JP5298857B2 - Method for producing antireflection film - Google Patents

Abstract

This invention provides an antireflection film which has excellent anti-dazzling properties and scratch resistance, has a low reflectance, and, when used in a display device, has excellent visibility. The antireflection film comprises a transparent base material, at least one anti-dazzling layer having a fine concavoconvex structure provided on the base material, and a low-refractive index layer provided on the anti-dazzling layer either directly or through another layer. The antireflection film is characterized in that the low-refractive index layer is formed by depositing very small droplets of a coating liquid having a solid content of 5 to 100% by mass and having a viscosity of 2 to 15 mPa s at 25ºC.

Description

The present invention relates to a method for producing an antireflection film having antiglare properties, and in particular, has excellent antiglare properties and scratch resistance, low reflectance, and excellent antireflection properties when used in polarizing plates and display devices. The present invention relates to a film manufacturing method .

  In recent years, development of thin and light notebook computers has been progressing. 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. Also, a computer provided with an anti-glare layer for improving visibility, and also provided with an anti-glare layer that prevents reflections and scatters the reflected light with a rough surface to obtain display performance with less glare. A liquid crystal image display device (also referred to as a liquid crystal display) such as a word processor or the like has been widely used.

  Various types and performance improvements have been made to the antireflection layer and antiglare layer depending on the application, and various front plates with these functions are attached to the polarizer of a liquid crystal display, etc., to improve visibility on the display. Therefore, a method of providing an antireflection function or an antiglare function is used.

  The antiglare layer reduces the visibility of the reflected image by blurring the outline of the image reflected on the surface, and reflection of the reflected image is noticeable when using an image display device such as a liquid crystal display, an organic EL display, or a plasma display. It is to prevent it from becoming.

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

  In recent years, as image quality has been improved, a display device having anti-glare properties and high contrast has been demanded. For example, when a conventional antiglare film such as the fine particle method is bonded to the outermost surface of a liquid crystal display device, there is a problem that the contrast is insufficient or the film surface is easily damaged. In addition, in the antireflection layer provided on the clear hard coat film, reflection of external light becomes a problem.

In order to cope with this problem, many techniques 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 Documents 3 to 8). reference.). However, when a thin antireflection layer is formed on the antiglare film by coating, the coating solution causes leveling, and the fine unevenness of the antiglare film is lost to some extent. Since the thickness of the prevention layer is different, a uniform antireflection effect cannot be obtained, and sufficient antiglare properties and contrast have not been obtained.
JP 59-58036 A JP-A-6-234175 JP 2005-227407 A JP 2000-84477 A JP 2001-281410 A Japanese Patent Laid-Open No. 2004-4404 JP 2004-125985 A JP 2004-24967 A

Therefore, the present invention has been made in view of the above problems, and its purpose is to produce an antireflection film that is excellent in antiglare property and scratch resistance, has low reflectance, and has excellent visibility when used in a display device. It is to provide a method .

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

1. A method for producing an antireflection film comprising at least one antiglare layer having a fine uneven structure on a transparent substrate, and forming a low refractive index layer directly or via another layer on the antiglare layer. The low refractive index layer is formed by an ink jet method, and the low refractive index layer is formed of a coating solution containing a solid content of 20 to 100% by mass and a viscosity at 25 ° C. of 6.5 to 15 mPa · s. The manufacturing method of the antireflection film characterized by these.

2. The low refractive index layer is formed of a coating liquid containing 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. of 60% or more of the mass excluding the solid content. The manufacturing method of the antireflection film as described in 1 above.

3. The coating solution is an ink containing a thermosetting resin or an actinic ray curable resin, and after landing the coating solution on a substrate, it is heated or irradiated with actinic rays within 0.1 seconds to 1 minute. 3. The method for producing an antireflection film according to item 1 or 2, which solidifies.

4). From the first item to the second item, the layer thickness hd1 of the low refractive index layer formed on the convex portion of the antiglare layer and the layer thickness hd2 of the low refractive index layer formed on the concave portion satisfy the following relational expression: 4. The method for producing an antireflection film according to any one of items 3 to 3.
(Formula) hd1 / hd2 ≧ 0.4

According to the present invention, a method for producing an antireflection film that is excellent in antiglare property and scratch resistance, has low reflectance, and has excellent visibility when used in a display device can be provided.

