WO2007046275A1

WO2007046275A1 - Glareless film, polarizing plate and display

Info

Publication number: WO2007046275A1
Application number: PCT/JP2006/320254
Authority: WO
Inventors: Sota Kawakami; Daiki Minamino
Original assignee: Konica Minolta Opto, Inc.
Priority date: 2005-10-19
Filing date: 2006-10-11
Publication date: 2007-04-26
Also published as: JPWO2007046275A1

Abstract

A glareless film in which reflection of external light and deterioration in contrast can be prevented effectively without causing deterioration in sharpness of a high by fine image due to reduction in pixel size, and a desired structure of micro protrusions and recesses is formed effectively and stably with high productivity. A polarizing plate and a display employing such glareless film are also provided. The glareless film has 10-10,000 micro protrusion structures per 1 mm2 on a base material film. In the micro protrusion structure, the long diameter of dot is 1-30 μm and the dot height is 0.5-10μm. Furthermore, a transparent resin layer is formed to cover the protrusion structure and the refractive index of the protrusion structure and that of the transparent resin layer are identical.

Description

Specification

Anti-glare film, polarizing plate and display device

Technical field

The present invention relates to an antiglare film, a polarizing plate and a display device, and has an antiglare film, a polarizing plate and an antiglare film which are excellent in antiglare property and have a desired fine uneven structure formed effectively and stably with high productivity. It relates to a display device.

Background art

In recent years, development of thin and light notebook personal computers has progressed. Along with this, the demand for thinner and higher performance protective films for polarizing plates used in display devices such as liquid crystal display devices is also increasing. In addition, an anti-reflection layer is provided to improve visibility, and an anti-glare layer that scatters reflected light with an uneven surface to obtain a display performance with less glare and less glare is provided. Liquid crystal image display devices (also known as liquid crystal displays) such as word processors and word processors have come to be widely used.

[0003] Various types and performance improvements of antireflection layers and antiglare layers have been made depending on applications, and various front plates having these functions are bonded to polarizers of liquid crystal displays, etc. A method of imparting an antireflection function or an antiglare function is used to improve visibility.

[0004] The antiglare layer reduces the visibility of the reflected image by blurring the outline of the image reflected on the surface, and the reflected image is reflected when using an image display device such as a liquid crystal display, an organic EL display, or a plasma display. It is intended not to worry about the complexity.

[0005] By providing an appropriate fine concavo-convex structure on the outermost surface of the front plate of the image display device, the above-described properties can be provided. For example, there are various methods such as a method using fine particles (for example, see Patent Document 1) and a method for embossing the surface (for example, see Patent Document 2).

[0006] However, in the method using fine particles, since the fine uneven structure is formed only by containing fine particles in the binder layer, it is necessary to appropriately disperse the fine particles. Anti-glare film that is difficult to form effectively and stably As a result, there was a great obstacle to obtaining a sufficient glare prevention effect. In particular, the method using fine particles cannot control the density of the fine particles, and the height of the convex portions is higher than the surroundings in the portion where the fine particles overlap, so that a stable uniform uneven structure cannot be formed. It was a drawback. Also, the method of forming a fine concavo-convex structure by embossing is inferior in productivity, and in particular, it is extremely difficult to stably form a fine concavo-convex structure.

[0007] Patent Document 3 describes a method of forming fine unevenness using phase separation of rosin using spinodal decomposition, but the state of phase separation changes depending on the reaction conditions and immediately stabilizes the antiglare film. Difficult to make.

[0008] Patent Document 4 discloses a technique in which a hard coat layer is provided on a cured resin dispersed in a dot shape so as to have a smooth surface. However, in the invention, the antiglare property is exhibited. In the present invention, it is not intended to smooth the film surface.

[0009] In recent years, a display device having anti-glare properties and high contrast has been demanded as image quality has been improved. For example, on the outermost surface of a liquid crystal display device, a conventional antiglare film such as a fine particle method has insufficient contrast, and a clear hard coat antireflection film has a problem of reflection of external light. In order to cope with this drawback, a number of technologies relating to an antiglare antireflection film in which an antireflection layer (low refractive index layer) due to light interference is coated on an antiglare film have been proposed (for example, Patent Document 3). (See ~ 8)) ₀ However, in order to obtain a display device with higher visibility, it is difficult to obtain sufficient anti-glare property and contrast.

[0010] Further, Patent Document 11 describes that an anti-glare node coat film is provided with an overcoat layer, which is intended for antifouling properties, easy cleaning properties, light reflection prevention properties, and the like. In the present invention, V, there is no description about covering the convex structure and exhibiting antiglare properties!

Patent Document 1: Japanese Patent Application Laid-Open No. 59-58036

Patent Document 2: JP-A-6-234175

Patent Document 3: Japanese Patent Laid-Open No. 2005-227407

Patent Document 4: Japanese Unexamined Patent Publication No. 2000-84477

Patent Document 5: Japanese Patent Laid-Open No. 2001-281410

Patent Document 6: Japanese Patent Application Laid-Open No. 2004-4404 Patent Document 7: Japanese Unexamined Patent Application Publication No. 2004-125985

Patent Document 8: Japanese Unexamined Patent Application Publication No. 2004-24967

Patent Document 9: Japanese Unexamined Patent Application Publication No. 2004-4777

Patent Document 10: Japanese Unexamined Patent Publication No. 2003-121620

Patent Document 11: Japanese Unexamined Patent Publication No. 2003-26832

Disclosure of the invention

Problems to be solved by the invention

Accordingly, the present invention has been made in view of the above problems, and its purpose is to capture external light and reduce contrast without reducing the sharpness of high-definition images due to pixel size reduction or the like. An object of the present invention is to provide an anti-glare film that can effectively prevent a decrease and has a desired fine relief structure formed effectively and stably with good productivity, and further to provide a polarizing plate and a display device using the anti-glare film.

Means for solving the problem

[0012] The above object of the present invention has been achieved by the following constitution.

[0013] 1. On a base film, 10 to 10 LOOOO fine convex structures with a major axis of dots of 1 to 30 μm and a dot height of 0.5 to 10 μm per lmm ² And an antiglare film characterized in that a transparent resin layer is formed so as to cover the convex structure part, and the refractive index of the convex structure part and the transparent resin layer is the same. .

[0014] 2. The antiglare film as described in 1 above, wherein an antireflection layer or an antifouling layer is further formed on the transparent resin layer.

[0015] 3. Surface roughness (R a) force of antiglare layer surface constituted by the convex structure part and the transparent resin layer 0 to: LOOOnm, average center distance (Sm) force of convex part or concave part 3. The antiglare film as described in 1 or 2 above, which is from 0 to 200 μm.

[0016] 4. The antiglare film according to any one of 1 to 3 above, wherein the thickness of the transparent resin layer is 1 to 5 m thicker than the height of the convex structure portion. .

[0017] 5. The antiglare film as described in any one of 1 to 4 above, wherein the convex structure part or the transparent resin layer is an actinic ray curable resin.

[0018] 6. The convex structure part or the transparent resin layer is a thermosetting resin. 5. The antiglare film according to any one of 1 to 4 above.

[0019] 7. The convex structure is formed from an ink composition containing at least 60% by mass of at least one solvent having a boiling point of 140 to 250 ° C and a viscosity measured at 25 ° C of 1 to 15 mPa's. The antiglare film according to any one of 1 to 6 above, which is characterized in that

[0020] 8. The antiglare film as described in 7 above, wherein the solvent is a compound represented by the following general formula (1).

Formula (1) Rl— O— (C H -0) n-R2

2x

Rl, R2: hydrogen atom, aryl group, alkyl group having 1 to 6 carbon atoms, alkoxyalkyl group, alkylcarbonyl group. The hydrocarbon chain may be linear or branched. However, at least one of Rl and R2 is a substituent other than a hydrogen atom.

n: Integer from 1 to 3

x: integer from 2 to 4

9. A polarizing plate characterized by using the antiglare film described in any one of 1 to 8 above.

[0021] 10. A display device using the antiglare film described in any one of 1 to 8 above and the polarizing plate described in 9 above.

The invention's effect

[0022] According to the present invention, it is possible to effectively prevent the reflection of external light and the decrease in contrast without reducing the sharpness of a high-definition image due to the reduction in pixel size, etc., and to produce a desired fine uneven structure. We were able to provide an anti-glare film that was well effective and stable, and also provided a polarizing plate and a display device using it.

Brief Description of Drawings

[0023] FIG. 1 is a schematic view showing a state where gentle irregularities are formed by covering both a convex structure portion and a portion without a convex structure portion with a transparent resin layer.

FIG. 2 is a schematic view of a fine concavo-convex structure portion preferable for the present invention.

FIG. 3 is a schematic diagram showing an example of flexographic printing used in the present invention.

[Fig. 4] A schematic diagram of flexographic printing by the two-roll method.

FIG. 5 is a schematic diagram of flexographic printing in which ink is supplied by an extrusion coater. FIG. 6 is a perspective view of an arlock roll.

FIG. 7 is a perspective view for explaining an AROX cell.

FIG. 8 is a cross-sectional view showing an example of an ink jet head that can be used in the ink jet method according to the present invention.

FIG. 9 is a schematic view showing an example of an inkjet head unit and a nozzle plate that can be used in the present invention.

FIG. 10 is a schematic diagram showing an example of an ink jet system that can be preferably used in the present invention.

FIG. 11 is an example of a method for forming a fine relief structure on a base film by flexographic printing.

[12] FIG. 12 is a diagram schematically showing an environment during observation when an antiglare antireflection film is applied to a liquid crystal display device.

[13] FIG. 13 is a view showing an effect of improving the antiglare property by covering the transparent resin layer.

Explanation of symbols

1 Seamless grease version

2 Oil-resisting roll

3 plate cylinder

4 Annix Throw

5 impression cylinder

6 Doctor blade

7 Phanten Ronore

8 Ink

9 Extrusion coater

10 Base film

11 Board

12 Piezoelectric element

13 Channel plate

13a Ink flow path b Wall

Common liquid chamber components Ink supply pipe Nozzle plate a Nozzle

Driving circuit printed board Lead part

Driving electrode

Groove

Protective plate

Fluid resistance

24 electrodes

Upper partition

Heater

Heater power

Heat transfer member

Actinic ray irradiation part Inkjet head Droplet

Nozzle

Noc Ronore

1 Fino Rem Ronore Base film coater

A, B, C Knock Roulette A, B Drying zone A, B, C UV irradiation part Ink supply tank 509 flexo oil and fat version

510 A Rock Throw

BEST MODE FOR CARRYING OUT THE INVENTION

[0025] The following is a detailed description of the best mode for carrying out the present invention. The present invention is not limited to these.

[0026] As a result of intensive studies on the above problems, the present inventors have found that the dots are separated from each other as described in Patent Document 11, and only the dots are in the state of a flat substrate between the dots. However, the flat base material portion does not exhibit satisfactory anti-glare properties, but by overcoating, the inter-dot flat base material portion is covered with an inclined overcoat, and the anti-glare property is remarkably improved. It is a thing.

FIG. 13 is a diagram showing the effect of improving the antiglare property by covering the transparent resin layer.

[0028] (Anti-glare evaluation method)

Using a dot-only anti-glare film and an anti-glare film coated with a transparent resin layer as a sample, measure the reflection angle distribution using Op-Tech's Go-Off Otometer GP-1-3D . Emitted diameter φ = 10mm, Received diameter φ = 3mm ₀

[0029] The numerical value 眩 of anti-glare property is expressed as a logarithmic value of an integral value of scattered light intensity at a scanning angle ± 1 to 3.5 ° (excluding a regular reflection region).

[0030] From the results of FIG.

[0031] Logarithm of scattered light intensity integral value Antiglare property

Dot only —1.5 low

Cover the dots with a transparent resin layer 0.48 High

The anti-glare film of the present invention has 10 to 10,000 fine convex structures per 1 mm ² on a base film having a long diameter of 1 to 30 111 and a dot height of 0.5 to 10 m. And a transparent resin layer is formed so as to cover the convex structure portion, and the refractive index of the convex structure portion and the transparent resin layer is the same.

[0032] The antiglare film of the present invention is prepared by forming the convex structure part (also referred to as a dot) by a pattern production method such as a gravure method, a screen printing method, a flexographic printing method, or an ink jet method. Is cured by actinic rays or heating, and then a microgravure method, It is produced by uniformly coating a transparent resin layer by a thin film uniform coating method such as an extrusion coating method, a wire bar method, a spray coating method, a flexographic printing method, or an ink jet method. At this time, the convex structure has a certain random arrangement in the plane by means of FM screening and the like, and the height is uniformly produced within a certain range, so that the surface roughness (Ra) is stable over the entire surface. In addition, since the unevenness is not formed at a uniform interval, moire is not generated between the pixels of the display. By appropriately setting the height of the convex structure and the film thickness of the transparent resin layer, irregularities with an appropriate and stable surface roughness are formed on the surface of the transparent resin layer, while maintaining the antiglare effect. Since haze increase due to light scattering is suppressed and white turbidity due to scattered light is suppressed, a high-contrast image can be seen. In addition, by making the refractive index of the convex structure portion the same as the refractive index of the transparent resin layer, it is possible to suppress the internal scattering effect and to suppress the glare of transmitted light from the display side.

[0033] According to the above gravure method, screen printing method, flexographic printing method, ink jet method, etc., the present inventors have an anti-glare property having a convex structure even at a printing speed of 10 mZ / min or more and 500 mZ / min. Films can be produced, and it is possible to effectively prevent external light reflection and contrast reduction without reducing the sharpness of high-definition images. · It has been found that a stably formed antiglare film can be obtained, and an antiglare antireflection film, a polarizing plate and a display device using the same can be obtained.

[0034] The method for forming the convex structure is not particularly limited, but in particular, the flexographic printing method has a high production speed and can form a fine convex structure, and the inkjet method has the presence of the convex structure. It is excellent in that the pattern can be changed flexibly, the cross-sectional shape of the convex structure can be formed into a bowl shape, and the surface shape after the provision of the transparent resin layer is smoothed into gentle irregularities.

[0035] Hereinafter, the present invention will be described in detail.

[0036] << Convex structure, transparent resin layer >>

The convex structure (also referred to as a dot) in the present invention will be described with reference to the drawings.

[0037] FIG. 1 shows that a convex structure portion is formed in a pattern on a base film, and a transparent resin layer is applied to form a transparent resin layer on both the convex structure portion and the portion without the convex structure portion. By covering It is the schematic diagram which showed a mode that a gentle unevenness | corrugation was formed.

[0038] The height of the dots defined in the present invention is defined as the height from the base film surface as a base to the top of the convex structure, and the long diameter of the dots is in contact with the base. Convex structure is defined as the maximum bottom length.

[0039] The fine convex structure portion on the surface can be measured by a commercially available stylus type surface roughness measuring machine or a commercially available optical interference type surface roughness measuring machine. For example, an optical interference type surface roughness measuring instrument [Accordingly, the range of about 4000 μm ² (55 m X 75 m)] [Two! As shown above, the colors are displayed and the height of the convex portion relative to the film surface and the diameter of the convex portion, which is the major axis of the convex structure portion, are measured. The number of convex structures can be obtained by converting the number of convex structures obtained per lmm ² . These measurements are taken as the average value of any 10 points in the relevant part of the substrate film.

[0040] FIG. 2 is a schematic view of a concavo-convex structure that is preferable for the present invention formed on a substrate film and is coated with a transparent resin layer.

[0041] Fig. 2 (a) is a perspective view of the convex structure portion, and (b) is a cross-sectional view.

[0042] The height of the convex portion when the surface roughness (Ra) is determined is indicated by e in the figure, and is the difference in height between the convex portion and the concave portion. The concavo-convex structure on the surface of the transparent resin 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, unevenness is measured two-dimensionally within a certain range with an optical interference type surface roughness measuring instrument, and the unevenness is color-coded as contour lines from the bottom side and displayed. Here, the height is determined with respect to the concave bottom adjacent to each fine concavo-convex structure as an average value.

[0043] The average center-to-center distance (Sm) between adjacent convex portions or concave portions is the same as that defined as the average length of the contour element curve in JIS B0601, and g (in this case, the convex portion) ), And the average of the distance between the centers of adjacent convex portions or concave portions with the vertex of the convex portion or concave portion as the center of the convex portion or concave portion. The average distance between convex parts or concave parts can be measured with a stylus type surface roughness measuring machine, etc. It is possible to obtain knowledge as a surface roughness curve by scanning the surface in a certain direction, measuring the movement change in the vertical direction of the measuring needle in that case, and recording the change. Measure the distance between Can be sought. Alternatively, it can be measured by an optical interference type surface roughness measuring machine as described above.

[0044] The surface roughness (Ra) defined in the present invention is defined by JIS B0601, and is a value obtained by the following formula expressed in micrometers (μm).

[0045] [Equation 1]

Ra = ^ | ^ | f (x dx

[0046] As a method of measuring the surface roughness (Ra), the measurement samples are measured in the above environment after being conditioned for 24 hours under the condition that the measurement samples do not overlap each other in an environment of 25 ° C and 65% RH. Can be requested. 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 with the sample sandwiched between them, a frame made of cardboard, etc., and fixing the four corners One of the methods. Examples of measuring devices that can be used include RSTPLUS non-contact three-dimensional micro surface shape measuring system (a typical example of an optical interference type surface roughness measuring machine) manufactured by WYKO.

[0047] The surface roughness (Ra) of the concavo-convex structure on the surface of the transparent resin layer of the present invention is from 50 to: LOOOnm, more preferably from 100 to 500 nm. The average distance between the centers (Sm) of the uneven structure on the surface of the transparent resin layer is preferably 10 to 200 μm, more preferably 10 to 50 μm. Beyond these ranges, it becomes difficult to achieve both an antiglare effect and contrast. Ra and Sm above are the height of the convex structure, the arrangement of the convex structure pattern, the adjustment of the thickness of the transparent resin layer, and the ink composition used for the transparent resin layer (ink liquid). It can be controlled by adjusting physical properties such as viscosity.

[0048] It is necessary for obtaining the effect of the present invention that the convex structure portion of the present invention and the transparent resin layer have the same refractive index, but the difference is that the refractive index difference is less than 0.02. Indicates that Furthermore, it is more preferable that the refractive index difference power ^.

[0049] The refractive index of the convex structure portion and the transparent resin layer is measured by applying an ink composition that forms the convex structure portion and the transparent resin layer to a substrate film, and applying the obtained film to the refractive index. It can be obtained by measuring with a meter. [0050] For example, the ink composition for forming the convex structure part and the transparent resin layer is applied using a micro gravure coater, dried at 90 ° C, and then the illuminance of the irradiated part is 0 using an ultraviolet lamp. lWZcm ² with an irradiation dose of 0.UZcm ² , cure the coating layer to form a 5 m thick film, and measure the refractive index with an Abbe refractometer.

[0051] Since the refractive index of the convex structure portion and the transparent resin layer is the same, internal scattering does not occur in the antiglare layer, and an image with high transparency and high blackness can be obtained.

[0052] In order to make the refractive index of the convex structure portion and the transparent resin layer the same, it is possible to adjust by appropriately selecting the material and configuration of the ink composition.

[0053] The convex structure portion has a dot major axis of 1 to 30 μm, more preferably 3 to 10 μm, and a dot height of 0.5 to: LO / zm, more preferably 2 to 5 m. The dot arrangement that preferably has a certain size and height is preferably random arrangement by a method such as FM screening. Here, the major axis of the dot represents the diameter when the dot is circular, and the diameter converted into the same area when the dot is triangular, quadrangular, polygonal or indefinite. The height of a dot means the difference in height of the highest part of a dot from a base film surface as above-mentioned.

