JP2005164890A - Long-sized antiglare film, antiglare and antireflection film, polarizing plate, display device using those, and antiglare processing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a long-sized antiglare film which realizes antiglare effect, visibility, and black sharpness in moving picture display, an antiglare antireflection film, a polarizing plate, a display device using them, and an antiglare processing method. <P>SOLUTION: The long-sized antiglare film is characterized in being provided with an antiglare layer which is made different in antiglare effect in the width direction and in the length direction. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a long antiglare film, an antiglare antireflection film, a polarizing plate, a display device using them, and an antiglare processing method.

  In recent years, development of large-screen display devices has progressed. Along with that, an anti-reflection layer was provided to improve visibility, and an anti-glare layer was provided to scatter the reflected light with an uneven surface to obtain a display performance with less glare and less glare. Many image display devices have been used.

  Various types and performance improvements have been made to the antireflection layer and antiglare layer depending on the application. By placing various films with these functions on the front of the display, antireflection is improved to improve visibility on the display. A method of imparting a function or an antiglare function is used. These optical films used as the front plate are provided with an antireflection layer or an antiglare layer formed by coating or sputtering.

  The antiglare layer blurs the outline of the image reflected on the surface so that reflection of the reflected image does not matter when using an image display device such as a liquid crystal display, an organic EL display, or a plasma display. In particular, the characteristics of the antiglare layer are becoming more and more important for large-screen displays with intense reflections.

  In order to provide the antiglare layer, such a property can be imparted by coating the antiglare layer on the surface of the base material or on the functional layer on the base material and providing appropriate irregularities on the surface. Conventionally, as a method for forming such irregularities, a method of adding fine particles to a coating solution has been disclosed (for example, see Patent Document 1). In addition, an embossing method disclosed in JP-A-6-234175, a method of transferring a mold in advance disclosed in JP-A-63-298201, and the like are known. However, the method of forming irregularities by embossing or transfer is generally inferior in productivity, and it is difficult to form a fine irregular structure or provide an irregular portion at a desired position.

  On the other hand, as a method for forming irregularities using fine particles, a method is used in which a coating liquid in which fine particles, for example, inorganic fine particles or organic fine particles are dispersed in a binder such as a resin, is prepared and applied to form an uneven structure on the surface. ing. This method is a pattern in which fine particles that form irregularities are present in the binder layer, and it is necessary to disperse the fine particles appropriately. Therefore, it is difficult to effectively form a desired irregular structure, resulting in anti-glare. It had a great obstacle to obtaining a sufficient anti-glare effect as a film. In addition, when changing the position and shape of the concavo-convex portion, it is necessary to correct the particle size, blending amount, film thickness, and the like of the fine particles, which makes it very complicated to switch the type. Moreover, in order to achieve a desired concavo-convex structure, it is necessary to use fine particles having a relatively large particle size, resulting in a decrease in sharpness and the like. In addition, in the method of forming the antiglare layer by the above-mentioned application, there is a drawback that the occurrence of uneven coating and the adhesion to the support or the lower layer are often lowered, and the productivity is also inferior. Therefore, the development of immediate improvement means is desired.

  In response to the above problems, as one method for forming a functional layer, an actinic ray curable resin or a thermosetting resin and a coating liquid containing various fine particles are applied on a substrate, and then irradiated or heated with actinic rays. A method is known in which the treatment is performed and cured (see, for example, Patent Documents 2 to 4). However, when an anti-glare layer is formed by an application method using an actinic ray curable resin or a thermosetting resin, a desired concavo-convex structure or concavo-convex portion position is effectively formed in the same manner as described above. For this purpose, it is necessary to appropriately control the coating solution and coating conditions, which increases the amount of work when switching between varieties, which is a factor that reduces productivity in multi-product production.

  On the other hand, various methods for forming an antireflection layer have been proposed to reduce reflection, but it is difficult to completely eliminate reflection, and sufficient visibility is obtained in an environment where there are many reflections on the screen. I couldn't. It is proposed to use the above-mentioned anti-glare layer in a display device having a large number of reflections such as a large screen. However, the image quality, particularly the contrast is deteriorated, and the black image is poor and the image quality remains unsatisfactory. It was. Therefore, a method of forming an antireflection layer on the antiglare layer has been proposed, but most of the antiglare layer is a method of imparting antiglare properties using fine particles, as described above. The antireflection layer was provided on the antiglare layer having a uniform predetermined antiglare property. However, when the screen size is increased, the visibility is different between the central portion and the peripheral portion of the screen, so that the effect of the conventional anti-glare film is insufficient.

In addition, in order to improve visibility, an anti-glare layer or an antireflection layer is conventionally provided on the surface of the display device. However, as the display device becomes more colored and higher in definition, the visibility is further improved. There is a need for antiglare and antireflection films.
JP 59-58036 A (Claims) JP 2001-310912 A (Claims) JP 2002-114928 A (Claims) JP 2002-120511 A (Claims)

  Accordingly, the present invention has been made in view of the above-mentioned problems, and the purpose thereof is a long anti-glare film and an anti-glare antireflection film that are compatible with the anti-glare effect, visibility and blackness when displaying a moving image. It is in providing a polarizing plate, a display apparatus using them, and an anti-glare processing method.

The object of the present invention with respect to the above problems is achieved by the following configuration.
(Claim 1)
A long anti-glare film characterized in that an anti-glare layer having different anti-glare properties in the width direction or the long direction is provided.
(Claim 2)
2. The antiglare layer according to claim 1, wherein at least one of centerline average roughness Ra, haze, and average length Sm of the contour curve element is different in the width direction or the length direction. Long anti-glare film.
(Claim 3)
3. The antiglare antireflection film, wherein the long antiglare film according to claim 1 further comprises an antireflection layer.
(Claim 4)
A polarizing plate having an antiglare layer having different antiglare properties in one polarizing plate and an optical compensation film on the back side thereof.
(Claim 5)
A display device comprising an antiglare layer exhibiting different antiglare properties in one display screen.
(Claim 6)
The display device according to claim 5, wherein an anti-glare layer having different anti-glare properties is provided in the central portion and the upper portion or the left and right portions.
(Claim 7)
An anti-glare processing method comprising providing an anti-glare layer having different anti-glare properties on one sheet-like or plate-like member.
(Claim 8)
The antiglare processing method according to claim 7, wherein the antiglare layer is formed by adhering ink droplets containing an antiglare property-imparting composition.

  INDUSTRIAL APPLICABILITY According to the present invention, a long anti-glare film, an anti-glare antireflection film, a polarizing plate, a polarizing plate, a display device using them, and an anti-glare anti-glare effect, visibility, and blackness when displaying a moving image. A processing method can be provided.

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

  As a result of intensive studies in view of the above problems, the present inventors used a long antiglare film characterized in that antiglare layers having different antiglare effects were provided in the width direction or the long direction. It was found that it can be solved by a display device. That is, the display device is not provided with an anti-glare film or an anti-glare antireflection film having a uniform anti-glare property on the screen, but depending on the angle at which the screen is viewed on a large-screen display device with high reflection. It has been found that optimum visibility can be provided by providing different unevenness and scattering characteristics at the center and peripheral portions of the screen so as to reduce the change in the antiglare effect. For example, the anti-glare layer on the top of the screen is designed so that the optimal anti-glare effect can be obtained for the reflection from above the back of the screen. For example, an anti-glare layer or a clear hard coat layer that emphasizes the contrast of the screen can be used.

  Specifically, the antiglare property is different from the surface roughness such as the centerline average roughness Ra and the average length Sm of the contour curve element defined by JIS B0601, or haze and internal scattering (internal haze). ) And the like. The difference in the antiglare property as used in the present invention does not mean a mere variation or unevenness of the antiglare layer itself, but it is intentionally changed to change the antiglare property in one display device. The purpose of this is to give a more favorable visual sensitivity by making different.

  As a method for producing long films having different antiglare properties, for example, when forming an antiglare layer by coating, the film thickness of the antiglare layer or a layer having a light scattering effect is changed in the width direction of the long film. There is a way. For example, by applying a coating composition containing fine particles so that it is thick at both ends of the long film and thin at the center of the width, the thickened portion increases the haze, increases the light scattering effect, and reduces the thickness. The light scattering effect is reduced in the portion, and the transmission sharpness can be improved. The film thickness may be periodically changed in the width direction according to the width of the long film and the screen size to be used. Of course, if necessary, both width ends can be made thinner and the center portion can be made thicker. Specifically, it can be changed 1.1 times or more with respect to the average film thickness. Examples of methods other than coating include a method of forming irregularities with an embossing roll having a mold. That is, the embossing roll is pressed against the thermoplastic resin layer or the curable resin layer in an uncured / semi-cured state to form irregularities, and the diameter of the embossing roll is changed in the width direction to thicken the center part. Or by changing the embossing roll pressure on the left and right, changing the embossing roll temperature on the left and right, and changing the shape of the unevenness. The antiglare effect in the width direction can be made different. You may combine making the thermoplastic resin layer or curable resin layer which forms an unevenness | corrugation contain microparticles | fine-particles, changing these film thicknesses, or changing a composition.

  A particularly preferable method is a method of forming an antiglare layer by adhering ink droplets containing an antiglare property-imparting composition, and when producing a variety of articles having antiglare layers having different antiglare effects. A processing method with excellent productivity can be provided. This method is particularly excellent when a roll-to-roll process is performed on a liquid crystal display device using a plastic substrate film, an organic EL, an electronic paper display, or the like. In particular, in a VA liquid crystal display device or the like, the polarizing axes are arranged so as to be in the vertical and horizontal directions of the screen. Therefore, when the antiglare film of a long film is cut out according to the screen, the long direction of the long film It is preferable because it is cut out so as to be orthogonal to the parallel. Alternatively, when a TN type liquid crystal display device is used in combination with a polarizer having an absorption axis in the 45 ° direction with respect to the long direction, a long film can be formed accordingly.

  Hereinafter, the present invention will be described in detail.

  In this invention, there is no restriction | limiting in particular in the method of providing the glare-proof layer from which a glare-proof effect differs in the width direction or a elongate direction on the base-material surface or the functional layer provided on the base material. For example, it is possible to use a method of applying the fine particles to the coating solution and applying it, or a method of forming by embossing. Particularly preferably, ink droplets containing an anti-glare imparting composition are attached to form irregularities. It is a method to do. Hereinafter, an ink jet method which is a preferred embodiment of the present invention will be described.

  An ink droplet containing an antiglare-imparting composition that forms a fine concavo-convex structure by an ink jet method is emitted onto a transparent substrate, and a width is formed on the surface of the substrate or a functional layer provided on the substrate. By forming an anti-glare layer having a fine concavo-convex structure with different anti-glare effects in the direction or the long direction, the anti-glare effect is excellent, and the sharpness, visibility and video during image observation are displayed. It has been found that the formation of an antiglare layer excellent in tightness can be realized, and the present invention has been achieved. In addition, the anti-glare antireflection film with less uneven color of reflected light can be realized by the configuration of the present invention.

As the fine concavo-convex structure of the antiglare layer, the center line average roughness (Ra) of the fine concavo-convex structure is preferably in the range of 0.05 to 5.0 μm, or the height a based on the concave bottom is It is preferable to make the convex part which is 0.1-10.0 micrometers into the range of 0-100 pieces per 100 micrometers ² and use actinic-light curable resin or a thermosetting resin as an anti-glare provision composition. Thus, the extremely fine uneven structure defined above can be realized. Furthermore, as the ink droplets by the ink jet method, two or more types of ink droplets having different compositions are used to form an uneven structure having different refractive indexes, or two or more types of ink droplets having different particle sizes are used. In addition, after forming a fine uneven structure on a transparent substrate with ink droplets having a large particle size, a finer uneven structure can be formed with ink droplets having a smaller particle diameter than the ink droplet, or ink The droplets preferably contain fine particles or fine droplets having a particle size smaller than that of the ink droplets, and thereby the objective effect of the present invention is further exhibited.

  Moreover, in the formation method of the anti-glare film of this invention, providing on the transparent base material which has the structure which forms the anti-glare layer prescribed | regulated above on a transparent base material, or one or more hard-coat layers. preferable. The hard coat layer at this time may be uncured when forming the concavo-convex structure of the antiglare layer, but the hard coat layer is preferably provided with the antiglare layer in a half-cured state (semi-cured state). In addition, it is more preferable to provide an antiglare layer after the surface of the hard coat layer is plasma-treated, or the hard coat layer contains a plasticizer. The adhesion of the antiglare layer can be increased.

  The method for forming an antiglare layer according to the present invention is such that an ink droplet containing an antiglare property-imparting composition that forms a fine concavo-convex structure by an ink jet method is ejected onto a transparent substrate, and the surface of the substrate is finely formed. One feature is to form an antiglare layer having an uneven structure.

  As one shape of the fine concavo-convex structure according to the present invention, a concavo-convex shape having a center line average roughness Ra specified by JIS B 0601 of 0.01 to 5 μm, preferably Ra is 0.07 to 1 μm, Most preferably, it has a concavo-convex shape with Ra of 0.1 to 0.5 μm. For example, Ra increases the anti-glare part, and vice versa. For example, Ra is preferably different by 0.05 μm or more.

  The center line average roughness Ra defined in the present invention is defined by JIS B0601, and represents a value obtained by the following formula expressed in micrometers (μm).

  The measurement method of the center line average roughness (Ra) can be determined by measuring in the above environment after conditioning for 24 hours in a 25 ° C., 65% RH environment under conditions where the measurement samples do not overlap each other. . The non-overlapping conditions mentioned here are, for example, a method of winding with the edge portion of the sample raised, a method of stacking paper between the sample and the sample, a frame made of cardboard, etc., and fixing its four corners One of the methods. Examples of the measuring apparatus that can be used include a RSTPLUS non-contact three-dimensional micro surface shape measuring system manufactured by WYKO.

  Moreover, it is preferable that the anti-glare layer of this invention is 0-40% of haze, and it is preferable to make it differ 1% or more within one screen. Haze can be measured according to JIS K7105.

  Further, in the antiglare layer according to the present invention, the average length Sm of the contour curve element defined by JIS B0601 is 1 to 80 μm, preferably 10 to 40 μm. These can be measured by the above-mentioned optical interference type surface roughness measuring machine.

Further, as another shape of the fine concavo-convex structure according to the present invention, it has 0 to 100 convex portions per 100 μm ² having a height a of 0.1 to 10.0 μm with respect to the concave bottom. preferable. For example, when increasing the antiglare property, the number of convex portions is increased. Or if the same number, increase the height. For example, it is preferable to vary the number of convex portions by 5 or more, or to increase the height a of the convex portions by 0.1 μm or more.

  FIG. 1 is a schematic view showing an example in which an antiglare layer having a concavo-convex structure is provided on a transparent substrate by an ink jet method.

