cycloolefin polymer used in the present invention is composed of a polymer resin containing an alicyclic structure.

  A preferred cycloolefin polymer is a resin obtained by polymerizing or copolymerizing a cyclic olefin. Examples of the cyclic olefin include norbornene, dicyclopentadiene, tetracyclododecene, ethyltetracyclododecene, ethylidenetetracyclododecene, tetracyclo [7.4.0.110, 13.02,7] trideca-2,4. Unsaturated hydrocarbons of polycyclic structures such as 6,11-tetraene and derivatives thereof; cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, cyclo Examples thereof include monocyclic unsaturated hydrocarbons such as octene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene, cycloheptene, cyclopentadiene, cyclohexadiene, and derivatives thereof. These cyclic olefins may have a polar group as a substituent. Examples of the polar group include a hydroxyl group, a carboxyl group, an alkoxyl group, an epoxy group, a glycidyl group, an oxycarbonyl group, a carbonyl group, an amino group, an ester group, and a carboxylic acid anhydride group. Or a carboxylic anhydride group is preferred.

  Preferred cycloolefin polymers may be those obtained by addition copolymerization of monomers other than cyclic olefins. Addition copolymerizable monomers include ethylene, propylene, 1-butene, 1-pentene and other ethylene or α-olefins; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl- Examples include dienes such as 1,4-hexadiene and 1,7-octadiene.

The cyclic olefin is obtained by an addition polymerization reaction or a metathesis ring-opening polymerization reaction. The polymerization is carried out in the presence of a catalyst. Examples of the addition polymerization catalyst include a polymerization catalyst composed of a vanadium compound and an organoaluminum compound. As a catalyst for ring-opening polymerization, a polymerization catalyst comprising a metal halide such as ruthenium, rhodium, palladium, osmium, iridium, platinum, nitrate or acetylacetone compound and a reducing agent; or titanium, vanadium, zirconium, tungsten, molybdenum Examples thereof include a polymerization catalyst comprising a metal halide such as acetylacetone compound and an organoaluminum compound. The polymerization temperature, pressure and the like are not particularly limited, but the polymerization is usually carried out at a polymerization temperature of -50 ° C to 100 ° C and a polymerization pressure of 0 to 490 N / cm ² .

  The cycloolefin polymer used in the present invention is preferably a polymer obtained by polymerizing or copolymerizing a cyclic olefin, followed by a hydrogenation reaction to change the unsaturated bond in the molecule to a saturated bond. The hydrogenation reaction is performed by blowing hydrogen in the presence of a known hydrogenation catalyst. Examples of hydrogenation catalysts include cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, transition metal compounds such as titanocene dichloride / n-butyllithium, zirconocene dichloride / sec-butyllithium, tetrabutoxytitanate / dimethylmagnesium / alkyl. Homogeneous catalyst consisting of a combination of metal compounds; heterogeneous metal catalyst such as nickel, palladium, platinum; nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth And a heterogeneous solid-supported catalyst in which a metal catalyst such as palladium / alumina is supported on a carrier.

  Or the following norbornene-type polymer is also mentioned as a cycloolefin polymer. The norbornene-based polymer preferably has a norbornene skeleton as a repeating unit. Specific examples thereof include JP-A-62-252406, JP-A-62-2252407, and JP-A-2-133413. JP-A-63-145324, JP-A-63-264626, JP-A-1-240517, JP-B-57-8815, JP-A-5-39403, JP-A-5-43663 JP-A-5-43834, JP-A-5-70655, JP-A-5-279554, JP-A-6-206985, JP-A-7-62028, JP-A-8-176411, Although what was described in Kaihei 9-241484 etc. can utilize preferably, it is not limited to these. Moreover, these may be used individually by 1 type and may use 2 or more types together.

  In the present invention, among the norbornene-based polymers, those having a repeating unit represented by any of the following structural formulas (I) to (IV) are preferable.

  In the structural formulas (I) to (IV), A, B, C and D each independently represent a hydrogen atom or a monovalent organic group.

  Among the norbornene-based polymers, a polymer obtained by metathesis polymerization of at least one compound represented by the following structural formula (V) or (VI) and an unsaturated cyclic compound copolymerizable therewith. A hydrogenated polymer obtained by hydrogenating is also preferred.

  In the structural formula, A, B, C and D each independently represent a hydrogen atom or a monovalent organic group.

  Here, A, B, C and D are not particularly limited, but preferably an organic group may be linked via a hydrogen atom, a halogen atom, a monovalent organic group, or at least a divalent linking group. These may be the same or different. A or B and C or D may form a monocyclic or polycyclic structure. Here, the at least divalent linking group includes a hetero atom typified by an oxygen atom, a sulfur atom, and a nitrogen atom, and examples thereof include ether, ester, carbonyl, urethane, amide, thioether, and the like. It is not limited. In addition, the organic group may be further substituted via the linking group.

  Examples of other monomers copolymerizable with the norbornene-based monomer include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, C2-C20 alpha olefins, such as 1-hexadecene, 1-octadecene, 1-eicocene, and derivatives thereof; cyclobutene, cyclopentene, cyclohexene, cyclooctene, 3a, 5,6,7a-tetrahydro-4,7 -Cycloolefins such as methano-1H-indene, and derivatives thereof; non 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, etc. Conjugated dienes; and the like are used. Among these, an α-olefin, particularly ethylene is preferable.

  These other monomers copolymerizable with the norbornene-based monomer can be used alone or in combination of two or more. In the case of addition copolymerization of a norbornene monomer and another monomer copolymerizable therewith, the ratio of the structural unit derived from the norbornene monomer and the structural unit derived from the other monomer copolymerizable in the addition copolymer However, it is appropriately selected so that the mass ratio is usually 30:70 to 99: 1, preferably 50:50 to 97: 3, more preferably 70:30 to 95: 5.

  When the unsaturated bond remaining in the molecular chain of the synthesized polymer is saturated by a hydrogenation reaction, the hydrogenation rate is 90% or more, preferably 95% or more, particularly from the viewpoint of light resistance deterioration, weather resistance deterioration, etc. Preferably it is 99% or more.

  In addition, examples of the cycloolefin polymer used in the present invention include thermoplastic saturated norbornene resins described in paragraph Nos. [0014] to [0019] of JP-A-5-2108, and paragraph Nos. [0015] of JP-A-2001-277430. ] To [0031] thermoplastic norbornene polymers, JP 2003-14901 paragraph Nos. [0008] to [0045] thermoplastic norbornene resins, JP 2003-139950 paragraph Nos. [0014] to [0028] Norbornene-based resin composition, paragraph Nos. [0029] to [0037] described in JP-A No. 2003-161832, paragraph Nos. [0027] to [0036] described in JP-A No. 2003-195268 Norbornene resin, Japanese Patent Application Laid-Open No. 2003-211589 Paragraph Nos. [0009] to [0023] alicyclic structure-containing polymer resin, norbornene polymer resin or vinyl alicyclic hydrocarbon heavy as described in JP-A-2003-212588, paragraph Nos. [0008] to [0024] Examples include coalesced resins.

  Specifically, ZEONEX, ZEONOR manufactured by Nippon Zeon Co., Ltd., Arton manufactured by JSR Corporation, APPEL manufactured by Mitsui Chemicals, Inc. (APL8008T, APL6509T, APL6013T, APL5014DP, APL6015T) and the like are preferably used.

  The molecular weight of the cycloolefin polymer used in the present invention is appropriately selected according to the purpose of use, and was measured by a gel permeation chromatography method of a cyclohexane solution (or a toluene solution when the polymer resin does not dissolve). When the polyisoprene or polystyrene-equivalent weight average molecular weight is usually in the range of 5,000 to 500,000, preferably 8,000 to 200,000, more preferably 10,000 to 100,000, the mechanical strength and molding processability of the molded body are high. Balanced and suitable.

  Moreover, when a low-volatile antioxidant is blended at a ratio of 0.01 to 5 parts by mass with respect to 100 parts by mass of the cycloolefin polymer, it can effectively prevent the polymer from being decomposed or colored during the molding process. I can do it.

As the antioxidant, an antioxidant having a vapor pressure at 20 ° C. of 10 ⁻⁵ Pa or less, particularly preferably 10 ⁻⁸ Pa or less is desirable. Antioxidants having a vapor pressure higher than 10 ⁻⁵ Pa cause foaming during extrusion molding, and the antioxidants volatilize from the surface of the molded product when exposed to high temperatures.

  Examples of the antioxidant that can be used in the present invention include the following, and one or several of these may be used in combination.

  Hintard phenol type: 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butylphenol, 4-hydroxymethyl-2,6-di-t-butylphenol, 2,6-di -T-butyl-α-methoxy-p-dimethyl-phenol, 2,4-di-t-amylphenol, t-butyl-m-cresol, 4-t-butylphenol, styrenated phenol, 3-t-butyl- 4-hydroxyanisole, 2,4-dimethyl-6-tert-butylphenol, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,5-di-tert-butyl-4 -Hydroxybenzylphosphonate-diethyl ester, 4,4'-bisphenol, 4,4'-bis- (2,6-di-t-butylphenol), , 2'-methylene-bis- (4-methyl-6-t-butylphenol), 2,2'-methylene-bis- (4-methyl-6-α-methylcyclohexylphenol), 4,4'-methylene- Bis- (2-methyl-6-t-butylphenol), 4,4'-methylene-bis- (2,6-di-t-butylphenol), 1,1'-methylene-bis- (2,6-di -T-butylnaphthol), 4,4'-butylidene-bis- (2,6-di-t-butyl-meta-cresol), 2,2'-thio-bis- (4-methyl-6-t- Butylphenol), di-o-cresol sulfide, 2,2'-thio-bis- (2-methyl-6-tert-butylphenol), 4,4'-thio-bis (3-methyl-6-tert-butylphenol) 4,4'-thio-bis- (2, -Di-sec-amylphenol), 1,1'-thio-bis- (2-naphthol), 3,5-di-t-butyl-4-hydroxybenzyl ether, 1,6-hexanediol-bis- [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thiobis (4-methyl-6) -T-butylphenol), N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), bis (3,5-di-t-butyl-4-hydroxy) Benzylphospho Acid ethyl) calcium, 1,3,5-trimethyl-2,4,6-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, triethylene glycol-bis [3- (3- t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6, -tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, Tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxygenyl) propionate], etc. .

  Aminophenols: normal butyl-p-aminophenol, normal butyroyl-p-aminophenol, normal peragonoyl-p-aminophenol, normal lauroyl-p-aminophenol, normal stearoyl-p-aminophenol, 2, 6 -Di-t-butyl-α-dimethyl, amino-p-cresol and the like.

  Hydroquinone series: hydroquinone, 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, hydroquinone methyl ether, hydroquinone monobenzyl ether, and the like.

  Phosphite triphosphite, tris (3,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene Phosphanite, 2-ethylhexyl octyl phosphite, etc.

  Others: 2-mercaptobenzothiazole zinc salt, dicatechol borate-di-o-tolylguanidine salt, nickel-dimethyldithiocarbamate, nickel-pentamethylene dithiocarbanate, mercaptobenzimidazole, 2-mercaptobenzimidazole zinc salt and the like.

  The cycloolefin polymer film may contain an additive that can be generally blended into a plastic film, if necessary. Examples of such additives include heat stabilizers, light stabilizers, ultraviolet absorbers, antistatic agents, lubricants, plasticizers, and fillers, and the content thereof is within a range that does not impair the purpose of the present invention. You can choose.

  There is no particular limitation on the method for forming the cycloolefin polymer film, and either a heat-melt molding method or a solution casting method can be used. The heat-melt molding method can be further classified into an extrusion molding method, a press molding method, an inflation molding method, an injection molding method, a blow molding method, a stretch molding method, etc. Among these methods, mechanical strength, surface accuracy are included. In order to obtain an excellent film, an extrusion molding method, an inflation molding method, and a press molding method are preferable, and an extrusion molding method is most preferable. The molding conditions are appropriately selected depending on the purpose of use and the molding method. In the case of the hot melt molding method, the cylinder temperature is usually in the range of 150 to 400 ° C, preferably 200 to 350 ° C, more preferably 230 to 330 ° C. Is set as appropriate. If the resin temperature is too low, fluidity will deteriorate, causing shrinkage and distortion in the film. If the resin temperature is too high, voids and silver streaks will occur due to thermal decomposition of the resin, and the film will turn yellow. Defects may occur. The thickness of the film is usually in the range of 5 to 300 μm, preferably 10 to 200 μm, more preferably 20 to 100 μm. When the thickness is too thin, handling at the time of lamination becomes difficult, and when it is too thick, the drying time after the lamination becomes long and the productivity is lowered.