It is a schematic diagram which shows the structure of the antireflection film of this invention. It is sectional drawing which shows an example of the inkjet head which can be used for the inkjet system used for this invention. It is the schematic which shows an example of the inkjet head part and nozzle plate which can be used by this invention. It is a schematic diagram which shows an example of the inkjet system which can be preferably used by this invention. It is the schematic diagram which showed a mode that gentle unevenness | corrugation was formed by covering both the convex part and the part without a convex part with a transparent resin layer. It is a schematic diagram of a fine uneven structure preferable for the present invention. It is a flow of contact angle measurement. It is an example of a method for forming a fine concavo-convex structure on a base film by an inkjet method.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Base film 11 Board | substrate 12 Piezoelectric element 13 Flow path plate 13a Ink flow path 13b Wall part 14 Common liquid chamber structural member 15 Ink supply pipe 16 Nozzle plate 16a Nozzle 17 Drive circuit printed board 18 Lead part 19 Drive electrode 20 Groove 21 Protective plate 22 Fluid resistance 23, 24 Electrode 25 Upper partition wall 26 Heater 27 Heater power supply 28 Heat transfer member 29 Actinic ray irradiation unit 30 Inkjet head 31 Liquid droplet 32 Nozzle 35 Back roll 101 Laminated roll 103 First coater 104A-D Back roll 105A ~ D Drying zone 106A ~ E Actinic ray irradiation part 107 Plasma processing part 108 Ink supply tank 109 Inkjet emitting part 110 Heating part 113 Winding roll

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

  Conventionally, for the purpose of improving contrast, there is a technique for applying an antireflection layer on an antiglare film having a fine uneven structure, but a coating solution for forming an antireflection layer on the fine uneven structure of an antiglare film Caused leveling, and the anti-glare performance intended by the fine concavo-convex structure was lost.

  As a result of intensive studies, the present inventors have made it possible to reduce the reflectance while maintaining the antiglare property by following the fine concavo-convex structure of the antiglare layer with the structure of the present invention, Further, the present inventors have found that the film strength and scratch resistance and scratch resistance can be improved.

That is, the antireflection film of the present invention the production method (hereinafter, also referred to as antiglare and antireflection film), at least 1 Soyu an antiglare layer having a fine uneven structure on a transparent substrate, and antiglare A method for producing an antireflection film in which a low refractive index layer is formed directly on the layer or via another layer, wherein the low refractive index layer is formed by an ink jet method, and the low refractive index layer is formed in an amount of 20 to 100 mass. % Solid content and a viscosity at 25 ° C. of 6.5 to 15 mPa · s.

Therefore, layer thickness hd2 of the low refractive index layer formed in a layer thickness hd1 and recessed portions of the low refractive index layer formed on the convex portion of the antiglare layer is a reflection preventing film which satisfies the following equation preferable.

(Formula) hd1 / hd2 ≧ 0.4
Further, the low refractive index layer is preferably formed by adhesion of fine droplets by an ink jet method.

  According to the ink jet method, a wet film thickness (hw) can be thinly applied using a coating solution (ink) having a high concentration and a high viscosity as compared with the formation of an antireflection layer by a conventional coating method. As a result, the present inventors have found that the solidification speed of the coating liquid is improved and leveling on the concavo-convex structure as in the conventional coating liquid can be avoided. Therefore, since the fine concavo-convex structure that exhibits antiglare property is formed in a state having the intended concavo-convex structure on the outermost surface of the antireflection film, the antiglare property is not impaired. In addition, since the film thickness is substantially uniform, the refractive index is further reduced, and the film strength and scratch resistance are improved.

  Hereinafter, the present invention will be described in detail.

<Low refractive index layer>
The refractive index of the low refractive index layer according to the present invention is preferably lower than the refractive index of the substrate film as the support, and is preferably in the range of 1.30 to 1.45 at 23 ° C. and a wavelength of 550 nm. The refractive index is obtained from the measurement result of the spectral reflectance of the antireflection layer provided on the hard coat layer. Spectral reflectivity is measured using FE-3000 (manufactured by Otsuka Electronics Co., Ltd.) after roughening the back surface of the sample and then performing light absorption treatment with black spray to prevent light reflection on the back surface. The refractive index is obtained by analyzing and fitting the spectral reflectance with FE-3000 software.