  FIG. 1A is a perspective view of an antiglare layer having a concavo-convex structure, and FIG. 1B is a cross-sectional view.

  In FIG. 1B, an example of an antiglare layer having a concavo-convex structure formed by ink droplets 3 by an ink jet method after providing one or more hard coat layers 2 on a transparent substrate 1. However, the height a based on the bottom of the recess defined in the present invention is defined as the height (μm) to the top of the concavo-convex structure with the hard coat layer surface as the bottom as the bottom.

Fine irregularities on the surface of the antiglare layer 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, the unevenness is measured two-dimensionally with respect to a range of about 4000 μm ² (55 μm × 75 μm) by an optical interference type surface roughness measuring device, and the unevenness is color-coded as contour lines from the bottom side and displayed.

Here, the number of convex portions having a height of 0.1 μm to 10 μm with respect to the adjacent bottom portion was counted and represented by the number per 100 μm ² area. The measurement is carried out by measuring arbitrary 10 points of the corresponding part of the antiglare antireflection film and obtaining the average value.

  In the present invention, as the shape of the concavo-convex structure constituting the antiglare layer, FIG. 1B shows an example in which a Conide type convex portion is landed, but the present invention is limited to the above concavo-convex structure. It is not a thing.

  FIG. 2 is a cross-sectional view illustrating an example of another uneven structure constituting the antiglare layer.

FIG. 2A shows an example of a concavo-convex structure landed in a spherical shape. This is achieved by appropriately adjusting the viscosity of the ink droplet to be emitted and the contact angle between the ink droplet and the ink landing surface. A concavo-convex structure with a simple shape can be formed. The method for forming a concavo-convex structure by the ink jet method of the present invention can form a concavo-convex structure having an arbitrary shape as compared with a conventional antiglare layer forming method such as a coating method, and in particular, a concavo-convex shape that is different in both the width direction and the longitudinal direction. It is a great feature that the amount of adhesion can be changed. Moreover, since the pattern formed during production can be changed, it can be used for various varieties.

  FIG. 2B is a cross-sectional view showing an example of an antiglare layer having a semicircular uneven structure.

  As an example of the arrangement of the concavo-convex structure, 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 this invention, the magnitude | size and shape of such a convex part can be changed and a glare-proof layer can be varied.

  The configuration of the antiglare antireflection film of the present invention is not particularly limited as long as an antiglare layer is formed on the transparent substrate, but preferably one or more hard coat layers are formed on the transparent substrate. After providing, it is preferable to provide the glare-proof layer which consists of an uneven | corrugated structure prescribed | regulated above with an inkjet system.

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

  FIG. 3 is a cross-sectional view showing an example of an inkjet head that can be used in the inkjet method according to the present invention.

3A is a cross-sectional view of the ink jet head, and FIG. 3B is an enlarged view taken along line AA in FIG. 3A. 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 portion, 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, 2
0 is a groove, 21 is a protective plate, 22 is a fluid resistance, 23 and 24 are electrodes, 25 is an upper partition, 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. 4 is a schematic view showing an example of an inkjet head unit and a nozzle plate that can be used in the present invention.

  4A is a sectional view of the head portion, and FIG. 4B is a plan view of the nozzle plate. In the figure, 1 is a transparent substrate, 31 is an ink droplet, 32 is a nozzle, and 29 is an actinic ray irradiation part. The ink droplet 31 ejected from the nozzle 32 flies in the direction of the transparent substrate 1 and adheres. The ink droplets that have landed on the transparent substrate 1 are immediately irradiated with actinic rays from the actinic ray irradiating unit 29 disposed upstream thereof and cured. Reference numeral 35 denotes a back roll for holding the transparent substrate 1.

  In the present invention, as shown in FIG. 4B, 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 method for forming the antiglare layer used in the present invention, it is preferable to use an inkjet method in which small ink droplets are ejected from multiple nozzles. FIG. 5 shows an example of an inkjet method that can be preferably used in the present invention. Indicates.

  In FIG. 5, a) in FIG. 5 is a method in which the inkjet head 10 is arranged in the width direction of the transparent substrate 1, and an anti-glare layer is formed on the surface of the transparent substrate 1 while being conveyed (line head method). FIG. 5 b) shows a method of forming an antiglare layer on the surface of the inkjet head 10 while moving in the sub-scanning direction (flat head method). FIG. 5 c) shows that the inkjet head 10 is transparent. This is a method of forming an antiglare layer on the surface of the substrate 1 while scanning in 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 an ink jet head of such a system, it is possible to easily form an uneven portion having an arbitrary pattern at an arbitrary position on the transparent substrate. Therefore, the ink jet method has a high degree of freedom and is superior to conventional coating methods and embossing methods.

  Reference numeral 29 in FIGS. 5A to 5C denotes an actinic ray irradiating unit used when an actinic ray curable resin described later is used as the ink.

  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. 5, b), and c).

  In the present invention, in order to form fine irregularities, the ink droplet is preferably 0.1 to 100 pl, more preferably 0.1 to 50 pl, and particularly preferably 0.1 to 10 pl. By emitting ink droplets under the above conditions, it is possible to obtain an antiglare antireflection film having fine irregularities with excellent visibility.

  The viscosity of the ink droplets is preferably 0.1 to 100 mPa · s at 25 ° C., more preferably 0.1 to 50 mPa · s.

  Next, the ink used in the ink jet system for forming the antiglare layer according to the present invention will be described.

  The ink according to the present invention is characterized by containing an antiglare property-imparting composition that forms a fine concavo-convex structure by an inkjet method, and the antiglare property-imparting composition includes an actinic ray curable resin or a heat A curable resin is preferred.

  First, the actinic ray curable resin according to the present invention will be described.

  The actinic ray curable resin is a resin that is cured through a crosslinking reaction or the like by irradiation with actinic rays such as ultraviolet rays or electron beams. Typical examples of the actinic ray curable resin include an ultraviolet curable resin, an electron beam curable resin, and the like, but a resin that is cured by irradiation with actinic rays other than ultraviolet rays and electron beams may 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.

  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, a mixture of 100 parts Unidic 17-806 (Dainippon Ink Co., Ltd.) and 1 part Coronate L (Nihon Polyurethane Co., Ltd.) described in JP-A-59-151110 is preferably used. .

  An ultraviolet curable polyester acrylate resin can be easily obtained by reacting a monomer such as 2-hydroxyethyl acrylate, glycidyl acrylate, or acrylic acid with a hydroxyl group or carboxyl group at the end of the polyester (see, for example, JP-A No. 59-151112).

  The ultraviolet curable epoxy acrylate resin is obtained by reacting a terminal hydroxyl group of an epoxy resin with a monomer such as acrylic acid, acrylic acid chloride, or glycidyl acrylate.

  Examples of ultraviolet curable polyol acrylate resins include ethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipenta. Examples include erythritol pentaacrylate, dipentaerythritol hexaacrylate, and alkyl-modified dipentaerythritol pentaacrylate.

  As an example of an ultraviolet curable epoxy acrylate resin and an ultraviolet curable epoxy resin, an epoxy actinic ray reactive compound that is usefully used is shown.

(A) Glycidyl ether of bisphenol A (this compound is obtained as a mixture having different degrees of polymerization by reaction of epichlorohydrin and bisphenol A)
(B) a compound having a glycidyl ether group by reacting a compound having two phenolic OHs such as bisphenol A with epichlorohydrin, ethylene oxide and / or propylene oxide (c) glycidyl ether of 4,4′-methylenebisphenol (D) Epoxy compound of phenol formaldehyde resin of novolak resin or resol resin (e) Compound having alicyclic epoxide, for example, bis (3,4-epoxycyclohexylmethyl) oxalate, bis (3,4-epoxycyclohexylmethyl) ) Adipate, bis (3,4-epoxy-6-cyclohexylmethyl) adipate, bis (3,4-epoxycyclohexylmethyl pimelate), 3,4-epoxycyclohexylmethyl-3,4-epoxy Rhohexanecarboxylate, 3,4-epoxy-1-methylcyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methyl-cyclohexylmethyl-3', 4'-epoxy-1 '-Methylcyclohexanecarboxylate, 3,4-epoxy-6-methyl-cyclohexylmethyl-3', 4'-epoxy-6'-methyl-1'-cyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl- 5 ', 5'-spiro-3 ", 4" -epoxy) cyclohexane-meta-dioxane (f) diglycidyl ethers of dibasic acids such as diglycidyl oxalate, diglycidyl adipate, diglycidyl tetrahydrophthalate, di Glycidyl hexahydrophthalate, diglycidyl Phthalate (g) Diglycidyl ether of glycol, for example, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, copoly (ethylene glycol-propylene glycol) di Glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether (h) Glycidyl ester of polymer acid, for example, polyglycidyl ester of polyacrylic acid, polyester diglycidyl ester (i) Polyhydric alcohol Glycidyl ethers such as glycerin triglycidyl ether, trimethylolpropane triglyceride Dil ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, glucose triglycidyl ether (j) As diglycidyl ether of 2-fluoroalkyl-1,2-diol, the low refractive index substance (K) Examples of the fluorine-containing alkane-terminated diol glycidyl ether include fluorine-containing epoxy compounds of the fluorine-containing resin of the low refractive index substance, and the like. I can do it.

  The molecular weight of the said epoxy compound is 2000 or less as an average molecular weight, Preferably it is 1000 or less.

  When the above epoxy compound is cured with actinic rays, it is effective to use a compound having a polyfunctional epoxy group (h) or (i) in order to increase the hardness.

  The photopolymerization initiator or photosensitizer for cationically polymerizing an epoxy actinic light-reactive compound is a compound capable of releasing a cationic polymerization initiating substance upon irradiation with actinic light, and particularly preferably, cationic polymerization is initiated by irradiation. A group of double salts of onium salts that release potent Lewis acids.

  The actinic ray-reactive compound epoxy resin forms a polymerized, crosslinked structure or network structure not by radical polymerization but by cationic polymerization. Unlike radical polymerization, it is a preferable actinic ray reactive resin because it is not affected by oxygen in the reaction system.

  The actinic ray-reactive epoxy resin useful in the present invention is polymerized by a photopolymerization initiator or a photosensitizer that releases a substance that initiates cationic polymerization upon irradiation with actinic rays. As the photopolymerization initiator, a group of double salts of onium salts that release a Lewis acid that initiates cationic polymerization by light irradiation is particularly preferable.

  A typical example is a compound represented by the following general formula (a).

General formula (a)
[(R ¹ ) _a (R ² ) _b (R ³ ) _c (R ⁴ ) _d Z] ^{w +} [MeX _v ] ^w-
Wherein cation is onium, Z is S, Se, Te, P, As, Sb, Bi, O, halogen (eg, I, Br, Cl), or N = N (diazo), R ¹ , R ² , R ³ and R ⁴ are organic groups which may be the same or different. a, b, c, and d are each an integer of 0 to 3, and a + b + c + d is equal to the valence of Z. Me is a metal or metalloid which is a central atom of a halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc. X is halogen, w is the net charge of the halogenated complex ion, and v is the number of halogen atoms in the halogenated complex ion.

Specific examples of the anion [MeX _v ] ^w− of the general formula (a) include tetrafluoroborate (BF ₄ ⁻ ), tetrafluorophosphate (PF ₄ ⁻ ), tetrafluoroantimonate (SbF ₄ ⁻ ), tetra Examples thereof include fluoroarsenate (AsF ₄ ⁻ ) and tetrachloroantimonate (SbCl ₄ ⁻ ).

Other anions include perchlorate ion (ClO ₄ ⁻ ), trifluoromethyl sulfite ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ), toluenesulfonate ion, and trinitrobenzene acid anion. An ion etc. can be mentioned.

  Among such onium salts, it is particularly effective to use an aromatic onium salt as a cationic polymerization initiator. Among them, aromatic halonium salts described in JP-A-50-151996, 50-158680, etc. VIA group aromatic onium salts described in Kaisho 50-151997, 52-30899, 59-55420, 55-125105, JP-A-56-8428, 56-149402, Preference is given to oxosulfoxonium salts described in JP-A-57-192429, aromatic diazonium salts described in JP-B-49-17040, thiopyrilum salts described in US Pat. No. 4,139,655, and the like. Moreover, an aluminum complex, a photodegradable silicon compound type | system | group polymerization initiator, etc. can be mentioned. The cationic polymerization initiator can be used in combination with a photosensitizer such as benzophenone, benzoin isopropyl ether, or thioxanthone.

  In the case of an actinic ray reactive compound having an epoxy acrylate group, a photosensitizer such as n-butylamine, triethylamine, or tri-n-butylphosphine can be used. The photosensitizer and photoinitiator used for the actinic ray reactive compound are sufficient to initiate the photoreaction at 0.1 to 15 parts by mass with respect to 100 parts by mass of the ultraviolet reactive compound, Preferably they are 1 mass part-10 mass parts. The sensitizer preferably has an absorption maximum from the near ultraviolet region to the visible light region.

  In the actinic ray curable resin composition useful in the present invention, the polymerization initiator is generally 0.1 to 15 parts by mass with respect to 100 parts by mass of the actinic ray curable epoxy resin (prepolymer). Use is preferable, and addition of 1 to 10 parts by mass is more preferable.

  An epoxy resin can be used in combination with the urethane acrylate type resin, polyether acrylate type resin, or the like. In this case, it is preferable to use an actinic ray radical polymerization initiator and an actinic ray cationic polymerization initiator in combination.

  Moreover, an oxetane compound can also be used for the anti-glare layer which concerns on this invention. The oxetane compound used is a compound having a three-membered oxetane ring containing oxygen or sulfur. Among them, a compound having an oxetane ring containing oxygen is preferable. The oxetane ring may be substituted with a halogen atom, a haloalkyl group, an arylalkyl group, an alkoxyl group, an allyloxy group, or an acetoxy group. Specifically, 3,3-bis (chloromethyl) oxetane, 3,3-bis (iodomethyl) oxetane, 3,3-bis (methoxymethyl) oxetane, 3,3-bis (phenoxymethyl) oxetane, 3-methyl -3 chloromethyloxetane, 3,3-bis (acetoxymethyl) oxetane, 3,3-bis (fluoromethyl) oxetane, 3,3-bis (bromomethyl) oxetane, 3,3-dimethyloxetane and the like. In the present invention, any of a monomer, an oligomer and a polymer may be used.

  Specific examples of the ultraviolet curable resin that can be used in the present invention include, for example, Adekaoptomer KR, BY series KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B. (Asahi Denka Kogyo 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 Industry Co., Ltd.), Seika Beam PHC2210 (S), PHCX -9 (K-3), PHC2213, DP-10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, CR900 (above, manufactured by Dainichi Seika Kogyo Co., Ltd.), KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (above, 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 (above, Dainippon Ink & Chemicals, Inc.), Aurex No. 340 clear (manufactured by China Paint Co., Ltd.), Sunrad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (above, Sanyo Chemical Industries, Ltd.) , SP-1509, SP-1507 (above, manufactured by Showa Polymer Co., Ltd.), RCC-15C (produced by Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (above, Toagosei Co., Ltd.) (Made by Co., Ltd.), or other commercially available products.