[0054] The FM screening method is a method of expressing light and shade by modulating the interval between dots, that is, the frequency, and the frequency (dot density) of hitting basic dots. FM screening methods are sometimes called random 'screening methods or strike stick' screening methods. The FM screening method refers to a method of modulating the periodicity, that is, the interval between dots. Specifically, Crystal Raster 'screening method (Agfa' Gevart '), Diamond' Screen method (Rhinotype 'Hell'), Class' screening method and full tone screening method (Cytex), Velvet screening method (Udala Koichihan), Accutone Screening (Dannery), Megadot 'Screening (American' Color '), Clear' Screening (Shiichiritsu), Monet 'Screening (Parco) ) Etc. are known. All of these methods have different dot generation algorithms, but are methods of expressing shading by changing the dot density, and can be said to be various aspects of the FM screening method.

In FM screening, the size of the dot on which ink is placed is constant, and the frequency of dot appearance changes according to the density of the image. The size of each dot in FM screening Since it is smaller than the halftone dot, it is possible to reproduce the required pattern with high resolution. Unlike so-called halftone dots, dots in FM screening are not periodically arranged. In FM screening, since the dot arrangement is not periodic, moire does not occur! / ,!

[0056] The transparent resin layer of the present invention is coated on the above-mentioned convex structure portion, and covers the convex structure portion, so that the unevenness formed only by the convex structure portion becomes smooth, and a preferable surface shape. As a result, excellent antiglare properties can be exhibited.

[0057] The thickness of the transparent resin layer is preferably 1 to 5 µm thicker than the height of the convex structure portion. Further, in order to cover the entire surface of the convex structure part, the coating film thickness is preferably 2 to 5 times the height of the convex structure part. If the coating solution is thick, the convex structure can be covered completely, but if it is too thick, it is affected by drying unevenness during drying and the uniformity of the thickness is impaired. It is preferable that 50% or more of the resin contained in the transparent resin layer is the same as the resin used in the convex structure part. This allows sufficient adhesion between the convex structure part and the transparent resin layer. And the refractive index can be made the same.

(Ink composition for forming convex structure part and transparent resin layer)

In the present invention, the composition forming the convex structure part and the transparent resin layer is referred to as an ink composition.

[0059] The ink composition for forming the convex structure portion and the transparent resin layer according to the present invention is not particularly limited, but is an actinic ray curable resin, a photopolymerization initiator, a photoreaction initiator, It preferably contains a photosensitizer, thermosetting resin, thermoplastic resin, ultraviolet absorber, fine particles, solvent and the like. As the solder, the above-mentioned actinic ray curable resin or thermosetting resin is preferable.

[0060] The refractive index of the ink composition can be selected in the range of 1.35-19-1. The transmittance of the ink composition is 80% or more, preferably 90% or more.

[0061] The viscosity of the ink composition is preferably 0.1 to 20 mPa's at a measurement temperature of 25 ° C, more preferably 0.5 to LOmPa's. If the viscosity is less than 0.5 mPa's, the viscosity is too low to obtain a convex structure pattern of the desired shape, and if it exceeds 20 mPa's, the fluidity of the ink is poor and the transferability of the ink is reduced. It is not preferable. [0062] Regarding the viscosity of the ink composition, at least one solvent having a boiling point of 140 to 250 ° C and a viscosity measured at 25 ° C of 1 to 15 mPa's described later is used in an amount of 60% by mass or more of the ink composition. It is preferable to adjust by this.

[0063] The viscosity of the ink is measured using a rotational, vibration, or capillary type viscometer that is not particularly limited as long as it has been tested with a standard solution for viscometer calibration specified in JIS Z 8809. be able to. The viscometer can be measured with Saybolt viscometer, Redwood viscometer, etc.For example, Tokimec, cone-plate E viscometer, Toki Sangyo E Type Viscome ter (rotary viscometer), Tokyo Keiki For example, B-type viscometer BL manufactured by Yamashita Electric Co., Ltd., FVM-80A manufactured by Yamaichi Electronics Co., Ltd., Viscoliner manufactured by Nametore Industry Co., Ltd., VISCO MATE MODEL VM-1 A manufactured by Yamaichi Electric Co., Ltd., and the like.

[0064] The actinic ray curable resin preferably used as the ink composition for forming the convex structure portion and the transparent resin layer of the present invention will be described.

[0065] 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 and an electron beam curable resin, and a resin that is cured by irradiation with an actinic ray other than an ultraviolet ray or an electron beam.

[0066] Examples of the ultraviolet curable resin include, for example, an ultraviolet curable acrylic urethane resin, an ultraviolet ray curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, and an ultraviolet curable polyol acrylate resin. Examples thereof include a resin and an ultraviolet curable epoxy resin.

[0067] UV-curable acrylic urethane-based resins are generally obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer, and further adding 2-hydroxy cetyl acrylate, 2-hydroxy ethynole methacrylate. (Hereinafter, only acrylate is included in the acrylate as including methacrylate), and 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 Dudic 17-806 (Dainippon Ink Co., Ltd.) and 1 part Coronate L (Nihon Polyurethane Co., Ltd.) described in JP-A-59-151110 is preferably used. It is done. [0068] UV-curable polyester acrylate resins generally have a hydroxyl group or carboxyl group at the end of a polyester reacted with a monomer such as 2-hydroxyethyl acrylate, glycidyl acrylate, or acrylate. It can be easily obtained (for example, JP-A-59-151112).

[0069] 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.

[0070] Examples of ultraviolet curable polyol acrylate-based resins include ethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane tritalylate, and pentaerythritol. Examples thereof include triatalylate, pentaerythritol tetraatalylate, dipentaerythritol pentaatalylate, dipentaerythritol hexaatalylate, alkyl-modified dipentaerythritol pentaatalylate, and the like.

[0071] As examples of the ultraviolet curable epoxy acrylate resin and the ultraviolet curable epoxy resin, an epoxy actinic ray reactive compound preferably used is shown.

[0072] (a) Glycidyl ether of bisphenol A (this compound is obtained as a mixture having different degrees of polymerization by the reaction of epichlorohydrin and bisphenol A)

(b) A compound having a glycidyl ether group at the terminal by reacting a compound having two phenolic OH such as bisphenol A with epichlorohydrin, ethylene oxide and Z or propylene oxide

(c) 4,4'-Methylenebisphenol glycidyl ether

(d) Epoxy compound of phenol formaldehyde resin of novolak resin or resole resin

(e) Compounds having an alicyclic epoxide, such as bis (3,4-epoxycyclohexylmethyl) oxalate, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4 epoxy 6-cyclohex Xinolemethinole) adipate, bis (3,4-epoxycyclohexylmethyl pimelate), 3, 4 epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3, 4 epoxy 1-methylcyclohexylmethy Lou 3 ', 4' Epoxycyclohexanecarboxylate, 3, 4 Epoxy 1-methyl-cyclohexylmethyl 3 ', 4' —Epoxy! / -Methylcyclohexane force Ruboxylate, 3, 4 Epoxy-6-Methyl-cyclohexylmethyl-3 ', 4' Epoxy 6'-Methinore! / -Cyclohexanoyl norboxoxylate, 2 -— (3,4 epoxyoxycyclohexylene 5,, 5 '—spiro 3 ,,, 4 ,, —epoxy) cyclohexane metadioxane

(f) Diglycidyl ethers of dibasic acids such as diglycidyl oxalate, diglycidyl adipate, diglycidyl tetrahydrophthalate, diglycidino hexahydrophthalate, diglycidyl phthalate

( _g ) Diglycidyl ether of glycol, for example, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl etherate, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, copoly (ethylene glycol propylene glycol) diglycidyl Ether, 1,4 butanediol diglycidyl ether, 1,6 hexanediol diglycidino oleore

(h) Glycidyl ester of polymer acid, for example, polyglycidyl ester polyacrylate

(i) Glycidyl ethers of polyhydric alcohols such as glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetradalysidyl ether, dalco-triglycidyl ether

(j) The diglycidyl ether of 2-fluoroalkyl-1,2-diol is the same as the compound examples given in the fluorine-containing epoxy compound of the fluorine-containing resin of the low refractive index substance.

Examples of the (k) fluorine-containing alkane-terminated diol daricidyl ether include fluorine-containing epoxy compounds of fluorine-containing resins having the above-described low refractive index materials.

The molecular weight of the epoxy compound is 2000 or less as an average molecular weight, preferably 1000 or less. [0074] When the above epoxy compound is cured with actinic rays, it is effective to use a compound having a polyfunctional epoxy group of (h) or (i) in order to increase the hardness. is there.

[0075] The photopolymerization initiator or photosensitizer for cationically polymerizing the epoxy-based actinic ray reactive compound is a compound capable of releasing the cationic polymerization initiator by irradiation with actinic rays, and is particularly preferable. Is a group of double salts that release a Lewis acid capable of initiating cationic polymerization upon irradiation.

[0076] The actinic ray-reactive composite epoxy resin forms a polymerized, crosslinked structure or network structure by cationic polymerization rather than by radical polymerization. Unlike radical polymerization, it is a preferred actinic ray-reactive resin because it is not affected by oxygen in the reaction system.

[0077] 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 upon irradiation with light is particularly preferred! /.

[0078] A typical example is a compound represented by the following general formula (a).

[0079] General formula (a)

[(R ¹ ) (R ² ) (R ³ ) (R ⁴ ) Z] ^ [MeX] ^w "

a b e d v

Where the cation is o-um and Z is S, Se, Te, P, As, Sb, Bi, 0, halogen (eg, I, Br, CI), or N = N (diazo) Yes,

R ⁴ is an organic group 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 the metal or metalloid that is the central atom of the halide complex. B, P, As ゝ Sb ゝ Fe ゝ Sn ゝ Bi ゝ Al, Ca ゝ In, Ti, Zn ゝ 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.

[0080] Anions of the above general formula (a) [Specific examples of MeX Γ- include tetrafluoroborate (BF-), tetrafluorophosphate (PF-), tetrafluoroantimonate (SbF -), Tetra

4 4 4 Fluoroarsenate (AsF-), Tetrachrome mouth antimonate (SbCl-), etc.

4 4

I can do it. [0081] Other anions include perchlorate ion (CIO "), trifluoromethyl sulfite.

Four

Ion (CF SO-), fonoreros norephonate ion (FSO-), tonorenos nolephonate ion,

3 3 3

And tri-trobenzene acid anion.

[0082] Among such salt salts, it is particularly effective to use an aromatic salt salt as a cationic polymerization initiator, and among them, JP-A-50-151996 and JP-A-50-158680. VIA group aromatic salts described in JP-A-50-151997, 52-30, ^ 159-55420, 55-125105, etc. Um salt, oxosulfoxo-um salt described in JP-A-56-8428, 56-149402, 57-192429, etc., and aromatic diazo-um salt described in JP-B-49-17040 The thiopyrilum salts described in U.S. Pat. No. 4,139,655 are preferred. Examples of the aluminum complex include photodegradable silicon compound-based polymerization initiators. The cationic polymerization initiator can be used in combination with a photosensitizer such as benzophenone, benzoin isopropyl ether or thixanthone.

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

[0084] In an ink composition containing an actinic ray curable resin useful for the present invention, the photopolymerization initiator is generally used in an amount of 100 parts by mass of an actinic ray curable epoxy resin (prepolymer). 0.1 to 15 parts by mass is more preferable, and an additive in the range of 1 to 10 parts by mass is preferable.

[0085] In addition, the epoxy resin can be used in combination with the urethane acrylate resin, polyether acrylate resin, etc. In this case, an actinic ray radical polymerization initiator and an actinic ray power thione polymerization initiator are used. It is preferable to use it together.

[0086] In the present invention, an oxetane compound can also be used as a photopolymerization initiator. V, the oxetane compound, has a three-membered oxetane ring containing oxygen or sulfur A compound. Among these, 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 aryloxy group, or an acetyloxy group. Specifically, 3,3-bis (chloromethyl) oxetane, 3,3-bis (odomethyl) oxetane, 3,3-bis (methoxymethyl) oxetane, 3,3-bis (phenoxymethyl) oxetane, 3-methyl- Examples include 3-chloromethyloxetane, 3,3-bis (acetoxymethyl) oxetane, 3,3-bis (fluoromethyl) oxetane, 3,3-bis (bromomethyl) oxetane, and 3,3-dimethyloxetane. In the present invention, any of a monomer, an oligomer and a polymer may be used.

[0087] Specific examples of the ultraviolet curable resin that can be used in the present invention include, for example, Ade force Optomer 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— 10

2, D—102, NS—101, FT—102Q8, MAG—1—P20, AG—106, M—101—C (manufactured by Guangei Chemical Co., Ltd.), Seika Beam PHC2210 (S), PHCX— 9 (K-3), PHC2213, DP-10, DP-20, DP-30, P1000, P1100, P1200, P130 0, P1400, P1500, P1600, SCR900 (above, manufactured by Dainichi Seiki Kogyo Co., Ltd.) , KRM703

3, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL292 02 (above, Daicel UC 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 (above, manufactured by Dainippon Ink & Chemicals, Inc.), Orex No. 340 Clear (made by China Paint Co., Ltd.) ), Sunrad H—601, RC—750, RC—700, RC—600, RC—500, RC—611, RC—612 (above, manufactured by Sanyo Kosei Co., Ltd.)

, SP-1509, SP-1507 (above, Showa Polymer Co., Ltd.), RCC-15C (Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (above, Dongguan) (Manufactured by Synthetic Co., Ltd.) or other commercially available ones.

[0088] The solid concentration of the actinic ray curable resin in the ink composition is 10 to 95% by mass, and the optimum concentration is selected depending on the coating method and the like.

[0089] Further, in the case where an ultraviolet curable resin is used as the actinic ray curable resin, the ultraviolet light is used. An ultraviolet absorber may be included in the ultraviolet curable resin composition so as not to interfere with the photocuring of the 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.

[0090] Specific examples of the ultraviolet absorber preferably used in the present invention include, for example, oxybenzozophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, Examples include, but are not limited to, nickel complex compounds.

[0091] The ink composition according to the present invention includes conductive fine particles such as SnO, ITO, and

2

It is also preferable to include an antistatic agent such as thione polymer particles. In the present invention, it is also preferable to add an antistatic agent to the transparent resin layer.

In the present invention, it is also preferable to include fine particles in the ink composition. For example, inorganic fine particles or organic fine particles can be added.

[0093] The inorganic fine particles include, for example, a compound containing silicon, silicon dioxide, acid aluminum, zirconium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium carbonate, hydrated calcium silicate, Aluminum silicate, magnesium silicate, phosphate, and the like are more preferable, and inorganic compounds containing zirconium and zirconium oxide are preferable, but silicon dioxide is particularly preferably used. These include particles having a spherical shape, a flat plate shape, an amorphous shape, and the like.

[0094] As fine particles of silicon dioxide, for example, commercially available products such as Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.) can be used.

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

[0096] Further, as the organic fine particles, polymethacrylic acid methyl acrylate fine resin particles, acryl styrene-based fine particles, polymethyl methacrylate fine particles, silicon-based fine particles, polystyrene-based fine particles, Polycarbonate resin fine particles, benzoguanamine resin fine particles, melamine resin fine particles, polyolefin resin fine particles, polyester resin Examples thereof include fine particles, polyamide-based resin fine particles, polyimide-based resin fine particles, and polyfluorinated styrene-based resin fine particles.

[0097] In the present invention, when both the convex structure portion and the transparent resin layer contain the fine particles, the average particle size is preferably 5 to 300 nm force S, more preferably 20 to LOOnm. Two or more kinds of fine particles having different particle diameters and refractive indexes may be contained. The content is preferably 5 to 50% by mass with respect to the convex structure part or the transparent resin layer.

[0098] In the present invention, when the convex structure portion or the transparent resin layer contains an actinic ray curable resin, an actinic ray irradiation method includes transferring the ink onto a transparent substrate, printing a solvent, etc. After evaporating, it is preferable to irradiate actinic rays. The timing of irradiation can be determined in consideration of the shape of the pattern to be formed.For example, when the ink is solvent-free, irradiation is performed immediately after transfer printing to 2 minutes later. Irradiation can be performed immediately after the solvent has been volatilized and after 2 minutes.

[0099] The term "immediately after transfer printing of the ink on the substrate film or the solvent in the ink has been volatilized" as used in the present invention specifically refers to a period of up to 5 seconds after the transfer printing. In addition, the irradiation of the active light may be in a half-cured state as long as the ink is lowered to the extent that the fluidity of the ink is reduced and a desired pattern shape can be formed. In this case, it can be completely cured by irradiating an active light source separately installed on the downstream side. In the present invention, it is preferable to use an actinic ray curable resin for forming the convex structure and forming the transparent resin layer.

[0100] The actinic ray that can be used in the present invention is not limited as long as it is a light source that activates the actinic ray curable resin formed into a pattern with ultraviolet rays, electron beams, γ rays, or the like. However, ultraviolet rays and electron beams are preferred. Especially when handling is easy and high-energy energy can be obtained easily, ultraviolet rays are preferred. As an ultraviolet light source for photopolymerizing an 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, KrF excimer laser, 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 lmjZcm ² or more, more preferably ²⁰ mjZcm ² to 10000 mjZcm ² and particularly preferably 50 m] A / cm ~ 2000mjZcm ^2.

[0101] Electron beams can also be used in the same manner. As an electron beam, 50 to 1 OOOke V emitted from various electron beam accelerators such as cockroft Walton type, bandegraph type, resonant transformer type, insulated core transformer type, linear type, dynamitron type, high frequency type, etc. Can be an electron beam having an energy of 100 to 300 keV.

[0102] In the present invention, the oxygen concentration in the atmosphere during irradiation with actinic rays is 10% or less, particularly

It is preferably 1% or less. In order to make this atmosphere, it is effective to introduce nitrogen gas or the like.

[0103] In the present invention, the substrate film or the like can also be heated in order to efficiently advance the curing reaction of actinic rays. The heating method is not particularly limited, but it is preferable to use a method such as a heat plate, a heat roll, a thermal head, or a method of spraying hot air on the surface of transfer-printed ink. Further, the back roll used on the opposite side across the base film of the flexographic printing section may be continuously heated as a heat roll.

[0104] The heating temperature cannot be generally specified depending on the type of actinic ray curable resin to be used, but is preferably within a temperature range that does not affect the base film such as thermal deformation. 30 to 200 ° C is preferable, and 50 to 120 ° C is more preferable, and 70 to 100 ° C is particularly preferable.

[0105] Next, the thermosetting resin used in the ink composition used for forming the convex structure portion or the transparent resin layer of the present invention will be described.

[0106] Examples of thermosetting resins that can be used in the present invention include unsaturated polyester resins, epoxy resins, vinyl ester resins, phenol resins, thermosetting polyimide resins, and thermosetting polyamideimides. And so on.

[0107] Examples of unsaturated polyester resins include orthophthalic acid resins, isophthalic acid resins, terephthalic acid resins, bisphenolic resins, propylene glycol-maleic acid resins, dicyclopentagen. However, the derivative was introduced into an unsaturated polyester composition to obtain a low molecular weight, or a low styrene volatile resin or a thermoplastic resin added with a film-forming wax compound (polyvinyl acetate). Low-shrinkage resin and unsaturated polyester with addition of resin, styrene 'butadiene copolymer, polystyrene, saturated polyester, etc.) Reactive types such as direct bromination of Br with Br2 or copolymerization of hept acid or dibromoneopentyl glycol, halogenated compounds such as chlorinated paraffin and tetrabromobisphenol, and antimony trioxide, Addition-type flame retardant resin using a combination of phosphorus compounds or hydroxyaluminum hydroxide as additive, toughness hybridized with polyurethane or silicone, or IPN toughness (high strength, high elastic modulus, High elongation) tough resin.

[0108] Examples of the epoxy resin include glycidyl ether type epoxy resin including bisphenol A type, novolak phenol type, bisphenol F type, brominated bisphenol A type, glycidylamine type, glycidyl ester type, ring And a special epoxy resin containing a heterocyclic fatty acid and a heterocyclic epoxy resin.