  The spectral reflectance of the antireflection layer is preferably as low as possible, but the average value in the visible light region wavelength is preferably 1.5% or less, and the minimum reflectance is preferably 0.8% or less. Moreover, it is preferable to have a flat reflection spectrum in the wavelength region of visible light.

  The structure of the antireflection film of the present invention is shown in FIG.

As shown in the figure, the antireflection film of the present invention has a low refractive index layer of 20 to 100% by mass on the antiglare layer, which will be described later, directly by ink jet method or via another layer. it is characterized in that the viscosity of including 25 ° C. to form a coating solution of 6.5 ~15mPa · s.

Therefore, layer thickness hd2 of the low refractive index layer formed in a layer thickness hd1 and recessed portions of the low refractive index layer formed on the convex portion of the antiglare layer is a reflection preventing film which satisfies the following equation preferable.

(Formula) hd1 / hd2 ≧ 0.4
Refer to FIG. 1B for hd1 and hd2.

The value of the layer thickness ratio hd1 / hd2 in the above formula is preferably 0.4 or more and 1.2 or less, more preferably 0.6 or more and 1.0 or less, and particularly preferably 0.8 or more and 1. 0 or less. When the layer thickness ratio is ≧ 0.4, an antiglare antireflection film having a low reflectance and having both antiglare properties and scratch resistance can be obtained.

  The thickness of the low refractive index layer is preferably in the range of 0.05 to 0.20 μm from the viewpoint of antireflection effect and scratch resistance, and more preferably 0.06 to 0.15 μm.

  The film thickness of the low refractive index layer can be obtained from a tomographic image of an electron microscope. About the created antireflection film, a tomographic photograph was taken at an enlargement magnification of 2 to 100,000 times, and the film thicknesses of 10 portions of each of the convex part and the concave part confirmed visually were measured and averaged from the tomographic picture using a scale. Was defined as the film thickness. A commercially available electron microscope can be used, for example, Hitachi Scanning Transmission Electron Microscope HD-2700.

  The method for forming the low refractive index layer by adhering microdroplets is not particularly limited, but it is preferable to use a known spray coating method or ink jet method, and in the present invention, particularly in terms of reproducibility and uniformity. It is preferable to use an inkjet method.

  Hereinafter, the formation of the low refractive index layer using the inkjet method will be described in detail.

  FIG. 2 is a cross-sectional view showing an example of an ink jet head used in an ink jet system suitable for the present invention.

  2A is a cross-sectional view of the inkjet head, and FIG. 2B is an enlarged view taken along the line AA in FIG. 2A. In the figure, 11 is a substrate, 12 is a piezoelectric element, 13 is a flow path plate, 13a is an ink flow path, 13b is a wall, 14 is a common liquid chamber constituent member, 14a is a common liquid chamber, 15 is an ink supply pipe, 16 Is a nozzle plate, 16a is a nozzle, 17 is a drive circuit printed board (PCB), 18 is a lead portion, 19 is a drive electrode, 20 is a groove, 21 is a protective plate, 22 is a fluid resistance, 23 and 24 are electrodes, 25 Is an upper partition, 26 is a heater, 27 is a heater power source, 28 is a heat transfer member, and 30 is an ink-jet head.

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

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

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

  FIG. 3 is a schematic view showing an example of an inkjet head unit and a nozzle plate that can be used in the present invention.

  3, (a) of FIG. 3 is a sectional view of the head portion, and (b) of FIG. 3 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 droplet 31 ejected from the nozzle 32 flies in the direction of the base film 10 and adheres. The ink droplets that have landed on the substrate film 10 are immediately irradiated with actinic rays from the actinic ray irradiating unit disposed upstream thereof, and are cured. Reference numeral 35 denotes a back roll for holding the base film 10.

  In the present invention, as shown in FIG. 3B, the nozzles of the inkjet head unit are preferably arranged in a staggered manner, and provided in multiple stages in parallel in the transport direction of the base film 10. preferable. Further, it is preferable that fine vibrations are applied to the ink jet head portion during ink ejection so that ink droplets land randomly on the transparent substrate. Thereby, generation | occurrence | production of an interference fringe can be suppressed. The fine vibration can be given by a high frequency voltage, a sound wave, an ultrasonic wave or the like, but is not particularly limited thereto.