  The wetting tension of the surface of the cycloolefin polymer film is preferably 40 mN / m or more, more preferably 50 mN / m or more, and further preferably 55 mN / m or more. When the surface wetting tension is in the above range, the adhesive strength between the film and the polarizing film is improved. In order to adjust the surface wetting tension, for example, corona discharge treatment, ozone spraying, ultraviolet irradiation, flame treatment, chemical treatment, and other known surface treatments can be performed.

  The sheet before stretching needs to have a thickness of about 50 to 500 μm, and the thickness unevenness is preferably as small as possible. The entire surface is within ± 8%, preferably within ± 6%, more preferably within ± 4%. is there.

  Similarly to the cellulose ester film, the cycloolefin polymer film may be stretched in a uniaxial direction and may be biaxially stretched in a direction orthogonal to the direction. For stretching, it is preferable to use the tenter device or the like.

  The draw ratio is 1.1 to 10 times, preferably 1.3 to 8 times.

  Stretching is usually performed in a temperature range of Tg to Tg + 50 ° C., preferably Tg to Tg + 40 ° C. of the resin constituting the sheet. If the stretching temperature is too low, it will break, and if it is too high, it will not be molecularly oriented.

  In the film thus obtained, the molecules are oriented by stretching, and a retardation having a desired size can be obtained. In the present invention, preferable retardation values are 70 to 400 nm for Rt, 30 to 300 nm for Ro, and more preferably 30 to 70 nm for Ro.

<Hard coat layer>
In the present invention, it is preferable to coat a hard coat layer on the surface of the thermoplastic resin film provided with the fine convex structure or on the opposite surface. The hard coat layer is preferably a hard coat layer containing an actinic radiation curable resin and fine particles.

  Examples of the fine particles include inorganic particles and organic particles. Examples of inorganic fine particles that can be used in the present invention include silicon oxide, titanium oxide, aluminum oxide, tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide, antimony oxide, magnesium oxide, calcium carbonate, calcium carbonate, talc, and clay. , Calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate, or a composite oxide thereof.

  Among these, silicon oxide, titanium oxide, tin oxide, indium oxide, ITO, zirconium oxide, antimony oxide, or a composite oxide thereof is preferably used.

  Organic fine particles include poly (meth) acrylate resins, silicon resins, polystyrene resins, polycarbonate resins, acrylic styrene resins, benzoguanamine resins, melamine resins, polyolefin resins, polyester resins, polyamide resins. Polyimide resin, polyfluorinated ethylene resin, etc. can be used. It is particularly preferable to contain conductive fine particles.

  Fine particles having a particle diameter of 5 nm to 10 μm are used, but particles of 5 nm to 5 μm are preferable. In particular, particles having a diameter larger than the average film thickness of the hard coat layer are useful for forming an antiglare hard coat layer. In the case where the antiglare property is not given, it is preferable to contain particles of 5 nm to 1 μm. A combination of fine particles having different compositions, particle sizes, and refractive indexes can also be used. For example, silicon oxide and zirconium oxide or silicon oxide and ITO fine particles can be used in combination.

  The actinic radiation curable resin refers to a resin that cures through a crosslinking reaction or the like by irradiation with actinic rays such as ultraviolet rays or electron beams. For example, a component containing a monomer having an ethylenically unsaturated double bond is preferably used and cured by irradiating an active ray such as an ultraviolet ray or an electron beam to form a hard coat layer. Typical examples of the actinic radiation curable resin include an ultraviolet curable resin and an electron beam curable resin, and a resin curable by ultraviolet irradiation is preferable.

  As the ultraviolet curable resin, for example, an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, or an ultraviolet curable epoxy resin is preferable. Used.

  UV curable acrylic urethane resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylates) in products obtained by reacting polyester polyols with isocyanate monomers or prepolymers. It can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate. For example, those described in JP-A-59-151110 can be used.

  For example, a mixture of 100 parts Unidic 17-806 (Dainippon Ink Co., Ltd.) and 1 part Coronate L (Nihon Polyurethane Co., Ltd.) is preferably used.

  Examples of UV curable polyester acrylate resins include those that are easily formed when 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers are generally reacted with polyester polyols. JP-A-59-151112 Can be used.

  Specific examples of the ultraviolet curable epoxy acrylate resin include an epoxy acrylate as an oligomer, a reactive diluent and a photoreaction initiator added thereto, and reacted to form an oligomer. The thing as described in 105738 can be used.

  Specific examples of UV curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, etc. I can list them.

  Specific examples of the photoreaction initiator of these ultraviolet curable resins include benzoin and its derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. You may use with a photosensitizer. The photoinitiator can also be used as a photosensitizer. In addition, when using an epoxy acrylate photoinitiator, a sensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used. For example, commercially available products such as Irgacure 184 and Irgacure 907 (manufactured by Ciba Specialty Chemicals) are preferably used. The photoreaction initiator or photosensitizer used in the ultraviolet curable resin composition is 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the composition.

  Examples of the resin monomer include general monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate, and styrene as monomers having one unsaturated double bond. As monomers having two or more unsaturated double bonds, ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyl dimethyl diacrylate, the above-mentioned trimethylolpropane Examples thereof include triacrylate and pentaerythritol tetraacryl ester.

  Examples of commercially available ultraviolet curable resins that can be used in the present invention include ADEKA OPTMER KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (Asahi Denka ( Co., Ltd.); Koeihard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS -101, FT-102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Co., Ltd.); Seika Beam PHC2210 (S), PHC X-9 (K-3), PHC2213, DP -10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (manufactured by Dainichi Seika Kogyo Co., Ltd.) KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (manufactured by Daicel UCB); RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102, RC-5120 RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by Dainippon Ink & Chemicals, Inc.); 340 clear (manufactured by China Paint Co., Ltd.); Sunrad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (manufactured by Sanyo Chemical Industries); SP -1509, SP-1507 (manufactured by Showa Polymer Co., Ltd.); RCC-15C (manufactured by Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (manufactured by Toagosei Co., Ltd.), DPHA (manufactured by Nippon Kayaku Co., Ltd.) or the like can be appropriately selected and used.

  Specific examples of compounds include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, and the like. .

  In addition, for adjusting the refractive index, hard coat coating solutions containing zirconium oxide ultrafine particle dispersions Desolite Z-7041 and Desolite Z-7042 (manufactured by JSR Co., Ltd.) can be used alone or in other ultraviolet curable resins. It can be added and mixed.

  The actinic radiation curable resin used in the present invention can be cured by irradiation with actinic rays such as electron beams or ultraviolet rays. For example, in the case of electron beam curing, 50 to 1000 KeV emitted from various electron beam accelerators such as a Cockloft Walton type, a bandegraph type, a resonant transformation type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type, Preferably, an electron beam or the like having an energy of 100 to 300 KeV is used, and in the case of ultraviolet curing, ultraviolet rays emitted from light beams such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp can be used. .

  The proportion of the actinic radiation curable resin composition and the fine particles is desirably blended so as to be 0.1 to 40 parts by mass with respect to 100 parts by mass of the resin composition.

  The refractive index of the hard coat layer used in the present invention is 1.5 to 2.0, more preferably 1.6 to 1.8. The refractive index of the cellulose ester film used as the transparent support is about 1.5. When the refractive index of the hard coat layer is too small, the antireflection property is lowered. Furthermore, when this is too large, the color of the reflected light of the optical film becomes strong, which is not preferable. The refractive index of the hard coat layer used in the present invention is particularly preferably in the range of 1.60 to 1.70 from the viewpoint of optical design for obtaining a low reflective film. The refractive index of the hard coat layer can be adjusted by the refractive index and content of the fine particles to be added.

  The film thickness of the hard coat layer used in the present invention is the average film thickness of 10 portions of the resin part of the hard coat layer when observed with a tomographic electron micrograph, and the film thickness of the present invention is sufficient durability. From the viewpoint of imparting impact resistance, the thickness of the hard coat layer is preferably in the range of 0.5 μm to 10.0 μm, and more preferably 1.0 μm to 5.0 μm. The hard coat layer may be composed of two or more layers.

  These hard coat layers can be coated by a known method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, or an ink jet method. The coating amount is suitably 0.1 to 30 μm, preferably 0.5 to 15 μm, as the wet film thickness.

As a light source for curing an ultraviolet curable resin by a photocuring reaction to form a cured film layer, any light source that generates ultraviolet rays can be used without any limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. The irradiation conditions vary depending on individual lamps, the dose of active ray is a 0.5 J / cm ² or less, preferably 0.1 J / cm ² or less.

The irradiation time for obtaining the irradiation amount of active rays is preferably about 0.1 second to 1 minute, and more preferably 0.1 to 10 seconds from the viewpoint of the curing efficiency or work efficiency of the curable resin. Moreover, it is preferable that the illuminance of these active ray irradiation parts is 50-150 mW / m < ² >.

  Moreover, when irradiating actinic radiation, it is preferable to carry out while applying tension | tensile_strength in the conveyance direction of a film, More preferably, it is performing applying tension | tensile_strength also in the width direction. The tension to be applied is preferably 30 to 300 N / m. The method for applying the tension is not particularly limited, and the tension may be applied in the conveying direction on the back roll, or the tension may be applied in the width direction or the biaxial direction by a tenter. This makes it possible to obtain a film having further excellent flatness.

  Examples of the organic solvent for the hard coat layer coating solution include hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone). , Esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, and other organic solvents can be appropriately selected or used by mixing them. Propylene glycol monoalkyl ether (1 to 4 carbon atoms of the alkyl group) or propylene glycol monoalkyl ether acetate ester (1 to 4 carbon atoms of the alkyl group) is 5% by mass or more, more preferably 5 to 80%. It is preferable to use the organic solvent containing at least mass%.

  Further, it is particularly preferable to add a silicon compound to the coating liquid for the hard coat layer. For example, polyether-modified silicone oil is preferably added. The number average molecular weight of the polyether-modified silicone oil is, for example, 1000 to 100000, preferably 2000 to 50000. If the number average molecular weight is less than 1000, the drying property of the coating film decreases, and conversely, the number average When the molecular weight exceeds 100,000, it tends to be difficult to bleed out to the coating surface.

  Commercially available silicon compounds include DKQ8-779 (trade name, manufactured by Dow Corning), SF3771, SF8410, SF8411, SF8419, SF8421, SF8428, SH200, SH510, SH1107, SH3749, SH3771, BX16-034, SH3746, SH3749, SH8400, SH3771M, SH3772M, SH3773M, SH3775M, BY-16-837, BY-16-839, BY-16-869, BY-16-870, BY-16-004, BY-16-891, BY-16 872, BY-16-874, BY22-008M, BY22-012M, FS-1265 (above, product names manufactured by Toray Dow Corning Silicone), KF-101, KF-100T, KF351, KF3 2, KF353, KF354, KF355, KF615, KF618, KF945, KF6004, Silicone X-22-945, X22-160AS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), XF3940, XF3949 (trade name, manufactured by Toshiba Silicone Co., Ltd.) ), Disparon LS-009 (manufactured by Enomoto Kasei Co., Ltd.), Granol 410 (manufactured by Kyoeisha Oil Chemical Co., Ltd.), TSF4440, TSF4441, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by GE Toshiba Silicone), BYK-306, BYK- 330, BYK-307, BYK-341, BYK-344, BYK-361 (manufactured by BYK-Japan) L series (for example, L7001, L-7006, L-7604, L-9000) manufactured by Nippon Unicar Co., Ltd. Y Over's, FZ series (FZ-2203, FZ-2206, FZ-2207) and the like, are preferably used.

  These components enhance the applicability to the substrate and the lower layer. When added to the outermost surface layer of the laminate, it not only improves the water repellency, oil repellency and antifouling properties of the coating film, but also exhibits an effect on the scratch resistance of the surface. These components are preferably added in a range of 0.01 to 3% by mass with respect to the solid component in the coating solution.

(Antireflection layer)
The optical film according to the present invention preferably further comprises an antireflection layer on the hard coat layer.

  In the present invention, the method for providing the antireflection layer is not particularly limited, and examples thereof include sputtering, atmospheric pressure plasma treatment, coating, and the like.

  As a method of forming the antireflection layer by coating, a method of dispersing metal oxide powder in a binder resin dissolved in a solvent, coating and drying, a method of using a polymer having a crosslinked structure as a binder resin, ethylenic unsaturated Examples of the method include a method of forming a layer by containing a monomer and a photopolymerization initiator and irradiating with actinic radiation.

  In the present invention, an antireflection layer is provided on a transparent long substrate film provided with a hard coat layer, and at least one of the antireflection layers is a low refractive index layer.

  Although the structure of a preferable optical film is shown below, it is not limited to these.