[0109] The bule ester resin is, for example, a product obtained by dissolving an oligomer obtained by ring-opening addition reaction of an ordinary epoxy resin and an unsaturated monobasic acid such as methacrylic acid in a monomer such as styrene. There are also special types such as vinyl monomers with vinyl groups at the molecular ends and side chains. Examples of the glycidyl ether-based epoxy resin resin include bisphenol, novolac, and brominated bisphenol, and special bull ester resins include butyl ester urethane, isocyanuric acid, There are chain bull ester type.

[0110] Phenolic resin is obtained by polycondensation using phenols and formaldehyde as raw materials, and is available in resol type and novolac type.

[0111] Examples of thermosetting polyimide resins include maleic acid-based polyimides such as polymaleimide amine, polyamino bismaleimide, bismaleimide · ο, ο '— diallyl bisphenol.

— Coffin, bismaleimide 'triazine resin, nadic acid-modified polyimide, acetylene-terminated polyimide, etc.

[0112] In addition, a part of the actinic ray curable resin described above can also be used as the thermosetting resin.

[0113] It should be noted that the ink composition comprising the thermosetting resin used in the present invention appropriately employs the anti-oxidation agent and ultraviolet absorber described in the ink composition containing actinic ray curable resin. Also good. [0114] In the present invention, when the convex structure portion or the transparent resin layer formed by flexographic printing or an ink jet method contains a thermosetting resin, the ink is transferred onto the base film as a heating method. It is preferable to perform heat treatment immediately after.

[0115] The term "immediately after transfer printing the ink according to the present invention on the base film" is specifically based on the pre-preferred state that the ink is preferably heated at the same time as the transfer printing or within 5 seconds. The temperature of the material film can be raised. For example, the base film can be wound on a heat roll, and the ink can be transferred by printing, more preferably at the same time as the transfer printing or for 2 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 will clog due to curing at the nozzle part. In addition, if the heating interval exceeds 5 seconds as necessary, a smooth fine relief structure can be obtained by causing the flow-printed ink to flow and deform.

[0116] The heating method is not particularly limited, but it is preferable to use a method such as a heat plate, a heat roll, a thermal head, or a method of spraying hot air on the surface of the ink printed by transfer printing. Further, the back roll provided on the opposite side across the base film of the flexographic printing section may be continuously heated as a heat roll. The heating temperature cannot be generally specified depending on the type of thermosetting resin to be used, but it is preferably in the temperature range that does not affect the heat deformation of the transparent substrate. 50 to 120 ° C is more preferable, and 70 to 100 ° C is particularly preferable.

[0117] As the ink composition used in the present invention, any of the above-mentioned actinic ray curable resin and thermosetting resin can be used for forming a convex structure or a transparent resin layer. In other words, actinic ray curable rosin is used.

[0118] The convex structure part and the transparent resin layer ink of the present invention include silicone oil, modified silicone oil, silicone surfactant, fluorine surfactant, fluorine resin, fluorine oligomer, and fluorine modified silicone. It is preferable to contain 0.1 parts by mass or more and 5 parts by mass or less of an activator such as oil or a fluorine-based silane coupling agent. If the amount added is too large, the transparent resin layer cannot be applied on the convex structure due to the water / oil repellent effect, and if the amount added is too small, the shape of the convex structure may not be constant. The amount of surfactant depends on the ink composition, solvent composition, and surface energy of the base material, so it is essential to add it. There is no.

[0119] The silicone oils used in the present invention can be roughly classified into straight silicone oils and modified silicone oils, depending on the type of organic group bonded to the silicon atom. Straight silicone oil refers to those bonded with a methyl group, a phenol group, or a hydrogen atom as a substituent. A modified silicone oil is one that has components derived secondarily from straight silicone oil. On the other hand, it can be classified from the reactivity of silicone oil. These are summarized as follows.

[0120] Silicone oil

1.Straight silicone talent

1— 1. Non-reactive silicone oil: dimethyl, methylphenol substitution, etc.

1-2. Reactive silicone oil: methyl hydrogen substitution, etc.

2. Modified silicone oil

Modified silicone oil is born by introducing various organic groups into dimethyl silicone oil.

2- 1. Non-reactive silicone oil: alkyl, alkyl Z aralkyl, alkyl Z polymer, polyether, higher fatty acid ester substitution, etc.

Alkyl / aralkyl-modified silicone oil is a silicone oil in which a part of methyl group of dimethyl silicone oil is replaced with a long-chain alkyl group or a phenyl alkyl group.

Polyether-modified silicone oil is a silicone-based polymeric surfactant in which hydrophilic polyoxyalkylene is introduced into hydrophobic dimethyl silicone,

Higher fatty acid-modified silicone oil is a silicone oil in which a part of methyl group of dimethyl silicone oil is replaced with higher fatty acid ester,

The amino-modified silicone oil is a silicone oil having a structure in which a part of the methyl group of the silicone oil is replaced with an aminoalkyl group.

Epoxy-modified silicone oil is a silicone oil having a structure in which a part of methyl group of silicone oil is replaced with an epoxy group-containing alkyl group,

Carboxyl-modified or alcohol-modified silicone oil Silicone oil with a structure in which part of the methyl group is substituted with a carboxyl group or a hydroxyl group-containing alkyl group

2- 2. Reactive silicone oil: Amide-containing epoxy, carboxyl, alcohol substitution, etc.

Of these, polyether-modified silicone oil is preferably added. The number average molecular weight of the polyether-modified silicone oil is, for example, 1,000 to 100,000, preferably 2000 to 50,000, and when the number average molecular weight is less than 1,000, the drying property of the coating film is decreased. When the molecular weight exceeds 100,000, it tends to be difficult to bleed out to the coating surface.

[0121] Specific products include L45, L9300, FZ-3704, FZ-3703, FZ-3720, FZ-3786, FZ-3501, FZ-3504, FZ from Nippon Car Co., Ltd. — 3508, FZ—3705, FZ—3707, FZ—3710, FZ—3750, FZ—3760, FZ—3785, FZ—378 5, Y—7499, Shinetsu Yakakusha KF96L, KF96, KF96H, KF99, KF54, KF965, KF968, KF56, KF995, KF351, KF352, KF353, KF354, KF355, KF615, KF618, KF945, KF6004, FL100 etc.

[0122] As the silicone surfactant used in the present invention, one obtained by substituting a part of methyl group of silicone oil with a hydrophilic group can be used. The position of substitution includes the side chain of silicone oil, both ends, one end, both end side chains, and the like. Examples of hydrophilic groups include polyether, polyglycerin, pyrrolidone, betaine, sulfate, phosphate, and quaternary salt.

[0123] A nonionic surfactant is a generic term for surfactants that do not have a group capable of dissociating into ions in an aqueous solution. However, in addition to a hydrophobic group, a hydroxyl group of a polyhydric alcohol can also be used as a hydrophilic group. It has a reoxyalkylene chain (polyoxyethylene) or the like as a hydrophilic group. The hydrophilicity becomes stronger as the number of alcoholic hydroxyl groups increases and as the polyoxyalkylene chain (polyoxyethylene chain) becomes longer. The nonionic surfactant used in the present invention preferably has dimethylpolysiloxane as a hydrophobic group.

[0124] When a nonionic surfactant in which the hydrophobic group is dimethylpolysiloxane and the hydrophilic group is also composed of polyoxyalkylene is used, unevenness of the low refractive index layer and the antifouling property of the film surface described later are improved. Polymethylsiloxane-powered hydrophobic groups are oriented on the surface to form a film surface that is resistant to contamination It is thought to do. This effect cannot be obtained by using other surfactants.

[0125] Specific examples of these nonionic active agents include, for example, Nippon Surfer Co., Ltd., silicone surfactants SILWET L-77, L-720, L-7001, L-7002, L- 7604, Y — 7006, FZ— 2101, FZ— 2104, FZ— 2105, FZ— 2110, FZ— 2118, FZ— 2 120, FZ— 2122, FZ— 2123, FZ— 2130, FZ— 2154, FZ— 2161 FZ-2162, FZ-2163, FZ-2164, FZ-2166, FZ-2191 and the like.

[0126] Further, SUPERSILWET SS-2801, SS-2802, SS-2803, SS-2804, SS-2805 and the like can be mentioned.

[0127] These nonionic surfactants are preferably composed of dimethylpolysiloxane having a hydrophobic group and polyoxyalkylene having a hydrophilic group. The structure includes a dimethylpolysiloxane structure portion and a polyoxyalkylene. A linear block copolymer in which chains are alternately and repeatedly bonded is preferable. It is excellent because it has a linear structure with a long chain length of the main chain skeleton. This is considered to be due to the fact that one activator molecule can be adsorbed on the surface of the silica fine particle so as to cover the surface of the silica fine particle at a plurality of locations by being a block copolymer in which hydrophilic groups and hydrophobic groups are alternately repeated.

Specific examples of these include, for example, silicone surfactants ABN SILWET FZ-2203, FZ-2207, FZ-2208, etc., manufactured by Nippon Car Co., Ltd.

[0129] Among these silicone oils or silicone surfactants, those having a polyether group are preferred.

[0130] The ink according to the present invention may contain a solvent, if necessary. 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.

[0131] Solvents that can be used in the ink according to the present invention include, for example, alcohols such as methanol, ethanol, 1 propanol, 2-propanol, and butanol; acetone, methyl ethyl ketone, cyclohexanone, and the like. Ketones; Ketone alcohols such as diacetone alcohol; Aromatic hydrocarbons such as benzene, toluene and xylene; Glycols such as ethylene glycol, propylene glycol and hexylene glycol; Ethyl cell solve, Butyl cell sorb, Ethyl carbide Tall, butyl carbitol, jetyl cell Glycol ethers such as sonolev, jetyl carbitol, propylene glycol monomethyl ether; esters such as N-methylpyrrolidone, dimethylformamide, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, amyl acetate; dimethyl ether, jeti Examples include ethers such as ruether, water and the like, and these can be used alone or in admixture of two or more.

[0132] In the ink composition forming the convex structure portion according to the present invention, among the above solvents, at least one solvent having a boiling point of 140 to 250 ° C and a viscosity of 1 to 15 mPa · _s at 25 ° C is used. As mentioned above, it is preferable that 60 mass% or more is contained. More preferably, at least one solvent having a boiling point of 180 to 230 ° C. and a viscosity of 1 to lOmPa · _s at 25 ° C. is contained in an amount of 70% by mass or more. The reason for this is that the solvent contained in the ink composition for forming a convex structure part is preferably volatilized and dried as quickly as the desired pattern shape is maintained after transfer printing or landing. If it exceeds the range, the adhesion to the base is inferior, drying unevenness occurs between the formed convex structure patterns, and the subsequent covering with the transparent resin layer is not uniformly performed, resulting in anti-glare. This is because deterioration of the physical properties of the conductive film, non-uniformity in the optical performance between the production lots and within the production lot, etc. are likely to occur.

[0133] The boiling point as used in the present invention is a boiling point under a pressure of 1 atm, that is, 1.013 x 10 ⁵ NZm ² . For the measurement of the boiling point, a known technique can be applied, and in the case of a simple substance, values described in documents such as a chemical handbook can also be referred to.

[0134] Among the solvents satisfying the above boiling point and viscosity, a compound represented by the following general formula (1) is more preferably used.

Formula (1) Rl— O— (C H -0) n-R2

2x

n: Integer from 1 to 3

x: integer from 2 to 4

More preferred are compounds wherein x = 2 or 3, and R2 is a acetyl group.

[0135] Specific examples of the solvent preferably used in the ink of the present invention include the following solvents. The power that can be gained.

[table 1]

[0137] Further, the compound represented by the general formula (1) is not specifically limited to the powers specifically mentioned in the following solvents.

[0138] [Table 2]

Viscosity Boiling point Compound represented by general formula (1) n X R1 R2

(mPa · s) (.c) Ethylene glycol monoethyl ether acetate

1 2 C2H5 COCHs 1.0 156 Also known as: ² -acetoxyl acetate

Echilenk "Recall Disassembling

1 2 COCIb COCHs 2.8 190 Alias: Ethylene diacetate

Ethylene glycol monobutyl ether acetate

1 2 C4H9 COCHs 1.5 192 Alias: Acetic acid ² — n-Butkischetil

2 2 C4H9 COCHs 3.0 247 Alias: Acetic acid ² — ( ² — n-Butkinethoxy) ethyl

Ethylene glycol monobutyl ether 1 2 C4H9 H 3.2 171 Jetylene glycol ethyl methyl ethereol 2 2 C2H5 CHs 1.0 .179 Jetylene glycol monoethyl ether 2 2 C2H5 C2H5 1.2 188 Jetylene glycol monomethyl ether 2 2 CHs H 3.5 194 Jetylene glycol monoethyl ether 2 2 C2HS H 3.7 202 Jetylene glycol monobutyl ether 2 2 C4H9 H 6.0 231 Triethylene glycol monomethyl ether 3 2 CHs H 7.0 245 Propylene Daricol monomethyl ether acetate 1 3 CHs COCH3 1.1 146 Dipropylene glycol monomethyl ether 2 3 CHs H 3.3 189 Tripropylene glycol monomethyl ether 3 3 CHs H 6.2 243

In addition to the above, ethylene glycol monoisopropyl ether, ethylene glycol mono-tert-butylene ethere, diethylene glycol mono-monopropylene ether, diethylene glycol mono-isopropyl ether, diethylene glycol mono-butyl ether, propylene glycol monolenoate Tenole, Propylene glycol monopropinoreateol, Propylene glycol monoisopropyl ether, Propylene glycol monobutinoate ether, Propylene glycol mono-t-butyl ether, Dipropylene glycol monoethyl ether, Dipropylene glycol monopropyl ether, Dipropylene glycol Rumonoisopropyl ether, dipropylene glycol monobutyl ether, ethylene glycol No-isopropyl ether acetate, ethylene glycol mono-t-butyl etherol acetate, diethylene glycol no-monomethylol etherate acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoisopropyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl Ether acetate, Propylene glycol monoisopropyl ether acetate, Propylene glycol monobutyl ether acetate, Propylene glycol monoethanol t Butinoleate alcoholate, Dipropylene glycol monoethanolate Diterpylene glycol monopropylene ether, dipropylene glycol monoisopropyl ether, ethylene glycol monomethoxymethyl ether, diethylene glycol monoethyl ether acetate (also known as 2- (ethoxyethoxy) ethyl acetate) ), Triethylene glycol dimethyl ether, diethylene glyconoresate acetate, propylene glycol diacetate (also known as 1,2-diacetoxypropane), dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether acetate, etc. are also preferably used. .

[0140] The convex structures and the pattern shape can be controlled by mixing solvents having different boiling points and viscosities from these solvents and changing the ratios as appropriate.

[0141] << Production of Convex Structure >>

An example of a method for producing the convex structure portion is shown below, but the present invention is not limited to this.

[0142] <Example of formation of convex structure by flexographic printing>

In general, flexographic printing is a printing method using a relief printing plate made of flexible rubber or resin and a solvent-based evaporation-drying ink mainly composed of water or alcohol.

[0143] A convex structure is formed in a pattern on the surface of the base film using flexographic printing, and a transparent resin layer is further formed thereon by microgravure method, extrusion coating method, wire bar method, flexographic printing method, By applying uniformly by a thin film uniform coating method such as an ink jet method, a fine concavo-convex structure can be formed while maintaining high productivity.

[0144] First, flexographic printing preferably used in the present invention will be described with reference to the drawings.

3 and 4 are schematic views showing an example of flexographic printing according to the present invention.

[0146] The continuously running substrate film 10 is sandwiched between a plate cylinder 3 composed of an impression cylinder 5, a resin plate roll 2, and a seamless resin plate 1 that forms a fine relief structure on the substrate film after transfer printing. Then, the ink 8 is supplied to the plate cylinder 3 by the arrox roll 4 whose amount of transfer ink is adjusted by the doctor blade 6, and transfer printing is performed on the base film.

[0147] In flexographic printing, ink is supplied to the plate cylinder 3 by the arlocks roll 4, and the ink amount on the arlocks roll surface is controlled by the doctor blade system shown in FIG. 3 or the two-roll shown in FIG. A method based on the method is generally known. Shown in Figure 4 In the two-roll method, ink 8 is supplied from the ink pan to the roller roll 4 by the fountain roll 7 and further supplied to the plate cylinder 3, and the ink is transferred to the base film 10 by transfer transfer. According to the method of FIG. 4, the ink 8 is adjusted by the number of engraving lines of the arlock roll 4 and the depth and shape of the cell, and between the fountain roll 7 and the arlock roll 4 3) The method shown in FIG. 3 is preferred in the present invention because the amount of ink supplied is controlled by the strength of the poop pressure and the amount of ink transferred is not stable.

[0148] As another method, Fig. 5 shows a schematic diagram of flexographic printing in which ink is supplied by an extrusion coater.

[0149] Ink 8 is extruded directly onto the seamless resin plate 1 mounted on the resin plate roll 2 by the extrusion coater 9, and is sandwiched between the plate cylinder 3 and the impression cylinder 5 on the base film 10 that is continuously running. Transfer printed. In this case, since there is no arrox roll, the amount of ink supplied depends on the accuracy of the extrusion coater.

[0150] In the doctor blade system shown in Fig. 3, the amount of ink transferred to the plate cylinder 3 is determined by the number of engraving lines of the arlock roll 4 and the shape of the cell, and the amount of ink transferred can be stabilized. The ink that fills the cells of the arrox roll uses the doctor blade to scatter excess ink on the surface of the arrox roll, so the transferred ink is determined by the number of engraving lines and the shape and volume of the cell. is there. For the cell of an arrox roll, for example, the surface of the iron cylinder is subjected to copper plating if necessary, and the cell is formed by engraving on the surface, and the surface processing with hardness is performed by using the nickel or chrome plating. . There are two types of arclox rolls, one with the copper cylinder surface plated with copper, or the other with ceramic coating. In the present invention, however, the wear resistance and the number of engraving lines can be easily reduced. The ceramic coated type is preferred.

[0151] FIG. 6 is a perspective view of an arlock roll.

FIG. 7 is a perspective view for explaining an AROX cell.

[0153] As shown in Fig. 6, the Erox roll 4 can be formed by chemical corrosion in the same manner as the gravure plate provided on the copper surface, but it tends to cause treatment of the corrosion liquid and variations in depth. In view of this, it is desirable to provide the cell b by machine or laser engraving. And the surface of an arrox roll is usually made by chrome plating after pressing with a mill. However, the point of abrasion resistance, corrosion resistance, and ink transferability is preferably one formed by spraying inorganic oxide such as acid chrome or tungsten carbide.

[0154] The sculpture shape of the Arrox roll 4 is not shown in the figure other than the lattice-type cell, but there are shapes such as a helicity type, a pyramid type, a diagonal type, and a hexagonal Herka pattern, Although it is not particularly limited, it is preferable to use a hammer pattern from the viewpoint of reproducibility of ink transfer during high-speed printing. The number of engraving lines and the depth d of the cell b shown in FIGS. 6 and 7 have a great influence on the amount of ink transferred, and form a fine uneven structure on the surface of the antiglare film according to the present invention. In this case, it is preferable that 600 lines Z2. 54 cm or more and the cell depth d is 5 to 30 m. The selection of the engraving shape and the number of lines is a force that is considered in accordance with the type of substrate to be printed and the number of lines on the printing screen. The bank a (non-recessed) of the cell should be small enough not to impair the wear resistance.Spot power that can increase the amount of ink charge is also preferred. It is preferable to provide 1 to 0.5 times. The arlock roll controls the amount of ink supplied to the printing plate by doctoring during flexographic printing. In the doctoring process, wear and damage occur, and the cell becomes shallow, causing a decrease in ink transfer. Therefore, compared to conventional metals (sculpture and chrome finish on iron or copper), ceramic arrox rolls can reduce the amount of wear caused by doctoring and greatly contribute to the repetitive stability of uneven patterns. .

[0155] The present invention preferably uses a flexographic printing apparatus as shown in Fig. 3 to provide a plate cylinder 3 in which a seamless resin plate 1 having a diameter of 50 to LOOOmm is mounted on a resin plate roll 2, and preferably ceramicsco. Ink transfer roll printing is performed on the base film 10 using the coated arrox roll 4, and the convex structure portion is formed on the base film by heating or irradiating with actinic rays.