  The method for forming a low refractive index layer of the present invention preferably uses an ink jet method in which small ink droplets are ejected from multiple nozzles. FIG. 4 shows an example of an ink jet system that can be preferably used in the present invention.

  4, (a) in FIG. 4 is a method in which the inkjet head 30 is arranged in the width direction of the transparent substrate film 10 and a low refractive index layer is formed on the surface of the transparent substrate film 10 while being conveyed ( (B) in FIG. 4 is a method (flat head method) in which the inkjet head 30 moves in the sub-scanning direction and forms a low refractive index layer on the surface thereof (c) in FIG. Is a method (capstan method) in which the inkjet head 30 forms a low refractive index layer on the surface of the transparent substrate film 10 while scanning in the width direction, and any method can be used. In the invention, the line head method is preferable from the viewpoint of productivity. In addition, you may attach the actinic ray irradiation part used when the below-mentioned actinic ray curable resin is used as an ink like 29 of (a)-(c) of FIG.

  Moreover, in this invention, you may provide another actinic ray irradiation part in the downstream of the conveyance direction of the base film of (a) of FIG. 4, (b), (c).

  In the present invention, in order to apply the low refractive index layer with a desired film thickness to the uneven shape of the antiglare layer, the ink droplet is preferably 0.1 to 20 pl, more preferably 0.5 to 10 pl, 0.5-5 pl is particularly preferred. Also, different ink droplet amounts may be ejected from different ink jet head portions, and ink may be ejected from the same ink jet head portion while changing the amount of liquid droplets. It may be.

  Next, the ink liquid composition for a low refractive index layer according to the present invention will be described.

  The ink composition for the low refractive index layer (also referred to as coating solution) used in the present invention is an organosilicon compound or a hydrolyzate or polycondensate thereof, hollow silica-based fine particles, actinic ray curable resin, thermosetting It is preferable to contain a resin or a metal alkoxide or a hydrolyzate thereof, and it is particularly preferable to contain an actinic ray curable resin having a refractive index of 1.45 or less or a thermosetting resin.

(Organic silicon compound)
The organosilicon compound that can be used in the ink composition for a low refractive index layer of the present invention is preferably a compound represented by the following general formula (1).

General formula (1) Si (OR) ₄
In the formula, R represents an alkyl group having 1 to 4 carbon atoms.

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

  As a method of 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 added to the dispersion of the hollow silica fine particles. The silicic 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, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

  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 (2).

In the formula, R ^{1 to} R ⁶ are alkyl groups having 1 to 16 carbon atoms, preferably 1 to 4 carbon atoms, halogenated alkyl groups having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, 6 to 12 carbon atoms, preferably 6 carbon atoms. 10 to 10 aryl groups, 7 to 14 carbon atoms, preferably 7 to 12 alkylaryl groups, arylalkyl groups, 2 to 8 carbon atoms, preferably 2 to 6 alkenyl groups, or 1 to 6 carbon atoms, preferably 1 to 3 alkoxy groups, a hydrogen atom or a halogen atom.

Rf represents-(CaHbFc)-, a is an integer of 1 to 12, b + c is 2a, b is an integer of 0 to 24, and c is an integer of 0 to 24. Such Rf is preferably a group having a fluoroalkylene group and an alkylene group. Specifically, as such a fluorine-containing silicone compound, (MeO) ₃ SiC ₂ H ₄ C ₂ F ₄ C ₂ H ₄ Si (MeO) ₃ , (MeO) ₃ SiC ₂ H ₄ C ₄ F ₈ C ₂ H ₄ Si (MeO) ₃ , (MeO) ₃ SiC ₂ H ₄ C ₆ F ₁₂ C ₂ H ₄ Si (MeO) ₃ , (H ₅ C ₂ O) ₃ SiC ₂ H ₄ C ₄ F ₈ C ₂ H Examples include methoxydisilane compounds represented by ₄ Si (OC ₂ H ₅ ) ₃ , (H ₅ C ₂ O) ₃ SiC ₂ H ₄ C ₆ F ₁₂ C ₂ H ₄ Si (OC ₂ H ₅ ) ₃ , and the like.