  Here, the hard coat layer and the antiglare layer mean the actinic radiation curable resin layer described above. In addition, the surface which gave the antiblocking process of this invention was described here as the backcoat layer.

Back coat layer / resin film / clear hard coat layer / low refractive index layer Back coat layer / resin film / clear hard coat layer / high refractive index layer / low refractive index layer Back coat layer / resin film / clear hard coat layer / medium Refractive index layer / High refractive index layer / Low refractive index layer Back coat layer / Resin film / Anti-glare layer / Low refractive index layer Back coat layer / Resin film / Anti-glare layer / High refractive index layer / Low refractive index layer Back coat Layer / resin film / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer Further, the middle refractive index layer or the high refractive index layer may also serve as the antistatic layer.

  In the optical film, a low refractive index layer is formed as an uppermost layer, a metal oxide layer of a high refractive index layer is formed between the hard coat layer, and further, between the hard coat layer and the high refractive index layer. It is preferable to provide a middle refractive index layer (metal oxide layer in which the refractive index is adjusted by changing the content of the metal oxide or the ratio to the resin binder and the type of metal) to reduce the reflectance.

  The low refractive index layer of the present invention preferably contains hollow fine particles.

  The hollow fine particles referred to here are (I) composite particles comprising porous particles and a coating layer provided on the surface of the porous particles, or (II) having cavities inside, and the content is a solvent, gas or Cavity particles filled with a porous material. The low refractive index layer may contain either (I) composite particles or (II) hollow particles, or may contain both.

  The hollow particles are particles having cavities inside, and the cavities are surrounded by particle walls. The cavity is filled with a content such as a solvent, a gas, or a porous material used at the time of preparation. It is desirable that the average particle diameter of such inorganic fine particles is in the range of 5 to 300 nm, preferably 10 to 200 nm. The average particle diameter of the inorganic fine particles used is appropriately selected according to the thickness of the transparent film to be formed, and is in the range of 2/3 to 1/10 of the film thickness of the transparent film such as the low refractive index layer to be formed. It is desirable to be in These inorganic fine particles are preferably used in a state of being dispersed in an appropriate medium in order to form a low refractive index layer. As the dispersion medium, water, alcohol (for example, methanol, ethanol, isopropyl alcohol), ketone (for example, methyl ethyl ketone, methyl isobutyl ketone), and ketone alcohol (for example, diacetone alcohol) are preferable.

  The thickness of the coating layer of the composite particles or the thickness of the particle walls of the hollow particles is desirably in the range of 1 to 20 nm, preferably 2 to 15 nm. In the case of composite particles, if the thickness of the coating layer is less than 1 nm, the particles may not be completely covered, and silicate monomers and oligomers with a low degree of polymerization, which are coating liquid components described later, are easy. In some cases, the inside of the composite particle enters the inside and the porosity of the inside is reduced, so that the effect of the low refractive index cannot be sufficiently obtained. When the thickness of the coating layer exceeds 20 nm, the silicic acid monomer and oligomer do not enter the inside, but the porosity (pore volume) of the composite particles is lowered and the effect of low refractive index is sufficiently obtained. It may not be possible. In the case of hollow particles, if the particle wall thickness is less than 1 nm, the particle shape may not be maintained, and even if the thickness exceeds 20 nm, the effect of low refractive index may not be sufficiently exhibited. is there.

The coating layer of the composite particles or the particle wall of the hollow particles is preferably composed mainly of silica. The coating layer of the composite particle or the particle wall of the hollow particle may contain a component other than silica, specifically, Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO _2. and _{CeO 2, P 2 O 3,} Sb 2 O 3, MoO 3, ZnO 2, WO 3 and the like. Examples of the porous particles constituting the composite particles include those made of silica, those made of silica and an inorganic compound other than silica, and those made of CaF ₂ , NaF, NaAlF ₆ , MgF, and the like. Of these, porous particles made of a composite oxide of silica and an inorganic compound other than silica are particularly suitable. Examples of inorganic compounds other than silica include Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , MoO ₃ , ZnO ₂ , WO _{3 and the} like. 1 type or 2 types or more can be mentioned. In such a porous particle, the molar ratio MOX / SiO ₂ when the silica is represented by SiO ₂ and the inorganic compound other than silica is represented by oxide (MOX) is 0.0001 to 1.0, preferably It is desirable to be in the range of 0.001 to 0.3. It is difficult to obtain porous particles having a molar ratio MOX / SiO ₂ of less than 0.0001, and even if obtained, those having a lower refractive index are not obtained. On the other hand, if the molar ratio MOX / SiO _{2 of} the porous particles exceeds 1.0, the ratio of silica decreases, so that particles having a small pore volume and a low refractive index may not be obtained.

  The pore volume of such porous particles is desirably in the range of 0.1 to 1.5 ml / g, preferably 0.2 to 1.5 ml / g. If the pore volume is less than 0.1 ml / g, particles having a sufficiently reduced refractive index cannot be obtained. If the pore volume exceeds 1.5 ml / g, the strength of the fine particles is lowered, and the strength of the resulting coating may be lowered. is there.

  Incidentally, the pore volume of such porous particles can be obtained by a mercury intrusion method. Examples of the contents of the hollow particles include a solvent, a gas, and a porous material used at the time of preparing the particles. The solvent may contain an unreacted particle precursor used in preparing the hollow particles, the catalyst used, and the like. Moreover, what consists of the compound illustrated by the said porous particle as a porous substance is mentioned. These contents may be composed of a single component or may be a mixture of a plurality of components.

  As a method for producing such inorganic fine particles, for example, the method for preparing composite oxide colloidal particles disclosed in paragraphs [0010] to [0033] of JP-A-7-133105 is suitably employed. Specifically, when the composite particles are composed of silica and an inorganic compound other than silica, the inorganic compound particles are produced from the following first to third steps.

First Step: Preparation of Porous Particle Precursor In the first step, an alkali aqueous solution of a silica raw material and an inorganic compound raw material other than silica is separately prepared in advance, or a silica raw material and an inorganic compound raw material other than silica are prepared in advance. A mixed aqueous solution is prepared, and this aqueous solution is gradually added to an aqueous alkaline solution having a pH of 10 or more while stirring according to the composite ratio of the target composite oxide to prepare a porous particle precursor.

  As the silica raw material, alkali metal, ammonium or organic base silicate is used. Sodium silicate (water glass) or potassium silicate is used as the alkali metal silicate. Examples of the organic base include quaternary ammonium salts such as tetraethylammonium salt, and amines such as monoethanolamine, diethanolamine, and triethanolamine. The ammonium silicate or the organic base silicate includes an alkaline solution obtained by adding ammonia, a quaternary ammonium hydroxide, an amine compound or the like to a silicic acid solution.

  In addition, alkali-soluble inorganic compounds are used as raw materials for inorganic compounds other than silica. Specifically, an oxo acid of an element selected from Al, B, Ti, Zr, Sn, Ce, P, Sb, Mo, Zn, W, etc., an alkali metal salt or alkaline earth metal salt of the oxo acid, ammonium Salts and quaternary ammonium salts. More specifically, sodium aluminate, sodium tetraborate, zirconyl ammonium carbonate, potassium antimonate, potassium stannate, sodium aluminosilicate, sodium molybdate, cerium ammonium nitrate, and sodium phosphate are suitable.

Although the pH value of the mixed aqueous solution changes simultaneously with the addition of these aqueous solutions, an operation for controlling the pH value within a predetermined range is not particularly required. The aqueous solution finally has a pH value determined by the type of inorganic oxide and the mixing ratio thereof. There is no restriction | limiting in particular in the addition rate of the aqueous solution at this time. Further, in the production of composite oxide particles, a dispersion of seed particles can be used as a starting material. The seed particles are not particularly limited, but inorganic oxides such as SiO ₂ , Al ₂ O ₃ , TiO ₂ or ZrO ₂ or fine particles of these composite oxides are used. Usually, these sols are used. I can do it. Furthermore, the porous particle precursor dispersion obtained by the above production method may be used as a seed particle dispersion. When the seed particle dispersion is used, the pH of the seed particle dispersion is adjusted to 10 or more, and then the aqueous solution of the compound is added to the above-described alkaline aqueous solution while stirring. Also in this case, it is not always necessary to control the pH of the dispersion. In this way, when seed particles are used, it is easy to control the particle size of the porous particles to be prepared, and particles having a uniform particle size can be obtained.

  The silica raw material and the inorganic compound raw material described above have high solubility on the alkali side. However, when both are mixed in this highly soluble pH region, the solubility of oxo acid ions such as silicate ions and aluminate ions decreases, and these composites precipitate and grow into fine particles, or seed particles. Particle deposition occurs on the top. Therefore, it is not always necessary to perform pH control as in the conventional method for precipitation and growth of fine particles.

The composite ratio of silica and inorganic compound other than silica in the first step is that the inorganic compound relative to silica is converted to oxide (MOx), and the molar ratio of MOx / SiO ₂ is 0.05 to 2.0, preferably It is desirable to be within the range of 0.2 to 2.0. Within this range, the pore volume of the porous particles increases as the proportion of silica decreases. However, even when the molar ratio exceeds 2.0, the pore volume of the porous particles hardly increases. On the other hand, when the molar ratio is less than 0.05, the pore volume becomes small. When preparing hollow particles, the molar ratio of MOx / SiO ₂ is preferably in the range of 0.25 to 2.0.

Second step: Removal of inorganic compound other than silica from porous particles In the second step, inorganic compounds other than silica (elements other than silicon and oxygen) are obtained from the porous particle precursor obtained in the first step. At least a portion is selectively removed. As a specific removal method, the inorganic compound in the porous particle precursor is dissolved and removed using a mineral acid or an organic acid, or is contacted with a cation exchange resin for ion exchange removal.

  The porous particle precursor obtained in the first step is a particle having a network structure in which silicon and an inorganic compound constituent element are bonded via oxygen. By removing inorganic compounds (elements other than silicon and oxygen) from such a porous particle precursor, porous particles having a more porous and large pore volume can be obtained. Further, if the amount of removing the inorganic oxide (elements other than silicon and oxygen) from the porous particle precursor is increased, the hollow particles can be prepared.

  In addition, prior to removing inorganic compounds other than silica from the porous particle precursor, a silicic acid solution obtained by removing the alkali metal salt of silica from the porous particle precursor dispersion obtained in the first step. Alternatively, it is preferable to form a silica protective film by adding a hydrolyzable organosilicon compound. The thickness of the silica protective film may be 0.5 to 15 nm. Even if the silica protective film is formed, the protective film in this step is porous and thin, so that it is possible to remove inorganic compounds other than silica described above from the porous particle precursor.

  By forming such a silica protective film, inorganic compounds other than the silica described above can be removed from the porous particle precursor while maintaining the particle shape. Moreover, when forming the silica coating layer described later, the pores of the porous particles are not blocked by the coating layer, and therefore, the silica coating layer described later is formed without reducing the pore volume. I can do it. Note that when the amount of the inorganic compound to be removed is small, the particles are not broken, and thus it is not always necessary to form a protective film.

  When preparing hollow particles, it is desirable to form this silica protective film. When preparing the hollow particles, the inorganic compound is removed to obtain a hollow particle precursor composed of a silica protective film, a solvent in the silica protective film, and an undissolved porous solid content. When a coating layer to be described later is formed on the precursor, the formed coating layer becomes a particle wall to form hollow particles.

  The amount of the silica source added for forming the silica protective film is preferably small as long as the particle shape can be maintained. If the amount of the silica source is too large, the silica protective film becomes too thick, and it may be difficult to remove inorganic compounds other than silica from the porous particle precursor. The hydrolyzable organosilicon compound used for forming the silica protective film includes a general formula RnSi (OR ′) 4-n [R, R ′: hydrocarbon such as alkyl group, aryl group, vinyl group, acrylic group, etc. An alkoxysilane represented by the group, n = 0, 1, 2, or 3] can be used. In particular, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

  As an addition method, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilane, pure water, and alcohol is added to the dispersion of the porous particles, and the alkoxysilane is hydrolyzed. The produced silicic acid polymer is deposited on the surface of the inorganic oxide particles. At this time, alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

  When the dispersion medium of the porous particle precursor is water alone or when the ratio of water to the organic solvent is high, a silica protective film can be formed using a silicic acid solution. When a silicic acid solution is used, a predetermined amount of the silicic acid solution is added to the dispersion, and at the same time an alkali is added to deposit the silicic acid solution on the surface of the porous particles. In addition, you may produce a silica protective film together using a silicic acid liquid and the said alkoxysilane.

Third Step: Formation of Silica Coating Layer In the third step, a hydrolyzable organosilicon compound or silicic acid solution is added to the porous particle dispersion prepared in the second step (in the case of hollow particles, a hollow particle precursor dispersion). Etc. is added to coat the surface of the particles with a polymer such as a hydrolyzable organosilicon compound or silicic acid solution to form a silica coating layer.