In the ink according to the present invention, a binder such as a known thermoplastic resin or a hydrophilic resin such as gelatin can be mixed with the actinic ray curable resin described above. These resins preferably have a polar group in the molecule. Examples of the polar _{group, -COOM, -OH, -NR 2,} -NR 3 X, -SO 3 M, -OSO 3 M, -PO 3 M 2, -OPO 3 M ( wherein, M represents a hydrogen atom, an alkali A metal or an ammonium group, X represents an acid that forms an amine salt, R represents a hydrogen atom or an alkyl group).

  In order to initiate photopolymerization or photocrosslinking reaction of the actinic ray reactive compound used in the present invention, the actinic ray reactive compound alone is initiated, but the induction period of polymerization is long or the initiation of polymerization is slow. For this reason, it is preferable to use a photosensitizer or a photoinitiator, whereby the polymerization can be accelerated.

  When the ink according to the present invention contains an actinic ray curable resin, a photoreaction initiator or a photosensitizer can be used during irradiation with actinic rays.

  Specific examples include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. Moreover, when using a photoreactant for the synthesis | combination of an epoxy acrylate-type resin, sensitizers, such as n-butylamine, a triethylamine, a tri-n-butylphosphine, can be used.

  Further, when an ultraviolet curable resin is used as the actinic ray curable resin, an ultraviolet absorber may be included in the ultraviolet curable resin composition to the extent that does not hinder the photocuring of the ultraviolet curable resin.

  As the ultraviolet absorber, those excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less and having little absorption of visible light having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display properties.

  Specific examples of the ultraviolet absorber preferably used in the present invention include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like. However, it is not limited to these.

  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, alkoxyl 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.

  Moreover, these groups described above may have an arbitrary substituent.

  Although the specific example of the ultraviolet absorber which concerns on this invention is given to the following, this invention is not limited to these.

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 UV-8: 2- (2H-benzotriazol-2-yl) -6 (Linear and side chain dodecyl) -4-methylphenol (TINUVIN171, manufactured by Ciba)
UV-9: Octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl- 4-Hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate (TINUVIN109, manufactured by Ciba)
Further, as the benzophenone-based ultraviolet absorber, a compound represented by the following general formula (2) is preferably used.

In the formula, Y represents a hydrogen atom, a halogen atom or an alkyl group, an alkenyl group, an alkoxyl 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 alkoxyl group represents, for example, an alkoxyl group having up to 18 carbon atoms, and the alkenyl group has, for example, carbon number An alkenyl group up to 16 represents an allyl group, a 2-butenyl group, or the like. In addition, as substituents to alkyl groups, alkenyl groups, and phenyl groups, halogen atoms such as chlorine atoms, bromine atoms, fluorine atoms, etc., hydroxyl groups, phenyl groups (this phenyl group is substituted with alkyl groups or halogen atoms, etc.) May be used).

  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-10: 2,4-dihydroxybenzophenone UV-11: 2,2'-dihydroxy-4-methoxybenzophenone UV-12: 2-hydroxy-4-methoxy-5-sulfobenzophenone UV-13: Bis (2-methoxy -4-hydroxy-5-benzoylphenylmethane)
As the ultraviolet absorber preferably used in the present invention, a benzotriazole-based ultraviolet absorber and a benzophenone-based ultraviolet absorber that are highly transparent and excellent in preventing the deterioration of the polarizing plate and the liquid crystal are preferable, and unnecessary coloring is less. A benzotriazole-based ultraviolet absorber is particularly preferably used.

  Moreover, the ultraviolet absorber whose distribution coefficient described in Unexamined-Japanese-Patent No. 2001-187825 is 9.2 or more improves the surface quality of a support body, and is excellent also in applicability | paintability. In particular, it is preferable to use an ultraviolet absorber having a distribution coefficient of 10.1 or more.

  Further, the polymer ultraviolet absorbers described in the general formula (1) or general formula (2) described in JP-A-6-148430 and the general formulas (3), (6), and (7) of Japanese Patent Application No. 2000-156039 ( Alternatively, an ultraviolet absorbing polymer) is also preferably used. As a polymer ultraviolet absorber, PUVA-30M (manufactured by Otsuka Chemical Co., Ltd.) and the like are commercially available.

  Moreover, in order to improve the heat resistance of the anti-glare layer formed by the inkjet method, an antioxidant that does not suppress the photocuring reaction can be selected and used. For example, hindered phenol derivatives, thiopropionic acid derivatives, phosphite derivatives and the like can be mentioned. Specifically, for example, 4,4′-thiobis (6-tert-3-methylphenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) mesitylene, di-octadecyl-4- Examples thereof include hydroxy-3,5-di-tert-butylbenzyl phosphate.

The ink according to the present invention preferably contains an antistatic agent such as conductive fine particles such as SnO ₂ , ITO, ZnO, and crosslinked cationic polymer particles. Moreover, you may add these compounds to the below-mentioned hard-coat layer provided on a transparent base material.

  In addition, 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%.

  In the present invention, when the antiglare layer formed by the ink jet method contains an actinic ray curable resin, the actinic ray irradiation method is as follows. Immediately after the ink droplet is landed on the transparent substrate, the actinic ray irradiation is performed immediately. It is preferable to start.

  The term “immediately after the ink droplets have landed on the transparent substrate” in the present invention specifically means that irradiation is preferably started between 0.001 and 2.0 seconds after the ink droplets land, more preferably Is between 0.001 and 1.0 seconds. If the irradiation interval of the irradiation light source is shorter than 0.001 seconds, the distance between the nozzle portion and the irradiation light source becomes too close, and the nozzle is contaminated by the sublimation substance due to the curing reaction or the irradiation light wraps around the ink emission portion. This is not preferable because nozzle clogging is caused by curing at the portion. Also, if the irradiation interval of the irradiation light source exceeds 2.0 seconds, it may be difficult to obtain the desired uneven structure defined in the present invention due to the flow, deformation, etc. of the landed ink droplets. Cost.

  In order to prevent light from wrapping around the nozzle part during the irradiation, it is preferable that the active light source irradiation part is disposed at a position where it does not directly act on the nozzle part of the ink jet head in the inkjet system of the present invention. It is preferable to provide a light shielding plate between them so that the active light beam does not act on the nozzle part of the inkjet head.

  Further, the irradiation with actinic rays immediately after the ink droplets have landed may be performed so that the fluidity of the landed ink droplets is lowered and a desired uneven structure can be formed. In this case, it can be cured completely by irradiating an active light source separately installed on the downstream side. By doing so, it is possible to prevent the actinic light from acting on the nozzle portion of the inkjet head and causing clogging.

The actinic ray that can be used in the present invention can be used without limitation as long as it is a light source that activates an actinic ray curable resin that is an antiglare property-imparting composition with ultraviolet rays, electron beams, γ rays, etc. Ultraviolet rays and electron beams are preferred, and ultraviolet rays are particularly preferred in that they are easy to handle and high energy can be easily obtained. As the ultraviolet light source for photopolymerizing the ultraviolet reactive compound, any light source that generates ultraviolet light can be used. 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. An ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation, or the like can also be used. Irradiation conditions vary depending on each lamp, but the amount of irradiation light is preferably 1 mJ / cm ² or more, more preferably 20 mJ / cm ^{2 to} 10000 mJ / cm ² , and particularly preferably 50 mJ / cm ^{2 to} 2000 mJ / cm ^2. It is.

  Moreover, an electron beam can be used similarly. As an electron beam, 50 to 1000 keV, preferably 100 to 100, emitted from various electron beam accelerators such as a cockroft Walton type, a bandegraph type, a resonance transformation type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type. An electron beam having an energy of 300 keV can be given.

  In the present invention, the oxygen concentration in the atmosphere at the time of actinic ray irradiation is more preferably 1% or less.

  Moreover, in this invention, in order to advance the hardening reaction of actinic light efficiently, a transparent base material etc. can also be heated. 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 used on the opposite side across 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 actinic ray curable resin to be used, but is preferably in a temperature range that does not affect the deformation of the transparent substrate, and preferably 30 to 200 ° C. Furthermore, 50-120 degreeC is preferable, Most preferably, it is 70-100 degreeC.

  Next, the thermosetting resin according to 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 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, antimony trioxide, phosphorus Compound combination Additive-type flame retardant resin that uses sesame or aluminum hydroxide as an additive, toughness resin that is hybridized with polyurethane or silicone, or IPN toughness (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, 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, you may use suitably the antioxidant and ultraviolet absorber which were described in the ink containing actinic-light curable resin for the ink consisting of the thermosetting resin which concerns on this invention.

  In the present invention, when the antiglare layer 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. On the other hand, if the heating interval exceeds 5.0 seconds, it becomes difficult to obtain the desired uneven structure defined in the present invention due to the flow and deformation of 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-mentioned actinic ray curable resins and thermosetting resins can be used as the antiglare property-imparting composition, but an actinic ray curable resin is preferably used.

  The ink according to the present invention may contain 0 to 99.9% by mass of a solvent as required. For example, 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, and cyclohexanone; ketones such as diacetone alcohol. Alcohols; aromatic hydrocarbons such as benzene, toluene, xylene; glycols such as ethylene glycol, propylene glycol, hexylene glycol; ethyl cellsolve, butylcellsolve, ethylcarbitol, butylcarbitol, diethylcellsolve, Glycol ethers such as diethyl carbitol and propylene glycol monomethyl ether; N-methylpyrrolidone, dimethylformamide, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, amino acetate Esters and the like; ethers such as diethyl ether, water and the like, can be used as a mixture thereof alone or in combination. 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.

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

  One of the preferable methods for forming the antiglare layer having a concavo-convex structure in the present invention is a method in which two or more ink droplets having different refractive indexes are emitted and formed. Specifically, it is preferable to use two or more ink droplets having a refractive index at 550 nm after curing of 0.01 or more different from each other because an antiglare layer having excellent visibility can be formed. It is preferable to combine ink droplets having different refractive index differences of 0.01 to 2.0, particularly 0.03 to 1.0. In the ink according to the present invention, there is no particular limitation as a method for satisfying the above conditions, for example, the type and addition amount of an actinic ray curable resin or a thermosetting resin, or the type and addition amount of a nonvolatile organic solvent, This can be realized by appropriately adjusting the type and amount of other additives. The refractive index of the antiglare layer formed of ink is preferably 1.4 to 2.0, and particularly preferably 1.57 to 1.8. The refractive index can be adjusted by the amount of metal oxide added.

  As another preferable method for forming the antiglare layer having a concavo-convex structure in the present invention, it is preferable to form two or more types of ink droplets having different particle diameters, more preferably ink droplets having a large particle diameter. After forming a fine concavo-convex structure on a transparent substrate, a finer concavo-convex structure is formed with ink droplets having a particle diameter smaller than that of the ink droplets.

  FIG. 6 shows an example in which a fine structure 71 is formed with ink droplets having a larger particle size after forming a fine structure 71 with ink droplets having a smaller particle size by an ink jet method on a transparent substrate. It is a schematic diagram to represent.

  FIG. 6A shows 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 the present invention, by forming ink droplets having different particle diameters as the ink for forming the concavo-convex structure, it is possible to form fine concavo-convexs that are less likely to cause interference fringes and that are excellent in the visibility of the display device. I can do it. Each ink droplet is preferably 0.1 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 minute droplets emitted later mainly to lower the solvent and volatilizing the solvent. By appropriately adjusting the solid content concentration of each ink droplet, it is possible to easily control the formation and shape of a fine concavo-convex structure.

  Furthermore, in the present invention, when forming a concavo-convex structure by combining ink droplets of different capacities, after a large ink droplet is landed on the transparent substrate, a finer ink droplet is landed thereon. Is preferred. Although a large ink droplet may be landed and a finer ink droplet may land on the uncured state, in the present invention, after the large ink droplet is landed, actinic rays are irradiated, Alternatively, it is preferable to perform a heat treatment so that the ink is cured more completely, or after being in a half-cured state, finer ink droplets are landed thereon.

  As another preferable method for forming the antiglare layer having a concavo-convex structure in the present invention, the ink droplet preferably contains fine particles having a particle diameter smaller than that of the ink droplet.

  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.

  As the fine particles of silicon dioxide, for example, commercially available products such as Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (above Nippon Aerosil Co., Ltd.) can be used.

  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, and polyfluoroethylene resin fine particles.

  The average particle size of the fine particles used in the present invention is preferably 0.001 to 10 μm, more preferably 0.005 to 3 μm, and particularly preferably 0.01 to 1 μm. You may contain 2 or more types of microparticles | fine-particles from which a particle size and refractive index differ.

  As another preferable method for forming the antiglare layer having a concavo-convex structure in the present invention, the ink droplets preferably contain fine droplets having a particle size smaller than the ink droplets.

  The fine droplets referred to in the present invention preferably have a smaller particle size than the ink droplets and are in a phase-separated state or are present in liquid form in the ink in the form of an emulsion. Is preferably not completely mixed, and after the ink is cured, the refractive index at 550 nm is preferably different from that of the ink droplet medium by 0.01 or more. Preferably, the refractive index is different from 0.01 to 2.0, and in particular, the refractive index is preferably different from 0.03 to 1.0.

  When fine particles are used for the ink droplets described above, the possibility of clogging the inkjet head remains, but a liquid material is particularly preferred because clogging is unlikely to occur. Moreover, it is preferable that the microdroplet itself also contains a curable component, and it is preferable to cure after landing. By using these, finer unevenness and light scattering effects can be obtained, and improvement in visibility can be expected.

  As the fine droplets according to the present invention, it is particularly preferable to use a metal alkoxide or a hydrolyzate or partial polymer thereof.

  Examples of the metal atom include Si, Ti, and Zr. Specific examples of the metal alkoxide that can be used in the present invention include tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, and dimethyldiethoxysilane. Examples include, but are not limited to, silane coupling agents, tetraisopropyl titanium, tetrabutyl titanium, tetrabutyl zirconium, tetraisopropyl zirconium, and tetraethoxy titanium. These metal alkoxides are cured by a curing process using actinic rays or the like after ink droplets have landed on the transparent substrate, and an uneven structure having a different refractive index can be formed depending on the type. In addition, solvent-soluble resins are preferably used as the fine droplets, and examples thereof include cellulose esters such as cellulose acetate propionate, cellulose acetate butyrate, and cellulose diacetate, and acrylic resins.

  Subsequently, the manufacturing method of the anti-glare film of this invention is demonstrated.