  If the fluorine-containing alkyl group-containing silane compound is included as a binder, the transparent film itself is hydrophobic, so the transparent film is not sufficiently densified and is porous or cracked. Even if it has a void or a void, entry into the transparent film by chemicals such as moisture, acid and alkali is suppressed. Furthermore, fine particles such as metals contained in the substrate surface or the lower layer do not react with chemicals such as moisture, acid and alkali. For this reason, such a transparent film has excellent chemical resistance.

  In addition, when a fluorine-substituted alkyl group-containing silane compound is included as a binder, not only such hydrophobicity but also good slipperiness (low contact resistance) is obtained, and thus a transparent film having excellent scratch resistance is obtained. be able to.

  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, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane. Ethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltri Acetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropyltri Ethoxysilane, γ- (β-glycidyloxyethoxy) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ- Acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N- Examples include β- (aminoethyl) -γ-aminopropyltrimethoxysilane and β-cyanoethyltriethoxysilane.

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

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

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

  Examples of the polymer used as the other binder of the low refractive index layer include polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, and alkyd resin.

(Hollow silica fine particles)
The low refractive index layer of the present invention preferably contains hollow silica-based fine particles having an outer shell layer and having a porous or hollow interior.

  The hollow silica-based fine particles are (I) composite particles comprising porous particles and a coating layer provided on the surface of the porous particles, or (II) having cavities inside, and the contents are solvent, gas or porous It is a hollow particle filled with a porous material. The low refractive index layer may contain either (I) composite particles or (II) hollow particles, or may contain both.

  The hollow particles are particles having cavities inside, and the cavities are surrounded by particle walls. The cavity is filled with 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 to be used are appropriately selected according to the thickness of the transparent coating to be formed, and may be in the range of 2/3 to 1/10 of the thickness of the transparent coating such as the low refractive index layer to be formed. desirable. 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, diacetone alcohol) are preferable.

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

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

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

  Incidentally, the pore volume of such porous particles can be determined by a mercury intrusion method. Examples of the contents of the hollow particles include a solvent, a gas, and a porous substance used at the time of preparing the particles. The solvent may contain an unreacted particle precursor used when preparing the hollow particles, the catalyst used, and the like. Examples of the porous substance include those composed of the compounds exemplified for the porous particles. These contents may be composed of a single component or may be a mixture of a plurality of components.

  As a method for producing such hollow silica-based fine particles, for example, the method for preparing complex oxide colloidal particles disclosed in paragraphs [0010] to [0033] of JP-A-7-133105 is suitably employed.

  The content of the hollow silica-based fine particles in the low refractive index layer is preferably 10 to 50% by mass. In order to obtain the effect of a low refractive index, the content is preferably 15% by mass or more, and when it exceeds 50% by mass, the binder component is decreased and the film strength becomes insufficient. Most preferably, it is 20-50 mass%.

(Actinic ray curable resin, thermosetting resin)
The low refractive index layer according to the present invention is more preferably formed from an actinic ray curable resin or a thermosetting resin. In particular, it is preferably formed from an actinic ray curable resin or a thermosetting resin having a refractive index of 1.45 or less in a film state.

  The actinic ray curable resin preferably used for the liquid composition of the low refractive index layer will be described.

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

  Examples of the ultraviolet curable resin include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. be able to.

  UV curable acrylic urethane resins generally include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylates) in products obtained by reacting polyester polyols with isocyanate monomers or prepolymers. It can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate. For example, a mixture of 100 parts Unidic 17-806 (Dainippon Ink Co., Ltd.) and 1 part Coronate L (Nihon Polyurethane Co., Ltd.) described in JP-A-59-151110 is preferably used. .

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

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

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

  As examples of the ultraviolet curable epoxy acrylate resin and the ultraviolet curable epoxy resin, preferred examples of the epoxy actinic ray reactive compound are shown.

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

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

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

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

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

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

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

Formula (a)
[(R1) a (R2) b (R3) c (R4) dZ] w ⁺ [MeXv] w ⁻
Wherein cation is onium, Z is S, Se, Te, P, As, Sb, Bi, O, halogen (eg, I, Br, Cl), or N = N (diazo), R1, R2, R3 and R4 are organic groups which may be the same or different. a, b, c, and d are each an integer of 0 to 3, and a + b + c + d is equal to the valence of Z. Me is a metal or metalloid which is a central atom of a halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc. X is halogen, w is the net charge of the halogenated complex ion, and v is the number of halogen atoms in the halogenated complex ion.