  Examples of the hydrolyzable organosilicon compound used for forming the silica coating layer include the general formula RnSi (OR ′) 4-n [R, R ′: alkyl group, aryl group, vinyl group, acrylic group as described above. Etc., and alkoxysilanes represented by n = 0, 1, 2, or 3] can be used. In particular, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

  As an addition method, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilane, pure water, and alcohol is used as a dispersion of the porous particles (in the case of hollow particles, a hollow particle precursor). In addition, the silicic acid polymer produced by hydrolyzing alkoxysilane is deposited on the surface of the porous particles (in the case of hollow particles, hollow particle precursors). At this time, alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

  When the dispersion medium of porous particles (in the case of hollow particles, the hollow particle precursor) is water alone or a mixed solvent with an organic solvent and the mixed solvent has a high ratio of water to the organic solvent, a silicate solution You may form a coating layer using. The silicic acid solution is an aqueous solution of a low silicic acid polymer obtained by dealkalizing an aqueous solution of an alkali metal silicate such as water glass by ion exchange treatment.

  The silicic acid solution is added to the dispersion of porous particles (in the case of hollow particles, hollow particle precursors), and at the same time, alkali is added to make the low-silicic acid polymer into porous particles (in the case of hollow particles, hollow particle precursors). ) Deposit on the surface. A silicic acid solution may be used in combination with the alkoxysilane for forming a coating layer. The addition amount of the organosilicon compound or silicic acid solution used for forming the coating layer only needs to be sufficient to cover the surface of the colloidal particles, and the finally obtained silica coating layer has a thickness of 1 to 20 nm. In such an amount, it is added in a dispersion of porous particles (in the case of hollow particles, hollow particle precursor) in a dispersion. When the silica protective film is formed, the organosilicon compound or the silicate solution is added in such an amount that the total thickness of the silica protective film and the silica coating layer is in the range of 1 to 20 nm.

  Next, the dispersion liquid of the particles on which the coating layer is formed is heat-treated. By the heat treatment, in the case of porous particles, the silica coating layer covering the surface of the porous particles is densified, and a dispersion of composite particles in which the porous particles are coated with the silica coating layer is obtained. In the case of a hollow particle precursor, the formed coating layer is densified to form hollow particle walls, and a dispersion of hollow particles having cavities filled with a solvent, gas, or porous solid content is obtained.

  The heat treatment temperature at this time is not particularly limited as long as it can close the fine pores of the silica coating layer, and is preferably in the range of 80 to 300 ° C. When the heat treatment temperature is less than 80 ° C., the fine pores of the silica coating layer may not be completely closed and densified, and the treatment time may take a long time. Further, when the heat treatment temperature exceeds 300 ° C. for a long time, fine particles may be formed, and the effect of low refractive index may not be obtained.

  The refractive index of the inorganic fine particles thus obtained is as low as less than 1.44. Such inorganic fine particles are presumed to have a low refractive index because the porosity inside the porous particles is maintained or the inside is hollow.

  As the binder matrix of the low refractive index layer, a fluorine-containing resin that is crosslinked by heat or ionizing radiation (hereinafter, also referred to as “fluorine-containing resin before crosslinking”) is preferably used.

  Preferred examples of the fluorine-containing resin before crosslinking include a fluorine-containing copolymer formed from a fluorine-containing vinyl monomer and a monomer for imparting a crosslinkable group. Specific examples of the fluorine-containing vinyl monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3 -Dioxoles, etc.), (meth) acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (produced by Osaka Organic Chemicals) or M-2020 (produced by Daikin)), fully or partially fluorinated vinyl ethers, etc. Is mentioned. As monomers for imparting a crosslinkable group, glycidyl methacrylate, vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, vinyl glycidyl ether, and other vinyl monomers having a crosslinkable functional group in advance in the molecule. , Vinyl monomers having a carboxyl group, hydroxyl group, amino group, sulfonic acid group, etc. (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyalkyl vinyl ether, hydroxyalkyl allyl) Ether, etc.). The latter can introduce a crosslinked structure after copolymerization by adding a compound that reacts with a functional group in the polymer and one or more reactive groups. No. 147739. Examples of the crosslinkable group include acryloyl, methacryloyl, isocyanate, epoxy, aziridine, oxazoline, aldehyde, carbonyl, hydrazine, carboxyl, methylol, and active methylene group. When the fluorine-containing copolymer is crosslinked by heating with a crosslinking group that reacts by heating, or a combination of an ethylenically unsaturated group and a thermal radical generator or an epoxy group and a thermal acid generator, it is a thermosetting type. In the case of crosslinking by irradiation with light (preferably ultraviolet rays, electron beams, etc.) by a combination of an ethylenically unsaturated group and a photo radical generator, or an epoxy group and a photo acid generator, the ionizing radiation curable type is used.

  In addition to the above monomers, a fluorine-containing copolymer formed by using a monomer other than the fluorine-containing vinyl monomer and the monomer for imparting a crosslinkable group may be used as the fluorine-containing resin before crosslinking. The monomer that can be used in combination is not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, 2-acrylic acid 2- Ethyl hexyl), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.), vinyl ethers (methyl vinyl ether) Etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.), acrylamides (N-tertbutylacrylamide, N-cyclohexylacrylamide, etc.), methacrylamides, Ronitoriru derivatives and the like can be mentioned. In addition, it is also preferable to introduce a polyorganosiloxane skeleton or a perfluoropolyether skeleton into the fluorinated copolymer in order to impart slipperiness and antifouling properties. For example, polyorganosiloxane or perfluoropolyether having an acrylic group, methacrylic group, vinyl ether group, styryl group or the like at the terminal is polymerized with the above monomer, and polyorganosiloxane or perfluoropolyester having a radical generating group at the terminal. It can be obtained by polymerization of the above monomers with ether, reaction of a polyorganosiloxane or perfluoropolyether having a functional group with a fluorine-containing copolymer, or the like.

  The proportion of each of the above monomers used to form the fluorinated copolymer before crosslinking is preferably 20 to 70 mol%, more preferably 40 to 70 mol%, more preferably 40 to 70 mol% of the fluorinated vinyl monomer. The amount of the monomer is preferably 1 to 20 mol%, more preferably 5 to 20 mol%, and the other monomer used in combination is preferably 10 to 70 mol%, more preferably 10 to 50 mol%.

  The fluorine-containing copolymer can be obtained by polymerizing these monomers in the presence of a radical polymerization initiator by means such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization.

  The fluorine-containing resin before crosslinking is commercially available and can be used. Examples of commercially available fluorine-containing resins before cross-linking include Cytop (Asahi Glass), Teflon (registered trademark) AF (DuPont), polyvinylidene fluoride, Lumiflon (Asahi Glass), Opstar (JSR), etc. Can be mentioned.

  The low refractive index layer containing a cross-linked fluororesin as a constituent component preferably has a dynamic friction coefficient in the range of 0.03 to 0.15 and a contact angle with water in the range of 90 to 120 degrees.

  The low refractive index layer containing a cross-linked fluorine-containing resin as a constituent component contains the aforementioned inorganic particles.

  Various sol-gel materials can also be used as a binder matrix for other low refractive index layers. As such a sol-gel material, metal alcoholates (alcohols such as silane, titanium, aluminum, and zirconium), organoalkoxy metal compounds, and hydrolysates thereof can be used. In particular, alkoxysilane, organoalkoxysilane and its hydrolyzate are preferable. Examples of these include tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, etc.), alkyltrialkoxysilane (methyltrimethoxysilane, ethyltrimethoxysilane, etc.), aryltrialkoxysilane (phenyltrimethoxysilane, etc.), dialkyl. Examples thereof include dialkoxysilane and diaryl dialkoxysilane. In addition, organoalkoxysilanes having various functional groups (vinyl trialkoxysilane, methylvinyl dialkoxysilane, γ-glycidyloxypropyltrialkoxysilane, γ-glycidyloxypropylmethyl dialkoxysilane, β- (3,4-epoxy) Dicyclohexyl) ethyltrialkoxysilane, γ-methacryloyloxypropyltrialkoxysilane, γ-aminopropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, γ-chloropropyltrialkoxysilane, etc.), perfluoroalkyl group-containing silane compounds ( For example, (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, etc.), containing fluoroalkyl ether group It is also preferable to use a run-compound. In particular, the use of a fluorine-containing silane compound is preferable in terms of lowering the refractive index of the layer and imparting water and oil repellency.

  The low refractive index layer preferably contains the polymer in an amount of 5 to 50% by mass. The polymer has a function of adhering fine particles and maintaining the structure of a low refractive index layer including voids. The amount of the polymer used is adjusted so that the strength of the low refractive index layer can be maintained without filling the voids. The amount of the polymer is preferably 10 to 30% by mass of the total amount of the low refractive index layer. In order to adhere the fine particles with the polymer, (1) the polymer is bonded to the surface treatment agent of the fine particles, (2) the fine particles are used as a core, and a polymer shell is formed around the fine particles. It is preferable to use a polymer as the binder. The polymer to be bonded to the surface treatment agent (1) is preferably the shell polymer (2) or the binder polymer (3). The polymer (2) is preferably formed around the fine particles by a polymerization reaction before preparing the coating solution for the low refractive index layer. The polymer (3) is preferably formed by adding a monomer to the coating solution for the low refractive index layer and performing a polymerization reaction simultaneously with or after the coating of the low refractive index layer. It is preferable to carry out in combination of two or all of the above (1) to (3), and to carry out in combination of (1) and (3) or (1) to (3) all combinations. Particularly preferred. (1) Surface treatment, (2) shell, and (3) binder will be described sequentially.

(1) Surface treatment It is preferable that the fine particles (particularly inorganic fine particles) are subjected to a surface treatment to improve the affinity with the polymer. The surface treatment can be classified into physical surface treatment such as plasma discharge treatment and corona discharge treatment, and chemical surface treatment using a coupling agent. It is preferable to carry out only chemical surface treatment or a combination of physical surface treatment and chemical surface treatment. As the coupling agent, an organoalkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Particles when made of SiO _2, surface treatment with a silane coupling agent can be particularly effectively conducted. As a specific example of the silane coupling agent, a silane coupling agent described later is preferably used.

  The surface treatment with the coupling agent can be carried out by adding the coupling agent to the fine particle dispersion and allowing the dispersion to stand at a temperature from room temperature to 60 ° C. for several hours to 10 days. In order to accelerate the surface treatment reaction, inorganic acids (for example, sulfuric acid, hydrochloric acid, nitric acid, chromic acid, hypochlorous acid, boric acid, orthosilicic acid, phosphoric acid, carbonic acid), organic acids (for example, acetic acid, polyacrylic acid, Benzenesulfonic acid, phenol, polyglutamic acid), or salts thereof (eg, metal salts, ammonium salts) may be added to the dispersion.

(2) Shell The polymer forming the shell is preferably a polymer having a saturated hydrocarbon as the main chain. A polymer containing a fluorine atom in the main chain or side chain is preferred, and a polymer containing a fluorine atom in the side chain is more preferred. Polyacrylic acid esters or polymethacrylic acid esters are preferred, and esters of fluorine-substituted alcohols with polyacrylic acid or polymethacrylic acid are most preferred. The refractive index of the shell polymer decreases as the content of fluorine atoms in the polymer increases. In order to lower the refractive index of the low refractive index layer, the shell polymer preferably contains 35 to 80% by mass of fluorine atoms, and more preferably contains 45 to 75% by mass of fluorine atoms. The polymer containing a fluorine atom is preferably synthesized by a polymerization reaction of an ethylenically unsaturated monomer containing a fluorine atom. Examples of ethylenically unsaturated monomers containing fluorine atoms include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole), Mention may be made of esters of fluorinated vinyl ethers and fluorine-substituted alcohols with acrylic acid or methacrylic acid.

  The polymer forming the shell may be a copolymer composed of a repeating unit containing a fluorine atom and a repeating unit not containing a fluorine atom. The repeating unit containing no fluorine atom is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer containing no fluorine atom. Examples of ethylenically unsaturated monomers that do not contain fluorine atoms include olefins (eg, ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride), acrylic acid esters (eg, methyl acrylate, ethyl acrylate, acrylic acid 2- Ethyl hexyl), methacrylic acid esters (for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate), styrene and its derivatives (for example, styrene, divinylbenzene, vinyltoluene, α-methylstyrene), vinyl ether ( For example, methyl vinyl ether), vinyl esters (for example, vinyl acetate, vinyl propionate, vinyl cinnamate), acrylamide (for example, N-tertbutylacrylamide, N-cyclohexylacrylic) Amides), methacrylamide and acrylonitrile.