[0156] The material of the above-mentioned slab roll 2 is not particularly limited, and is preferably a metal such as iron, stainless steel or aluminum, or a synthetic or natural rubber, as long as it can maintain the strength. A composite member of metal and rubber may be used. In the present invention, the diameter of the resin plate roll 2 is selected so that the diameter (roll diameter) when the seamless resin plate 1 is mounted on the resin plate roll 2 is in the range of 50 to: LOOO mm. If you can. If the diameter of the seamless resin plate 1 is less than 50mm This is not preferable because the rotational speed is too high to maintain the strength, and the pattern repeating pattern of the convex structure portion is short and the anti-glare effect is reduced. If the diameter exceeds 1000 mm, the apparatus becomes too large, which is expensive to operate and disadvantageous in terms of cost. In addition, uneven rotation is likely to occur, and the pattern formation accuracy decreases.

[0157] In the present invention, it is preferable to use a photosensitive resin plate to which photopolymerization of a polymer and a monomer as a photoreactive substance is applied as the resin plate used for the seamless resin plate 1. This photosensitive resin plate includes a photopolymer, a monomer that is photopolymerized by exposure to ultraviolet rays, a sensitizer that initiates photopolymerization between the polymer and the monomer, and a plasticizer that adjusts the physical properties of the plate material. The composition is made of the composition, and the above pattern is engraved on the photosensitive resin plate by a conventional mask making, or the photosensitive resin layer provided on the entire surface of the cylinder (axial core) is irradiated with laser light. By doing so, the pattern can be directly engraved.

[0158] As the photosensitive resin composition used in the present invention, those known for flexographic printing plates can be used. In general, a composition mainly composed of a binder polymer, at least one ethylenically unsaturated monomer and a photoinitiator is used. Furthermore, additives such as a sensitizer, a thermal polymerization inhibitor, a plasticizer, and a colorant can be included depending on the properties required for the photosensitive resin layer.

[0159] As the Noinder polymer, for example, a thermoplastic elastomer obtained by polymerizing a monobule-substituted aromatic hydrocarbon monomer and a synergistic monomer is used. Monobutyl-substituted aromatic hydrocarbon monomers include styrene, α-methyl styrene, ρ-methyl styrene, ρ-methoxy styrene, and conjugated gen monomers include butadiene and isoprene. Specific examples include styrene butadiene styrene block copolymer and styrene isoprene styrene block copolymer.

[0160] The at least one ethylenically unsaturated monomer is compatible with the binder polymer. For example, t-butyl alcohol is an ester of lauryl alcohol and an acrylic acid or methacrylic acid, or lauryl maleimide or cyclohexane. Maleyl derivatives such as xylmaleimide and benzylmaleimide, alcohol and fumaric acid esters such as dioctyl fumarate, hexanediol di (meth) acrylate, Examples thereof include esters of polyhydric alcohols such as nandiol di (meth) acrylate and trimethylolpropane tri (meth) acrylate and acrylic acid and methacrylic acid.

[0161] Photoinitiators include aromatic ketones such as benzophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, a-methylol benzoin methyl ether, α-methoxybenzoin methyl ether, 2, It is used in combination with a known photopolymerization initiator such as 2-benzoin ethers such as 2-jetoxy-lucacetophenone.

[0162] The photosensitive resin layer can be prepared by various methods. For example, the raw materials to be blended may be dissolved and mixed in a suitable solvent, for example, a solvent such as black mouth form, tetrachloroethylene, methyl ethyl ketone, or toluene, and coated on a suitable support by a coater. Alternatively, it can be cast into a mold to evaporate the solvent and be used as a plate as it is. Further, without using a solvent, it can be kneaded with an edder or a roll mill and formed into a plate having a desired thickness by an extruder, an injection molding machine, a press or the like.

[0163] When the photosensitive resin sheet is wound around the resin plate roll, the sheet is accurately cut and used so that there is no gap between the ends of the photosensitive resin in order to form a seamless resin plate. It is necessary. Usually, after winding the photosensitive resin plate around the resin plate roll, the photosensitive resin is heated to a temperature higher than the soft point of the photosensitive resin to melt-bond the ends of the photosensitive resin. The heating time is usually 20 minutes to 1 hour, and is determined based on the fact that the ends are fused according to the temperature and the softness point of the resin. In the next step, it is preferable for seamless processing that the surface of the photosensitive resin is polished with a grinder to completely eliminate the joints, and at the same time the accuracy is given, and then the heating treatment is performed again above the soft point of the photosensitive resin. . The time is about 10 to 40 minutes, depending on the temperature, and is done until the entire surface of the photosensitive resin becomes glossy. If heating is continued for a long time, the accuracy of the printing plate is impaired, so it is desirable to process within one hour. In addition, a photosensitive resin layer should be applied to make the base material rubber, polyester film, aluminum plate, steel plate, or aluminum resin plate roll that can be mounted on the cylinder, seamless so that there is no seam. You can also.

[0164] In the present invention, the rubber hardness of the seamless resin plate is preferably in the range of 30 to 80 degrees, and the rubber hardness of the resin plate is within this range for performing transfer printing of a stable fine uneven structure with high accuracy. It is preferable that it exists in a range. Since the rubber hardness of the roll-shaped seamless resin plate 1 is also affected by the thickness of the resin plate, the thickness is preferably in the range of 30 to 80 degrees in the resin plate having a thickness of 0.5 to LOmm. Better ,. More preferably, it is in the range of 40 to 80 degrees.

[0165] If the rubber hardness of the resin plate is less than 30 degrees, it is not preferable because the plate is too soft and it is difficult to form a desired fine uneven structure, and the plate itself is easily worn. If the rubber hardness of the stencil plate exceeds 80 degrees, the plate cylinder rotates at a high speed and lacks flexibility when printing, and the reproducibility of the ink transfer amount is poor. Rubber hardness Shown as a value measured with a durometer in accordance with the method described in IS K 6253.

[0166] Mask plate making is used as a method for imprinting a pattern with a fine relief structure on a seamless resin plate. In mask plate making, a resin plate provided with a layer of photosensitive resin material is covered with a negative film as an original mask and exposed. The photosensitive resin layer is hardened or insolubilized by light, particularly ultraviolet energy having a wavelength of 350 to 45 Onm. The uncured resin in the unexposed area is maintained in a soluble state in water, an aqueous alkaline solution, or an organic solvent such as alcohol. Accordingly, the unexposed area is washed out with a solvent corresponding to the unexposed area (development process), so that only the exposed area remains and forms a relief printing plate (flexographic printing plate).

[0167] Further, as a recent printing plate method, a complete endless plate can be produced by directly engraving a cured resin plate with a laser beam or an engraving machine based on a corrected image signal! . Alternatively, an unexposed photosensitive resin plate can be scanned with a laser beam modulated with a modified image signal in a cylindrical shape and patterned, and then developed in the usual manner from the viewpoint of forming an endless plate. I like it.

[0168] By flexographic printing, 10 to 10000 fine convex structures with a long diameter of dots of 1 to 30 μm and dot height O. 5 to 10 μm per lmm ² on the base film. By making

The convex structure part of the present invention is formed.

Next, an example of forming the convex structure portion by the ink jet method used in the present invention will be described.

FIG. 8 is a cross-sectional view showing an example of an inkjet head that can be used in the inkjet method used in the present invention. [0171] Fig. 8 (a) is a cross-sectional view of the inkjet head, and Fig. 8 (b) is an enlarged view taken along line AA in Fig. 8 (a). In the figure, 11 is a substrate, 12 is a piezoelectric element, 13 is a flow path plate, 13a is an ink flow path, 13b is a wall, 14 is a common liquid chamber component, 14a is a common liquid chamber, 15 is an ink supply pipe, 16 is the nozzle plate, 16a is the nozzle, 17 is the drive circuit printed board (PCB), 18 is the lead, 19 is the drive electrode, 20 is the groove, 21 is the protective plate, 22 is the fluid resistance, 23 and 24 are the electrodes 25 is an upper partition wall, 26 is a heater, 27 is a heater power supply, 28 is a heat transfer member, and 30 is an inkjet head.

[0172] In the integrated inkjet head 30, the laminated piezoelectric element 12 having the electrodes 23, 24 is subjected to groove processing in the direction of the flow path 13a corresponding to the flow path 13a. And drive piezoelectric element 12b and non-drive piezoelectric element 12a. The groove 20 is filled with a filler. The flow path plate 13 is joined to the piezoelectric element 12 that has been subjected to the groove processing via the upper partition wall 25. That is, the upper partition wall 25 is supported by the non-driving piezoelectric element 12a and the wall portion 13b separating the adjacent flow path. The width of the driving piezoelectric element 12b is slightly narrower than the width of the flow path 13a, and the driving piezoelectric element 12b selected by the driving circuit on the driving circuit printed board (PCB) is driven when a pulse signal voltage is applied. The piezoelectric element 12b changes in the thickness direction, and the volume of the flow path 13a changes via the upper partition 25. As a result, ink droplets are ejected from the nozzles 16a of the nozzle plate 16.

[0173] 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 and to carry the heat from the heater 26 to the vicinity of the nozzle surface to warm the air near the nozzle surface. A material with good thermal conductivity is used. For example, preferred materials include metals such as aluminum, iron, nickel, copper, and stainless steel, and ceramics such as SiC, BeO, and A1N.

[0174] 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. Displacement in which the volume of the flow path is reduced again after giving a signal for holding the flow volume to the piezoelectric element so that the flow volume is increased with respect to the selected flow path. By applying the pulse signal that gives the ink, the ink force S is ejected from the nozzle corresponding to the flow path. FIG. 9 is a schematic view showing an example of an inkjet head unit and a nozzle plate that can be used in the present invention.

In FIG. 9, (a) of FIG. 9 is a cross-sectional view of the head portion, and (b) of FIG. 9 is a plan view of the nozzle plate. In the figure, 10 is a substrate film, 31 is an ink droplet, 32 is a nozzle, and 29 is an actinic ray irradiation part. The ink droplets 31 ejected from the nozzle 32 fly in the direction of the substrate film 10 and adhere. The ink droplets that have landed on the base film 10 are immediately irradiated with actinic rays from an actinic ray irradiating unit disposed upstream thereof and cured. Reference numeral 35 denotes a back roll for holding the substrate film 10.

In the present invention, as shown in FIG. 9 (b), the nozzles of the inkjet head part are preferably arranged in a zigzag pattern, and are arranged in multiple stages in parallel in the transport direction of the base film 10. It is preferable to provide it. In addition, it is preferable to apply fine vibrations to the ink jet head portion during ink ejection so that ink droplets randomly land on the transparent substrate. Thereby, generation of interference fringes can be suppressed. The fine vibration is a force that can be applied by a high-frequency voltage, a sound wave, an ultrasonic wave, or the like, but is not limited to these.

[0178] The convex structure forming method used in the present invention is preferably an ink jet method in which a small nozzle droplet is ejected from a multi-nozzle cover. FIG. 10 shows an example of an ink jet system that can be preferably used in the present invention.

In FIG. 10, (a) in FIG. 10 is a method in which the inkjet head 30 is arranged in the width direction of the base film 10 and a convex structure is formed on the surface of the base film 10 while being transported. (Line head method), (b) in FIG. 10 is a method of forming a convex structure on the surface of the inkjet head 30 while moving in the sub-scanning direction (flat head method), and c) in FIG. Ink jet head 30 force A method of forming a convex structure portion on the surface of the base film 10 while scanning the width direction on the base film 10 (capstan method). V, displacement method can also be used, but in the present invention In view of productivity, the line head method is preferable. Note that reference numeral 29 in FIGS. 10A to 10C denotes an actinic ray irradiating unit used when an actinic ray curable resin described later is used as the ink.

[0180] In the present invention, another actinic ray irradiation unit may be provided on the downstream side in the conveyance direction of the base film in (a), (b), and (c) of FIG. [0181] In the present invention, in order to form a fine convex structure, 0.1 to: LOOpl is preferable as an ink droplet, 0.1 to 50pl is more preferable, and 0.1 to LOLO is particularly preferable. . By ejecting ink droplets under the above conditions, it is possible to obtain a fine convex structure in which the major axis of the dot is 1 to 30 m and the height of the dot is 0.5 to LO / zm.

[0182] The viscosity of the ink droplet is preferably 0.1 to 20 mPa's at 25 ° C, more preferably 0.5 to LOmPa's.

[0183] The transparent resin layer is composed of an actinic ray curable resin, a photopolymerization initiator, a photoinitiator, a photosensitizer, a thermosetting resin, and a thermoplastic as described in detail in the above-mentioned convex structure section. An ink composition is prepared by appropriately using a resin, an ultraviolet absorber, fine particles, a solvent, and the like, and further coated on the convex structure portion by an arbitrary coating method.

[0184] The method of applying the transparent resin layer is not particularly limited, but the ink composition may be made of grabiaco ■ ~ "'~", Dipco ^ ~ "Ta'~", renoku ■ ~ "sco ■ It is preferable to coat by a known method such as ~ "'~", wire ¹ "" no- ¹ "" co ¹ "" ta "~, die coater, ink jet method, flexographic printing method.

Next, FIG. 11 shows an example of the formation of a convex structure portion by flexographic printing preferably used in the present invention and the formation of a transparent resin layer by a coating method using a die coater that is subsequently performed.

In FIG. 11, the base film 502 fed out from the roll 501 is conveyed, and the flexographic printing part A is coated with a pattern-like convex structure part by flexographic printing. Here, the ink liquid is supplied from the ink supply tank 508 to the arrox roll 510, and the ink is transferred to the resin plate 509 having a pattern structure which is a flexographic printing section. When the actinic ray curable resin is used for the transfer-printed ink, the actinic ray irradiation unit 506A disposed after the resin plate 509, which is a flexographic printing unit, uses actinic light, such as ultraviolet rays. Irradiate to cure. When the ink uses thermosetting resin, it is heated and cured by a drying zone 505A, for example, a heat plate. Also preferred is the method of heating the back roll 5 04A as a heat roll!

[0187] In the flexographic printing part A, the actinic light irradiation part 506A and the stencil plate 509 should be moderately attached so as not to directly affect the ink of the actinic light irradiation part 506A. Install a light-shielding wall between the actinic ray irradiation unit 506A and the resin plate 509. It is preferable to place them. Also, in order to prevent the heat of the drying zone 505A from directly affecting the ink of the resin plate 509, the resin plate 509 is covered with a heat insulating cover, or the drying air in the drying zone 505A is blocked as shown in the figure. It is preferable to install such a partition.

[0188] The base film 502 that has been cured to such an extent that the pattern formed by the transfer-printed ink can be maintained, completes curing by evaporating unnecessary organic solvent and the like in the drying zone 505A.

[0189] Next, in the transparent resin layer coating part B, the composition for the hard coat layer supplied from the coater 503 is applied to the entire surface including the convex structure part, and the convex structure part non-formed part is formed. An uneven structure is formed between them. When the transparent resin layer contains actinic ray curable resin, actinic rays are irradiated by the actinic ray irradiation sections 506B and 506C. Further, it is dried and solidified by the drying zone 505B.

[0190] In the actinic ray irradiation sections 506A, B, and C, it is preferable to irradiate the base films 502 on the back holes 504A, B, and C that are temperature-controlled at 20 to 120 ° C. .

[0191] In the present invention, the method for forming a pattern-like convex structure portion by flexographic printing is preferably performed while the substrate film is transferred at 1 to 500 mZmin, preferably 10 to 300 mZmin.

[0192] The base film used for transfer printing of the ink is preferably subjected to slow charging immediately before it is preferable that there is no unevenness in charging, or it may be uniformly charged.

[0193] Further, the anti-glare property such as haze and transmission sharpness was measured for the pattern formed by transfer printing of the ink, and it was confirmed that it was a predetermined value. It is preferable to adjust the ink by feeding back and replace the resin plate.

[0194] <Base film>

The substrate film used in the present invention is easy to manufacture, has good adhesion to the actinic ray curable resin layer, is optically isotropic, and is optically transparent. Etc. are preferred and listed as requirements.

[0195] The term "transparent" as used in the present invention means a visible light transmittance of 60% or more, preferably 80

% Or more, particularly preferably 90% or more.

[0196] There is no particular limitation as long as it has the above-mentioned properties. Cellulose esterores such as Inolem, Cellulose Triacetate Finolem, Cellulose Acetate Propionate Finolem, Cellulose Acetate Butyrate Finolem, Polyester Film, Polycarbonate Film, Polyarylate Film, Polysulfone (Polyether) (Including sulfone) film, polyester film such as polyethylene terephthalate and polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, polyvinylidene chloride film, polybutyl alcohol film, polyethylene alcohol film, syndiotactic polystyrene Film, polycarbonate film, norbornene resin film, polymethylpentene film, polyester Ether ketone film, polyether ketone imide film, a polyamide film include fluorine 榭脂 film, nylon film, polymethyl methacrylate Tari acetate film, acrylic film or a glass plate or the like. Of these, polycarbonate film, polyester film, norbornene resin film, and cellulose ester film are preferable.

[0197] The norbornene-based resin film preferably used in the present invention is an amorphous polyolefin film having a norbornene structure, for example, APO manufactured by Mitsui Petrochemical Co., Ltd., ZEONEX manufactured by Nippon Zeon Co., Ltd., There is ARTON etc. made by JSR Corporation.

In the present invention, it is particularly preferable to use a cellulose ester film. As senorelose esterolate, cellulose acetate butyrate, sennellose acetate phthalate, and cellulose acetate propionate are preferred, although senorelose acetate, senololose acetate butyrate, and cellulose acetate propionate are preferred. . As commercially available cellulose ester films, for example, Co-Camino Nortack KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC12UR, KC4FR (manufactured by Co-Power Minoltopto Co., Ltd.) View power such as surface, transparency, and adhesiveness is preferably used. These films may be films produced by melt casting film formation or films produced by solution casting film formation.

[0199] 《Anti-glare anti-reflection film》

The present invention provides a fine concavo-convex structure of an antiglare film having the convex structure portion and a transparent resin layer. It is preferable to provide an antiglare antireflection film by providing the following low refractive index layer on the surface having a structure.

[0200] In particular, in the present invention, the low refractive index layer is coated with a low refractive index layer coating solution containing hollow silica-based fine particles that have an outer shell layer and are porous or hollow inside! It is preferable to do this.

[0201] <Low refractive index layer>

The refractive index of the low refractive index layer according to the present invention is lower than the refractive index of the substrate film as the support, and is 23 ° C., wavelength 550 nm SlJ constant, and 1.30 to: L 45 Better!/,.

[0202] The film thickness of the low refractive index layer is preferably 5 nm to 0.5 μm, more preferably 10 nm to 0.3 μm, and 30 ηπ! Most preferred is ~ 0.2 m.

[0203] The composition for forming a low refractive index layer used in the present invention comprises (a) an organosilicon compound represented by the following general formula (2) or a hydrolyzate thereof or a polycondensate thereof; It is preferable that hollow silica-based fine particles having a shell layer and having a porous or hollow interior constitute the composition.

[0204] General formula (2) Si (OR)

Four

(In the formula, R is an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms.) In addition, a solvent, and if necessary, a silane coupling agent, a curing agent and the like may be added.

[Hollow silica-based fine particles]

First, the hollow silica fine particles having the outer shell layer represented by the above (b) and having a porous or hollow inside will be described.

[0206] The hollow silica-based fine particle comprises (I) a porous particle and a composite particle that works with the coating layer provided on the surface of the porous particle, or (II) a cavity inside, and the content is a solvent, Cavity particles filled with gas or porous material. In addition, the low refractive index layer includes (I) composite particles or (II) hollow particles! /, Misalignment! /, If necessary, both are included! /, Even! / ,.

[0207] The hollow particles are particles having cavities inside, and the cavities are surrounded by particle walls.