  FIG. 7 is a schematic diagram illustrating an example of a flow of a process of providing an antiglare layer on a transparent substrate by an inkjet method. Specifically, after a hard coat layer or a light diffusion layer is coated on a transparent substrate by a coating method, a flow for forming an antiglare layer having an uneven structure by an ink jet method is shown.

  In FIG. 7, the transparent base material 502 fed out from the roll 501 is transported, and a hard coat layer is applied by the first coater 503 of the extrusion method at the first coater station A. At this time, the hard coat layer may be a single layer structure or a plurality of layers. Further, the film thickness may be changed in the width direction. In particular, a light diffusion layer containing fine particles can be provided, and by changing the film thickness of the light diffusion layer with the width, the haze, particularly the internal haze can be varied with the width. The transparent substrate 502 on which the hard coat 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. After drying, when an actinic ray curable resin is used as a binder for the hard coat layer, the actinic ray irradiating unit 506A cures by irradiating actinic rays, for example, ultraviolet rays or the like. It can be controlled to be in a half cure state. The substrate 502 can be irradiated with the actinic ray irradiation unit 506A while being wound on a back roll whose temperature is controlled at 20 to 120 ° C.

  Subsequently, although it conveys to the 2nd coater station B which provides the glare-proof layer using an inkjet system, it is preferable that a hard-coat layer is a half-cure state. Alternatively, it is preferable to perform a surface treatment in the plasma treatment unit 507 before forming the antiglare layer. 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. 4B in a zigzag manner over the entire width of the transparent base material, emits ink droplets onto the hard coat layer, and is applied to the surface. An uneven 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 0.1 to 100 pl and in some cases 0.1 to 10 pl are emitted, the flying property of the ink droplets is 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, and 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 uneven 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.

  When the actinic ray curable resin is used, the landed ink droplets are cured by irradiating with actinic rays, for example, ultraviolet rays or the like by the actinic ray irradiating unit 506B arranged after the inkjet emitting unit 509. Further, when the ink droplet uses a thermosetting resin, the ink droplet is heated and cured by a heating unit 510, for example, a heat plate. A method of heating the back roll 504B as a heat roll is also preferable.

  In the second coater station B, the actinic ray irradiation unit 506B and the inkjet emission unit 509 are arranged at appropriate intervals so that the irradiation light of the actinic ray irradiation unit 506B does not directly affect the inkjet nozzles of the inkjet emission unit 509. Alternatively, it is preferable to install a light shielding wall or the like between the actinic ray irradiation unit 506B and the inkjet emission unit 509. Further, in order to prevent the heat of the heating unit 510 from directly affecting the ink jet nozzle of the ink jet emitting unit 509, the ink jet emitting unit 509 is covered with a heat insulating cover, or as shown in FIG. It is preferable to arrange on the back side of the material 502 so as not to affect the ink jet emitting portion 509.

  The transparent substrate 502 that has been cured to such an extent that the concavo-convex structure formed by the landed ink droplets can be maintained is evaporated in the drying zone 505B, and then an unnecessary organic solvent is evaporated in the actinic ray irradiation unit 506C. Irradiation with actinic rays completes the curing.

  In the generated light irradiation unit 506C, it is preferable to irradiate the transparent substrate 502 on the back roll whose temperature is controlled to 20 to 120 ° C. with active light.

  Next, an example of the antiglare layer having different antiglare effects formed as described above will be described with reference to the drawings.

  FIG. 8 shows a schematic diagram of a fine uneven pattern on the long anti-glare film F drawn out from the original winding 101. As can be seen from the cross-sectional view, the film has large uneven portions 103 at both ends of the film, and is formed by controlling the emission of ink so that the uneven portions 104 become smaller as going to the center. By cutting out two panels 102 from the long antiglare film F as shown in the figure, a display having a screen as shown in FIG. 11C is obtained. In other words, anti-glare that prevents the reflection of light from above by providing a large uneven portion 103 at the top, and provides image characteristics with high sharpness and contrast by providing a small uneven portion 104 at the bottom of the screen. A display device that is compatible with both visibility and visibility can be obtained.

  FIG. 9 shows another example. By changing the concavo-convex pattern, the anti-glare properties at both ends of the screen are high as shown in FIG. The panel for the display device with the For example, the central portion can be a clear hard coat layer.

  FIG. 10 shows another example. By changing the concavo-convex pattern, a display panel having high anti-glare properties at the four corners of the screen, sharpness at the center, and high contrast image characteristics can be obtained. Cut out.

  FIG. 11 and FIG. 12 are examples of display device screens having various uneven patterns according to the present invention. The present invention is not limited to these, but in any case, since uneven portions are formed by ink jetting, the uneven portions as shown in (A) to (F) can be easily arranged by controlling the pattern. Note that different anti-glare properties within one screen is preferably, for example, that the center portion of the screen is a clear hard coat layer or weak anti-glare property and the screen periphery portion, particularly the upper portion, is provided with appropriate anti-glare properties. The anti-glare property of the boundary is preferably smoothly changed to such an extent that it cannot be visually recognized. For example, the center line surface roughness Ra is changed to be 0.1 to 1 μm at the periphery of the screen with respect to 0 to 0.1 μm at the center of the screen. It is preferable to change it to 5 to 40% at the periphery of the screen.

  FIG. 13 is a diagram schematically showing a reduction in reflected light when applied to a liquid crystal display device. Observe the image with excellent sharpness and contrast by providing a large concavo-convex part at the top of the LCD screen, reducing the reflection of the upper illumination, and providing a relatively small concavo-convex part in the center or lowering the haze. I can do it.

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

  In the present invention, it is preferable to use a thermoplastic resin film as the base material of the antiglare 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.

  The thermoplastic resin film used in the present invention is particularly preferably composed mainly of cellulose ester. Hereinafter, cellulose ester will be described as a representative example of a preferred thermoplastic resin.

  The ratio Mw / Mn of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the cellulose ester 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.

  Moreover, it is preferable that the number average molecular weights (Mn) of a cellulose ester are 80000-200000.

  When the molecular weight of the cellulose ester is large and the molecular weight distribution is small, it is presumed that the applied plasticizer and ultraviolet absorber are difficult to elute when the actinic radiation curable resin layer is applied. This effect is presumed to be more remarkable when the cellulose ester molecules are oriented in the in-plane direction by stretching. It is also preferable that the total acyl group substitution degree of the cellulose ester is in the range of 2.6 to 2.9, and that an unsubstituted hydroxyl group remains in the cellulose main chain at an appropriate ratio. It is considered that the elution of the absorbent is prevented and the flatness is maintained. The plasticizer to be used is not particularly limited, but preferably contains at least two plasticizers. In that case, it is preferable that the phosphate ester type plasticizer generally used conventionally is not contained substantially. “Substantially not contained” means that the content of the phosphate plasticizer is less than 1% by mass with respect to the total solid content in the cellulose ester film, preferably 0.1% by mass. % And particularly preferably 0% by mass (below the detection limit).

  Particularly preferably, at least one of the plasticizers is a polyhydric alcohol ester plasticizer, which is considered to prevent the elution of other plasticizers, and is more effective than when used alone.

<Cellulose ester>
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.

  In the cellulose ester used in the present invention, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), Mw / Mn is preferably 1.4 to 3.0 as described above, and more preferably 1.7. It is the range of -2.2.

  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.

  Preferred cellulose esters other than cellulose triacetate have 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.

<Plasticizer>
The plasticizer is not particularly limited, but preferably at least a plasticizer selected from a polyhydric alcohol ester plasticizer, a phthalate ester, a citrate ester, a fatty acid ester, a glycolate plasticizer, a polycarboxylic acid ester, and the like. It is preferable to include 1 type. 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. Moreover, it is preferable not to contain phosphate ester plasticizers, such as a triphenyl phosphate, substantially. “Substantially not containing” means that the content of the phosphoric ester plasticizer is less than 1% by mass, preferably 0.1% by mass, particularly preferably not added.

  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.

  The polyhydric alcohol ester plasticizer is preferably contained in an amount of 1 to 12% by mass, particularly preferably 3 to 11% by mass. If the amount is too small, deterioration of the flatness is recognized, and if too much, bleeding out tends to occur. The mass ratio between the polyhydric alcohol ester plasticizer and the other plasticizer is preferably in the range of 1: 4 to 4: 1, more preferably 1: 3 to 3: 1. If the amount of the plasticizer added is too large or too small, the film is liable to be deformed, which is not preferable.

<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, the compound represented by the general formula (1) can be preferably used. Furthermore, the ultraviolet absorber preferably used in the present invention is a benzophenone ultraviolet absorber or a triazine ultraviolet absorber.

  As the benzophenone-based ultraviolet absorber, the compound represented by the general formula (2) is preferably used.

  As the triazine-based ultraviolet absorber, a compound having a 1,3,5-triazine ring is preferably used, and among them, a compound represented by the following general formula (I) is preferable.

In the general formula (I), X ¹ is a single bond, —NR ₄ —, —O— or —S—; X ² is a single bond, —NR ₅ —, —O— or —S—; X ³ is a single bond, —NR ₆ —, —O— or —S—; R ¹ , R ² and R ³ are an alkyl group, an alkenyl group, an aryl group or a heterocyclic group; and R ₄ , R ₅ and R ₆ are a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. The compound represented by the general formula (I) is particularly preferably a melamine compound.

In the melamine compound, in the general formula (I), X ¹ , X ² and X ³ are —NR ₄ —, —NR ₅ — and —NR ₆ —, respectively, or X ¹ , X ² and X 3 ³ is a single bond, and R ¹ , R ² and R ³ are heterocyclic groups having a free valence on the nitrogen atom. ^{-X 1 -R 1, -X 2 -R} 2 and -X ³ -R ³ are preferably the same substituents. R ¹ , R ² and R ³ are particularly preferably aryl groups. R ₄ , R ₅ and R ₆ are particularly preferably a hydrogen atom.

  The alkyl group is preferably a chain alkyl group rather than a cyclic alkyl group. A linear alkyl group is preferred to a branched alkyl group.

  The number of carbon atoms of the alkyl group is preferably 1-30, more preferably 1-20, still more preferably 1-10, still more preferably 1-8, 6 is most preferred. The alkyl group may have a substituent.

  Specific examples of the substituent include a halogen atom, an alkoxy group (for example, each group such as methoxy, ethoxy, and epoxyethyloxy) and an acyloxy group (for example, acryloyloxy, methacryloyloxy). The alkenyl group is preferably a chain alkenyl group rather than a cyclic alkenyl group. A linear alkenyl group is preferable to a branched chain alkenyl group. The number of carbon atoms in the alkenyl group is preferably 2 to 30, more preferably 2 to 20, still more preferably 2 to 10, still more preferably 2 to 8, 6 is most preferred. The alkenyl group may have a substituent.

  Specific examples of the substituent include a halogen atom, an alkoxy group (for example, each group such as methoxy, ethoxy, and epoxyethyloxy) or an acyloxy group (for example, each group such as acryloyloxy and methacryloyloxy).

  The aryl group is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aryl group may have a substituent.

  Specific examples of the substituent include, for example, a halogen atom, hydroxyl, cyano, nitro, carboxyl, alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, acyloxy group, alkoxycarbonyl group, alkenyloxy Carbonyl group, aryloxycarbonyl group, sulfamoyl, alkyl-substituted sulfamoyl group, alkenyl-substituted sulfamoyl group, aryl-substituted sulfamoyl group, sulfonamido group, carbamoyl, alkyl-substituted carmoyl group, alkenyl-substituted carbamoyl group, aryl-substituted carbamoyl group, amide group, alkylthio Groups, alkenylthio groups, arylthio groups and acyl groups are included. The said alkyl group is synonymous with the alkyl group mentioned above.

  The alkyl group of the alkoxy group, acyloxy group, alkoxycarbonyl group, alkyl-substituted sulfamoyl group, sulfonamido group, alkyl-substituted carbamoyl group, amide group, alkylthio group and acyl group is also synonymous with the alkyl group described above.

  The said alkenyl group is synonymous with the alkenyl group mentioned above.

  The alkenyl part of the alkenyloxy group, acyloxy group, alkenyloxycarbonyl group, alkenyl-substituted sulfamoyl group, sulfonamide group, alkenyl-substituted carbamoyl group, amide group, alkenylthio group and acyl group is also synonymous with the alkenyl group described above.

  Specific examples of the aryl group include phenyl, α-naphthyl, β-naphthyl, 4-methoxyphenyl, 3,4-diethoxyphenyl, 4-octyloxyphenyl, and 4-dodecyloxyphenyl. Can be mentioned.

  Examples of the aryloxy group, acyloxy group, aryloxycarbonyl group, aryl-substituted sulfamoyl group, sulfonamido group, aryl-substituted carbamoyl group, amide group, arylthio group, and acyl group are the same as the above aryl group.

When X ¹ , X ² or X ³ is —NR—, —O— or —S—, the heterocyclic group preferably has aromaticity.

  The heterocyclic ring in the heterocyclic group having aromaticity is generally an unsaturated heterocyclic ring, preferably a heterocyclic ring having the largest number of double bonds. The heterocyclic ring is preferably a 5-membered ring, a 6-membered ring or a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and most preferably a 6-membered ring.

  The hetero atom in the heterocyclic ring is preferably each atom such as N, S or O, and particularly preferably an N atom.

  As the heterocyclic ring having aromaticity, a pyridine ring (as the heterocyclic group, for example, each group such as 2-pyridyl or 4-pyridyl) is particularly preferable. The heterocyclic group may have a substituent. Examples of the substituent of the heterocyclic group are the same as the examples of the substituent of the aryl moiety.

When X ¹ , X ² or X ³ is a single bond, the heterocyclic group is preferably a heterocyclic group having a free valence on the nitrogen atom. The heterocyclic group having a free valence on the nitrogen atom is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, and a 5-membered ring. Is most preferred. The heterocyclic group may have a plurality of nitrogen atoms.

  Moreover, the hetero atom in a heterocyclic group may have hetero atoms other than a nitrogen atom (for example, O atom, S atom). The heterocyclic group may have a substituent. Specific examples of the substituent of the heterocyclic group are the same as the specific examples of the substituent of the aryl moiety.

  Specific examples of the heterocyclic group having a free valence on the nitrogen atom are shown below.

  The molecular weight of the compound having a 1,3,5-triazine ring is preferably 300 to 2,000. The boiling point of the compound is preferably 260 ° C. or higher. The boiling point can be measured using a commercially available measuring device (for example, TG / DTA100, manufactured by Seiko Electronics Industry Co., Ltd.).

  Specific examples of the compound having a 1,3,5-triazine ring are shown below.

  In addition, several R shown below represents the same group.