Specific examples of the anion [MeXv] w− of the general formula (a) include tetrafluoroborate (BF ₄ ⁻ ), tetrafluorophosphate (PF ₄ ⁻ ), tetrafluoroantimonate (SbF ₄ ⁻ ), tetrafluoro Examples include arsenate (AsF ₄ ⁻ ) and tetrachloroantimonate (SbCl ₄ ⁻ ).

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

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

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

  In the ink liquid containing an actinic ray curable resin useful in the present invention, the photopolymerization initiator is generally 0.1 to 15 parts by mass with respect to 100 parts by mass of the actinic ray curable epoxy resin (prepolymer). The use of parts by mass is preferable, and addition of 1 to 10 parts by mass is more preferable.

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

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

  Specific examples of the ultraviolet curable resin that can be used in the present invention include, for example, Adekaoptomer KR, BY series KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B. (Asahi Denka Kogyo Co., Ltd.), Koeihard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T -102, D-102, NS-101, FT-102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Industry Co., Ltd.), Seika Beam PHC2210 (S), PHCX -9 (K-3), PHC2213, DP-10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, CR900 (above, manufactured by Dainichi Seika Kogyo Co., Ltd.), KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (above, Daicel UCB), RC-5015, RC-5016, RC-5020, RC -5031, RC-5100, RC-5102, RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (above, Dainippon Ink & Chemicals, Inc.), Aurex No. 340 clear (manufactured by China Paint Co., Ltd.), Sunrad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (above, Sanyo Chemical Industries, Ltd.) , SP-1509, SP-1507 (above, manufactured by Showa Polymer Co., Ltd.), RCC-15C (produced by Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (above, Toagosei Co., Ltd.) (Made by Co., Ltd.), or other commercially available products.

  Further, when an ultraviolet curable resin is used as the actinic ray curable resin, an ultraviolet absorber may be included in the ultraviolet curable resin composition to the extent that does not hinder the photocuring of the ultraviolet curable resin. As the ultraviolet absorber, those excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less and having little absorption of visible light having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display properties.

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

The actinic ray that can be used in the present invention can be used without limitation as long as it is a light source that activates the actinic ray curable resin formed in a pattern with ultraviolet rays, electron beams, γ rays, etc. Electron beams are preferable, and ultraviolet rays are particularly preferable in that they are easy to handle and high energy can be easily obtained. As the ultraviolet light source for photopolymerizing the ultraviolet reactive compound, any light source that generates ultraviolet light can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. An ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation, or the like can also be used. Irradiation conditions vary depending on each lamp, but the amount of irradiation light is preferably 1 mJ / cm ² or more, more preferably 20 mJ / cm ^{2 to} 10000 mJ / cm ² , and particularly preferably 50 mJ / cm ^{2 to} 2000 mJ / cm ^2. It is.

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

  In the present invention, the oxygen concentration in the atmosphere upon irradiation with actinic rays is preferably 10% or less, particularly preferably 1% or less. In order to obtain this atmosphere, it is effective to introduce nitrogen gas or the like.

  Moreover, in this invention, in order to advance the hardening reaction of actinic light efficiently, a base film etc. can also be heated. The heating method is not particularly limited, but it is preferable to use a heat plate, a heat roll, a thermal head, or a method of spraying hot air on the landed ink surface. Moreover, you may heat continuously by using the back roll used on the opposite side across the base film of a flexographic printing part as a heat roll.

  The heating temperature cannot be generally specified depending on the type of actinic ray curable resin to be used, but is preferably in a temperature range that does not affect the base film such as thermal deformation, and is preferably 30 to 200 ° C. Furthermore, 50-120 degreeC is preferable, Most preferably, it is 70-100 degreeC.

  Next, the thermosetting resin used for the ink composition for the low refractive index layer of the present invention will be described.

  Examples of the thermosetting resin used in the present invention include unsaturated polyester resins, epoxy resins, vinyl ester resins, phenol resins, thermosetting polyimide resins, and thermosetting polyamideimides.

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

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

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

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

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

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

  In addition, the antioxidant and ultraviolet absorber described in the ink liquid composition containing an actinic ray curable resin may be appropriately used for the ink liquid and the liquid composition made of the thermosetting resin used in the present invention. .