  When the binder polymer (3) described later is used in combination, a crosslinkable functional group may be introduced into the shell polymer to chemically bond the shell polymer and the binder polymer by crosslinking. The shell polymer may have crystallinity. When the glass transition temperature (Tg) of the shell polymer is higher than the temperature at the time of forming the low refractive index layer, it is easy to maintain microvoids in the low refractive index layer. However, if Tg is higher than the temperature at which the low refractive index layer is formed, the fine particles are not fused, and the low refractive index layer may not be formed as a continuous layer (resulting in a decrease in strength). In that case, it is desirable to use a binder polymer (3) described later in combination, and form the low refractive index layer as a continuous layer with the binder polymer. By forming a polymer shell around the fine particles, core-shell fine particles are obtained. The core-shell fine particles preferably contain 5 to 90% by volume of a core composed of inorganic fine particles, and more preferably 15 to 80% by volume. Two or more kinds of core-shell fine particles may be used in combination. Further, inorganic fine particles having no shell and core-shell particles may be used in combination.

(3) Binder The binder polymer is preferably a polymer having a saturated hydrocarbon or polyether as the main chain, and more preferably a polymer having a saturated hydrocarbon as the main chain. The binder polymer is preferably crosslinked. The polymer having a saturated hydrocarbon as the main chain is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer. In order to obtain a crosslinked binder polymer, it is preferable to use a monomer having two or more ethylenically unsaturated groups. Examples of monomers having two or more ethylenically unsaturated groups include esters of polyhydric alcohols and (meth) acrylic acid (for example, ethylene glycol di (meth) acrylate, 1,4-dichlorohexane diacrylate, pentaerythritol). Tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate), vinylbenzene and its derivatives For example, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloyl ethyl ester, 1,4-divinylcyclohexanone), vinyl sulfone (eg, divinyl sulfone), acrylamide (eg, methylene bisacrylamide) and methacrylamide Can be mentioned. The polymer having a polyether as the main chain is preferably synthesized by a ring-opening polymerization reaction of a polyfunctional epoxy compound. Instead of or in addition to the monomer having two or more ethylenically unsaturated groups, a crosslinked structure may be introduced into the binder polymer by the reaction of a crosslinkable group. Examples of crosslinkable functional groups include isocyanate groups, epoxy groups, aziridine groups, oxazoline groups, aldehyde groups, carbonyl groups, hydrazine groups, carboxyl groups, methylol groups, and active methylene groups. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. The cross-linking group is not limited to the above compound, and may be one that exhibits reactivity as a result of decomposition of the functional group. As the polymerization initiator used for the polymerization reaction and the crosslinking reaction of the binder polymer, a thermal polymerization initiator or a photopolymerization initiator is used, and the photopolymerization initiator is more preferable. Examples of photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds , Fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone. Examples of benzoins include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Examples of benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  The binder polymer is preferably formed by adding a monomer to the coating solution for the low refractive index layer, and at the same time as or after the coating of the low refractive index layer, by a polymerization reaction (further crosslinking reaction if necessary). Even if a small amount of polymer (for example, polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, alkyd resin) is added to the coating solution for the low refractive index layer Good.

  Moreover, it is preferable to add a slipping agent to the low refractive index layer or other refractive index layers of the present invention, and scratch resistance can be improved by imparting slipperiness. As the slip agent, silicon oil or a wax-like substance is preferably used. For example, a compound represented by the following general formula is preferable.

General formula R ₁ COR ₂
In the formula, R ₁ represents a saturated or unsaturated aliphatic hydrocarbon group having 12 or more carbon atoms. An alkyl group or an alkenyl group is preferable, and an alkyl group or alkenyl group having 16 or more carbon atoms is more preferable. R ₂ represents —OM ₁ group (M ₁ represents an alkali metal such as Na or K), —OH group, —NH ₂ group, or —OR ₃ group (R ₃ represents a saturated or unsaturated group having 12 or more carbon atoms. R ₂ represents a saturated aliphatic hydrocarbon group, preferably an alkyl group or an alkenyl group, and R ₂ is preferably an —OH group, —NH ₂ group, or —OR ₃ group. Specifically, higher fatty acids such as behenic acid, stearamide, and pentacoic acid, or derivatives thereof, and carnauba wax, beeswax, and montan wax containing many of these components as natural products can also be preferably used. Polyorganosiloxane as disclosed in JP-B-53-292, higher fatty acid amide as disclosed in US Pat. No. 4,275,146, JP-B 58-33541, British patent No. 927,446 or JP-A-55-126238 and 58-90633, higher fatty acid esters (fatty acids having 10 to 24 carbon atoms and 10 to 24 carbon atoms). Esters of alcohols), and higher fatty acid metal salts as disclosed in U.S. Pat. No. 3,933,516, dicarboxylic acids having up to 10 carbon atoms as disclosed in JP-A-51-37217 A polyester compound comprising an acid and an aliphatic or cycloaliphatic diol, a dicarboxylic acid disclosed in JP-A-7-13292, It can be mentioned oligo polyester or the like from the Le.

For example, the amount of slip agent to be used in the low refractive index layer is preferably ^{0.01mg / m 2 ~10mg / m 2} .

  In the present invention, in order to reduce the reflectance, it is also preferable to provide a high refractive index layer between the transparent support provided with the active ray curable resin layer and the low refractive index layer. In addition, it is more preferable to provide a middle refractive index layer between the transparent support and the high refractive index layer in order to reduce the reflectance. The refractive index of the high refractive index layer is preferably 1.55 to 2.30, and more preferably 1.57 to 2.20. The refractive index of the medium refractive index layer is adjusted to be an intermediate value between the refractive index of the transparent support and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.55-1.80. The thickness of the high refractive index layer and the medium refractive index layer is preferably 5 nm to 1 μm, more preferably 10 nm to 0.2 μm, and most preferably 30 nm to 0.1 μm. The haze of the high refractive index layer and the medium refractive index layer is preferably 5% or less, more preferably 3% or less, and most preferably 1% or less. The strength of the high refractive index layer and the medium refractive index layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher, with a pencil hardness of 1 kg.

  Among the refractive index layers used in the present invention, the high refractive index layer was formed by applying and drying a coating solution containing a monomer, oligomer or hydrolyzate of an organic titanium compound represented by the following general formula. A layer of 55 to 2.5 is preferred.

General formula Ti (OR ¹ ) ₄
In the formula, R ¹ is preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms, preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Moreover, the monomer, oligomer, or hydrolyzate thereof of an organic titanium compound reacts like -Ti-O-Ti- when an alkoxide group is hydrolyzed to form a crosslinked structure, thereby forming a cured layer.

Examples of the monomer or oligomer of the organic titanium compound used in the present invention include Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₃ H ₇ ) ₄ , Ti (O-i- _{C 3 H 7) 4, Ti} (O-n-C 4 H 9) 4, Ti (O-n-C 3 H 7) 4 2-10 mer, Ti (O-i-C 3 H 7) Preferred examples include ₄ to 10 mer of ₄ and 2 to 10 mer of Ti (On-C ₄ H ₉ ) ₄ . These may be used alone or in combination of two or more. Of these _{Ti (O-n-C 3} H 7) 4, Ti (O-i-C 3 H 7) 4, Ti (O-n-C 4 H 9) 4, Ti (O-n-C 3 H 7 ) ₄ to 10-mer and Ti (On-C ₄ H ₉ ) ₄ to 10-mer are particularly preferable.

  Among the coating solutions for the high refractive index layer used in the present invention, it is preferable to add the organic titanium compound to a solution in which water and an organic solvent described later are sequentially added. When water is added later, hydrolysis / polymerization does not proceed uniformly, and white turbidity occurs or film strength decreases. After the water and the organic solvent are added, it is preferable that they are stirred and mixed and dissolved in order to mix well.

  Further, as another method, it is also a preferred embodiment that an organic titanium compound and an organic solvent are mixed and this mixed solution is added to the mixed and stirred solution of water and the organic solvent.

Moreover, it is preferable that the quantity of water is the range of 0.25-3 mol with respect to 1 mol of organic titanium compounds. When the amount is less than 0.25 mol, hydrolysis and polymerization are not sufficiently progressed and the film strength is lowered. If it exceeds 3 moles, hydrolysis and polymerization will proceed excessively, resulting in generation of coarse TiO ₂ particles and white turbidity. Therefore, the amount of water needs to be adjusted within the above range.

  Moreover, it is preferable that the content rate of water is less than 10 mass% with respect to the coating liquid total amount. If the water content is 10% by mass or more with respect to the total amount of the coating solution, it is not preferable because the stability of the coating solution with time deteriorates and white turbidity occurs.

  Here, the organic solvent is preferably a water-miscible organic solvent. Examples of the water-miscible organic solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc.), many Monohydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), polyvalent Alcohol ethers (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether) , Ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol mono Phenyl ether, propylene glycol monophenyl ether, etc.), amines (eg, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine) , Triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocyclic rings (For example, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc.), sulfoxides (for example, dimethyl sulfoxide, etc.), sulfones (for example, , Sulfolane and the like), urea, acetonitrile, acetone and the like, and alcohols, polyhydric alcohols, and polyhydric alcohol ethers are particularly preferable. The amount of these organic solvents used may be adjusted as described above so that the water content is less than 10% by mass with respect to the total amount of the coating solution.

  The monomer, oligomer or hydrolyzate of the organic titanium compound used in the present invention preferably occupies 50.0% by mass to 98.0% by mass in the solid content contained in the coating solution. The solid content ratio is more preferably 50% by mass to 90% by mass, and further preferably 55% by mass to 90% by mass. In addition, it is also preferable to add to the coating composition a polymer of an organic titanium compound (a product obtained by crosslinking the organic titanium compound in advance by hydrolysis) or titanium oxide fine particles.

  The high refractive index layer and medium refractive index layer used in the present invention preferably include those containing metal oxide particles as fine particles and further containing a binder polymer.

  Alternatively, when the organic titanium compound hydrolyzed / polymerized by the coating liquid preparation method and the metal oxide particles are combined, the metal oxide particles and the hydrolyzed / polymerized organic titanium compound are firmly bonded, and the hardness of the particles A strong coating film having the flexibility of a uniform film can be obtained.

The metal oxide particles used for the high refractive index layer and the medium refractive index layer preferably have a refractive index of 1.80 to 2.80, and more preferably 1.90 to 2.80. The mass average diameter of the primary particles of the metal oxide particles is preferably 1 to 150 nm, more preferably 1 to 100 nm, and most preferably 1 to 80 nm. The mass average diameter of the metal oxide particles in the layer is preferably 1 to 200 nm, more preferably 5 to 150 nm, still more preferably 10 to 100 nm, and more preferably 10 to 80 nm. Most preferred. The average particle diameter of the metal oxide particles is measured by a light scattering method if it is 20-30 nm or more, and by an electron micrograph if it is 20-30 nm or less. The specific surface area of metal oxide particles, as measured values by the BET method is preferably from 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, with 30 to 150 m ² / g Most preferably it is.

  Examples of the metal oxide particles include at least one selected from Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S. Specific examples of the metal oxide include titanium dioxide (eg, rutile, rutile / anatase mixed crystal, anatase, amorphous structure), tin oxide, indium oxide, zinc oxide, and zirconium oxide. Of these, titanium oxide, tin oxide, and indium oxide are particularly preferable. The metal oxide particles are mainly composed of oxides of these metals, can further contain other elements, and fine particles imparted with conductivity are also preferably used. The main component means a component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S.

  The metal oxide particles are preferably surface-treated. The surface treatment can be performed using an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include alumina, silica, zirconium oxide and iron oxide. Of these, alumina and silica are preferable. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Of these, a silane coupling agent is most preferable.

  Specific examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane. Methoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxy Propyltriethoxysilane, γ- (β-glycidyloxyethoxy) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, Examples include N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane and β-cyanoethyltriethoxysilane.

  Examples of silane coupling agents having a disubstituted alkyl group with respect to silicon include dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, and γ-glycidyloxypropylmethyldiethoxysilane. Γ-glycidyloxypropylmethyldimethoxysilane, γ-glycidyloxypropylphenyldiethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldi Ethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimeth Shishiran, .gamma.-mercaptopropyl methyl diethoxy silane, .gamma.-aminopropyl methyl dimethoxy silane, .gamma.-aminopropyl methyl diethoxy silane, methyl vinyl dimethoxy silane, and methyl vinyl diethoxy silane.

  Of these, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropyltrimethoxysilane having a double bond in the molecule. Γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-methacryloyloxypropylmethyldiethoxy having a disubstituted alkyl group with respect to silicon Silane, methylvinyldimethoxysilane and methylvinyldiethoxysilane are preferred, and γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxypro Pyrtrimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and γ-methacryloyloxypropylmethyldiethoxysilane are particularly preferred.