(1) Butyl (2) 2-Methoxy-2-ethoxyethyl (3) 5-Undecenyl (4) Phenyl (5) 4-Ethoxycarbonylphenyl (6) 4-Butoxyphenyl (7) p-Biphenylyl (8) 4 -Pyridyl (9) 2-naphthyl (10) 2-methylphenyl (11) 3,4-dimethoxyphenyl (12) 2-furyl

(14) phenyl (15) 3-ethoxycarbonylphenyl (16) 3-butoxyphenyl (17) m-biphenylyl (18) 3-phenylthiophenyl (19) 3-chlorophenyl (20) 3-benzoylphenyl (21) 3 -Acetoxyphenyl (22) 3-benzoyloxyphenyl (23) 3-phenoxycarbonylphenyl (24) 3-methoxyphenyl (25) 3-anilinophenyl (26) 3-isobutyrylaminophenyl (27) 3-phenoxy Carbonylaminophenyl (28) 3- (3-ethylureido) phenyl (29) 3- (3,3-diethylureido) phenyl (30) 3-methylphenyl (31) 3-phenoxyphenyl (32) 3-hydroxyphenyl (33) 4-Ethoxycarbonylphenyl (34) 4-butoxyphenyl (35) p-biphenylyl (36) 4-phenylthiophenyl (37) 4-chlorophenyl (38) 4-benzoylphenyl (39) 4-acetoxyphenyl (40) 4-benzoyloxyphenyl ( 41) 4-phenoxycarbonylphenyl (42) 4-methoxyphenyl (43) 4-anilinophenyl (44) 4-isobutyrylaminophenyl (45) 4-phenoxycarbonylaminophenyl (46) 4- (3-ethyl (Ureido) phenyl (47) 4- (3,3-diethylureido) phenyl (48) 4-methylphenyl (49) 4-phenoxyphenyl (50) 4-hydroxyphenyl (51) 3,4-diethoxycarbonylphenyl ( 52) 3,4-dibutoxyphenyl (53) 3 -Diphenylphenyl (54) 3,4-diphenylthiophenyl (55) 3,4-dichlorophenyl (56) 3,4-dibenzoylphenyl (57) 3,4-diacetoxyphenyl (58) 3,4-dibenzoyl Oxyphenyl (59) 3,4-diphenoxycarbonylphenyl (60) 3,4-dimethoxyphenyl (61) 3,4-dianilinophenyl (62) 3,4-dimethylphenyl (63) 3,4-diphenoxy Phenyl (64) 3,4-dihydroxyphenyl (65) 2-naphthyl (66) 3,4,5-triethoxycarbonylphenyl (67) 3,4,5-tributoxyphenyl (68) 3,4,5- Triphenylphenyl (69) 3,4,5-triphenylthiophenyl (70) 3,4,5-trichlorophenyl (71) 3,4,5-tribenzoylphenyl (72) 3,4,5-triacetoxyphenyl (73) 3,4,5-tribenzoyloxyphenyl (74) 3,4,5-triphenoxycarbonylphenyl (75) 3,4,5-trimethoxyphenyl (76) 3,4,5-trianilinophenyl (77) 3,4,5-trimethylphenyl (78) 3,4,5-triphenoxyphenyl (79 ) 3,4,5-trihydroxyphenyl

(80) phenyl (81) 3-ethoxycarbonylphenyl (82) 3-butoxyphenyl (83) m-biphenylyl (84) 3-phenylthiophenyl (85) 3-chlorophenyl (86) 3-benzoylphenyl (87) 3 -Acetoxyphenyl (88) 3-benzoyloxyphenyl (89) 3-phenoxycarbonylphenyl (90) 3-methoxyphenyl (91) 3-anilinophenyl (92) 3-isobutyrylaminophenyl (93) 3-phenoxy Carbonylaminophenyl (94) 3- (3-ethylureido) phenyl (95) 3- (3,3-diethylureido) phenyl (96) 3-methylphenyl (97) 3-phenoxyphenyl (98) 3-hydroxyphenyl (99) 4-Ethoxycarbonylphenyl (100) 4-butoxyphenyl (101) p-biphenylyl (102) 4-phenylthiophenyl (103) 4-chlorophenyl (104) 4-benzoylphenyl (105) 4-acetoxyphenyl (106) 4-benzoyloxyphenyl ( 107) 4-phenoxycarbonylphenyl (108) 4-methoxyphenyl (109) 4-anilinophenyl (110) 4-isobutyrylaminophenyl (111) 4-phenoxycarbonylaminophenyl (112) 4- (3-ethyl (Ureido) phenyl (113) 4- (3,3-diethylureido) phenyl (114) 4-methylphenyl (115) 4-phenoxyphenyl (116) 4-hydroxyphenyl (117) 3,4-diethoxycarbonylphenyl ( 118) 3 , 4-dibutoxyphenyl (119) 3,4-diphenylphenyl (120) 3,4-diphenylthiophenyl (121) 3,4-dichlorophenyl (122) 3,4-dibenzoylphenyl (123) 3,4- Diacetoxyphenyl (124) 3,4-dibenzoyloxyphenyl (125) 3,4-diphenoxycarbonylphenyl (126) 3,4-dimethoxyphenyl (127) 3,4-dianilinophenyl (128) 3,4 -Dimethylphenyl (129) 3,4-diphenoxyphenyl (130) 3,4-dihydroxyphenyl (131) 2-naphthyl (132) 3,4,5-triethoxycarbonylphenyl (133) 3,4,5- Tributoxyphenyl (134) 3,4,5-triphenylphenyl (135) 3 4,5-triphenylthiophenyl (136) 3,4,5-trichlorophenyl (137) 3,4,5-tribenzoylphenyl (138) 3,4,5-triacetoxyphenyl (139) 3,4 5-tribenzoyloxyphenyl (140) 3,4,5-triphenoxycarbonylphenyl (141) 3,4,5-trimethoxyphenyl (142) 3,4,5-trianilinophenyl (143) 3,4 , 5-trimethylphenyl (144) 3,4,5-triphenoxyphenyl (145) 3,4,5-trihydroxyphenyl

(146) phenyl (147) 4-ethoxycarbonylphenyl (148) 4-butoxyphenyl (149) p-biphenylyl (150) 4-phenylthiophenyl (151) 4-chlorophenyl (152) 4-benzoylphenyl (153) 4 -Acetoxyphenyl (154) 4-benzoyloxyphenyl (155) 4-phenoxycarbonylphenyl (156) 4-methoxyphenyl (157) 4-anilinophenyl (158) 4-isobutyrylaminophenyl (159) 4-phenoxy Carbonylaminophenyl (160) 4- (3-ethylureido) phenyl (161) 4- (3,3-diethylureido) phenyl (162) 4-methylphenyl (163) 4-phenoxyphenyl (164) 4-hydroxyphenyl

(165) phenyl (166) 4-ethoxycarbonylphenyl (167) 4-butoxyphenyl (168) p-biphenylyl (169) 4-phenylthiophenyl (170) 4-chlorophenyl (171) 4-benzoylphenyl (172) 4 -Acetoxyphenyl (173) 4-benzoyloxyphenyl (174) 4-phenoxycarbonylphenyl (175) 4-methoxyphenyl (176) 4-anilinophenyl (177) 4-isobutyrylaminophenyl (178) 4-phenoxy Carbonylaminophenyl (179) 4- (3-ethylureido) phenyl (180) 4- (3,3-diethylureido) phenyl (181) 4-methylphenyl (182) 4-phenoxyphenyl (183) 4-hydroxyphenyl

(184) phenyl (185) 4-ethoxycarbonylphenyl (186) 4-butoxyphenyl (187) p-biphenylyl (188) 4-phenylthiophenyl (189) 4-chlorophenyl (190) 4-benzoylphenyl (191) 4 -Acetoxyphenyl (192) 4-benzoyloxyphenyl (193) 4-phenoxycarbonylphenyl (194) 4-methoxyphenyl (195) 4-anilinophenyl (196) 4-isobutyrylaminophenyl (197) 4-phenoxy Carbonylaminophenyl (198) 4- (3-ethylureido) phenyl (199) 4- (3,3-diethylureido) phenyl (200) 4-methylphenyl (201) 4-phenoxyphenyl (202) 4-hydroxyphenyl

(203) phenyl (204) 4-ethoxycarbonylphenyl (205) 4-butoxyphenyl (206) p-biphenylyl (207) 4-phenylthiophenyl (208) 4-chlorophenyl (209) 4-benzoylphenyl (210) 4 -Acetoxyphenyl (211) 4-benzoyloxyphenyl (212) 4-phenoxycarbonylphenyl (213) 4-methoxyphenyl (214) 4-anilinophenyl (215) 4-isobutyrylaminophenyl (216) 4-phenoxy Carbonylaminophenyl (217) 4- (3-ethylureido) phenyl (218) 4- (3,3-diethylureido) phenyl (219) 4-methylphenyl (220) 4-phenoxyphenyl (221) 4-hydroxyphenyl

(222) phenyl (223) 4-butylphenyl (224) 4- (2-methoxy-2-ethoxyethyl) phenyl (225) 4- (5-nonenyl) phenyl (226) p-biphenylyl (227) 4-ethoxy Carbonylphenyl (228) 4-butoxyphenyl (229) 4-methylphenyl (230) 4-chlorophenyl (231) 4-phenylthiophenyl (232) 4-benzoylphenyl (233) 4-acetoxyphenyl (234) 4-benzoyl Oxyphenyl (235) 4-phenoxycarbonylphenyl (236) 4-methoxyphenyl (237) 4-anilinophenyl (238) 4-isobutyrylaminophenyl (239) 4-phenoxycarbonylaminophenyl (240) 4- ( 3-ethylureido Phenyl (241) 4- (3,3-diethylureido) phenyl (242) 4-phenoxyphenyl (243) 4-hydroxyphenyl (244) 3-butylphenyl (245) 3- (2-methoxy-2-ethoxyethyl) ) Phenyl (246) 3- (5-nonenyl) phenyl (247) m-biphenylyl (248) 3-ethoxycarbonylphenyl (249) 3-butoxyphenyl (250) 3-methylphenyl (251) 3-chlorophenyl (252) 3-phenylthiophenyl (253) 3-benzoylphenyl (254) 3-acetoxyphenyl (255) 3-benzoyloxyphenyl (256) 3-phenoxycarbonylphenyl (257) 3-methoxyphenyl (258) 3-anilinophenyl (259) 3-I Butyrylaminophenyl (260) 3-phenoxycarbonylaminophenyl (261) 3- (3-ethylureido) phenyl (262) 3- (3,3-diethylureido) phenyl (263) 3-phenoxyphenyl (264) 3 -Hydroxyphenyl (265) 2-butylphenyl (266) 2- (2-methoxy-2-ethoxyethyl) phenyl (267) 2- (5-nonenyl) phenyl (268) o-biphenylyl (269) 2-ethoxycarbonyl Phenyl (270) 2-Butoxyphenyl (271) 2-Methylphenyl (272) 2-Chlorophenyl (273) 2-Phenylthiophenyl (274) 2-Benzoylphenyl (275) 2-Acetoxyphenyl (276) 2-Benzoyloxy Phenyl (277) 2 Phenoxycarbonylphenyl (278) 2-methoxyphenyl (279) 2-anilinophenyl (280) 2-isobutyrylaminophenyl (281) 2-phenoxycarbonylaminophenyl (282) 2- (3-ethylureido) phenyl ( 283) 2- (3,3-diethylureido) phenyl (284) 2-phenoxyphenyl (285) 2-hydroxyphenyl (286) 3,4-dibutylphenyl (287) 3,4-di (2-methoxy-2) -Ethoxyethyl) phenyl (288) 3,4-diphenylphenyl (289) 3,4-diethoxycarbonylphenyl (290) 3,4-didodecyloxyphenyl (291) 3,4-dimethylphenyl (292) 3, 4-dichlorophenyl (293) 3,4-dibenzoyl Enyl (294) 3,4-diacetoxyphenyl (295) 3,4-dimethoxyphenyl (296) 3,4-di-N-methylaminophenyl (297) 3,4-diisobutyrylaminophenyl (298) 3 , 4-diphenoxyphenyl (299) 3,4-dihydroxyphenyl (300) 3,5-dibutylphenyl (301) 3,5-di (2-methoxy-2-ethoxyethyl) phenyl (302) 3,5- Diphenylphenyl (303) 3,5-diethoxycarbonylphenyl (304) 3,5-didodecyloxyphenyl (305) 3,5-dimethylphenyl (306) 3,5-dichlorophenyl (307) 3,5-dibenzoyl Phenyl (308) 3,5-diacetoxyphenyl (309) 3,5-dimethoxyphenyl (3 0) 3,5-di-N-methylaminophenyl (311) 3,5-diisobutyrylaminophenyl (312) 3,5-diphenoxyphenyl (313) 3,5-dihydroxyphenyl (314) 2,4 -Dibutylphenyl (315) 2,4-di (2-methoxy-2-ethoxyethyl) phenyl (316) 2,4-diphenylphenyl (317) 2,4-diethoxycarbonylphenyl (318) 2,4-di Dodecyloxyphenyl (319) 2,4-dimethylphenyl (320) 2,4-dichlorophenyl (321) 2,4-dibenzoylphenyl (322) 2,4-diacetoxyphenyl (323) 2,4-dimethoxyphenyl ( 324) 2,4-di-N-methylaminophenyl (325) 2,4-diisobutyrylaminopheny (326) 2,4-diphenoxyphenyl (327) 2,4-dihydroxyphenyl (328) 2,3-dibutylphenyl (329) 2,3-di (2-methoxy-2-ethoxyethyl) phenyl (330) 2,3-diphenylphenyl (331) 2,3-diethoxycarbonylphenyl (332) 2,3-didodecyloxyphenyl (333) 2,3-dimethylphenyl (334) 2,3-dichlorophenyl (335) 2, 3-dibenzoylphenyl (336) 2,3-diacetoxyphenyl (337) 2,3-dimethoxyphenyl (338) 2,3-di-N-methylaminophenyl (339) 2,3-diisobutyrylaminophenyl (340) 2,3-diphenoxyphenyl (341) 2,3-dihydroxyphenyl (342 ) 2,6-dibutylphenyl (343) 2,6-di (2-methoxy-2-ethoxyethyl) phenyl (344) 2,6-diphenylphenyl (345) 2,6-diethoxycarbonylphenyl (346) 2 , 6-didodecyloxyphenyl (347) 2,6-dimethylphenyl (348) 2,6-dichlorophenyl (349) 2,6-dibenzoylphenyl (350) 2,6-diacetoxyphenyl (351) 2,6 -Dimethoxyphenyl (352) 2,6-di-N-methylaminophenyl (353) 2,6-diisobutyrylaminophenyl (354) 2,6-diphenoxyphenyl (355) 2,6-dihydroxyphenyl (356 ) 3,4,5-tributylphenyl (357) 3,4,5-tri (2-methoxy-2-ethoxy) Til) phenyl (358) 3,4,5-triphenylphenyl (359) 3,4,5-triethoxycarbonylphenyl (360) 3,4,5-tridodecyloxyphenyl (361) 3,4,5- Trimethylphenyl (362) 3,4,5-trichlorophenyl (363) 3,4,5-tribenzoylphenyl (364) 3,4,5-triacetoxyphenyl (365) 3,4,5-trimethoxyphenyl ( 366) 3,4,5-tri-N-methylaminophenyl (367) 3,4,5-triisobutyrylaminophenyl (368) 3,4,5-triphenoxyphenyl (369) 3,4,5 -Trihydroxyphenyl (370) 2,4,6-tributylphenyl (371) 2,4,6-tri (2-methoxy-2-ethoxyethyl) B) phenyl (372) 2,4,6-triphenylphenyl (373) 2,4,6-triethoxycarbonylphenyl (374) 2,4,6-tridodecyloxyphenyl (375) 2,4,6- Trimethylphenyl (376) 2,4,6-trichlorophenyl (377) 2,4,6-tribenzoylphenyl (378) 2,4,6-triacetoxyphenyl (379) 2,4,6-trimethoxyphenyl ( 380) 2,4,6-tri-N-methylaminophenyl (381) 2,4,6-triisobutyrylaminophenyl (382) 2,4,6-triphenoxyphenyl (383) 2,4,6 -Trihydroxyphenyl (384) Pentafluorophenyl (385) Pentachlorophenyl (386) Pentamethoxyphenyl (38 7) 6-N-methylsulfamoyl-8-methoxy-2-naphthyl (388) 5-N-methylsulfamoyl-2-naphthyl (389) 6-N-phenylsulfamoyl-2-naphthyl (390) ) 5-Ethoxy-7-N-methylsulfamoyl-2-naphthyl (391) 3-methoxy-2-naphthyl (392) 1-ethoxy-2-naphthyl (393) 6-N-phenylsulfamoyl-8 -Methoxy-2-naphthyl (394) 5-methoxy-7-N-phenylsulfamoyl-2-naphthyl (395) 1- (4-methylphenyl) -2-naphthyl (396) 6,8-di-N -Methylsulfamoyl-2-naphthyl (397) 6-N-2-acetoxyethylsulfamoyl-8-methoxy-2-naphthyl (398) 5-acetoxy-7 N-phenylsulfamoyl-2-naphthyl (399) 3-benzoyloxy-2-naphthyl (400) 5-acetylamino-1-naphthyl (401) 2-methoxy-1-naphthyl (402) 4-phenoxy-1 -Naphtyl (403) 5-N-methylsulfamoyl-1-naphthyl (404) 3-N-methylcarbamoyl-4-hydroxy-1-naphthyl (405) 5-methoxy-6-N-ethylsulfamoyl- 1-naphthyl (406) 7-tetradecyloxy-1-naphthyl (407) 4- (4-methylphenoxy) -1-naphthyl (408) 6-N-methylsulfamoyl-1-naphthyl (409) 3- N, N-dimethylcarbamoyl-4-methoxy-1-naphthyl (410) 5-methoxy-6-N-benzylsulfamoyl -1-naphthyl (411) 3,6-di-N-phenylsulfamoyl-1-naphthyl (412) methyl (413) ethyl (414) butyl (415) octyl (416) dodecyl (417) 2-butoxy- 2-Ethoxyethyl (418) benzyl (419) 4-methoxybenzyl