The cavity is filled with contents such as a solvent, a gas, or a porous material used at the time of preparation. It is desirable that the average particle size of such hollow fine particles is in the range of 5 to 300 nm, preferably 10 to 200 nm. The hollow fine particles used are the thickness of the transparent film to be formed. Depending on the thickness, the thickness of the transparent coating such as a low refractive index layer to be formed is 2Z3 to 1

It is desirable to be in the range of ZlO. These hollow 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, diaceton alcohol) are preferable.

[0208] 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 coating layer thickness is less than lnm, the particles may not be completely covered. The composite particles may easily enter the interior of the composite particle and the internal porosity may be reduced, and the low refractive index effect may not be sufficiently obtained. In addition, when the thickness of the coating layer exceeds 20 nm, the above-mentioned carboxylic 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 sufficient. May not be obtained. 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 is not sufficiently exhibited. There is.

[0209] The coating layer of the composite particles or the particle wall of the hollow particles preferably contains silica as a main component. In addition, specific components other than silica may be included. Al O, B 2 O, TiO

2 3 2 3 2

ZrO, SnO, CeO, PO, SbO, MoO, ZnO, WO and the like. Composite grain

2 2 2 2 3 2 3 3 2 3

Examples of the porous particles constituting the core include those made of silica, those made of silica and inorganic compounds other than silica, and those made of CaF, NaF, NaAlF, MgF, and the like. this

2 6

Of these, porous particles having a complex acidity of silica and an inorganic compound other than silica are particularly preferable. Inorganic compounds other than silica include Al 2 O, B 2 O, TiO, ZrO, SnO, and CeO.

2 3 2 3 2 2 2 2

, PO, SbO, MoO, ZnO, WO, etc.

2 3 2 3 3 2 3

. In such porous particles, silica is represented by SiO, and inorganic compounds other than silica are oxidized.

2

Molar ratio expressed in terms of product (MO) MO / SiO force 0.0001 ~: L 0, preferably 0

X X 2

It is desirable to be in the range of 001 to 0.3. The molar ratio of porous particles MO / SiO is 0.0.

X 2

Refractive index is difficult to obtain less than 001, and even if obtained, the pore volume is small Low particle size cannot be obtained. Also, the molar ratio of porous particles MO / SiO force exceeds 1.0

X 2

If the ratio of silica is reduced, the pore volume is increased, and it may be difficult to obtain a material having a lower refractive index.

[0210] The pore volume of such porous particles is desirably in the range of 0.1 to 1.5 ml Zg, preferably 0.2 to 1.5 ml Zg. If the pore volume is less than 0.1 mlZg, particles having a sufficiently low refractive index cannot be obtained, and if it exceeds 1.5 mlZg, the strength of the fine particles may be lowered, and the strength of the resulting film may be lowered.

[0211] The pore volume of such porous particles can be determined by mercury porosimetry. Examples of the contents of the hollow particles include the solvent, gas, and porous material used at the time of particle preparation. The solvent may contain unreacted particle precursors used in preparing the hollow particles, the catalyst used, and the like. In addition, examples of the porous material include compounds having the compound power exemplified by the porous particles. These contents may consist of a single component or a mixture of multiple components.

[0212] As a method for producing such hollow fine particles, for example, the method for preparing composite oxide colloidal particles disclosed in Step Nos. [0010] to [0033] of JP-A-7-133105 is preferably employed. The

[0213] (Organic silicon compound)

In the organic silicon compound represented by the general formula (2), R represents an alkyl group having 1 to 4 carbon atoms.

[0214] Specifically, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane and the like are preferably used.

[0215] As a method for adding to the low refractive index layer, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these tetraalkoxysilane, pure water, and alcohol is used. In addition to this dispersion, the carboxylic acid polymer produced by hydrolyzing tetraalkoxysilane is deposited on the surface of the hollow silica fine particles. At this time, tetraalkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, alkali metal hydroxide or amines can be used. As the acid catalyst, various inorganic acids and organic acids can be used. [0216] In the present invention, the low refractive index layer may contain a fluorine-substituted alkyl group-containing silane compound represented by the following general formula (3).

[0217] [Chemical formula 1] General formula (3)

R ² R ⁴

R ¹ -Si-Rf-Si-R ⁶

R ³ R ⁵

[0218] The fluorine-substituted alkyl group-containing silane compound represented by the general formula (3) will be described.

[0219] In the formula, 1 ^ to 1 ^ are alkyl groups having 1 to 16 carbon atoms, preferably 1 to 4 carbon atoms, 1 to 6 carbon atoms, preferably 1 to 4 halogenated alkyl groups, 6 to 12 carbon atoms. Preferably 6 to 10 aryl groups, 7 to 14 carbon atoms, preferably 7 to 12 alkyl aryl groups, aryl alkyl groups, 2 to 8 carbon atoms, preferably 2 to 6 alkyl groups, or An alkoxy group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, a hydrogen atom or a halogen atom.

[0220] Rf represents — (C H F) —, a is an integer from 1 to 12, b + c is 2a, b is an integer from 0 to 24 a c

C represents an integer of 0 to 24. Such Rf is preferably a group having a fluoroalkylene group and an alkylene group. Specifically, such fluorine-containing silicone compounds include (MeO) SiC H C F C H Si (MeO), (MeO) SiC H C F C H Si (MeO), (

3 2 4 2 4 2 4 3 3 2 4 4 8 2 4 3

MeO) SiC H C F C H Si (MeO), (H C O) SiC H C F C H Si (OC H), (

3 2 4 6 12 2 4 3 5 2 3 2 4 4 8 2 4 2 5 3

Methoxydisilane compounds represented by H C O) SiC H C F C H Si (OC H)

5 2 3 2 4 6 12 2 4 2 5 3

It is done.

[0221] As the noinder, if the fluorine-substituted alkyl group-containing silane compound is included! /, Since the formed transparent film itself has hydrophobicity, the transparent film is not sufficiently densified. Even if it is porous or has cracks or voids, entry into the transparent film by water or chemicals such as acid or alkali is suppressed. Furthermore, fine particles such as metals contained in the conductive layer, which is the substrate surface or the lower layer, do not react with chemicals such as moisture or acid or alkali. For this reason, such a transparent film has excellent chemical resistance. [0222] When a fluorine-substituted alkyl group-containing silane compound is included as a binder, not only the hydrophobicity but also the slipperiness is good (the contact resistance is low), and thus the scratch strength is increased. An excellent transparent film can be obtained. Furthermore, when the binder contains a fluorine-substituted alkyl group-containing silane compound having such a structural unit, when the conductive layer is formed in the lower layer, the shrinkage of the binder is equivalent to that of the conductive layer. Since these are close to each other, a transparent film having excellent adhesion to the conductive layer can be formed. Furthermore, when the transparent film is heat-treated, the conductive layer does not peel off due to the difference in shrinkage rate, and a portion having no electrical contact with the transparent conductive layer does not occur. For this reason, sufficient conductivity can be maintained for the entire film.

[0223] A transparent coating comprising a fluorine-substituted alkyl group-containing silane compound and the hollow silica fine particles having the outer shell layer and being porous or hollow inside has a high scratch strength and an eraser. An excellent transparent film can be formed on the basis of high pencil hardness and high film strength evaluated by strength or nail strength.

[0224] The low refractive index layer according to the present invention may contain a silane coupling agent! Silane coupling agents include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, etyltrimethoxysilane, etyltriethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane. Ethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropylpropyltriethoxy Silane, _{Ί—Clopropropyltriacetoxysilane} , 3, 3, 3-trifluoropropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, y-glycidyloxypropyl Triethoxysilane, γ- (j8-Darishizinolexoxyethoxy) propinoretrimethoxysilane, j8 (3,4-epoxycyclohexyl) ethyltrimethoxysilane, mono (3,4-epoxycyclohexyl) ethyltrioxysilane , Γ-Ataryloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyl triethoxysilane, _Ί -mercaptopropyltrimethoxysilane, γ-mercaptopro Built triethoxysilane, Ν- | 8-(aminoethynole) y-aminopropyltrimethoxysilane and β-Cyanoethyltriethoxysilane can be mentioned.

[0225] Examples of silane coupling agents having a disubstituted alkyl group with respect to silicon include dimethylenoresimethoxymethoxysilane, pheninolemethinoresimethoxymethoxysilane, dimethylenolegetoxysilane, pheninolemethinolegetoxy. Silane, _{グリ} -Glycidinore _{xyloxypropenolemethino} lesoxy silane _Lufenyl dioxy silane, γ-chloropropyl methoxy silane, dimethyl diacetoxy silane, γ-Atalo yloxy propyl methyl dimethoxy silane, γ-Atari oxy oxypropyl methyl Getoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyljetoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ mercaptopropylmethyljetoxy Run-, .gamma. § amino propyl methyl dimethoxy silane, .gamma. § amino propyl methyl jet Kishishi run, Mechirubi - dimethoxysilane and Mechirubi - Rougier butoxy silane.

[0226] Among these, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, γ-atarylloyoxypropyltrimethoxysilane and γ-methacryloyloxy having a double bond in the molecule. Propyltrimethoxysilane, which has a disubstituted alkyl group with respect to silicon, γ-Ataryloxypropyl propylmethyldimethoxysilane, γ Ataryloxypropylmethyl jetoxysilane, oral pyrmethylmethoxysilane, methylbiphenyl two dimethoxysilane and Mechirubi two Rujeto Kishishiran is preferred instrument y- Atari Roy Ruo trimethoxysilane and γ- methacryloyloxy Ruo _{trimethoxysilane,} Ί - Atari Roy Ruo carboxypropyl methyl dimethacrylate Toki Silane, .gamma. Atari Roy Ruo carboxypropyl methyl jet silane, .gamma. methacrylonitrile I Ruo propyl methyl dimethoxy silane and .gamma.-methacryloyloxy Ruo propyl methylol Rougier butoxy silane is particularly preferred.

[0227] 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 orthokeys (eg, methyl orthokeate, ethyl orthokete, η-propyl orthokeate, i-propyl orthokeate, n-butyl orthokeate, ortho (Sec-butyl cate, t-butyl orthokeate) and hydrolysates thereof.

[0228] Examples of the polymer used as the other binder in the low refractive index layer include polybutyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, dicetinoresenololose, triacetinol. Examples include senorelose, nitrosenololose, polyesterol and alkyd rosin.

[0229] The low refractive index layer preferably contains 5 to 80 mass% of the binder as a whole. The binder 1 has a function of adhering the hollow silica fine particles and maintaining the structure of the low refractive index layer including voids. The amount of the binder used is adjusted so that the strength of the low refractive index layer can be maintained without filling the voids.

[0230] (Solvent)

The low refractive index layer according to the present invention preferably contains an organic solvent. Specific examples of organic solvents include alcohols (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), esters (eg, Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, propyl 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, jetyl ether) , Dioxane, tetrahydric furan), ether alcohol (For example, 1

-Methoxy-1-2-propanol). Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

[0231] The content of the organic solvent is preferably 1 to 4% by mass of the solid content concentration in the low refractive index layer coating composition. 1% by weight or more is preferred to prevent uniform coating and prevent uniform coating of organic solvents. If it exceeds 4% by weight, the drying load increases, which is not preferable because it increases the size of the drying equipment and increases the time. .

[0232] <High refractive index layer>

In the present invention, in order to further improve the antireflection property, a plurality of the following high refractive index layers can be provided below the low refractive index layer. [0233] A high refractive index layer preferable for the present invention contains (c) metal oxide fine particles having an average particle diameter of 10 to 200 nm, (d) a metal compound, and (e) an actinic ray curable resin. It is preferable.

[0234] (Metal oxide fine particles)

The high refractive index layer of the present invention preferably contains metal oxide fine particles. Types of metal oxide fine particles are not particularly limited Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S force Metal oxides having at least one element selected can be used, and these metal oxide fine particles are doped with a small amount of atoms such as Al, In, Sn, Sb, Nb, halogen elements, Ta, etc. You can do it. A mixture of these may also be used. In the present invention, at least one selected from among zirconium oxide, antimony oxide, tin oxide, zinc oxide, indium-tin oxide (ITO), antimony-doped tin oxide (ATO), and zinc antimonate. The metal oxide fine particles are preferably used as the main component, and indium tin oxide (ITO) is particularly preferable.

[0235] The average particle diameter of the primary particles of the metal oxide fine particles is in the range of 10 nm to 200 nm, and particularly preferably 10 to 150 nm. The average particle size of metal oxide fine particles can be measured from electron micrographs using a scanning electron microscope (SEM), etc., and a particle size distribution meter that uses dynamic light scattering or static light scattering. You can also measure by If the particle size is too small, aggregation tends to occur and the dispersibility deteriorates. If the particle size is too large, the haze is remarkably increased. The shape of the metal oxide fine particles is preferably a rice granular shape, a spherical shape, a cubic shape, a spindle shape, a needle shape, or an irregular shape.

[0236] The refractive index of the high refractive index layer is specifically higher than the refractive index of the substrate film as the support, and is in the range of 1.50-1.90 at 23 ° C and wavelength of 550 nm. It is preferable. The means for adjusting the refractive index of the high refractive index layer is dominated by the type and amount of metal oxide fine particles, so the refractive index of the metal oxide fine particles is preferably 1.80-2.60. 1. 85-2.50 is more preferable.

[0237] The metal oxide fine particles may be surface-treated with an organic compound. By modifying the surface of the metal oxide fine particles with an organic compound, the dispersion stability in an organic solvent is improved, the dispersion particle size can be easily controlled, and aggregation and sedimentation over time can be suppressed. it can. For this reason, the amount of surface modification with a preferable organic compound is 0.1% with respect to metal oxide particles. It is 0.5 mass%-5 mass%, More preferably, it is 0.5 mass%-3 mass%. Examples of organic compounds used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents and titanate coupling agents. Of these, the silane coupling agents described below are preferred. You can combine two or more surface treatments.

[0238] The thickness of the high refractive index layer containing the metal oxide fine particles is 5ηπ! It is preferable that it is ˜1 μm, and it is more preferable that it is 10 nm to 0.2 m, and it is most preferable that it is 30 nm to 0.1 m.

[0239] The ratio of the metal oxide fine particles to be used and a binder such as actinic ray curable resin to be described later varies depending on the kind of metal oxide fine particles, the particle size, etc., but the volume ratio of the former 1% versus the latter 2 Therefore, the latter 1 is preferable to the former 2.

In the present invention, the amount of the metal oxide fine particles used in the present invention is preferably 5% by mass to 85% by mass in the high refractive index layer, more preferably 10% by mass to 80% by mass. 20-75% by weight is most preferred. If the amount used is small, the desired refractive index and the effect of the present invention cannot be obtained, and if it is too large, the film strength deteriorates.

[0241] The metal oxide fine particles are supplied to a coating solution for forming a high 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 ( E.g., diacetone alcohol), esters (e.g., methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyrate formate), aliphatic hydrocarbons (e.g., hexane, cyclohexane) Hexane), halogenated hydrocarbons (eg, methyl chloride, chloroform, carbon tetrachloride), aromatic hydrocarbons (eg, benzene, toluene, xylene), amides (eg, dimethylformamide, dimethylacetate) Amide, n-methylbiphenyl), ether (eg, jetyl ether, dioxane) , Tetrahydride furan) and ether alcohol (eg, 1-methoxy-2-propanol). Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable. [0242] The metal oxide fine particles can be dispersed in the medium using a disperser. Examples of the dispersing machine include a sand grinder mill (eg, a bead mill with a pin), 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. In addition, 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 etastruder.

[0243] In the present invention, metal oxide fine particles having a core Z shell structure may be further contained. One shell may be formed around the core, or a plurality of layers may be formed in order to further improve the light resistance. The core is preferably completely covered by the shell.

[0244] The core can use titanium oxide (rutile type, anatase type, amorphous type, etc.), zirconium oxide, dumbbell, cerium oxide, indium oxide doped with tin, tin oxide doped with antimony, etc. The main component is rutile titanium oxide.

[0245] The shell preferably contains an inorganic compound other than titanium oxide as a main component and also forms a metal oxide or sulfide force. For example, inorganic materials mainly composed of silicon dioxide (silica), aluminum oxide (alumina), zirconium oxide, dumbbell, tin oxide, antimony oxide, indium oxide, iron oxide, zinc oxide zinc, etc. A compound is used. Of these, alumina, silica and zirconium (acid zirconium) are preferable. A mixture of these may also be used.

[0246] The coating amount of the shell with respect to the core is 2 to 50% by mass in average coating amount. Preferably it is 3-40 mass%, More preferably, it is 4-25 mass%. When the coating amount of the shell is large, the refractive index of the fine particles is lowered, and when the coating amount is too small, the light resistance is deteriorated. Use two or more metal oxide fine particles in combination.

[0247] As the core of titanium oxide, a core produced by a liquid phase method or a gas phase method can be used. Examples of methods for forming the shell around the core include, for example, U.S. Pat. No. 3,410,708, JP-B 58-47061, U.S. Pat. No. 2,885,366, and 3,437,502. No. 1, British Patent No. 1,134,249, U.S. Pat.No. 3,383,231, British Patent No. 2,629,953, No. 1,365,999, etc. be able to.

[0248] (Metal compound)

The metal compound used in the present invention is a compound represented by the following general formula (4) or a key thereof. A rate-i compound can be used.

[0249] General formula (4) A MB

In the formula, Μ represents a metal atom, Α represents a hydrolyzable functional group or a hydrocarbon group having a hydrolyzable functional group, and B represents an atomic group covalently or ionically bonded to the metal atom M. X represents the valence of the metal atom M, and n represents an integer of 2 or more and X or less.

[0250] Examples of the hydrolyzable functional group A include an alkoxyl group, a halogen such as a chloro atom, an ester group, an amide group, and the like. The metal compound belonging to the above formula (4) includes an alkoxide having two or more alkoxyl groups bonded directly to a metal atom, or a chelate compound thereof. Preferable metal compounds include titanium alkoxides, zinc alkoxides, and chelate compounds thereof. Titanium alkoxide has a high reaction rate and a high refractive index and is easy to handle. However, since it has a photocatalytic action, its light resistance deteriorates when added in large quantities. Zirconium alkoxide has a high refractive index but tends to become cloudy, so care must be taken in dew point management during coating. In addition, titanium alkoxide has the effect of accelerating the reaction of UV-cured resin and metal alkoxide, so that the physical properties of the coating film can be improved by adding a small amount.

[0251] Examples of the titanium alkoxide include tetramethoxy titanium, tetraethoxy titanium, tetra-iso-propoxy titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetra-sec-butoxy titanium, tetra-tert-butoxy titanium. Etc.

Zirconium alkoxides include, for example, tetramethoxyzirconium, tetraethoxyzinorecordium, tetra-iso-propoxyzirconium, tetra-n-propoxyzirconium, tetra-n-butoxyzirconium, tetra-sec-butoxyzirconium, tetra-tert-butoxy Zirconium etc. are mentioned.

[0253] Preferred chelating agents for forming a chelate compound by coordination with a free metal compound include alkanolamines such as diethanolamine and triethanolamine, ethylene glycol, diethylene glycol, and propylene glycol. And glycols such as acetylacetone, acetylacetoacetate and the like having a molecular weight of 10,000 or less. By using these chelating agents, it is possible to form a chelate compound which is stable against moisture mixing and is excellent in the effect of reinforcing the coating film. [0254] The addition amount of the metal compound is preferably adjusted so that the content of the metal oxide derived from the metal compound contained in the high refractive index layer is 0.3 to 5% by mass. When the amount is less than 3% by mass, the scratch resistance is insufficient. When the amount exceeds 5% by mass, the light resistance tends to deteriorate.