  Two or more coupling agents may be used in combination. In addition to the silane coupling agents shown above, other silane coupling agents may be used. Other silane coupling agents include alkyl esters of orthosilicate (eg, methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, i-propyl orthosilicate, n-butyl orthosilicate, sec-butyl orthosilicate, orthosilicate). Acid t-butyl) and its hydrolyzate.

  The surface treatment with the coupling agent can be carried out by adding the coupling agent to the fine particle dispersion and allowing the dispersion to stand at a temperature from room temperature to 60 ° C. for several hours to 10 days. In order to accelerate the surface treatment reaction, inorganic acids (for example, sulfuric acid, hydrochloric acid, nitric acid, chromic acid, hypochlorous acid, boric acid, orthosilicic acid, phosphoric acid, carbonic acid), organic acids (for example, acetic acid, polyacrylic acid, Benzenesulfonic acid, phenol, polyglutamic acid), or salts thereof (eg, metal salts, ammonium salts) may be added to the dispersion.

  These silane coupling agents are preferably hydrolyzed with a necessary amount of water in advance. When the silane coupling agent is hydrolyzed, the surfaces of the organic titanium compound and the metal oxide particles described above are easy to react and a stronger film is formed. It is also preferable to add a hydrolyzed silane coupling agent to the coating solution in advance. The water used for this hydrolysis can also be used for the hydrolysis / polymerization of the organic titanium compound.

  In the present invention, the treatment may be performed by combining two or more kinds of surface treatments. The shape of the metal oxide particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape. Two or more kinds of metal oxide particles may be used in the high refractive index layer or the middle refractive index layer.

  The ratio of the metal oxide particles in the high refractive index layer and the medium refractive index layer is preferably 5 to 65% by volume, more preferably 10 to 60% by volume, and still more preferably 20 to 55% by volume. is there.

  The metal oxide particles are supplied to a coating solution for forming a high refractive index layer and a medium refractive index layer in a dispersion state dispersed in a medium. As a dispersion medium for metal oxide particles, it is preferable to use a liquid having a boiling point of 60 to 170 ° C. Specific examples of the dispersion solvent include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ketone alcohol (eg, diacetone alcohol). , Esters (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene) Chloride, chloroform, carbon tetrachloride), aromatic hydrocarbons (eg, benzene, toluene, xylene), amides (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ethers (eg, diethyl ether, dioxane, Tiger hydrofuran), ether alcohols (e.g., 1-methoxy-2-propanol). Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

  The metal oxide particles can be dispersed in the medium using a disperser. Examples of the disperser include a sand grinder mill (eg, a bead mill with pins), a high-speed impeller mill, a pebble mill, a roller mill, an attritor, and a colloid mill. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.

  The high refractive index layer and medium refractive index layer used in the present invention preferably use a polymer having a crosslinked structure (hereinafter also referred to as a crosslinked polymer) as a binder polymer. Examples of the crosslinked polymer include polymers having a saturated hydrocarbon chain such as polyolefin (hereinafter collectively referred to as polyolefin), and crosslinked products such as polyether, polyurea, polyurethane, polyester, polyamine, polyamide, and melamine resin. Among them, a crosslinked product of polyolefin, polyether and polyurethane is preferred, a crosslinked product of polyolefin and polyether is more preferred, and a crosslinked product of polyolefin is most preferred. Further, it is further preferable that the crosslinked polymer has an anionic group. The anionic group has a function of maintaining the dispersion state of the inorganic fine particles, and the crosslinked structure has a function of imparting a film forming ability to the polymer and strengthening the film. The anionic group may be directly bonded to the polymer chain or may be bonded to the polymer chain via a linking group, but is bonded to the main chain as a side chain via the linking group. Is preferred.

  Examples of the anionic group include a carboxylic acid group (carboxyl), a sulfonic acid group (sulfo), and a phosphoric acid group (phosphono). Of these, sulfonic acid groups and phosphoric acid groups are preferred. Here, the anionic group may be in a salt state. The cation that forms a salt with the anionic group is preferably an alkali metal ion. Moreover, the proton of the anionic group may be dissociated. The linking group that binds the anionic group and the polymer chain is preferably a divalent group selected from —CO—, —O—, an alkylene group, an arylene group, and combinations thereof. The crosslinked polymer which is a preferable binder polymer is preferably a copolymer having a repeating unit having an anionic group and a repeating unit having a crosslinked structure. In this case, the ratio of the repeating unit having an anionic group in the copolymer is preferably 2 to 96% by mass, more preferably 4 to 94% by mass, and most preferably 6 to 92% by mass. preferable. The repeating unit may have two or more anionic groups.

  The crosslinked polymer having an anionic group may contain other repeating units (a repeating unit having neither an anionic group nor a crosslinked structure). Other repeating units are preferably a repeating unit having an amino group or a quaternary ammonium group and a repeating unit having a benzene ring. The amino group or quaternary ammonium group has a function of maintaining the dispersed state of the inorganic fine particles, like the anionic group. The benzene ring has a function of increasing the refractive index of the high refractive index layer. The amino group, the quaternary ammonium group, and the benzene ring can obtain the same effect even if they are contained in a repeating unit having an anionic group or a repeating unit having a crosslinked structure.

  In the crosslinked polymer containing a repeating unit having an amino group or a quaternary ammonium group as a constituent unit, the amino group or quaternary ammonium group may be directly bonded to the polymer chain, or may be a side chain via a linking group. May be bonded to the polymer chain, but the latter is more preferred. The amino group or quaternary ammonium group is preferably a secondary amino group, a tertiary amino group or a quaternary ammonium group, more preferably a tertiary amino group or a quaternary ammonium group. The group bonded to the nitrogen atom of the secondary amino group, tertiary amino group or quaternary ammonium group is preferably an alkyl group, more preferably an alkyl group having 1 to 12 carbon atoms, still more preferably carbon number. 1 to 6 alkyl groups. The counter ion of the quaternary ammonium group is preferably a halide ion. The linking group that connects the amino group or quaternary ammonium group to the polymer chain is a divalent group selected from —CO—, —NH—, —O—, an alkylene group, an arylene group, and combinations thereof. Is preferred. When the crosslinked polymer includes a repeating unit having an amino group or a quaternary ammonium group, the ratio is preferably 0.06 to 32% by mass, more preferably 0.08 to 30% by mass, Most preferably, it is 0.1-28 mass%.

  The cross-linked polymer is prepared by blending a monomer for generating a cross-linked polymer to prepare a coating solution for forming a high refractive index layer and a medium refractive index layer, and is generated by a polymerization reaction simultaneously with or after coating of the coating solution. Is preferred. Each layer is formed with the production of the crosslinked polymer. The monomer having an anionic group functions as a dispersant for inorganic fine particles in the coating solution. The monomer having an anionic group is preferably used in an amount of 1 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 10 to 30% by mass with respect to the inorganic fine particles. The monomer having an amino group or a quaternary ammonium group functions as a dispersion aid in the coating solution. The monomer having an amino group or a quaternary ammonium group is preferably used in an amount of 3 to 33% by mass based on the monomer having an anionic group. These monomers can be made to function effectively before application of the coating liquid by a method of forming a crosslinked polymer by a polymerization reaction simultaneously with or after application of the coating liquid.

  As the monomer used in the present invention, a monomer having two or more ethylenically unsaturated groups is most preferable, and examples thereof include esters of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di ( (Meth) acrylate, 1,4-dichlorohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester Terpolyacrylate), vinylbenzene and its derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide (E.g., methylenebisacrylamide) and methacrylamide. Commercially available monomers may be used as the monomer having an anionic group and the monomer having an amino group or a quaternary ammonium group. As a commercially available monomer having a commercially available anionic group, KAYAMAPMPM-21, PM-2 (manufactured by Nippon Kayaku Co., Ltd.), Antox MS-60, MS-2N, MS-NH4 (manufactured by Nippon Emulsifier Co., Ltd.) , Aronix M-5000, M-6000, M-8000 series (manufactured by Toagosei Chemical Industry Co., Ltd.), Biscote # 2000 series (manufactured by Osaka Organic Chemical Industry Co., Ltd.), New Frontier GX-8289 (Daiichi Kogyo Seiyaku) NK ester CB-1, A-SA (manufactured by Shin-Nakamura Chemical Co., Ltd.), AR-100, MR-100, MR-200 (manufactured by Eighth Chemical Industry Co., Ltd.), and the like. It is done. Examples of commercially available monomers having a commercially available amino group or quaternary ammonium group include DMAA (manufactured by Osaka Organic Chemical Industry Co., Ltd.), DMAEA, DMAPAA (manufactured by Kojin Co., Ltd.), and Bremer QA (Nippon Yushi Co., Ltd.). ) And New Frontier C-1615 (Daiichi Kogyo Seiyaku Co., Ltd.).

  For the polymerization reaction of the polymer, a photopolymerization reaction or a thermal polymerization reaction can be used. A photopolymerization reaction is particularly preferable. A polymerization initiator is preferably used for the polymerization reaction. For example, the thermal polymerization initiator mentioned later used in order to form the binder polymer of a hard-coat layer, and a photoinitiator are mentioned.

  A commercially available polymerization initiator may be used as the polymerization initiator. In addition to the polymerization initiator, a polymerization accelerator may be used. The addition amount of the polymerization initiator and the polymerization accelerator is preferably in the range of 0.2 to 10% by mass of the total amount of monomers. The coating liquid (dispersion of inorganic fine particles containing monomer) may be heated to promote polymerization of the monomer (or oligomer). Moreover, it may heat after the photopolymerization reaction after application | coating, and may additionally process the thermosetting reaction of the formed polymer.

  For the medium refractive index layer and the high refractive index layer, it is preferable to use a polymer having a relatively high refractive index. Examples of the polymer having a high refractive index include polystyrene, styrene copolymer, polycarbonate, melamine resin, phenol resin, epoxy resin, and polyurethane obtained by reaction of cyclic (alicyclic or aromatic) isocyanate and polyol. . Polymers having other cyclic (aromatic, heterocyclic, alicyclic) groups and polymers having halogen atoms other than fluorine as substituents can also be used with a high refractive index.

  Each layer of the antireflection layer is formed by dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, micro gravure coating, extrusion coating, spray coating, and inkjet. It can be formed by coating.

<Polarizer>
The polarizing plate of the present invention will be described.

  The polarizing plate can be produced by a general method. The back side of the optical film of the present invention is subjected to alkali saponification treatment, and the treated optical film is bonded to at least one surface of a polarizing film prepared by immersing and stretching in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution. It is preferable. The optical film may be used on the other surface, or another polarizing plate protective film may be used. As a polarizing plate protective film used on the opposite surface side, as a commercially available cellulose ester film, KC8UX2M, KC4UX, KC5UX, KC4UY, KC8UY, KC12UR, KC8UCR-1, KC8UCR-2, KC8UCR-3, KC8UCR-4, KC8UXW- H (manufactured by Konica Minolta Opto Co., Ltd.) and the like are preferably used. These can be made into a polarizing plate by using the same type of film on both sides of the polarizer, or a polarizing plate can be formed by combining different types of films. These polarizing plates can be used on the front surface or the back surface (backlight side) of the display device. For example, it can be used in combination with KC8UY / polarizer / KC12UR, KC8UX2M / polarizer / KC8UCR-3, KC8UXW-H / polarizer / KC8UCR4, KCUXW-H / polarizer / KCUCR-3, and the like. In contrast to the optical film of the present invention, the polarizing plate protective film used on the other surface has an in-plane retardation Ro of 590 nm, an optical compensation film having a phase difference of 20 to 70 nm and Rt of 70 to 400 nm. It is preferable that These can be produced, for example, by the methods described in JP-A-2002-71957, paragraph numbers [0014] to [0078] and JP-A-2003-170492, paragraphs [0064] to [0252]. Alternatively, it is preferable to use a polarizing plate protective film that also serves as an optical compensation film having an optically anisotropic layer formed by aligning a liquid crystal compound such as a discotic liquid crystal. For example, the optically anisotropic layer can be formed by the method described in paragraph numbers [0033] to [0053] of JP-A-2003-98348. By using it in combination with the optical film of the present invention, a polarizing plate having excellent flatness and a stable viewing angle expansion effect can be obtained.

  The polarizing film, which is the main component of the polarizing plate, is an element that transmits only light having a polarization plane in a certain direction. A typical polarizing film known at present is a polyvinyl alcohol polarizing film, which is a polyvinyl alcohol film. There are one in which iodine is dyed on a system film and one in which dichroic dye is dyed. As the polarizing film, a polyvinyl alcohol aqueous solution is formed and dyed by uniaxially stretching or dyed, or uniaxially stretched after dyeing, and then preferably subjected to a durability treatment with a boron compound. On the surface of the polarizing film, one side of the optical film of the present invention is bonded to form a polarizing plate. It is preferably bonded with an aqueous adhesive mainly composed of completely saponified polyvinyl alcohol or the like.