(424) Methyl (425) Phenyl (426) Butyl

(430) methyl (431) ethyl (432) butyl (433) octyl (434) dodecyl (435) 2-butoxy-2-ethoxyethyl (436) benzyl (437) 4-methoxybenzyl

  In the present invention, a melamine polymer may be used as the compound having a 1,3,5-triazine ring. The melamine polymer is preferably synthesized by a polymerization reaction between a melamine compound represented by the following general formula (II) and a carbonyl compound.

In the above synthetic reaction scheme, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.

  The alkyl group, alkenyl group, aryl group, heterocyclic group, and substituents thereof have the same meanings as the groups and substituents described in the general formula (I).

  The polymerization reaction between the melamine compound and the carbonyl compound is the same as the method for synthesizing a normal melamine resin (for example, melamine formaldehyde resin). Moreover, you may use a commercially available melamine polymer (melamine resin).

  The molecular weight of the melamine polymer is preferably 2,000 to 400,000. Specific examples of the repeating unit of the melamine polymer are shown below.

MP-1: R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ : CH ₂ OH
^{MP-2: R 13, R} 14, R 15, R 16: CH 2 OCH 3
^{MP-3: R 13, R} 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-4: R 13, R} 14, R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-5: R 13, R} 14, R 15, R 16: CH 2 NHCOCH = CH 2
^{MP-6: R 13, R} 14, R 15, R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-7: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 OCH 3
^{MP-8: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 OCH 3
^{MP-9: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 OCH 3
^{MP-10: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 OCH 3
^{MP-11: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 OCH 3
^{MP-12: R 13, R} 14, R 16: CH 2 OCH 3; R 15: CH 2 OH
^{MP-13: R 13, R} 16: CH 2 OCH 3; R 14, R 15: CH 2 OH
^{MP-14: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-i-C 4 H 9
^{MP-15: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-i-C 4 H 9
^{MP-16: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-17: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-i-C 4 H 9
^{MP-18: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-19: R 13, R} 14, R 16: CH 2 O-i-C 4 H 9; R 15: CH 2 OH
^{MP-20: R 13, R} 16: CH 2 O-i-C 4 H 9; R 14, R 15: CH 2 OH
MP-21: R ¹³ , R ¹⁴ , R ¹⁵ : CH ₂ OH; R ¹⁶ : CH _{2 On} -C ₄ H ₉
^{MP-22: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-23: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-24: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9
^{MP-25: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2O -n-C 4 H 9
^{MP-26: R 13, R} 14, R 16: CH 2 O-n-C 4 H 9; R 15: CH 2 OH
^{MP-27: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14, R 15: CH 2 OH
^{MP-28: R 13, R} 14: CH 2 OH; R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-29: R 13, R} 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-30: R 13, R} 16: CH 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-31: R 13: CH} 2 OH; R 14, R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-32: R 13: CH} 2 OH; R 14, R 16: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-33: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-34: R 13: CH} 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-35: R 13, R} 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-36: R 13, R} 16: CH 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-37: R 13: CH} 2 OCH 3; R 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-38: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH
^{MP-39: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C4H9; R 16: CH 2 NHCOCH = CH 2
^{MP-40: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-41: R 13: CH} 2 OH; R 14: CH 2 O-n-C 4 H 9; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-42: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-43: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-44: R 13: CH} 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2
^{MP-45: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-46: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-47: R 13: CH} 2 OH; R 14: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-48: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-49: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-50: R 13: CH} 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2

^{MP-51: R 13, R} 14, R 15, R 16: CH 2 OH
^{MP-52: R 13, R} 14, R 15, R 16: CH 2 OCH 3
^{MP-53: R 13, R} 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-54: R 13, R} 14, R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-55: R 13, R} 14, R 15, R 16: CH 2 NHCOCH = CH 2
^{MP-56: R 13, R} 14, R 15, R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-57: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 OCH 3
^{MP-58: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 OCH 3
^{MP-59: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 OCH 3
^{MP-60: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 OCH 3
^{MP-61: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 OCH 3
^{MP-62: R 13, R} 14, R 16: CH 2 OCH 3; R 15: CH 2 OH
^{MP-63: R 13, R} 16: CH 2 OCH 3; R 14, R 15: CH 2 OH
^{MP-64: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-i-C 4 H 9
^{MP-65: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-i-C 4 H 9
^{MP-66: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-67: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-i-C 4 H 9
^{MP-68: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-69: R 13, R} 14, R 16: CH 2 O-i-C 4 H 9; R 15: CH 2 OH
^{MP-70: R 13, R} 16: CH 2 O-i-C 4 H 9; R 14, R 15: CH 2 OH
^{MP-71: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-72: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-73: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-74: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9
^{MP-75: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-76: R 13, R} 14, R 16: CH 2 O-n-C 4 H 9; R 15: CH 2 OH
^{MP-77: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14, R 15: CH 2 OH
^{MP-78: R 13, R} 14: CH 2 OH; R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-79: R 13, R} 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-80: R 13, R} 16: CH 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-81: R 13: CH} 2 OH; R 14, R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-82: R 13: CH} 2 OH; R 14, R 16: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-83: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-84: R 13: CH} 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-85: R 13, R} 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-86: R 13, R} 16: CH 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-87: R 13: CH} 2 OCH 3; R 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-88: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH
^{MP-89: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-90: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-91: R 13: CH} 2 OH; R 14: CH 2 O-n-C 4 H 9; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-92: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-93: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-94: R 13: CH} 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2
^{MP-95: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-96: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-97: R 13: CH} 2 OH; R 14: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-98: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-99: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-100: R 13: CH} 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2

^{MP-101: R 13, R} 14, R 15, R 16: CH 2 OH
^{MP-102: R 13, R} 14, R 15, R 16: CH 2 OCH 3
^{MP-103: R 13, R} 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-104: R 13, R} 14, R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-105: R 13, R} 14, R 15, R 16: CH 2 NHCOCH = CH 2
^{MP-106: R 13, R} 14, R 15, R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-107: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 OCH 3
^{MP-108: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 OCH 3
^{MP-109: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 OCH 3
^{MP-110: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 OCH 3
^{MP-111: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 OCH 3
^{MP-112: R 13, R} 14, R 16: CH 2 OCH 3; R 15: CH 2 OH
^{MP-113: R 13, R} 16: CH 2 OCH 3; R 14, R 15: CH 2 OH
^{MP-114: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-i-C 4 H 9
^{MP-115: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-i-C 4 H 9
^{MP-116: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-117: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-i-C 4 H 9
^{MP-118: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-119: R 13, R} 14, R 16: CH 2 O-i-C 4 H 9; R 15: CH 2 OH
^{MP-120: R 13, R} 16: CH 2 O-i-C 4 H 9; R 14, R 15: CH 2 OH
^{MP-121: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-122: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-123: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-124: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9
^{MP-125: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-126: R 13, R} 14, R 16: CH 2 O-n-C 4 H 9; R 15: CH 2 OH
^{MP-127: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14, R 15: CH 2 OH
^{MP-128: R 13, R} 14: CH 2 OH; R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-129: R 13, R} 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-130: R 13, R} 16: CH 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-131: R 13: CH} 2 OH; R 14, R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-132: R 13: CH} 2 OH; R 14, R 16: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-133: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-134: R 13: CH} 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-135: R 13, R} 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-136: R 13, R} 16: CH 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-137: R 13: CH} 2 OCH 3; R 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-138: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH
^{MP-139: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-140: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-141: R 13: CH} 2 OH; R 14: CH 2 O-n-C 4 H 9; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-142: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-143: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-144: R 13: CH} 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2
^{MP-145: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-146: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-147: R 13: CH} 2 OH; R 14: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-148: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-149: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-150: R 13: CH} 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2

^{MP-151: R 13, R} 14, R 15, R 16: CH 2 OH
^{MP-152: R 13, R} 14, R 15, R 16: CH 2 OCH 3
^{MP-153: R 13, R} 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-154: R 13, R} 14, R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-155: R 13, R} 14, R 15, R 16: CH 2 NHCOCH = CH 2
^{MP-156: R 13, R} 14, R 15, R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-157: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 OCH 3
^{MP-158: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 OCH 3
^{MP-159: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 OCH 3
^{MP-160: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 OCH 3
^{MP-161: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 OCH 3
^{MP-162: R 13, R} 14, R 16: CH 2 OCH 3; R 15: CH 2 OH
^{MP-163: R 13, R} 16: CH 2 OCH 3; R 14, R 15: CH 2 OH
^{MP-164: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-i-C 4 H 9
^{MP-165: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-i-C 4 H 9
^{MP-166: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-167: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-i-C 4 H 9
^{MP-168: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-i-C 4 H 9
^{MP-169: R 13, R} 14, R 16: CH 2 O-i-C 4 H 9; R 15: CH 2 OH
^{MP-170: R 13, R} 16: CH 2 O-i-C 4 H 9; R 14, R 15: CH 2 OH
^{MP-171: R 13, R} 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-172: R 13, R} 14, R 16: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-173: R 13, R} 14: CH 2 OH; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-174: R 13, R} 16: CH 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9
^{MP-175: R 13: CH} 2 OH; R 14, R 15, R 16: CH 2 O-n-C 4 H 9
MP-176: R ¹³ , R ¹⁴ , R ¹⁶ : CH _{2 On} -C ₄ H ₉ ; R ¹⁵ : CH ₂ OH
^{MP-177: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14, R 15: CH 2 OH
^{MP-178: R 13, R} 14: CH 2 OH; R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-179: R 13, R} 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-180: R 13, R} 16: CH 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-181: R 13: CH} 2 OH; R 14, R 15: CH 2 OCH 3; R 16: CH 2 O-n-C 4 H 9
^{MP-182: R 13: CH} 2 OH; R 14, R 16: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9
^{MP-183: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15, R 16: CH 2 O-n-C 4 H 9
^{MP-184: R 13: CH} 2 OH; R 14, R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 OCH 3
^{MP-185: R 13, R} 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2O -n-C 4 H 9
^{MP-186: R 13, R} 16: CH 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9
^{MP-187: R 13: CH} 2 OCH 3; R 14, R 15: CH 2 OH; R 16: CH 2 O-n-C 4 H 9
^{MP-188: R 13, R} 16: CH 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH
^{MP-189: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-190: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-191: R 13: CH} 2 OH; R 14: CH 2 O-n-C 4 H 9; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-192: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 O-n-C 4 H 9; R 16: CH 2 NHCOCH = CH 2
^{MP-193: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 O-n-C 4 H 9
^{MP-194: R 13: CH} 2 O-n-C 4 H 9; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2
^{MP-195: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-196: R 13: CH} 2 OH; R 14: CH 2 OCH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-197: R 13: CH} 2 OH; R 14: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 OCH 3
^{MP-198: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 16: CH 2 NHCOCH = CH 2
^{MP-199: R 13: CH} 2 OCH 3; R 14: CH 2 OH; R 15: CH 2 NHCOCH = CH 2; R 16: CH 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3
^{MP-200: R 13: CH} 2 NHCO (CH 2) 7 CH = CH (CH 2) 7 CH 3; R 14: CH 2 OCH 3; R 15: CH 2 OH; R 16: CH 2 NHCOCH = CH 2
In the present invention, a copolymer obtained by combining two or more of the above repeating units may be used. Two or more homopolymers or copolymers may be used in combination.

  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 of adding the UV absorber may be added to the dope after the UV absorber is dissolved 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, the operating 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 preferably contains 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 0.05 to 10% by mass, particularly preferably 0.1 to 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.

  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. These fine particles can be added for the purpose of imparting an internal scattering effect in addition to lowering the friction coefficient.