[0255] (Actinic ray curable resin)

Actinic ray curable resin is added as a binder for metal oxide fine particles in order to improve the film formability and physical properties of the coating film. Actinic ray curable resin is a monomer or oligomer having two or more functional groups that undergo polymerization reaction directly by irradiation of actinic rays such as ultraviolet rays or electron beams or indirectly by the action of a photopolymerization initiator. Can be used. Examples of the functional group include a group having an unsaturated double bond such as a (meth) ataryloxy group, an epoxy group, and a silanol group. Of these, radically polymerizable monomers and oligomers having two or more unsaturated double bonds can be preferably used. A photopolymerization initiator may be combined as necessary. Examples of such actinic ray curable resin include polyfunctional attareito toy compounds, pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and It is preferable that the compound is selected from the group power consisting of dipentaerythritol polyfunctional metatalylate. Here, the polyfunctional ate relato toy compound is a compound having two or more allyloyloxy groups and Z or methacryloxy groups in the molecule.

[0256] Examples of the monomer of the polyfunctional talarito toy compound include ethylene glycol ditalylate, diethylene glycol ditalylate, 1,6-hexanediol ditalylate, neopentylglycol ditalylate, and triglyceride. Methylolpropane tritalylate, trimethylolethane tritalylate, tetramethylol methane tritalylate, tetramethylol methane tetratalylate, pentaglycerol tritalylate, pentaerythritol diatalate, pentaerythritol tritalylate, pentaerythritol tetra Atalylate, Glycerin triatalylate, Dipentaerythritol triatalylate, Dipentaerythritol Tetraatalylate, Dipentaerythritol Pentaatalylate , Dipentaerythritol hexaoxatalylate, tris (atallyloyloxetyl) isocyanurate, ethylene glycol dimetatalylate, diethylene glycol dimetatalylate, 1,6-hexanediol dimetatalylate, neopentyl glycol dimetatalylate, tri Methylolpropane trimeta Tallylate, trimethylol ethane trimethacrylate, tetramethylol methane trimethalate, tetramethylol methane tetramethalate, pentaglycerol trimetatalylate, pentaerythritol dimetatalylate, pentaerythritol trimetatalylate, pentaerythritol tetrametatalylate Glycerol trimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate, and dipentaerythritol hexamethacrylate. These compounds may be used alone or in combination of two or more. In addition, the above monomer

It may be an oligomer such as a dimer or trimer.

[0257] The addition amount of the actinic ray curable resin is preferably less than 50% by mass in the solid content of the high refractive index composition.

[0258] In order to accelerate the curing of the actinic radiation curable resin according to the present invention, the photopolymerization initiator and the acrylic compound having two or more polymerizable unsaturated bonds in the molecule were used in a mass ratio of 3: 7. ~ 1:

It is preferable to contain 9.

Specific examples of the photopolymerization initiator include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, _a amioxime ester, thixanthone, and derivatives thereof.

[0260] (Solvent)

Examples of the organic solvent used for coating the high refractive index layer of the present invention include alcohols (for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, and pentaanol). , Hexanol, cyclohexanol, benzyl alcohol, etc.), polyhydric alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexane) Diol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), polyhydric alcohol ethers (for example, ethylenic glycolanol monomer) Chinoleatenore, ethyleneglycolenomonochinenoatenore, ethyleneglycolenoremonobutinoreethenore, diethyleneglycololemonomethinoreatenore, jetylene glycolenoremonomethinoreatenore, diethyleneglycolenoremonobutinoreatenore, Professional Pyreneglycolole monomethinoreether, propyleneglycololemonobutinoreether, ethyleneglycololemonomethinoreateolate, triethyleneglycolenomonomethinoreether, triethyleneglycolenomonomethinoreether, ethyleneglycol Nomonophenyl ether, propylene glycol monophenol ether, etc.), amines (eg ethanolamine, diethanolamine, triethanolamine, N-methyljetanolamine, N-ethyljetanolamine, Morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyljetylenetriamine, tetramethylpropylenediamine, etc. ), Amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocyclics (eg, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexylpyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc.), sulfoxides (eg, dimethyl sulfoxide, etc.), sulfones (eg, sulfolane, etc.), urea, acetonitryl, acetone, etc. In particular, alcohols, polyhydric alcohols, and polyhydric alcohol ethers are preferred.

[0261] (Anti-fouling layer)

The antiglare film or antiglare antireflection film of the present invention is preferably provided with an antifouling layer on the outermost layer.

[0262] The antifouling layer preferable for the present invention preferably contains a fluorine-containing silane compound in the antifouling layer forming composition, and is coated with a silane compound solution having a fluoroalkyl group or a fluoroalkyl ether group. To make. In particular, it is preferred that the fluorine-containing silane compound is silazane or alkoxysilane.

[0263] In addition, among the silane compounds having the fluoroalkyl group or the fluoroalkyl ether group, one Si atom is bonded to Si atoms at a ratio of 1 or less with respect to one Si atom having a fluoroalkyl group in the silane compound. The remainder is preferably a silane compound which is a hydrolyzable group or a siloxane linking group.

Here, the hydrolyzable group is a group such as an alkoxy group, for example, and becomes a hydroxyl group by hydrolysis, whereby the silanic compound forms a polycondensate.

[0265] For example, the above silane compound is a by-product alcohol with water (in the presence of an acid catalyst if necessary). In general, the reaction is carried out in the range of room temperature to 100 ° C. while distilling off the solvent. As a result, the alkoxysilane is (partially) hydrolyzed to cause a partial condensation reaction, and can be obtained as a hydrolyzate having a hydroxyl group. The degree of hydrolysis and condensation can be appropriately adjusted depending on the amount of water to be reacted. However, in the present invention, water is not actively added to the silane compound solution used for the antifouling treatment, and after the preparation, It is preferred to dilute the solid content of the solution thinly to cause a hydrolysis reaction with moisture in the air during drying.

[0266] Preferably, in the composition for forming an antifouling layer, the silane compound having a fluoroalkyl group is represented by the following general formula (5), and the concentration of the silane compound is 0.01 to It is to be used as a solution diluted to 5% by mass and subjected to antifouling treatment.

[0267] Formula (5) CF (CF) (CH) — Si— (ORa)

3 2 m 2 n 3

Here, m is an integer of 1-10. n is an integer from 0 to 10. Ra represents the same or different alkyl group.

[0268] In the compound represented by the general formula (5), Ra is preferably an alkyl group having 3 or less carbon atoms and capable of acting only on carbon and hydrogen, for example, a group such as methyl, ethyl, and isopropyl.

[0269] Examples of the silane compound having a fluoroalkyl group or a fluoroalkyl ether group preferably used in the present invention include CF (CH) Si (OCH), CF (CH

3 2 2 3 3 3 2

) Si (OC H), CF (CH) Si (OC H), CF (CH) Si (OC H), CF (CF) (C

2 2 5 3 3 2 2 3 7 3 3 2 2 4 9 3 3 2 5

H) Si (OCH), CF (CF) (CH) Si (OC H), CF (CF) (CH) Si (OC H)

2 2 3 3 3 2 5 2 2 2 5 3 3 2 5 2 2 3 7 3

, CF (CF) (CH) Si (OCH), CF (CF) (CH) Si (OC H), CF (CF) (C

3 2 7 2 2 3 3 3 2 7 2 2 2 5 3 3 2 7

H) Si (OC H), CF (CF) (CH) Si (OCH) (OC H), CF (CF) (CH) Si

2 2 3 7 3 3 2 7 2 2 3 3 7 2 3 2 7 2 2

(OCH) OC H, CF (CF) (CH) SiCH (OCH), CF (CF) (CH) SiCH (

3 2 3 7 3 2 7 2 2 3 3 2 3 2 7 2 2 3

OC H), CF (CF) (CH) SiCH (OC H), (CF) CF (CF) (CH) Si (OC

2 5 2 3 2 7 2 2 3 3 7 2 3 2 2 8 2 2

H), C F CONH (CH) Si (OC H), C F SO NH (CH) Si (OC H), C F

3 3 7 15 2 3 2 5 3 8 17 2 2 3 2 5 3 8 17

(CH) OCONH (CH) Si (OCH), CF (CF) (CH) Si (CH) (OCH), CF

2 2 2 3 3 3 3 2 7 2 2 3 3 2 3

(CF) (CH) Si (CH) (OC H), CF (CF) (CH) Si (CH) (OC H), CF (

2 7 2 2 3 2 5 2 3 2 7 2 2 3 3 7 2 3

CF) (CH) Si (C H) (OCH), CF (CF) (CH) Si (C H) (OC H), CF (C

2 7 2 2 2 5 3 2 3 2 7 2 2 2 5 3 7 2 3

H) Si (CH) (OCH), CF (CH) Si (CH) (OC H), CF (CH) Si (CH) (O

2 2 3 3 2 3 2 2 3 2 5 2 3 2 2 3 CH), CF (CF) (CH) Si (CH) (OCH), CF (CF) (CH) Si (CH) (OC

3 7 2 3 2 5 2 2 3 3 2 3 2 5 2 2 3 3

H), CF (CF) 0 (CF) (CH) Si (OC H), C F CH O (CH) Si (OC H)

7 2 3 2 2 2 3 2 2 3 7 7 15 2 2 3 2 5 3,

C F SO O (CH) Si (OC H), C F (CH) OCHO (CH) Si (OCH), etc.

8 17 2 2 3 2 5 3 8 17 2 2 2 3 3 3

[0270] Examples of the fluorine-based silane compounds include KP801M, X-24-9146, Shinichi Shingaku Kogyo Co., Ltd. Optool DSX, FG5010 manufactured by Fluoro Technology Co., Ltd., etc., and as a compound for surface treatment, perfluoroalkylsilazane, monofluoroalkylsilane, or perfluoropolyether group-containing silane Examples of the compound include perfluoroalkyl trialkoxysilane, perfluoropolyether trialkoxysilane, and perfluoropolyether ditrialkoxysilane.

[0271] When these silanic compounds are used, they are 0.01 to 10% by mass, preferably 0.03 to 5% by mass, more preferably 0.05 to 2% by mass in an organic solvent not containing fluorine. It is preferably used in a state diluted to%.

[0272] In the present invention, fluorine-free organic solvents are preferably used for preparing the silane compound solution. Examples thereof include the following.

[0273] Solvents for the coating composition for the antifouling layer used in the present invention include propylene glycol mono (C1-C4) alkyl ether and Z or propylene glycol mono (C1-C4) alkyl ether ester, propylene glycol Specific examples of mono (C1 to C4) alkyl ethers include propylene glycol monomethyl ether (PGME), propylene glycol monomethenoleatenore, propylene glycolenolemono-n-propinoreethenole, propylene alcohol monoisopropyl Ether, propylene glycol monobutyl ether, etc. In addition, propylene glycol mono (C1 to C4) alkyl ether esters are particularly propylene glycol monoalkyl ether acetates, specifically propylene glycol monomono methinoate etherate, propylene glycol monomethenoate etherate acetate. Tate etc. are mentioned. Propylene glycol mono (C1-C4) alkyl ether and / or propylene glycol mono (C1-C4) alkyl ether ester, such as methanol, ethanol, propanol, _n -butanol, 2-butanol, t-butanol, Alcohols such as clohexanol, ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetone, esters such as ethyl acetate, methyl acetate, ethyl lactate, isopropyl acetate, amyl acetate, ethyl butyrate, benzene, toluene, xylene And hydrocarbons such as dioxane, N, N-dimethylformamide and other solvents. Alternatively, these solvents are used by being appropriately mixed. The solvent to be mixed is not particularly limited to these.

[0274] Particularly preferred! /, As the solvent, one or more organic solvents selected from ethanol, isopropyl alcohol, propylene glycol, and propylene glycol monomethyl ether carbonate.

[0275] Among these solvents, those having a boiling point of less than 100 ° C (low-boiling solvent) such as methanol, ethanol and isopropyl alcohol, and boiling points such as propylene glycol monomethyl ether and n-butyl alcohol It is preferable to use a solvent having a boiling point of 100 ° C. or higher (high boiling solvent). It is particularly preferable to use a solvent having a boiling point of 60 to 98 ° C. and that having a boiling point of 100 to 160 ° C. When used in combination, the ratio of the low-boiling point solvent to the high-boiling point solvent is preferably 98.0% by mass or more in the composition of the low-boiling solvent and 0.5-2% by mass of the high-boiling solvent.

[0276] In the composition for forming an antifouling layer used in the present invention, it is preferable to adjust the pH to 5.0 or less by adding an acid. Since the acid promotes hydrolysis of the silane compound and acts as a catalyst for the polycondensation reaction, the polycondensation film of the silane compound can be easily formed on the surface of the base material, and the antifouling property can be enhanced. The pH is good in the range of 1.5 to 5.0. Below 1.5, the acidity of the solution is too strong, and there is a risk of damaging the container and piping. Above 5 the reaction is difficult to proceed. The pH is preferably in the range of 2.0 to 4.0.

[0277] In the present invention, the silanic compound solution used for the antifouling treatment is not actively added with water, and after the preparation, a hydrolysis reaction is caused mainly by moisture in the air at the time of drying. Is preferred. Therefore, it is used when the solid content concentration of the solution is diluted. If too much water is added to the treatment solution, the pot life will be shortened accordingly.

[0278] In the present invention, sulfuric acid, hydrochloric acid, nitric acid, hypochlorous acid, boric acid, hydrofluoric acid, preferably inorganic acids such as hydrochloric acid and nitric acid, as well as sulfo groups (also referred to as sulfonic acid groups) or carboxyl groups. Group Organic acids such as acetic acid, polyacrylic acid, benzenesulfonic acid, p-toluenesulfonic acid, methylsulfonic acid and the like are used. The organic acid is more preferably a compound having a hydroxyl group and a carboxyl group in one molecule, for example, hydroxydicarboxylic acid such as citrate or tartaric acid. Further, the organic acid is more preferably a water-soluble acid. For example, in addition to the above citrate and tartaric acid, levulinic acid, formic acid, propionic acid, malic acid, succinic acid, methyl succinic acid, fumaric acid, oxalic acid. Oral acetic acid, pyruvic acid, 2-oxoglutaric acid, glycolic acid, D-glyceric acid, D-darconic acid, malonic acid, maleic acid, oxalic acid, isochenic acid, lactic acid and the like are preferably used. Also, benzoic acid, hydroxybenzoic acid, atorvaic acid and the like can be used as appropriate.

[0279] The addition amount is 0.1 parts by mass to 10 parts by mass, preferably 0.2 parts by mass to 5 parts by mass with respect to 100 parts by mass of the partial hydrolyzate of the silane compound. As for the amount of water added, an amount equivalent to 100% to 300%, preferably 100% to 200%, should be added as long as the partial hydrolyzate is theoretically capable of 100% hydrolysis. Gayo! /.

[0280] By using a fluorine-containing silane compound, it is preferable only in terms of lowering the refractive index of the antifouling layer and imparting water repellency and oil repellency, and it is particularly excellent in blocking between films. effective.

[0281] (Formation of antireflection layer)

In the present invention, the method for providing the antireflection layer is not particularly limited, but it is preferably formed by coating.

[0282] In the present invention, a concavo-convex structure is formed on a base film by a convex structure portion and a transparent resin layer, and the above-described high refractive index layer composition and low refractive index layer composition are used in sequence. It is preferable to produce an antireflection layer by the coating step. It is also preferable to coat the antifouling layer.

[0283] Preferred antiglare antireflection films are shown below, but are not limited thereto. Here, the antiglare layer of the present invention means a layer comprising the convex structure portion and the transparent resin layer according to the present invention.

[0284] Base film Z Antiglare layer of the present invention Z Low refractive index layer

Base film Z Antiglare layer of the present invention Z High refractive index layer Z Low refractive index layer Base film z Antistatic layer z Antiglare layer of the present invention z Low refractive index layer Base film z Antistatic layer Z Antiglare layer of the present invention Z High refractive index layer Z Low refractive index layer Base film z of the present invention Antiglare layer Z Low refractive index layer Z Antifouling layer

Base film z Antiglare layer of the present invention Z High refractive index layer Z Low refractive index layer Z Antifouling layer

Base film z Antistatic layer Z Antiglare layer of the present invention Z Low refractive index layer Z Antifouling layer

Base film z Antistatic layer Z Antiglare layer of the present invention Z High refractive index layer Z Low refractive index layer Z Antifouling layer

In the present invention, after the antiglare layer of the present invention is formed, the surface of the antiglare layer of the present invention is subjected to surface treatment, and the surface treatment of the antiglare layer of the present invention is applied to the low refractive index according to the present invention. It is preferable to form a layer (and a high refractive index layer). It is also preferable to subject the low refractive index layer to a surface treatment before providing the antifouling layer.

Examples of the surface treatment include cleaning methods, alkali treatment methods, flame plasma treatment methods, high-frequency discharge plasma methods, electron beam methods, ion beam methods, sputtering methods, acid treatments, corona treatment methods, and atmospheric pressure glow discharge plasma methods. The alkali treatment method and the corona treatment method are preferred, and the alkali treatment method can be used particularly preferably. Corona treatment is a treatment performed by applying a high voltage of lkV or more between electrodes under atmospheric pressure and discharging it, and is a device that is commercially available from Kasuga Electric Co., Ltd., Toyo Electric Co., Ltd., etc. Can be used. The intensity of the corona discharge treatment depends on the distance between the electrodes, the output per unit area, and the generator frequency. One of the electrodes of the corona treatment device (A electrode) can be a commercially available one, but the material can be selected from aluminum or stainless steel. The other is an electrode (B electrode) for holding the plastic film, and is a roll electrode installed at a certain distance from the A electrode so that the corona treatment is performed stably and uniformly. This can also be a commercially available material, and the material is a roll made of aluminum, stainless steel, or a metal thereof, and ceramic, silicon, EPT rubber, hyperon rubber, etc. are lined. Is preferably used. The frequency used for the corona treatment used in the present invention is a frequency of 20 kHz or more and 100 kHz or less, and a frequency of 30 kHz to 60 kHz is preferable! When the frequency is lowered, the uniformity of the corona treatment is deteriorated and unevenness of the corona treatment occurs. Also, as the frequency increases, a high-power corona treatment There is no particular problem when performing processing, but when performing low-output corona processing, it becomes difficult to perform stable processing, resulting in processing unevenness. The output of the corona treatment is 1 to 5 wmin. Zm ² , but an output of ^{2 to 4} wmin. Zm ² is preferable. The distance between the electrode and the film is 5 mm or more and 50 mm or less, and preferably 10 mm or more and 35 mm or less. When the gap opens, a higher voltage is required to maintain a constant output, and unevenness is likely to occur. If the gap is too narrow, the applied voltage becomes too low and unevenness is likely to occur. Furthermore, when the film is transported and continuously processed, the film comes into contact with the electrodes and scratches are generated.

[0286] The alkali treatment method is not particularly limited as long as it is a method in which a film provided with a hard coat layer is immersed in an alkaline aqueous solution.

[0287] As the alkaline aqueous solution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous ammonia solution, or the like can be used, and among them, an aqueous sodium hydroxide solution is preferable.

[0288] The alkali concentration of the alkali aqueous solution, for example Mizusani匕sodium concentration is preferably 0.1 to 25 mass%, 0.5 to 15 weight ^_0/0 is more preferable.

[0289] The alkali treatment temperature is usually 10 to 80 ° C, preferably 20 to 60 ° C.

[0290] The alkali treatment time is 5 seconds to 5 minutes, preferably 30 seconds to 3 minutes. It is preferable to neutralize the alkali-treated film with acid water and then wash it thoroughly with water.

[0291] Each layer of the antireflection layer is formed on the concavo-convex structure portion and the transparent resin layer by the dip coating method, the air knife coating method, the curtain coating method, the roller coating method, the wire bar coating method, the gravure coating method, and the micro gravure method. It can be formed by coating using a coating method or an etching coating method. When coating, the substrate film should be rolled up in the form of a roll after applying the above-mentioned coating, drying and curing treatment, with the state force being rolled up in a width of 1.4 to 4 m. Preferred.