  The polarizing plate using the optical film of the present invention has less curl and excellent flatness, does not cause foreign matter failure, and further improves visibility by combining with an optical compensation film in combination with an increased viewing angle. done.

<Display device>
By incorporating the polarizing plate of the present invention into a display device, the display device of the present invention having various visibility can be manufactured. The optical film of the present invention is preferably a reflective, transmissive, transflective LCD, or TN, STN, OCB, HAN, VA (PVA, MVA), IPS, or other driving LCD. Used. Further, the optical film of the present invention has remarkably little color unevenness and glare of the reflected light of the antireflection layer, and is excellent in flatness, such as a plasma display, a field emission display, an organic EL display, an inorganic EL display, and electronic paper. It is preferably used for various display devices. In particular, a large-screen display device with a screen of 30 or more types, particularly 30 to 54 types, has less color unevenness, glare and wavy unevenness, and has an effect that eyes are not tired even during long-time viewing.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.

Example 1
<Preparation of cellulose ester film 1>
(Silicon dioxide dispersion A)
Aerosil 972V (manufactured by Nippon Aerosil Co., Ltd.) 12 parts by mass (average primary particle diameter 16 nm, apparent specific gravity 90 g / liter)
88 parts by mass of ethanol or more was stirred and mixed with a dissolver for 30 minutes, and then dispersed with Manton Gorin. 88 parts by mass of methylene chloride was added to the silicon dioxide dispersion A while stirring and mixed with a dissolver for 30 minutes to prepare a silicon dioxide dispersion dilution A.

(Preparation of inline additive solution A)
1,3,5 triazine compound (compound D having the following structure) 12 parts by mass Methylene chloride 100 parts by mass

  The above was put into a sealed container, heated, stirred and completely dissolved and filtered.

  To this, 36 parts by mass of silicon dioxide dispersion diluent A was added with stirring. After further stirring for 30 minutes, cellulose acetate propionate (acetyl group substitution degree 1.9, propionyl group substitution degree 0.8) 6 masses. The mixture was added with stirring, and further stirred for 60 minutes, and then filtered through a polypropylene wind cartridge filter TCW-PPS-1N manufactured by Advantech Toyo Co., Ltd. to prepare an in-line additive solution A.

(Preparation of dope solution A)
Cellulose ester (cellulose triacetate synthesized from linter cotton)
100 parts by mass (Mn = 148000, Mw = 310000, Mw / Mn = 2.1, acetyl group substitution degree 2.9)
Trimethylolpropane tribenzoate (the following compound) 5.0 parts by mass Ethylphthalyl ethyl glycolate 5.5 parts by mass Methylene chloride 440 parts by mass Ethanol 40 parts by mass

  The above was put into a closed container, heated and stirred, and completely dissolved. Azumi filter paper No. No. 24 was used for filtration to prepare a dope solution. 2 parts by mass of the above-mentioned inline additive A is added to 100 parts by mass of the filtered dope liquid A, and the mixture is sufficiently mixed with an inline mixer (Toray static type in-pipe mixer Hi-Mixer, SWJ). Using the apparatus, it was cast uniformly on a stainless steel band support at a temperature of 35 ° C. and a width of 1.8 m. With the stainless steel band support, the solvent was evaporated until the residual solvent amount became 120%, and then peeled off from the stainless steel band support. The peeled cellulose ester web was evaporated at 40 ° C., slit to 1.6 m width, and then stretched 1.1 times at 120 ° C. in the TD direction (direction perpendicular to the film transport direction) with a tenter. . The residual solvent amount when starting stretching with a tenter was 25%. Then, drying was completed while transporting the heating zone at 110 ° C. and 120 ° C. with a number of rolls, slitting to a width of 1.4 m, winding at both ends of the film with a width of 15 mm and an average height of 10 μm, A cellulose ester film was obtained. The draw ratio in the MD direction (the same direction as the film transport direction) immediately after peeling calculated from the rotational speed of the stainless steel band support and the operating speed of the tenter was 1.1 times. The residual solvent amount of the cellulose ester film was 0.1%, the average film thickness was 80 μm, and the winding number was 3000 m. This was designated as Sample Film 1.

<< Coating of back coat layer 1 >>
The following coating composition 1 for a backcoat layer was prepared by filtering with a filter having a particle capture efficiency of 3 μm of 99% or more and 0.5 μm or less and a particle capture efficiency of 10% or less. The backcoat layer coating composition 1 was applied to the surface of the cellulose ester film 1 opposite to the surface in contact with the stainless steel band support with an extrusion coater so that the wet film thickness was 15 μm, and the coating composition was 90 ° C. Dry for 30 seconds. This was designated as Sample Film 2.

<Backcoat layer coating composition 1>
Diacetyl cellulose (acetyl group substitution degree 2.4) 0.5 parts by weight Acetone 70 parts by weight Methanol 20 parts by weight Propylene glycol monomethyl ether 10 parts by weight 2% acetone-dispersed ultrafine silica AEROSIL 200V (manufactured by Nippon Aerosil Co., Ltd.)
0.2 parts by mass (Silica fine particles were added dispersed in methanol to be added.)
<< Formation of Fine Convex Structure 1: Present Invention >>
<Preparation of cellulose ester film 2>
In the production of the cellulose ester film 1, the average film thickness is 80 μm in the same manner except that the silicon dioxide dispersion diluent A is not added to the in-line additive liquid A and the ink droplets are uniformly emitted to the film surface by the following inkjet method. A cellulose ester film 2 having a winding number of 3000 m was produced. This was designated as Sample Film 3.

The following inkjet head is installed at the position 10B in FIG. 9, and the following ink liquid 1 is emitted as an ink droplet at 1 pl by the inkjet method on the surface opposite to the surface in contact with the stainless steel band support of the cellulose ester film 2. After landing, the film was dried at 85 ° C. to form a fine convex structure having 50 convex portions having a height a of 0.01 to 0.5 μm per 1000 μm ^{2 based} on the film surface. The shape of the convex portion approximated to (b) of FIG.

<Inkjet ejection method>
As the inkjet emission device, a line head method (FIG. 5A) was used, and 10 inkjet heads having a predetermined number of nozzles having a nozzle diameter of 3.5 μm were prepared. An ink jet head having the structure shown in FIG. 4 was used.

  The ink supply system is composed of an ink supply tank, a filter, a piezo-type ink jet head, and piping. The ink supply tank to the ink jet head section is insulated and heated (40 ° C.), and the emission temperature is 40 ° C. The driving frequency was 20 kHz.

<Composition of ink liquid 1>
Cellulose acetate propionate (total acyl group substitution degree 2.7, acetyl group substitution degree 1.90, propionyl group substitution degree 0.8) 0.5 parts by mass Acetone 70 parts by mass Methanol 20 parts by mass Propylene glycol monomethyl ether 10 parts by mass Part << Formation of Fine Convex Structure 2: Present Invention >>
Similarly, the ink liquid 1 used for forming the fine convex structure 1 is ejected by an ink jet method, dried at 85 ° C. after landing of the ink liquid, and the height a based on the film surface is 0.01 to 0.00. A fine convex structure having 100 convex portions of 5 μm per 1000 μm ² was formed. This was designated as Sample Film 4.

<< Formation of Fine Convex Structure 3: Present Invention >>
Similarly, the following ink liquid 2 is emitted by the ink jet method, dried at 85 ° C. after landing of the ink liquid, the height a based on the film surface is 0.03 to 0.3 μm, and the diameter b of the convex portion A fine convex structure having 200 convex portions of 0.1 to 1 μm per 1000 μm ² was formed. This was designated as Sample Film 5.

<Composition of ink liquid 2>
Diacetylcellulose (acetyl group substitution degree 2.4) 0.5 parts by weight Acetone 70 parts by weight Methanol 20 parts by weight Propylene glycol monomethyl ether 10 parts by weight 2% ultrafine silica dispersion Aerosil R972V (manufactured by Nippon Aerosil Co., Ltd.)
10 parts by mass (0.2 parts by mass as silica fine particles)
<< Formation of Fine Convex Structure 4: Present Invention >>
Using the following ink liquid 3, it is emitted by an ink jet method, dried at 85 ° C. after landing of the ink liquid, and a convex portion having a height a of 0.02 to 0.1 μm with respect to the film surface as 1000 μm ² . A fine convex structure having 500 pieces was formed. This was designated as Sample Film 6.

<Composition of ink liquid 3>
Cellulose acetate propionate (total acyl group substitution degree 2.7, acetyl group substitution degree 1.90, propionyl group substitution degree 0.8) 0.5 parts by mass Methyl acetate 70 parts by mass Ethanol 20 parts by mass 2% ultrafine silica Ethanol dispersion Aerosil 200V (manufactured by Nippon Aerosil Co., Ltd.)
10 parts by mass (0.2 parts by mass as silica fine particles)
<< Formation of Fine Convex Structure 5: Present Invention >>
Using the following ink liquid 4, the ink is emitted onto the cellulose ester film 2 by an ink jet method, dried at 85 ° C. after landing of the ink liquid, and the height a based on the film surface is 0.1 to 0.3 μm. A fine convex structure having 10 convex portions per 1000 μm ² was formed. This was designated as Sample Film 7.

<Composition of ink liquid 4>
Diacetyl cellulose (acetyl group substitution degree 2.4) 2 parts by mass Methyl ethyl ketone 70 parts by mass Methanol 30 parts by mass Cross-linked acrylic fine particle methyl ethyl ketone dispersion (particle size 0.06-0.15 μm) MS-300K (manufactured by Soken Chemical Co., Ltd.) 1 part by mass (0.35 parts by mass as particles)
Sample films 1 to 7 shown in Table 1 were produced as described above.

  The following hard coat layer was applied to the surface opposite to the surface provided with the fine convex structure of each of the prepared sample films 1 to 7.

<Applying hard coat layer>
On the film sample, the following hard coat layer coating composition is applied with a die coater so as to form a uniform coating layer, and the temperature and speed of the hot air are gradually increased and finally dried at 85 ° C., followed by activation. Ultraviolet rays were irradiated from the light irradiation part at an irradiation intensity of 0.1 J / cm ² , and a clear hard coat layer having a dry film thickness of 5 μm was provided.

<Hard coat layer coating composition>
Dipentaerythritol hexaacrylate monomer 60 parts by mass Dipentaerythritol hexaacrylate dimer 20 parts by mass Dipentaerythritol hexaacrylate trimer or higher component 20 parts by mass Photoinitiator 4 parts by mass (Irgacure 184 (Ciba Specialty Chemicals (Made by Co., Ltd.))
Propylene glycol monomethyl ether 75 parts by mass Methyl ethyl ketone 75 parts by mass Next, the following antireflection layer was provided on the hard coat layer to prepare antireflection films 1 to 7.

<< Preparation of antireflection layer (low refractive index layer 1) >>
The following low refractive index layer composition 1 was applied with a die coater, dried at 80 ° C. for 5 minutes, further thermally cured at 120 ° C. for 5 minutes, and further cured by irradiating ultraviolet rays at 175 mJ / cm ^2. The low refractive index layer 1 was provided so as to be 95 nm. The refractive index of the low refractive index layer 1 was 1.45.

<Preparation of tetraethoxysilane hydrolyzate A>
Tetraethoxysilane hydrolyzate A was prepared by mixing 580 g of tetraethoxysilane and 1144 g of ethanol, and adding an acetic acid aqueous solution thereto, followed by stirring at room temperature (25 ° C.) for 1 hour.

<Low refractive index layer composition 1>
Propylene glycol monomethyl ether 303 parts by mass Isopropyl alcohol 305 parts by mass Tetraethoxysilane hydrolyzate A 139 parts by mass γ-methacryloxypropyltrimethoxysilane (KBM503 manufactured by Shin-Etsu Chemical Co., Ltd.) 1.6 parts by mass 10% FZ-2207, propylene glycol Monomethyl ether solution (Nihon Unicar Co., Ltd.) 1.3 parts by mass Next, a polarizing plate was prepared using each antireflection film.

<Production of polarizing plate>
A polyvinyl alcohol film having a thickness of 120 μm was uniaxially stretched (temperature: 110 ° C., stretch ratio: 5 times). This was immersed in an aqueous solution composed of 0.075 g of iodine, 5 g of potassium iodide and 100 g of water for 60 seconds, and then immersed in an aqueous solution of 68 ° C. composed of 6 g of potassium iodide, 7.5 g of boric acid and 100 g of water. This was washed with water and dried to obtain a polarizing film.