<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 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) and the cellulose acetate propionate are good. As a solvent, cellulose acetate (acetyl group substitution degree 2.8) is a poor solvent.

  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 mamaco. 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.

  The material of the filter medium is not particularly limited, and a normal filter medium can be used. However, a plastic filter medium such as polypropylene and Teflon (R) and a metal filter medium such as stainless steel are preferable because there is no loss of fibers. . 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%. The amount of residual solvent contained in the film when forming irregularities with the mold is preferably 150 to 0.1% by mass, more preferably 80 to 0.1% by mass, and still more preferably 40 to 0.1% by mass. 10 to 0.1% by mass is particularly preferable.

  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 a cellulose ester film for an antiglare film of the present invention, the web is stretched in the transport direction (MD stretching) where the amount of residual solvent of the web immediately after peeling from the metal support is large, and both ends of the web are further stretched. It is preferable to perform stretching in the width direction by a tenter method gripped with a clip or the like. 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 150 ° 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. In particular, it was difficult to obtain an antiglare film excellent in flatness and hardness with a thin film of 10 to 70 μm. However, according to the present invention, a thin antiglare film excellent in flatness and hardness was obtained. The film thickness of the cellulose ester film is particularly preferably 10 to 70 [mu] m. More preferably, it is 20-70 micrometers. Most preferably, it is 35-70 micrometers.

  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 antiglare film of the present invention preferably has a width of 1 to 4 m. Moreover, it is preferable that the unevenness | corrugation of the surface which provides the hard-coat layer of a cellulose-ester film has 0.05-10 micrometers of centerline average roughness (Ra) prescribed | regulated by JISB0601.

<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 stored for 24 hours at 23 ° C. and 55% RH, and a tensile test is performed at a pulling speed of 100 mm / min with a chuck distance 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)
Transmittance T is 380, 400, 500 nm from spectral transmittance τ (λ) obtained every 10 nm in a wavelength region of 350-700 nm using a spectral altimeter U-3400 (Hitachi, Ltd.). Transmittance can be calculated.

  The haze by the following measurement of the cellulose ester film used in the present invention is preferably less than 10%, more preferably less than 1%, 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 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.

<Hard coat layer>
In the present invention, it is preferable to coat a hard coat layer on the thermoplastic resin film. The hard coat layer is preferably a hard coat layer containing an actinic radiation curable resin and fine particles. Thereby, it is possible to produce an antiglare antireflection film which exhibits a sufficient antiglare effect and exhibits excellent transmission clarity.

  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.

  Of 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, and particles of 5 nm to 5 μm are particularly preferable. In particular, particles having a diameter larger than the average thickness of the hard coat layer may increase glare, and it is preferable that the amount added is reduced or not contained at all. According to the present invention, excellent antiglare properties can be obtained without containing large particles. Particularly preferably, it contains 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 Corporation); 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 (Sanyo Chemical Industries, Ltd.); 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, hard coat coating liquids containing ultrafine zirconium oxide dispersions for refractive index adjustment Desolite Z-7041 and Desolite Z-7042 (manufactured by JSR Corporation) can also 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. 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 antiglare antireflection 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 depending on 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 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 film 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.

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 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 Yushi 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.

  As the coating method of the hard coat layer coating solution, the above-described methods can be used. The coating amount is suitably 0.1 to 30 μm, preferably 0.5 to 15 μm, as the wet film thickness.

<Back coat layer>
It is preferable to provide a backcoat layer on the surface opposite to the side on which the antiglare layer of the antiglare film of the present invention is provided. The back coat layer is provided to correct curling caused by the formation of an uneven surface, a hard coat layer, and other layers. That is, the degree of curling can be balanced by imparting the property of being rounded with the surface on which the backcoat layer is provided facing inward. Alternatively, the back coat layer is coated as an anti-blocking layer, and in that case, it is preferable that fine particles are added to the back coat layer coating composition in order to provide an anti-blocking function.

  As fine particles added to the back coat layer, examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, tin oxide, and oxidation. Mention may be made of indium, zinc oxide, ITO, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. Fine particles containing silicon are preferable in terms of low haze, and silicon dioxide is particularly preferable.

  These fine particles are commercially available under the trade names of, for example, Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, and TT600 (manufactured by Nippon Aerosil Co., Ltd.). . 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, fluorine resin, and acrylic 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 anti-blocking effect while keeping haze low. The antiglare antireflection film used in the present invention preferably has a dynamic friction coefficient on the back side of the hard coat layer of 0.9 or less, particularly 0.1 to 0.9.

  The fine particles contained in the backcoat layer are preferably contained in an amount of 0.1 to 50% by mass, more preferably 0.1 to 10% by mass with respect to the binder. When the back coat layer is provided, the increase in haze is preferably 1% or less, more preferably 0.5% or less, and particularly preferably 0.0 to 0.1%.

  Specifically, the back coat layer is formed by applying a composition containing a solvent for dissolving or swelling a cellulose ester film. The solvent used may include a solvent to be dissolved and / or a solvent to be swollen in addition to a solvent to be swelled, a composition in which these are mixed at an appropriate ratio depending on the degree of curling of the transparent resin film and the type of resin, and This is done using the coating amount.

  In order to enhance the curl prevention function, it is effective to increase the mixing ratio of the solvent for dissolving the solvent composition to be used and / or the solvent for swelling, and to decrease the ratio of the solvent not to be dissolved. This mixing ratio is preferably (solvent to be dissolved and / or solvent to be swollen) :( solvent to be dissolved) = 10: 0 to 1: 9. Examples of the solvent for dissolving or swelling the transparent resin film contained in such a mixed composition include dioxane, acetone, methyl ethyl ketone, N, N-dimethylformamide, methyl acetate, ethyl acetate, trichloroethylene, methylene chloride, and ethylene chloride. , Tetrachloroethane, trichloroethane, chloroform and the like. Examples of the solvent that does not dissolve include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butanol, cyclohexanol, and hydrocarbons (toluene, xylene).

  These coating compositions are preferably applied to the surface of the transparent resin film with a wet film thickness of 1 to 100 μm using a gravure coater, dip coater, reverse coater, wire bar coater, die coater, spray coating, ink jet coating or the like. Is particularly preferably 5 to 30 μm. Examples of the resin used as the binder of the backcoat layer include vinyl chloride-vinyl acetate copolymer, vinyl chloride resin, vinyl acetate resin, vinyl acetate-vinyl alcohol copolymer, partially hydrolyzed vinyl chloride-vinyl acetate copolymer. Polymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer, ethylene-vinyl alcohol copolymer, chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, etc. Vinyl polymer or copolymer, nitrocellulose, cellulose acetate propionate (preferably acetyl group substitution degree 1.8-2.3, propionyl group substitution degree 0.1-1.0), diacetyl cellulose, cellulose Cellulose derivatives such as acetate butyrate resin, maleic acid and / or Or acrylic acid copolymer, acrylic ester copolymer, acrylonitrile-styrene copolymer, chlorinated polyethylene, acrylonitrile-chlorinated polyethylene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylic resin Rubber resins such as polyvinyl acetal resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, styrene-butadiene resin, butadiene-acrylonitrile resin, Examples thereof include, but are not limited to, silicone resins and fluorine resins. For example, as an acrylic resin, Acrypet MD, VH, MF, V (manufactured by Mitsubishi Rayon Co., Ltd.), Hyperl M-4003, M-4005, M-4006, M-4202, M-5000, M-5001, M-4501 (manufactured by Negami Kogyo Co., Ltd.), Dialnal BR-50, BR-52, BR-53, BR-60, BR-64, BR-73, BR-75, BR-77, BR-79, BR -80, BR-82, BR-83, BR-85, BR-87, BR-88, BR-90, BR-93, BR-95, BR-100, BR-101, BR-102, BR-105 BR-106, BR-107, BR-108, BR-112, BR-113, BR-115, BR-116, BR-117, BR-118, etc. (Mitsubishi Rayon Co., Ltd.) acrylic and The methacrylic monomers such as various homopolymers and copolymers were prepared as raw materials are commercially available, can also be selected preferred mono from this appropriate.

  Particularly preferred are cellulose resin layers such as diacetylcellulose and cellulose acetate propionate.

  The order of coating the back coat layer may be before or after the hard coat layer of the cellulose ester film is coated, but when the back coat layer also serves as an anti-blocking layer, it is preferably coated first. Alternatively, the backcoat layer can be applied in two or more steps.

(Antireflection layer)
The antiglare antireflection film according to the present invention has a low refractive index layer containing at least a fluorine-containing resin or inorganic fine particles on a hard coat layer, and the inorganic fine particles are provided on the porous particles and the surface of the porous particles. It is preferable that the composite particles have a coating layer formed, or hollow particles filled with a solvent, a gas, or a porous material.

  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 cellulose ester 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 anti-glare antireflection film is shown below, it is not limited to these.

  Here, the hard coat layer means the actinic radiation curable resin layer described above.

Cellulose ester film / antiglare layer / hard coat layer / low refractive index layer Cellulose ester film / antiglare layer / hard coat layer / high refractive index layer / low refractive index layer cellulose ester film / antiglare layer / hard coat layer / medium Refractive index layer / High refractive index layer / Low refractive index layer Cellulose ester film / hard coat layer / antiglare layer / low refractive index layer Cellulose ester film / hard coat layer / antiglare layer / high refractive index layer / low refractive index layer Cellulose ester film / hard coat layer / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer Any of the above-mentioned back coats on the side opposite to the side coated with the hard coat layer of the cellulose ester film It is preferable to provide a layer.

  Further, the middle refractive index layer or the high refractive index layer may also serve as the antistatic layer.

  In the antiglare antireflection film, a low refractive index layer is formed as the uppermost layer, and a metal oxide layer of a high refractive index layer is formed between the hard coat layer and the hard coat layer and the high refractive index layer. Providing a middle refractive index layer (metal oxide content or ratio with resin binder, metal oxide layer with the refractive index adjusted by changing the type of metal) between the two is to reduce reflectivity Is preferable.

  Composite particles having porous particles and a coating layer provided on the surface of the porous particles, preferably contained in the low refractive index layer of the present invention, or hollow particles filled with a solvent, gas, or porous substance inside Will be described.

  The inorganic fine particle is (I) a composite particle comprising a porous particle and a coating layer provided on the surface of the porous particle, or (II) a cavity inside, and the content is a solvent, a gas or a porous substance It is a hollow particle filled with. 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 porous particles, 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 silica ratio 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. It grows on the top and particle growth occurs. 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. Further, 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 (R) AF (DuPont), polyvinylidene fluoride, Lumiflon (Asahi Glass), Opstar (JSR) and the like. It is done.

  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.

  Particularly preferred silicone oils are the compounds listed in Table 1.

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 weight 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 weight 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 antiglare antireflection film of the present invention is subjected to alkali saponification treatment, and the antiglare antireflection film thus treated is immersed and stretched in an iodine solution. It is preferable to bond using an aqueous polyvinyl alcohol solution. The antiglare antireflection film may be used on the other surface, or another polarizing plate protective film may be used. As the polarizing plate protective film used on the back side, KC8UX2MW, KC4UX, KC5UX, KC4UY, KC8UY, KC12UR, KC8UCR-3 (manufactured by Konica Minolta Opto Co., Ltd.) and the like are preferably used as commercially available cellulose ester films. With respect to the antiglare antireflection film of the present invention, the polarizing plate protective film used on the other surface has an in-plane retardation Ro of 590 nm, a phase difference of 20 to 70 nm, and Rt of 100 to 400 nm. An optical compensation film is preferable. 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 antiglare antireflection 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 antiglare antireflection 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.

  Conventional anti-glare anti-reflection films could not achieve both anti-reflection and contrast (for example, black spots) in an environment affected by reflections of lighting from the ceiling or external light. The polarizing plate using the anti-glare anti-reflection film of the invention achieves both the prevention of image reflection at the periphery of the screen and the contrast at the center, and further improves the visibility in combination with the expansion of the viewing angle by combining an optical compensation film. I was able to bring it.

<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 anti-glare anti-reflection film of the present invention is a reflection type, transmission type, transflective LCD or TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS type, etc. It is preferably used in LCDs. Further, the antiglare antireflection film of the present invention has remarkably little color unevenness and glaring of the reflected light of the antireflection layer, and is excellent in flatness, plasma display, field emission display, organic EL display, inorganic EL display, It is also preferably used for various display devices such as electronic paper. 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.

<Preparation of cellulose ester film>
(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 while stirring, and the mixture was stirred and mixed for 30 minutes with a dissolver to prepare 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, and the mixture was further stirred for 30 minutes, and then 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 sealed 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 an apparatus (FIG. 2), the film was uniformly cast 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 is 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, the film is wound by applying a knurling process 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 (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.

<Application of antiglare layer 1>
On the cellulose ester film, the following antiglare layer 1 coating composition is coated 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. Then, UV rays were irradiated from the actinic ray irradiation part at an irradiation intensity of 115 mJ / cm ² , an antiglare layer 1 having a dry film thickness of 5 μm was provided, and a back coat layer described later was provided on the back surface to obtain an antiglare film 1. .

<Anti-glare layer 1 coating composition>
Dipentaerythritol hexaacrylate monomer 60 parts by mass Dipentaerythritol hexaacrylate dimer 20 parts by mass Components of dipentaerythritol hexaacrylate trimer or higher
20 parts by weight Synthetic silica particles (average particle size 1.8 μm) 8 parts by weight Photoreaction initiator 4 parts by weight (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
75 parts by mass of propylene glycol monomethyl ether 75 parts by mass of methyl ethyl ketone (coating of back coat layer)
The following coating composition 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. This back coat layer coating composition was applied to the surface opposite to the surface provided with the antiglare layer 1 with an extrusion coater so as to have a wet film thickness of 15 μm, and dried at 90 ° C. for 30 seconds.

<Coating liquid for back coat layer>
Diacetyl cellulose (acetyl group substitution degree 2.4) 0.5 parts by mass Acetone 70 parts by mass Methanol 20 parts by mass Propylene glycol monomethyl ether 10 parts by mass Ultrafine silica AEROSIL 200V (manufactured by Nippon Aerosil Co., Ltd.)
0.002 parts by mass (The silica fine particles were added dispersed in methanol to be added.)
<< Formation of antiglare layer 2 >>
After a semi-cured UV curable resin layer is provided on the cellulose ester film produced by the above-described method, the density of ink droplets landed in the width direction or the longitudinal direction is changed by the ink jet method. Concavities and convexities having different antiglare properties were formed to produce an antiglare film 2.

<Coating of hard coat layer>
A coating solution for hard coat layer having the following composition was prepared as a coating solution, applied onto the cellulose ester film using a microgravure coater so that the film thickness after curing was 3 μm, and the solvent was evaporated and dried, followed by UV irradiation. A semi-hardened hard coat layer was formed by irradiation.