[0292] Further, the antiglare antireflection film using the antiglare film of the present invention is obtained by laminating the antireflection layer on a base film and then winding it in a roll shape at 50 to 150 ° C. 1 ~

It can manufacture by the manufacturing method which heat-processes in the range for 30 days. The duration of the heat treatment may be determined appropriately according to the set temperature.For example, if it is 50 ° C, it is preferably 3 days or more and less than 30 days, and if it is 150 ° C, it is in the range of 1 to 3 days. Is preferred. Normal It is preferable to set it at a relatively low temperature for about 3 to 7 days at around 50 to 80 ° C so that the heat treatment effect on the outside of the heel, the center of the heel, and the core portion is not biased.

[0293] In order to stably perform the heat treatment, it is necessary to perform in a place where the temperature and humidity can be adjusted, and it is preferable to perform in a heat treatment chamber such as a clean room without dust.

[0294] When winding the antiglare film coated with a functional thin film such as the antireflection layer or the antifouling layer in a roll shape, any material can be used as the winding core, whether it is a cylindrical core. However, it is preferably a hollow plastic core, and the plastic material may be any heat-resistant plastic that can withstand the heat treatment temperature. For example, phenol resin, xylene resin. Examples thereof include resins such as fat, melamine resin, polyester resin, and epoxy resin. A thermosetting resin reinforced with a filler such as glass fiber is preferred.

[0295] The winding number of these winding cores is preferably 100 windings or more, and more preferably 500 windings or more. The winding thickness is more preferably 5 cm or more.

[0296] When the functional film is coated on the long base film in this manner and the roll wound around the plastic core is wound and the heat treatment is performed, the roll is rotated. The preferred rotation may be continuous or intermittent rotation where a speed of less than one rotation per minute is preferred. In addition, it is preferable that the roll is rewinded once or more during the heating period.

[0297] In order to rotate the long antiglare film roll wound around the core during the heat treatment, it is preferable to provide a dedicated turntable in the heat treatment chamber.

[0298] In the case of intermittent rotation, it is preferable that the stop time is within 10 hours. It is preferable that the stop position is uniform in the circumferential direction. The stop time is preferably 10 minutes. It is more preferable to be within the range. Most preferred is continuous rotation.

[0299] The rotation speed for continuous rotation is preferably set to 10 hours or less for one rotation, and if it is fast, it will be a burden on the apparatus, so a range of 15 minutes to 2 hours is preferable. Good.

[0300] In the case of a dedicated carriage having a rotation function, it is preferable that the optical film tool can be rotated during movement and storage. In this case, this occurs when the storage period is long. Rotation functions effectively as a measure against rack band.

[0301] (Polarizing plate)

The polarizing plate can be produced by a general method. Anti-glare film and anti-glare film of the present invention The back side of the anti-glare antireflection film is subjected to alkali hatching treatment, and is immersed and stretched in an iodine solution. It is preferable to bond together using an aqueous solution. The film may be used on the other surface, or another polarizing plate protective film may be used. Commercially available cellulose ester films (for example, Coyukamino Noretak KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC12UR, KC4FR, or more, made by Co-Camino Nortop Co., Ltd.) are also preferred. In contrast to the antiglare film and 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, 30 to 300 nm, and Rt of 70 to 400 nm. It preferably has a phase difference. These can be produced, for example, by the methods described in JP-A-2002-71957 and Japanese Patent Application No. 2002-155395. 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 JP-A-2003-98348. By using in combination with the antiglare film and the antiglare antireflection film of the present invention, a polarizing plate having excellent flatness and a stable viewing angle widening effect can be obtained.

[0302] A polarizing film, which is a main component of a polarizing plate, is an element that passes only light having a polarization plane in a certain direction. A typical polarizing film that is currently known is a polyvinyl alcohol polarizing film. There are two types: polybutalolic film dyed with iodine and dichroic dye. 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 film and the antiglare antireflection film of the present invention is bonded to form a polarizing plate. Preferably, they are bonded together with a water-based adhesive whose main component is complete acid polybutyl alcohol or the like. [0303] (Display device)

By incorporating the polarizing plate of the present invention into a display device, various display devices of the present invention with excellent visibility can be manufactured. Anti-glare film and anti-glare anti-reflection film of the present invention are reflective type, transmissive type, transflective type LCD or TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS type It is preferably used in LCDs with various drive systems. Further, the antiglare film and the antiglare antireflection film of the present invention have excellent flatness, and are preferably used for various display devices such as a plasma display, a field emission display, an organic EL display, an inorganic EL display, and electronic paper. It is done. Especially for large screen display devices of S30 type or higher, especially 30 to 54 type, the effect of eliminating white spots at the periphery of the screen is maintained for a long period of time. MVA liquid crystal display devices, IPS liquid crystal display devices A remarkable effect is observed in the setting. In particular, the effect of the present invention was that the eyes did not get tired even during long-time appreciation with less color unevenness, glare and wavy unevenness.

Example

[0304] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

[0305] Example 1

(Production of cellulose ester film 1)

A cellulose ester solution (dope) was prepared using the following cellulose ester, plasticizer, ultraviolet absorber, fine particles and solvent, and cellulose ester film 1 was prepared by a solution casting film forming method.

[0306] Cellulose ester (cellulose triacetate, acetyl substitution degree of 2.9, Mn = 160 000, Mw / Mn = l. 8) 100 kg

Plasticizer (Trimethylolpropane tribenzoate) 5kg

Plasticizer (Ethylphthalyl Ethyl Dalicolate) 5kg

UV absorber (Tinubin 109, manufactured by Ciba Specialty Chemicals Co., Ltd.)

1. Okg

UV absorber (Chinbin 171; manufactured by Ciba Specialty Chemicals Co., Ltd.)

1. Okg Fine particles (Aerosil R972V, Nippon Aerosil Co., Ltd.) 0.3 kg

Solvent (methyl acetate) 440kg

Solvent (ethanol) 110kg

A cellulose ester solution (dope) was prepared using the above cellulose ester, plasticizer, ultraviolet absorber, fine particles and solvent.

[0307] Next, the cellulose ester solution whose temperature was adjusted to 33 ° C was fed to a die and uniformly cast from a die slit onto a stainless steel belt. The cast part of the stainless belt was heated from the back with hot water of 37 ° C. After casting, the dope film on the metal support (casted on a stainless steel belt, hereinafter referred to as the web) is dried by applying hot air of 44 ° C, and the residual solvent in the peeling is peeled off at 120% by weight. Applying the tension during stretching, the film was stretched to a longitudinal stretching ratio of 1 ×, and then the web edge was gripped with a tenter while the residual solvent amount was from 35% to 10% by weight. In the hand direction, the film was stretched so as to have a draw ratio of 1.1 times. After stretching, hold for several seconds while maintaining its width, relax the tension in the width direction, release the width holding, and further convey it for 20 minutes in the third drying zone set at 125 ° C, Drying was performed to produce a cellulose ester film 1 having a width of 1.5 m, a film thickness of 80 μm, and a length of 3000 m.

[Preparation of anti-glare film 1 with fine particle-added powder]

On the surface of the cellulose ester film 1 (B side; surface in contact with the support mirror surface such as a stainless steel band used in the casting film forming method; support side), the following coating liquid for hard coat layer 1 is filtered through a polypropylene filter with a pore size of 20 μm to prepare a hard coat layer coating solution, which is applied using a micro gravure coater, dried at 90 ° C, and then irradiated with an ultraviolet lamp. Was 0.1 lWZcm ² and the irradiation amount was 0.1 ljZcm ² , the coating layer was cured to form an antiglare node coat layer having a thickness of 5 m, and antiglare film 1 was produced. As a result of measuring the average surface roughness (Ra) of the formed irregularities using an optical interference type surface roughness measuring machine manufactured by WYKO, it was 0.55 m.

[0309] The average distance between the centers of the convex portions was 77 m.

[0310] A coating solution excluding synthetic silica fine particles was prepared separately from the coating solution 1 for hard coat layer, and the film prepared under the same coating and curing conditions as described above was measured with an Abbe refractometer. Was 1.517. [0311] (Hardcoat layer coating solution 1)

The following materials were stirred and mixed to obtain hard coat layer coating solution 1.

[0312] Acrylic monomer; KAYARAD DPHA (dipentaerythritol hexaatalylate, Nippon Kayaku) 200 parts by mass

Photopolymerization initiator (Irgacure 184 (Ciba Specialty Chemicals Co., Ltd.))

25 parts by mass

110 parts by mass of propylene glycol monomethyl ether 110 parts by mass of ethyl acetate

Synthetic silica fine particles Average particle size 1. 40 parts by mass Surfactant (Silicone surfactant; FZ2207 (manufactured by Nippon Car) 10% by mass propylene glycol monomethyl ether solution)

[Preparation of antiglare film 2 by embossing]

In the production of the cellulose ester film 1, a roll provided with a ridge after stretching with a tenter (after forming the irregularities, the height of the convex part 1 / ζ πι, the size of the convex part (long side) 10 m, the distance between the convex parts B side of the film (the side that was in contact with the stainless steel band support is the B side) with the film containing the solvent sandwiched between the concave and convex part where the back roll force is also configured) The opposite side is the A side, and a hot roll with a saddle shape is pressed against the M rule, a back roll is placed on the A side, and the unevenness is formed on the B side by passing between both rolls. An embossed cellulose ester film 2 was produced in the same manner except that the film was formed, and a static elimination wire was installed in the vicinity of the concavo-convex forming part to suppress charging of the film.

[0313] On the surface of the above-mentioned embossed cellulose ester film 2 (B surface side; surface in contact with a mirror surface of a support such as a stainless steel band used in the casting film forming method; support side), the following hardware The coating layer coating solution 2 is filtered through a polypropylene filter having a pore size of 20 μm to prepare a hard coating layer coating solution, which is applied using a micro gravure coater, dried at 90 ° C, and then an ultraviolet lamp. The coating layer was cured with an illuminance of 0.1 lWZcm ² and an irradiation amount of 0.UZcm ² to form an antiglare hard coat layer having a thickness of 5 m, thereby producing an antiglare film 2. [0314] As a result of measuring the average surface roughness (Ra) of the formed unevenness using an optical interference surface roughness measuring machine manufactured by WYKO, it was 0.82 m. The average center distance of the protrusions was 65 μm.

[0315] A film prepared by separately applying the coating solution 2 for hard coat layer under the same coating and curing conditions as described above was measured with an Abbe refractometer, and the refractive index was 1.521.

[0316] (Hardcoat layer coating solution 2)

Acrylic monomer; KAYARAD DPHA (dipentaerythritol hexaatalylate, Nippon Kayaku) 60 parts by mass

40 parts by mass of trimethylolpropane tritalylate

4 parts by mass

50 parts by mass of ethyl acetate

Propylene glycol monomethyl ether 50 parts by weight Silicone compound 0.5 parts by weight

(BYK- 307 (by Big Chemie Japan))

[Preparation of Antiglare Films 3 to 16 with Convex Structures by Flexographic Printing Method] Surface of the above prepared cellulose ester film 1 (A surface side; on a mirror surface of a support such as a stainless steel band used in the casting film forming method) On the contact surface (support side), prepare the following convex structure part ink liquids 1 to 6 by filtering them with a polypropylene filter with a pore size of 20 μm, and flexographically print the convex structure part using the manufacturing device shown in FIG. Formed. The flexographic printing pattern used was a crystal “raster one” screening method from Agfa Gebalt, with a pattern of 2400-4000 dpi (2.5 dots per 54 cm) and 1-10% density.

[0317] After forming the convex structure, it was dried at 90 ° C in the drying zone 505A, and then cured using an ultraviolet lamp 506A at an ultraviolet illuminance of 0.1 lWZcm ² and an irradiation dose of 0.1 ljZcm ² . In addition, the average height of the convex structure was controlled by controlling the amount of coating liquid supplied from the Arox roll.

[0318] (Seamless resin version)

Photosensitive rosin plate: 98 parts of 2-hydroxyethyl acrylate and butanediol dialkylate A core-shell type microgel (core Z shell = 2Zl) obtained by reacting a core obtained by reacting 1 part with 20 parts of methacrylic acid and 80 parts of N-butyl acrylate. Trimethylol propane ethoxytri A photosensitive resin composition obtained by mixing 25 g of attalylate and 4 g of 2,2-dimethoxy-2-phenylacetophenone was applied onto a polyester film having a thickness of 2 mm, and then an ultraviolet ray having a wavelength of 360 nm. From this, lOOOnj / cm was exposed to obtain a printing master for laser engraving. Next, engrave the fine relief structure under the following laser engraving conditions, and attach it to the resin plate roll while vacuuming as shown in Fig. 3. When the whole is heated at 120 ° C for 20 minutes, the joints disappear and a seamless resin plate is obtained. became.

[0319] The resin plate diameter was 500 mm, and the rubber hardness of the resin plate was 50. Rubber hardness Measured with a durometer according to the method described in ί. IS K 6253.

[0320] On the convex structure thus prepared, the following ink solution for transparent resin layer 1 to 3 was applied while changing the film thickness by the reduced pressure extrusion method, and antiglare described in Tables 3 and 4 was applied. Films 3 to 16 were produced.

[0321] [Preparation of anti-glare film 17-31 having convex structure by inkjet method]

On the surface of the cellulose ester film 1 (B side; surface in contact with the support mirror surface of the stainless steel band used in the casting film forming method; support side) 6 is ejected as ink droplets by ink jet method at 2 to 16 pl, and after 0.2 seconds after drying, it is hardened with a UV light illuminance of 0.1 lWZcm ² and a dose of 0.1 ljZcm ² A convex structure was formed.

[0322] The inkjet ejection device uses the line head method (Fig. 10 (a)) and the nozzle diameter is 3.

Ten inkjet heads with 256 nozzles of 5 μm were prepared. The ink jet head having the configuration shown in FIG. 9 was used. The ink supply system consists of an ink supply tank, a filter, a piezo-type inkjet head, and piping. The ink supply tank to the inkjet head section is insulated and heated (40 ° C), and the emission temperature is The driving frequency was 40 ° C and the driving frequency was 20kHz. For anti-glare films 17, 18, and 29, convex structures were prepared using electrostatic ink jetting with ink droplets of lpl or less.

[0323] On the convex structure thus prepared, the following ink solution for transparent resin layer 1 to 3 was applied while changing the film thickness by the reduced pressure extrusion method, and antiglare described in Tables 3 and 4 was applied. Sex film 17-30 Produced. The antiglare film 31 was not coated with a transparent resin layer on the antiglare film 20.

[0324] (Ink liquid for convex structure 1)

Acrylic monomer; KAYARAD DPHA (dipentaerythritol hexaatalylate, Nippon Kayaku) 70 parts by mass

30 parts by mass of trimethylolpropane tritalylate

4 parts by mass

50 parts by mass of ethyl acetate

Propylene glycol monomethyl ether 50 parts by mass Silicone compound (BYK-307 (manufactured by Big Chemie Japan)) 0.2 part by mass The above composition was mixed and stirred to prepare ink liquid 1 for convex structure.

[0325] After applying and drying Ink Liquid 1 for the convex structure, the UV illuminance is 0.1 lWZcm ² and the irradiation dose is

0. A film prepared by curing with ljZcm ² was measured with an Abbe refractometer, and the refractive index was 1.5.

It was 22.

[0326] (Ink liquid for convex structure 2)

Acrylic monomer; KAYARAD DPHA (Dipentaerythritol Hexaatalylate

, Nippon Kayaku) 100 parts by mass

30 parts by mass of trimethylolpropane tritalylate

ITO dispersed particles (average particle size 65nm) 70 parts by mass

10 parts by mass

Silicone compound (BYK- 307 (by Big Chemie Japan)) 0.2 parts by mass Propylene glycol monomethyl ether 100 parts by mass Ethyl acetate 100 parts by mass

The above composition was mixed and stirred to prepare an ink liquid 2 for convex structures.

[0327] After the ink layer 2 for the convex structure was applied and dried, the film prepared by curing with an ultraviolet illuminance of 0.1 lWZcm ² and an irradiation amount of 0.1 ljZcm ² was measured with an Abbe refractometer, Refractive index is 1.5 56.

[0328] (Ink liquid for convex structure 3)

Acrylic monomer; KAYARAD DPHA (dipentaerythritol hexaatalylate, Nippon Kayaku) 100 parts by mass

50 parts by mass of trimethylolpropane tritalylate

Oxidized titanium fine particle dispersion (Oxidized titanium fine particle concentration 20% by mass, dispersion solvent isopropanol, particle size 35 nm) 50 parts by mass

10 parts by mass

Propylene glycol monomethyl ether 100 parts by weight Methyl ethyl ketone 100 parts by weight

Surfactant (polydimethylsiloxane; KF96 (manufactured by Shin-Etsu Chemical Co., Ltd.)) 0.2 part by mass The above composition was mixed and stirred to prepare an ink liquid 3 for convex structures.

[0329] After applying and drying Ink Liquid 3 for the convex structure, the UV illuminance is 0.1 lWZcm ² and the irradiation amount is

0. When the film made by curing with ljZcm ² was measured with Abbe's refractometer, the refractive index was 1.5.

73.

[0330] (Ink liquid for convex structure 4)

Acrylic monomer; KAYARAD DPHA (Dipentaerythritol Hexaatalylate

, Nippon Kayaku) 70 parts by mass

30 parts by mass of trimethylolpropane tritalylate

4 parts by mass

150 parts by mass of ethyl acetate

Propylene glycol monomethyl ether 150 parts by mass Silicone compound (BYK-307 (manufactured by Big Chemie Japan)) 0.2 part by mass The above composition was mixed and stirred to prepare an ink liquid 4 for convex structure parts.

[0331] The film prepared by applying and drying the ink liquid 4 for the convex structure part after curing with an ultraviolet ray illuminance of 0.1 lWZcm ² and an irradiation amount of 0.1 ljZcm ² was measured with an Abbe refractometer, Refractive index is 1.5 It was 22.

[0332] (Ink liquid for convex structure 5)

30 parts by mass of trimethylolpropane tritalylate

ITO dispersed particles (average particle size 65nm) 50 parts by mass

10 parts by mass

Silicone compound (BYK- 307 (manufactured by Big Chemie Japan)) 0.2 parts by mass Propylene glycol monomethyl ether 300 parts by mass Ethyl acetate 300 parts by mass

The above composition was mixed and stirred to prepare an ink liquid 5 for convex structures.

[0333] Ink liquid 5 for convex structure, after coating and drying, UV illumination is 0.1 lWZcm ² and irradiation dose is 0

A film made by curing with UZcm ² was measured with an Abbe refractometer. The refractive index was 1.55.

It was 6.

[0334] (Ink liquid for convex structure 6)

Acrylic monomer; KAYARAD DPHA (Dipentaerythritol Hexaatalylate

, Nippon Kayaku) 100 parts by mass

30 parts by mass of trimethylolpropane tritalylate

Oxidized titanium fine particle dispersion (Oxidized titanium fine particle concentration 20% by mass, dispersion solvent isopropanol, particle size 35 nm) 70 parts by mass

10 parts by mass

150 parts by mass of propylene glycol monomethyl ether 150 parts by weight of methinoreethino ketone

Surfactant (polydimethylsiloxane; KF96 (manufactured by Shin-Etsu Chemical Co., Ltd.)) 0.2 part by mass The above composition was mixed and stirred to prepare an ink liquid 6 for convex structures.

[0335] After applying and drying Ink Liquid 6 for the convex structure, the UV illuminance is 0.1 lWZcm ² and the irradiation amount is When a film prepared by curing at 0. lj / cm ² was measured with an Abbe refractometer, the refractive index was 1.573.

[0336] (Ink liquid for transparent resin layer 1)

40 parts by mass of trimethylolpropane tritalylate

4 parts by mass

50 parts by mass of ethyl acetate

Propylene glycol monomethyl ether 50 parts by mass Silicone compound (BYK-307 (manufactured by Big Chemie Japan)) 0.5 part by mass The above composition was mixed and stirred to prepare ink solution 1 for a transparent resin layer.

[0337] The film prepared by coating the ink solution 1 for the transparent resin layer with an ultraviolet ray illuminance of 0.1 lWZcm ² and an irradiation dose of 0.1 ljZcm ² after coating and drying was measured with an Abbe refractometer. The refractive index is

1. 522.