  Then, according to the following processes 1-5, the polarizing film, the said antireflection films 1-7, and the cellulose ester film of the back side were bonded together, and the polarizing plate was produced. As the polarizing plate protective film on the back side, a cellulose ester film R (Ro = 43 nm, Rt = 132 nm) having a retardation produced by the following method was used as a polarizing plate.

  Step 1: Soaked in a 1 mol / L sodium hydroxide solution at 50 ° C. for 60 seconds, then washed with water and dried to obtain a saponified cellulose ester film bonded to the polarizer.

  Step 2: The polarizing film was immersed in a polyvinyl alcohol adhesive tank having a solid content of 2% by mass for 1 to 2 seconds.

  Step 3: Lightly wipe off the excess adhesive adhering to the polarizing film in Step 2, place it on the cellulose ester film treated in Step 1, and then stack and arrange so that the antireflection layer is on the outside did.

Step 4: The antireflection film, the polarizing film, and the cellulose ester film sample laminated in Step 3 were bonded at a pressure of 20 to 30 N / cm ² and a conveyance speed of about 2 m / min.

  Step 5: A polarizing plate prepared in Step 4 in a dryer at 80 ° C., the cellulose ester film, and the antireflection films 1 to 7 were bonded to each other for 2 minutes to prepare polarizing plates 1 to 7. For the polarizing plate used on the backlight side of the display device, a cellulose ester film with a hard coat layer (KC8UXW-H, manufactured by Konica Minolta Opto) and the cellulose ester film R are used as a polarizing plate protective film. A polarizing plate produced in the same manner was used.

<Preparation of cellulose ester film R>
(Preparation of dope solution E)
Cellulose ester (cellulose acetate propionate acetyl group substitution degree 1.9, propionyl group substitution degree 0.8) 100 parts by mass (Mn = 100000, Mw = 220,000, Mw / Mn = 2.2)
Triphenyl phosphate 8 parts by weight Ethylphthalyl ethyl glycolate 2 parts by weight Methylene chloride 300 parts by weight Ethanol 60 parts by weight The above is put into a sealed container, heated and stirred, and completely dissolved. Azumi Filter Paper Co., Ltd. Azumi filter paper No. No. 24 was filtered to prepare a dope solution E.

(Silicon dioxide dispersion E)
Aerosil 972V (manufactured by Nippon Aerosil Co., Ltd.) 10 parts by mass Ethanol 75 parts by mass The above was stirred and mixed with a dissolver for 30 minutes, and then dispersed with Manton Gorin. 75 parts by mass of methylene chloride was added to the silicon dioxide dispersion while stirring, and the mixture was stirred and mixed for 30 minutes with a dissolver to prepare a silicon dioxide dispersion dilution E.

(Preparation of inline additive solution E)
Methylene chloride 100 parts by mass Tinuvin 109 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 4 parts by mass Tinuvin 171 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 4 parts by mass Tinuvin 326 (manufactured by Ciba Specialty Chemicals Co., Ltd.) 2 parts by mass The solution was put into a container, heated, stirred and completely dissolved and filtered.

  To this, 20 parts by mass of silicon dioxide dispersion diluent E was added with stirring, and further stirred for 30 minutes, and then cellulose ester (cellulose acetate propionate acetyl group substitution degree 1.9, propionyl group substitution degree 0.8). 5 parts by mass was added with stirring, and the mixture was further stirred for 60 minutes, and then filtered through a polypropylene wind cartridge filter TCW-PPS-1N manufactured by Advantech Toyo Co., Ltd. to prepare an in-line additive solution E.

  Add 4 parts by mass of the filtered inline additive E to 100 parts by mass of the filtered dope solution E, mix thoroughly with an inline mixer (Toray static type in-pipe mixer Hi-Mixer, SWJ), and then belt cast Using the apparatus, it was cast uniformly on a stainless steel band support at a temperature of 35 ° C. and a width of 1.8 m. With the stainless steel band support, the solvent was evaporated until the amount of residual solvent reached 100%, and then peeled off from the stainless steel band support. The web of the peeled cellulose ester film was evaporated at 55 ° C, slit to 1.6 m width, and then stretched 1.3 times at 130 ° C in the TD direction (direction perpendicular to the film transport direction) with a tenter. did. At this time, the residual solvent amount when starting stretching with a tenter was 18%. Then, drying was completed while transporting the drying zone at 120 ° C. and 110 ° C. with a number of rolls, slitting to a width of 1.4 m, applying a knurling process with a width of 15 mm and an average height of 10 μm at both ends of the film, and winding, A cellulose ester film R was obtained. The amount of residual solvent was 0.1%, the average film thickness was 80 μm, and the number of turns was 3000 m. This cellulose ester film had Ro = 43 nm and Rt = 132 nm, had a slow axis in the width direction, and the deviation angle of the slow axis with respect to the width direction was within ± 0.6 degrees.

<Production of liquid crystal display device>
A liquid crystal panel was produced as follows, and the characteristics as a liquid crystal display device were evaluated.

  The polarizing plate on the surface of the commercially available 32-inch liquid crystal television (MVA type cell) previously bonded was peeled off, and the prepared polarizing plates 1 to 7 were each bonded to the glass surface of the liquid crystal cell.

  At that time, the direction of bonding of the polarizing plate is such that the surface of the optical compensation film (retardation film) is on the liquid crystal cell side and the absorption axis is in the same direction as the polarizing plate previously bonded. The liquid crystal display devices 1 to 7 were respectively produced.

  The following evaluation was performed for each of the sample film, the antireflection film, the polarizing plate, and the liquid crystal display device produced as described above.

<Evaluation>
(Evaluation of blocking properties)
After the sample film was stored for 1 month in a warehouse with a roll length of 3000 m, the occurrence of blocking was visually evaluated according to the following criteria.

○: No blocking ○ △: There is no trace or deformation in the sample to the extent that a light peeling sound is made. △: There is no deformation but a trace remains in the sample. △ ×: There is no deformation but a trace remains clearly. Unevenness remains in the sample (dynamic friction coefficient)
The dynamic friction coefficient between the film surface and the back surface of the sample film is cut out so that the front and back surfaces of the film are in contact with each other according to JIS-K-7125 (1987), a 200 g weight is placed, the sample moving speed is 100 mm / min, and the contact area. The weight was pulled horizontally under the condition of 80 mm × 200 mm, the average load (F) while the weight was moving was measured, and the dynamic friction coefficient (μ) was obtained from the following formula. The smaller the dynamic friction coefficient, the less “squeaking” occurs.

Coefficient of dynamic friction = F (g) / weight of weight (g)
(Sample film foreign material failure)
The foreign matter failure of the obtained sample film was confirmed visually.

A: Number of foreign matter failures with a diameter of 10 μm or more per 100 m of film length 0: Less than 3 foreign matter failures with a diameter of 10 μm or more per 100 m of film length Δ: Number of foreign matter failures with a diameter of 10 μm or more per 100 m of film length Less than 3 to 10 ×: Number of foreign matter failures with a diameter of 10 μm or more per 100 m film length 10 or more (number of foreign matter failures in the antireflection layer)
By visual inspection of the coating film of the antireflection film, the number of protrusions and / or dents that appear to have a diameter of 150 μm or more was counted per 1 m ² .

  The above counted number of foreign matters was evaluated based on the following.

○: No foreign matter △: Some foreign matter was observed ×: Many foreign materials were observed (bubbles on the bonding surface (interface between the polarizer and the resin film), foreign matter failure evaluation)
At the time of polarizing plate sample preparation, the following rank evaluation was performed visually for fine bubbles and foreign matter failures at the interface at the time of bonding between the polarizer and the resin film.

○: No bubbles or foreign matters △: Some bubbles or foreign matters were observed ×: Many bubbles or foreign matters were observed (uneven color of reflected light)
Using the obtained liquid crystal display device, unevenness of reflected light due to foreign matter failure or coating unevenness was evaluated as follows.

○: No change in the color tone of the reflected light is observed Δ: A slight change in the color tone of the reflected light is observed ×: A color change in the reflected light is partially recognized Sample film, antireflection film, polarizing plate, liquid crystal display device The above evaluation results are shown in Table 1 below.

  From the above table, it can be seen that the sample film of the present invention is an optical film that is excellent in slipperiness, anti-blocking and foreign matter failure even if it is a wide substrate. Further, it was found that the antireflection film and the polarizing plate of the present invention have improved foreign matter failure and can provide a liquid crystal display device with high display quality.

Example 2
The hard coat layer is formed on the cellulose ester film 2 using the hard coat layer coating composition of Example 1 using the apparatus shown in FIG. After providing, the convex part formation was performed by the inkjet method similarly to formation of the fine convex structure 3 in the surface opposite to a hard-coat layer, and the cellulose-ester film 8 was produced. Next, an antireflection layer (low refractive index layer 1) was provided to form an antireflection film 8, and similarly, a polarizing plate 8 and a liquid crystal display device 8 were produced.

  When the obtained sample was evaluated in the same manner as in Example 1, it was possible to provide a liquid crystal display device with high display quality by reproducing Example 1 and having excellent slipperiness, prevention of blocking and foreign matter failure. I understood.

Example 3
In the same manner as in the formation of the fine convex structure 3 in Example 1, the height a based on the film surface is 0.03 to 0.00 mm on the cellulose ester film 2 using the ink liquid 2 up to 1000 m from the winding core. A fine convex structure having 3 convex portions having a convex portion diameter b of 0.1 to 1 μm and 400 convex portions per 1000 μm ² is formed, and 200 convex portions are provided from 1000 to 2000 m. A fine convex structure was formed, and a fine convex structure having 50 convex portions from 2000 m to 3000 m was formed to produce a cellulose ester film 9.

  In order to evaluate the blocking property of this film, the original film of the sample film was stored in the warehouse for 6 months with a winding length of 3000 m, and when blocking was observed, no blocking or abnormal winding appearance was observed. It was.

It is a schematic diagram which shows an example which provided the fine convex structure which has an antiblocking function with an inkjet system on a transparent base film. It is sectional drawing which shows an example of another convex structure. It is the schematic which shows the discharge angle of an ink, and the discharge method. It is sectional drawing which shows an example of the inkjet head which can be used for the inkjet method which concerns on this invention. It is the schematic which shows an example of the inkjet head part and nozzle plate which can be used by this invention. It is a schematic diagram which shows an example of the inkjet system which can be preferably used by this invention. It is a schematic diagram showing an example in which a fine convex structure is formed with ink droplets having a smaller particle diameter after the fine convex structure is formed with ink droplets having a large particle diameter by an inkjet method. It is sectional drawing which shows an example of the convex part which made the ink droplet contain fine particle. It is a schematic diagram which shows the flow which added the process of providing a fine convex structure with an inkjet system to the process of manufacturing a transparent base material by solution casting. It is a schematic diagram which shows the flow which added the process of providing a fine convex structure with an inkjet system to the process of manufacturing a transparent base material by melt casting. It is a schematic diagram which shows the flow of another process which provides a fine convex structure with an inkjet system on a transparent base material.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 14, 502 Transparent base material 2 Functional layer 3 Ink droplet 4 Fine particle 10 Inkjet head 11 Support body 12 Casting die 21 Melting die 22 Film-forming roll 501 Film roll 503 1st coater 504A, B Back roll 505A, B Drying zone 506 Ultraviolet irradiation unit 508 Ink supply tank 509 Inkjet emission unit

Claims (12)

A method for producing an optical film, comprising: depositing ink droplets on a transparent substrate film to form a fine convex structure on at least one surface of the substrate surface and performing an anti-blocking process. ^2. The optical film according to claim 1, wherein the fine convex structure has 1 to 1000 convex portions having a convex portion height a of 0.01 to 0.5 μm per 1000 μm ² . Production method. The method for producing an optical film according to claim 1, wherein the ink droplet includes a thermoplastic resin, an actinic ray curable resin, or a thermosetting resin. The method for producing an optical film according to claim 1, wherein the ink droplet contains fine particles. The width | variety of the said transparent base film is 1.4m-4m, The manufacturing method of the optical film of any one of Claims 1-4 characterized by the above-mentioned. The said transparent base film is a cellulose-ester film or a cycloolefin polymer film, The manufacturing method of the optical film of any one of Claims 1-5 characterized by the above-mentioned. The optical film manufactured by the manufacturing method of the optical film of any one of Claims 1-6. The optical film according to claim 7, wherein a hard coat layer is provided on at least one surface of the optical film. The optical film according to claim 8, further comprising an antireflection layer provided on the hard coat layer. A polarizing plate comprising the optical film according to claim 7. A display device comprising the optical film according to claim 7. A display device comprising the polarizing plate according to claim 10.

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