<Coating liquid for hard coat layer>
Dipentaerythritol hexaacrylate 70 parts by weight Trimethylolpropane triacrylate 30 parts by weight Photoinitiator 4 parts by weight (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
Ethyl acetate 150 parts by mass Propylene glycol monomethyl ether 150 parts by mass Silicon compound 0.4 parts by mass (BYK-307 (by Big Chemie Japan))
Zirconium oxide fine particles (average particle size 10 nm) were added so that the film formed on the composition had a refractive index of 1.60. Zirconium oxide was previously dispersed using a part of the solvent added to the coating solution.

Next, on the semi-cured ultraviolet curable resin layer, as shown in FIG. 8, the following antiglare layer ink liquid 1 is used so that the ink landing density increases toward the both ends of the wide film as shown in FIG. Is ejected as ink droplets by ink jet method at 1 pl, and after landing, UV rays are irradiated from the actinic ray irradiation part with an irradiation intensity of 0.1 J / cm ² and cured. And dried at 85 ° C., and further irradiated with ultraviolet rays at an irradiation intensity of 0.2 J / cm ² , the center line average roughness Ra at both width ends is 0.3 μm, and the height a based on the bottom of the recess is 0. a convex portion is .1~10.0μm have 5 per 100 [mu] m ^2, the lateral center portion as the convex portion in Ra0.01μm so as not to impact the ink becomes zero per 100 [mu] m ² , Ra gradually increases at the center and both ends Forming an antiglare layer 2 was set to be 0.3μm from 0.01 [mu] m, anti-glare film was obtained 2. Incidentally, the haze was 2% or more higher at the film edge and center.

<Inkjet ejection method>
As the inkjet emission device, a line head method (FIG. 4A) 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. 3 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 anti-glare layer ink liquid 1>
Dipentaerythritol hexaacrylate 70 parts by weight Trimethylolpropane triacrylate 30 parts by weight Photoinitiator 4 parts by weight (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
Propylene glycol monomethyl ether 50 parts by mass Acetone 1000 parts by mass Zirconium oxide fine particles (average particle diameter 10 nm) were added so that the refractive index of the film formed on the composition was 1.60. Zirconium oxide was previously dispersed using a part of the solvent added to the coating solution.

<< Formation of Antiglare Layer 3 >>
Similarly to the formation of the anti-glare layer 2, the anti-glare layer ink liquid used in the anti-glare layer 2 is emitted onto the semi-cured ultraviolet curable resin layer by the same ink jet method, and the pattern shown in FIG. 8 is obtained. Thus, an antiglare layer was formed. Thereafter, after the ink liquid has landed, it was cured by irradiating with ultraviolet rays with an irradiation intensity of 0.1 J / cm ² from the actinic ray irradiating portion, and then gradually increasing the temperature and speed of the hot air and finally drying at 85 ° C. When irradiated with ultraviolet rays at an irradiation intensity of ² J / cm ² , the center line average roughness Ra of the concavo-convex part having a large film end is 0.5 μm, and the height a based on the bottom of the concave part is 0.1 to 10.0 μm. Are 20 convex portions per 100 μm ² , the center line average roughness Ra of the small uneven portion at the center is 0.1 μm, and the height a based on the bottom of the concave portion is 0.1 to 10.0 μm. The antiglare layer 3 having three convex portions per 1000 μm ² was formed, and the antiglare film 3 was obtained. Incidentally, the haze was 4% or more higher at the film edge and center.

<< Formation of Antiglare Layer 4 >>
The antiglare layer having the pattern shown in FIG. 9 was formed in the same manner as the antiglare layer 3 to obtain an antiglare film 4.

<< Formation of Antiglare Layer 5 >>
The antiglare layer having the pattern shown in FIG. 10 was formed in the same manner as the antiglare layer 3 to obtain an antiglare film 5.

  Subsequently, the following low refractive index layer was provided on the antiglare films 1 to 5 to produce antiglare antireflection films 1 to 5.

<< Preparation of antireflection layer (low refractive index layer 1) >>
First, composite particles were prepared.

(Preparation of composite particles P-1)
A reaction mother liquor was prepared by mixing 100 g of silica sol having an average particle diameter of 5 nm and a SiO2 concentration of 20 mass% and 1900 g of pure water, and heated to 80 ° C. The pH of this reaction mother liquor was 10.5, and 9000 g of a 1.5 mass% sodium silicate aqueous solution as SiO2 and 9000 g of a 0.5 mass% sodium aluminate aqueous solution as Al2O3 were simultaneously added to the mother liquor. Meanwhile, the temperature of the reaction solution was kept at 80 ° C. The pH of the reaction solution rose to 12.5 immediately after the addition of sodium silicate and sodium aluminate, and hardly changed thereafter. After completion of the addition, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a dispersion (A) of SiO 2 · Al 2 O 3 porous particle precursor having a solid content concentration of 20% by mass. (First step)
1900 g of pure water was added to 100 g of the dispersion (A) of the porous particle precursor obtained above and heated to 95 ° C., and while maintaining this temperature, an aqueous sodium silicate solution (1.5 g mass% as SiO 2) 27000 g and 27000 g of an aqueous sodium aluminate solution (0.5% by mass as Al 2 O 3) were gradually added at the same time, and particle growth was performed using the particles of the dispersion liquid (A) of the porous particle precursor as seed particles. After completion of the addition, the mixture was cooled to room temperature, washed with an ultrafiltration membrane, and concentrated to obtain a dispersion (B) of a SiO 2 · Al 2 O 3 porous particle precursor having a solid content concentration of 20% by mass. (First step)
500 g of this porous particle precursor dispersion (B) is taken, and then the aluminum salt dissolved in the ultrafiltration membrane is separated while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, and a part of aluminum is removed. A dispersion (C) of SiO 2 / Al 2 O 3 porous particles was prepared. (Second step)
A mixture of 1500 g of the porous particle dispersion (C), 500 g of pure water, 1750 g of ethanol and 626 g of 28% ammonia water was heated to 35 ° C., and then 104 g of ethyl silicate (SiO 228 mass%) was added. The surface of the porous particles was coated with a hydrolyzed polycondensate of ethyl silicate. Next, after concentration to a solid content concentration of 5% by mass with an evaporator, ammonia water with a concentration of 15% by mass was added to adjust the pH to 10, and heat treatment was performed at 180 ° C. for 2 hours in an autoclave. A dispersion of the substituted composite particles (P-1) having a solid content concentration of 20% by mass was prepared. (Third step)
Table 2 shows the average particle diameter, SiO2 / MOx (molar ratio), and refractive index of the composite particles (P-1). Here, the average particle diameter was measured by a dynamic light scattering method, and the refractive index was measured by the following method using Series A, AA made by CARGILL as a standard refractive liquid.

<Measuring method of particle refractive index>
(1) The particle dispersion is taken in an evaporator and the dispersion medium is evaporated.

  (2) This is dried at 120 ° C. to obtain a powder.

  (3) A standard refraction liquid having a known refractive index is dropped on a glass plate of a few drops, and the above powder is mixed therewith.

  (4) The operation of (3) above is performed with various standard refractive liquids, and the refractive index of the standard refractive liquid when the mixed liquid becomes transparent is used as the refractive index of the colloidal particles.

<Surface treatment and coating of low refractive index layer 1>
(surface treatment)
The above antiglare films 1 to 5 are immersed in a 1.5N-NaOH aqueous solution heated to 50 ° C. for 2 minutes for alkali treatment, washed with water, and then immersed in a 0.5 mass% -H 2 SO 4 aqueous solution at room temperature for 30 seconds. It was tempered, washed with water and dried.

(Preparation of low refractive index layer 1)
The average particle size is 60 nm and the refractive index is 1. with respect to a matrix in which Si (OC ₂ H ₅ ) ₄ is mixed at 95 mol% and CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ is mixed at 5 mol%. A low refractive index coating agent was prepared by adding 50% by mass of 38 composite particles (P-1), using 1.0N-HCl as a catalyst, and further diluting with a solvent. A coating solution is applied with a film thickness of 0.1 μm on the antiglare hard coat film subjected to the above surface treatment using a micro gravure method, dried at 120 ° C. for 1 minute, and irradiated with ultraviolet rays to have a refractive index of 1.41. The low refractive index layer 1 was formed.

  Next, a polarizing plate was prepared using each antiglare 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 anti-glare antireflection film 1-5, 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 on the side to be 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 antiglare 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: The polarizing film prepared in Step 4 in a dryer at 80 ° C., the cellulose ester film, and the antiglare antireflection films 1 to 5 are dried for 2 minutes to prepare polarizing plates 1 to 5. did. For the polarizing plate used on the back side of the display device, a polarizing plate protective film prepared in the same manner using a cellulose ester film (KC8UY, manufactured by Konica Minolta Opto) and the cellulose ester film R is used. did.

<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 = 70000, Mw = 220,000, Mw / Mn = 3.14)
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 weight Tinuvin 109 (manufactured by Ciba Specialty Chemicals) 4 parts by weight Tinuvin 171 (manufactured by Ciba Specialty Chemicals) 4 parts by weight Tinuvin 326 (manufactured by Ciba Specialty Chemicals) 2 parts by weight The solution was put into a container, heated, and completely dissolved and filtered while stirring.

  To this was added 20 parts by mass of silicon dioxide dispersion diluent E 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 many rolls, slitting to a width of 1.4 m, knurling with a width of 15 mm and an average height of 10 μm was applied to both ends of the film, and wound up. 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 4000 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 (VA cell) previously bonded was peeled off, and the prepared polarizing plates 1 to 5 were bonded to the glass surface of the liquid crystal cell, respectively.

  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 5 were respectively produced. Moreover, the used polarizing plate was arrange | positioned so that the glare-proof property of a screen upper part might become high. That is, the polarizing plate 2 was cut out in the cut-out panel shape shown in FIG. 11C, and the polarizing plates 3 to 5 were cut out in the shape shown in Table 3 (uneven pattern in the screen of the display device). .

<Evaluation>
Using the obtained liquid crystal display devices 1 to 5, it is observed in an environment as shown in FIG. 13, and the anti-glare effect, the visibility, and the black margin when displaying a video are visually observed according to the following criteria, respectively. evaluated. In addition, 10 40W fluorescent lamps (FLR40S-EX-D / M manufactured by Matsushita Electric) were installed on the ceiling. Moreover, it evaluated in the state which external light inserts from a window.

(Anti-glare effect)
Illumination and reflection of external light were evaluated as follows.

○: The outline of the fluorescent lamp and the external light are blurred and the reflection is not noticeable. △: The outline of the fluorescent lamp and the reflection of the external light are slightly recognized. X: The outline of the fluorescent lamp and the external light are understood. I'm worried about the reflection (glare)
About the produced display apparatus, the glare was determined visually.

◎: Glare is not known at all ○: Glare is slightly understood △: Slight glare is observed ×: Glare is very worrisome (Visibility and black spots when video is displayed)
As described above, a moving image of a TV program was displayed on the same display in an environment where artificial lighting by a fluorescent lamp and external light from a window were inserted from the ceiling, and a comparative experiment was performed. A moving image was observed at a position 1 m away from the front of the display, and sensory evaluation was performed.

○: The upper part of the screen does not bother the reflection of fluorescent light, and the central part of the screen looks black even when there is external light. There is no sense of incongruity during observation or immediately after observation. A slight reflection of the light is observed, and if there is external light in the center of the screen, the black color is slightly lacking and slightly tired after observation. X: A slight reflection of the fluorescent light is observed at the top of the screen, and the center of the screen Table 3 below shows the above evaluation results.

  The liquid crystal display devices 2 to 5 using the antiglare antireflection film of the present invention have an excellent antiglare effect with respect to the comparative liquid crystal display device 1 without being concerned about reflection of reflected light due to upper illumination and external light. It was also found that the blackness at the time of displaying visibility and moving images can be improved.

  In other words, it has an excellent anti-glare effect against the image of the upper part of the screen due to lighting from the ceiling, etc., and even with the influence of external light, the contrast at the center of the screen etc. is high and black spots are visible at the same time It was possible to provide a display device with excellent performance.

It is a schematic diagram which shows an example which provided the glare-proof layer which consists of uneven structure with an inkjet system on a transparent base material. It is sectional drawing which shows an example of the other uneven structure which comprises the glare-proof layer which concerns on this invention. 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 of forming a finer concavo-convex structure with an ink droplet having a smaller particle diameter after forming a fine structure with an ink droplet having a larger particle size by an inkjet method. It is a schematic diagram which shows an example of the flow which provides an anti-glare layer by the inkjet system on a transparent base material, and manufactures an anti-glare antireflection film. It is a schematic diagram of the fine uneven | corrugated pattern on the elongate anti-glare film which concerns on this invention. It is a schematic diagram of the other example of the fine uneven | corrugated pattern on the elongate anti-glare film which concerns on this invention. It is a schematic diagram of another example of the fine uneven | corrugated pattern on the elongate anti-glare film which concerns on this invention. It is an example of the display apparatus screen which has the various uneven | corrugated pattern which concerns on this invention. It is an example of the display apparatus screen which has the various uneven | corrugated pattern which concerns on this invention. It is the figure which showed typically reduction of the reflected light when the anti-glare antireflection film which concerns on this invention is applied to a liquid crystal display device.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1,502, F Transparent base material 2 Hard-coat layer 3, 31 Ink droplet 10 Inkjet head 12 Piezoelectric element 29, 106A-E Actinic ray irradiation part 35 Back roll 51 Endless stainless steel belt 52 Die 53 Drying zone 55 Casting part 56 Peeling part 101 Film original winding 102 Cutting panel 103 Large uneven part 104 Small uneven part 501 Lamination roll 503 First coater 504A, B Back roll 505A, B Drying zone 507 Plasma processing part 508 Ink supply tank 509 Inkjet emitting part 510 Heating part

Claims (8)

A long anti-glare film characterized in that an anti-glare layer having different anti-glare properties in the width direction or the long direction is provided. 2. The antiglare layer according to claim 1, wherein at least one of centerline average roughness Ra, haze, and average length Sm of the contour curve element is different in the width direction or the length direction. Long anti-glare film. 3. The antiglare antireflection film, wherein the long antiglare film according to claim 1 further comprises an antireflection layer. A polarizing plate having an anti-glare layer having different anti-glare properties in one polarizing plate and an optical compensation film on the back side thereof. A display device comprising an anti-glare layer having different anti-glare properties within one display screen. The display device according to claim 5, wherein an anti-glare layer having different anti-glare properties is provided in the central portion and the upper portion or the left and right portions. An anti-glare processing method comprising providing anti-glare layers having different anti-glare properties on one sheet-like or plate-like member. The antiglare processing method according to claim 7, wherein the antiglare layer is formed by adhering ink droplets containing an antiglare imparting composition.

Images