[0338] (Ink liquid for transparent resin layer 2)

Acrylic monomer; KAYARAD DPHA (Dipentaerythritol Hexaatalylate

, Nippon Kayaku) 100 parts by mass

30 parts by mass of trimethylolpropane tritalylate

ITO dispersed particles (average particle size 65nm) 70 parts by mass

Surfactant (Silicone surfactant; FZ2207 (manufactured by Nippon Car))

0.5 parts by mass

50 parts by mass of propylene glycol monomethyl ether 500 parts by mass

The viscosity of the ink liquid was 40 ° C, and measured using a B-type viscometer BL manufactured by Tokyo Keiki Co., Ltd.

[0339] The above composition was mixed and stirred to prepare Ink Liquid 2 for the transparent resin layer.

[0340] Ink liquid 2 for transparent resin layer was applied, dried and irradiated with UV illumination of 0.1 lWZcm ² When a film prepared by curing at an amount of 0.1 lj / cm ² was measured with an Abbe refractometer, the refractive index was 1.556.

[0341] (Ink liquid for transparent resin layer 3)

30 parts by mass of trimethylolpropane tritalylate

Dispersion of silicon oxide fine particles (concentration of silicon oxide fine particles 20% by mass, dispersion solvent isopropanol, particle size 35 nm) 100 parts by mass

10 parts by mass

Surfactant (Silicone surfactant; FZ2207 (manufactured by Nippon Car))

0.5 parts by mass

The above composition was mixed and stirred to prepare an ink liquid 3 for a transparent resin layer.

[0342] The film prepared by applying the ink solution 3 for the transparent resin layer after being dried and cured with an ultraviolet illuminance of 0.1 lWZcm ² and an irradiation dose of 0.1 ljZcm ² was measured with an Abbe refractometer. The refractive index was 1.471.

[0343] << Measurement, Evaluation >>

(Measurement of convex structure diameter, convex structure height, number of convex structures, Ra, Sm)

The convex structure part diameter, convex structure part height, and number of convex structure parts (per lmm ² ) were measured using an optical interference type surface roughness measuring machine manufactured by WYKO using the film sample before applying the transparent resin layer. ¾4000 μm ² ($ aH (55 ^ m X 75 ^ m) was measured two-dimensionally, and the convex part was color-coded and displayed as a contour line from the bottom side, and the convex part height relative to the film surface was displayed. The length of the convex part, which is the major axis of the convex structure part, was measured, and the number of convex structure parts was obtained by converting the number of convex structure parts obtained per lmm ² . Ten arbitrary points of the relevant part of the material film were measured and obtained as an average value.

[0344] The surface roughness (Ra) and the average center-to-center distance (Sm) were measured using JIS B0601 using an optical interference surface roughness measuring machine manufactured by WYKO, using the sample after forming the transparent resin layer. It was measured by the measurement method. [0345] (Anti-glare effect)

In an office with a window, each film was spread on a desk, and fluorescent lighting on the ceiling and reflection of external light on the film were evaluated as follows.

[0346] 5: The outline of the fluorescent lamp and the outside light are blurred and I don't mind the reflection at all.

4: Between 5 and 3

3: Fluorescent light outline and slight reflection of outside light are recognized

2: halfway between 3 and 1

1: The outline of the fluorescent lamp and the external light are understood and the reflection is anxious

(Glare)

The produced film was visually checked for glare.

[0347] 5: I don't know any glare

4: Very little glare

3: I understand a slight glare

2: halfway between 3 and 1

1: I am very worried about glare

(Cloudy)

The produced film was visually judged for white turbidity.

[0348] 5: I don't care about cloudiness at all

4: Between 5 and 3

3: I feel a little cloudy

2: halfway between 3 and 1

1: I'm worried about the cloudiness

The above measurement and evaluation results are shown in Table 3 and Table 4 below.

[0349] [Table 3]

* 1 ΡΈ Screening concentration pattern

From Tables 3 and 4, the antiglare film 1 imparted with a fine concavo-convex structure by means of fine particle-added powder was inferior in power, glare, and white turbidity due to dispersion of fine particle dispersibility. The anti-glare film 2 with a fine uneven structure by embossing was slightly inferior in anti-glare effect and glare, and cloudy. In addition, the height and size of the fine concavo-convex structure differed between the head and tail of the antiglare film 2, and clogging due to the film dissolved in a part of the saddle was observed when the saddle was observed. [0352] On the other hand, the antiglare films 3 to 28 of the present invention were excellent in antiglare effect and glare, and were not at the level of white turbidity. In addition, the height and size of the fine concavo-convex structure at the front and rear of the anti-glare film are uniform, and it has been found that it has high uniformity and production stability.

[0353] In contrast to the anti-glare film 31 in which the uneven portion is covered with the transparent resin layer, the anti-glare film 20 in which the uneven portion is covered with the transparent resin layer is effective in improving the anti-glare property. Is clear.

[0354] Example 2

Next, the following surface treatment was performed on the surface of the hard coat layer or the transparent resin layer of the antiglare film 1 to 30 produced in Example 1.

[0355] <Surface treatment>

Alkali treatment: Each anti-glare film was immersed in 1.5molZl-NaOH aqueous solution heated to 50 ° C for 2 minutes for alkali treatment, washed with water, and then washed with 0.5 mass% -HSO aqueous solution at room temperature.

twenty four

It was pulverized for 30 seconds to neutralize, washed with water and dried.

[Preparation of antiglare antireflection film]

Next, the following low refractive index layer was applied on the hard coat layer or transparent resin layer of the antiglare films 1 to 30.

[0357] (Preparation of antireflection layer: low refractive index layer)

The following low refractive index layer coating composition 1 is applied by an extrusion coater, dried at 100 ° C for 1 minute, cured by UV irradiation at 0. UZcm ² and further cured at 120 ° C for 5 minutes. Then, a low refractive index layer was provided so as to have a thickness of 95 nm, and antiglare antireflection films 1 to 30 were produced. The refractive index of this low refractive index layer was 1.37.

[0358] The anti-glare anti-reflection film produced! /, Using a spectrophotometer (manufactured by JASCO Corporation), spectral reflectance at an incident angle of 5 ° in the wavelength region of 380 to 780 nm Was measured. Since the antireflection performance is wide and the reflectance is smaller in the wavelength region, the lower the reflectance in the range of 450 to 650 nm, the measurement result power was determined. In the measurement, the back side on the observation side was roughened, and then light absorption treatment was performed using a black spray to prevent reflection of light on the back side of the film, and the reflectance was measured. As a result of the measurement, all of the above antiglare antireflection films have a reflectance of 0.7 to 1.2 and show good results. [0359] (Preparation of low refractive index layer coating composition 1)

Hydrolyzate A was prepared by mixing 289 g of tetraethoxysilane and 553 g of ethanol, adding 157 g of a 0.15% acetic acid aqueous solution, and stirring in water nose at 25 ° C. for 30 hours.

[0360] Tetraethoxysilane hydrolyzate A 110 parts by mass

Hollow silica fine particles (P-2 below) 30 parts by mass of dispersion

KBM503 (Silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) 4 parts by mass 3% by mass of 10% propylene glycol monomethyl ether solution of linear dimethyl silicone-EO block copolymer (FZ-2207, manufactured by Nippon Car Co., Ltd.)

Propylene glycol monomethyl ether 400 parts by mass Isopropyl alcohol 400 parts by mass

A mixture of 100 g of silica sol with an average particle size of 5 nm and SiO concentration of 20 mass% and 1900 g of pure water 8

2

Warmed to 0 ° C. The pH of this reaction mother liquor is 10.5, and 0.98 mass as SiO in the mother liquor.

2

9000 g of 1% sodium silicate aqueous solution and 1.02 mass% sodium aluminate as Al O

twenty three

9000 g of aqueous solution was added simultaneously. 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, and after that, almost unchanged. After completion of the addition, the reaction solution is cooled to room temperature, washed with an ultrafiltration membrane, and a solid content concentration of 20 mass% SiO ·

2

An Al 2 O core particle dispersion was prepared. (Process (a))

twenty three

1700 g of pure water was added to 500 g of this core particle dispersion and heated to 98 ° C, and while maintaining this temperature, a sodium silicate aqueous solution obtained by dealkalizing with a cation exchange resin ( (SiO concentration: 3.5% by mass) of core particles with the addition of 3000 g to form the first silica coating layer

2

A dispersion was obtained. (Process (b))

Next, 1125 g of pure water was added to 500 g of the core particle dispersion formed with the first silica coating layer having a solid content concentration of 13% by washing with an ultrafiltration membrane, and further concentrated hydrochloric acid (35.5%) was added dropwise. The pH was adjusted to 0.1 and dealumination was performed. Next, the aluminum salt dissolved in the ultrafiltration membrane is separated while adding 10 L of pH 3 hydrochloric acid aqueous solution and 5 L of pure water, and the first silica coating layer is separated. SiO · Α1 ΟPorous particle dispersion with some of the constituents of the core particles forming

2 2 3

Was prepared (step (c)). A mixture of 1500 g of the above porous particle dispersion, 500 g of pure water, 1,750 g of ethanol, and 626 g of 28% ammonia water was heated to 35 ° C., and then 104 g of ethylsilique HSiO (28 mass%) was added. 1Surface of porous particles with silica coating

2

Was coated with a hydrolyzed polycondensate of ethyl silicate to form a second silica coating layer. Next, in V, a silica-based silica fine particle (P-2) dispersion with a solid concentration of 20% by mass was prepared by replacing the solvent with ethanol using an ultrafiltration membrane.

[0361] The thickness of the first silica coating layer of the hollow silica-based fine particles was 3 nm, the average particle size was 47 nm, M Ox / SiO 2 (molar ratio) was 0.0041, and the refractive index was 1.28. Where the average particle size is dynamic

2

It was measured by a light scattering method.

[Preparation of polarizing plate]

Next, polarizing plates were prepared using each of the antiglare and antireflection films 1 to 30.

[0363] A 120 m thick polybulal alcohol film was uniaxially stretched (temperature: 110 ° C, stretch ratio: 5 times). This was immersed in an aqueous solution consisting of 0.075 g of iodine, 5 g of potassium yowi and 100 g of water for 60 seconds, and then immersed in an aqueous solution of 68 ° C. consisting 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.

[0364] Next, according to the following steps 1 to 5, the polarizing film and the antiglare antireflection film 1 to 30, the cellulose ester film on the back side, Co-Camino Nortack KC8UCR5 (manufactured by Co-force Minolopt Co., Ltd.) The polarizing plate was produced by bonding. The polarizing plate protective film on the back side was a cellulose ester film having a phase difference, and the retardation values were Ro = 43 nm and Rt = 132 nm.

[0365] Step 1: An antiglare antireflection film in which the side to be bonded to the polarizing film is hatched by dipping in a 1 mol ZL sodium hydroxide solution at 50 ° C for 60 seconds, then washing with water and drying. A cellulose ester film was obtained.

[0366] Step 2: The polarizing film was immersed in a polybulal alcohol adhesive tank having a solid content of 2% by mass for 1 to 2 seconds.

[0367] Step 3: Lightly wipe off excess adhesive adhering to the polarizing film in Step 2, and place it on the anti-glare antireflection film or cellulose ester film processed in Step 1, and Lamination was done with the anti-reflection layer on the outside.

[0368] 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 NZcm ² and a conveying speed of about ² mZ.

[0369] Step 5: A sample obtained by bonding the polarizing film, the cellulose ester film, and the antiglare antireflection film 1 to 30 prepared in Step 4 in a dryer at 80 ° C is dried for 2 minutes to obtain a polarizing plate 1 ~ 30 were made.

[0370] <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.

[0371] A commercially available 32-inch liquid crystal television (MVA cell) was previously bonded, the polarizing plate on the surface was peeled off, and the above-prepared polarizing plates 1 to 30 were each bonded to the glass surface of the liquid crystal cell. did.

[0372] At that time, the direction of bonding of the polarizing plate is such that the surface of the cellulose ester film having a phase difference is on the liquid crystal cell side and in the same direction as the polarizing plate previously bonded. Liquid crystal display devices 1 to 30 were respectively produced so that the absorption axis was directed.

[0373] << Evaluation >>

The obtained liquid crystal display devices 1 to 30 were observed in an environment as shown in FIG. Visual evaluation was made according to the criteria. In addition, 10 40W fluorescent lamps (FLR40S—EX-D / M manufactured by Matsushita Electric) were installed on the ceiling. The window force was also evaluated in the state where external light was inserted.

[0374] (Visibility and black spots when displaying video)

As described above, we performed a comparative experiment by displaying a TV program video on the same display in an environment where artificial light from a fluorescent lamp and external light from window power were inserted. A moving image was observed at a position lm away from the front of the display for sensory evaluation.

[0375] 5: I don't mind the reflection of the fluorescent lamp at the top of the screen, and the center of the screen looks black even when there is external light.

4: Between 5 and 3

3: Slight reflection of fluorescent light at the top of the screen is recognized, and the center of the screen is slightly tired after observation if there is external light.

2: Between 3 and 1 1: Reflection of fluorescent light at the top of the screen is recognized, and the center of the screen lacks black spots due to external light, and eyes are tired when looking

Anti-glare antireflection film The composition of the liquid crystal display and the evaluation results are shown in Table 5 below.

[Table 5]

From Table 5, the liquid crystal display device 1 provided with a fine uneven structure by means of a fine particle additive is Due to dispersion of dispersibility, the antiglare effect and glare improvement were in progress, and the black color was inferior. The liquid crystal display device 2 provided with a fine concavo-convex structure by embossing had difficulty in forming a uniform concavo-convex structure, and was inferior to glare and black solids.

[0378] On the other hand, liquid crystal display devices 3 to 28 using the antiglare and antireflection film of the present invention include:

It is clear that it is excellent in antiglare effect, glare and blackness.

[0379] Example 3

[Preparation of anti-glare film 32 to 51 having convex structure portion by inkjet method] The same procedure except that ink liquid 4 for convex structure portion prepared in Example 1 was changed to the solvent and amount shown in Table 6. Method to prepare the ink liquid 7 for the convex structure, and display it by the inkjet method.

The convex structure described in 7 was formed.

[0380] The viscosity of each solvent was measured at 25 ° C using Piscomate VM-1G (manufactured by Yamaichi Electronics Co., Ltd.).

[0381] After applying ink liquid 7 for convex structure to substrate film and drying · Abbe's refractometer is made by curing with UV illumination of 0.1 lW / cm 2 and irradiation dose of 0 UZcm ² The refractive index was 1.522 as measured by.

[0382] [Preparation of antiglare film 32-51]

On the produced convex structure part, the ink solution 1 for transparent resin layer prepared in Example 1 was applied by a reduced pressure extrusion method to produce antiglare films 32 to 51.

[0383] [Evaluation of partial unevenness of antiglare film]

The produced anti-glare film was cut into A4 size (297 x 210mm), and the anti-glare layer was formed on the black acrylic board with 1mm thickness on the surface (acrylic resin manufactured by Nitto Seiryo Co., Ltd. The back surface was not reflected and the partial unevenness of the antiglare layer was visually determined according to the following criteria. For comparison, the comparative antiglare films 1 and 2 produced in Example 1 and the antiglare film 19 of the present invention were evaluated simultaneously.

[0384] 5 ... No partial unevenness

4 ... There is almost no partial unevenness

3… Partial unevenness can be confirmed faintly

2 ··· Partial unevenness but no practical problem! / 1 ···· Partial unevenness is clearly visible

Table 8 shows the measurement results.

[Preparation of antiglare antireflection film]

A low refractive index layer was coated on the transparent resin layer of the antiglare films 32 to 51 by the method described in Example 2.

[0386] [Evaluation of glare in minute range]

The obtained antiglare antireflection film was bonded to a glass substrate and fixed on a mask pattern (aperture ratio 25%) on a light box [Co-Power Minolta Co., Ltd .: AD-LUX SLIM A4]. In addition, the degree of glare in a minute range was observed with a magnifier (Tokai Sangyo Co., Ltd .: peak zoom magnifier 10-20 times) and magnified 20 times, and evaluated according to the following criteria.

[0387] As a comparison, the comparative antiglare antireflection films 1 and 2 produced in Example 2 and the antiglare antireflection film 19 of the present invention were evaluated simultaneously.

[0388] 5 · 'No glare in a minute range! / ヽ

4 ·· 'The glare of the minute range is almost not! / ヽ

3 ·· 'There is a slight glare, but there is no practical problem! / 問題

2 ... A slight range of glare is observed

1 · · 'There are many glare in a minute range

Table 8 shows the measurement results.

[0389] [Table 6]

§3

§ S]] 918

* 1: FM screening concentration pattern

Antiglare Antiglare Film Evaluation of Antiglare Antireflection Film

Antiglare

Anti-reflective

FINEREM Anti-glare remarks Minor range of notes Anti-glare effect Glare

No. Cloudiness

Partial unevenness Glitter

No.

1 1 2 4 1 2 1 Comparative example

2 2 1 3 3 2 2 Comparative example

19 19 2 5 5 5 3 Present invention

32 32 2 5 o 5 3 The present invention

33 33 2 5 5 5 3 The present invention

34 34 2 5 5 5 3 The present invention

35 35 2 5 5 5 3 The present invention

36 36 2 5 5 5 3 Present invention

37 37 2 5 5 5 5 Present invention

38 38 2 5 5 5 4 Present invention

39 39 2 5 5 5 4 Present invention

40 40 2 5 5 5 5 Present invention

41 41 2 5 5 5 5 Present invention

42 42 2 5 5 5 4 Present invention

43 43 3 5 5 5 4 Present invention

44 44 3 5 5 5 4 Present invention

45 45 4 5 5 5 5 Present invention

46 46 3 5 5 5 4 Present invention

47 47 4 5 5 5 5 Present invention

48 48 4 5 5 5 5 Present invention

49 49 5 5 5 5 5 Present invention

50 50 5 5 5 5 5 Present invention

51 51 3 5 5 5 4 Invention From Table 8, the antiglare film of the invention has excellent antiglare effect, glare and white turbidity, as well as glare and antiglare parts in a minute range. It is clear that it is excellent in manufacturing stability with little unevenness.

Claims

The scope of the claims

[1] On the base film, 10 to 10 LOOOO fine convex structures with a long diameter of 1 to 30 μm and a dot height of 0.5 to 10 μm per lmm ² Furthermore, a transparent resin layer is formed so as to cover the convex structure part, and the refractive index of the convex structure part and the transparent resin layer is the same.

[2] The antiglare film according to claim 1, wherein an antireflection layer or an antifouling layer is further formed on the transparent resin layer.

[3] The surface roughness (Ra) of the surface of the antiglare layer constituted by the convex structure portion and the transparent resin layer is

3. The antiglare film according to claim 1, wherein the antiglare film is 50 to: L000 nm, an average center-to-center distance (Sm) force between convex portions or concave portions of 0 to 200 μm.

[4] The prevention according to any one of claims 1 to 3, wherein the thickness of the transparent resin layer is 5 to 5 m thicker than the height of the convex structure portion. Dazzle film.

[5] The antiglare film according to any one of claims 1 to 4, wherein the convex structure part or the transparent resin layer is an actinic ray curable resin. .

[6] The antiglare film according to any one of [1] to [4], wherein the convex structure part or the transparent resin layer is a thermosetting resin.

[7] An ink composition containing at least 60% by mass of at least one solvent having a convex structure having a boiling point of 140 to 250 ° C and a viscosity measured at 25 ° C of 1 to 15 mPa's. The antiglare film according to any one of claims 1 to 6, wherein the antiglare film is formed.

[8] The antiglare film according to [7], wherein the solvent is a compound represented by the following general formula (1).

Formula (1) Rl— O— (C H -0) n-R2

2x

n: Integer from 1 to 3

x: integer from 2 to 4

[9] The antiglare film described in any one of claims 1 to 8 is used. A polarizing plate.

A display device comprising the antiglare film according to any one of claims 1 to 8, and the polarizing plate according to claim 9.