  The method for heating the thermosetting resin is not particularly limited, but it is preferable to use a method such as a heat plate, a heat roll, a thermal head, or hot air. Moreover, you may heat continuously as a heat roll the back roll used for film conveyance. The heating temperature cannot be generally defined by the type of thermosetting resin to be used, but is preferably in a temperature range that does not affect the heat deformation of the transparent substrate, preferably 30 to 200 ° C, Furthermore, 50-120 degreeC is preferable, Especially preferably, it is 70-100 degreeC.

<Fluorine resin>
In the present invention, it is preferable to use an actinic ray curable resin or a thermosetting resin having a refractive index of 1.45 or less in a film state, but a more preferable refractive index is in the range of 1.30 to 1.40.

(Measurement of refractive index)
The refractive index can be measured by applying a liquid composition containing the above resin to a substrate film and measuring the resulting film with a refractometer.

For example, a liquid composition containing a resin is applied using a micro gravure coater, dried at 90 ° C., and then irradiated using an ultraviolet lamp with an irradiance of 0.1 W / cm ² and an irradiation dose of 0.1 J / The coating layer is cured as cm ² to form a film having a thickness of 5 μm, and the refractive index is measured with an Abbe refractometer.

  Among the actinic ray curable resins or thermosetting resin compounds, fluorine-containing acrylic monomers, fluorine-containing polymers having one or more fluorine atoms and one or more acryloyl groups and / or methacryloyl groups in the molecule, or It preferably contains a fluorine-containing oligomer.

  A compound represented by the following general formula (b) or general formula (c) is preferably used.

In the general formula (b), R ¹ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a halogen atom. R ^f represents a fully or partially fluorinated alkyl group, alkenyl group, heterocycle, or aryl group. R ² and R ³ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, a hetero group, an aryl group, or a group defined by the above Rf. R ¹ , R ² , R ³ , and R ^f may each have a substituent other than a fluorine atom. Further, any two or more groups may be bonded to R ² , R ³ , and R ^f to form a ring structure.

In the general formula (b), A represents a fully or partially fluorinated n-valent organic group. R ⁴ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a halogen atom. R ⁴ may have a substituent other than a fluorine atom. n represents an integer of 2 to 8.

  Specific examples of the fluorine atom-containing acrylate compound include, for example, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, and 1H, 1H-perfluoro. -N-butyl (meth) acrylate, 1H, 1H-perfluoro-n-pentyl (meth) acrylate, 1H, 1H-perfluoro-n-hexyl (meth) acrylate, 1H, 1H-perfluoro-n-octyl (meth) acrylate 1H, 1H-perfluoro-n-decyl (meth) acrylate, 1H, 1H-perfluoro-n-dodecyl (meth) acrylate, 1H, 1H-perfluoroisobutyl (meth) acrylate, 1H, 1H-perfluoroisooctyl (meth) Acrylate, 1H, 1H-Perfluor Isododecyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-perfluoropentyl (meth) acrylate, 1H, 1H, 7H-perfluoroheptyl (meth) acrylate, 1H, 1H, 9H-perfluorononyl (meth) acrylate, 1H, 1H, 11H-perfluoroundecyl (meth) acrylate, 3,3,3-trifluoropropyl (meth) acrylate, 3,3,4,4,4-penta Fluorobutyl (meth) acrylate, 2- (perfluoro-n-propyl) ethyl (meth) acrylate, 2- (perfluoro-n-butyl) ethyl (meth) acrylate, 2- (perfluoro-n-hexyl) ethyl (meth) Acrylate, 2- (perfluoro-n-oct L) ethyl (meth) acrylate, 2- (perfluoro-n-decyl) ethyl (meth) acrylate, 2- (perfluoroisobutyl) ethyl (meth) acrylate, 2- (perfluoroisooctyl) ethyl (meth) acrylate, 3, 3,4,4-tetrafluorobutyl (meth) acrylate, 1H, 1H, 6H-perfluorohexyl (meth) acrylate, 1H, 1H, 8H-perfluorooctyl (meth) acrylate, 1H, 1H, 10H-perfluorodecyl (meth) ) Acrylate, 1H, 1H, 12H-perfluorododecyl (meth) acrylate, pentaerythritol diacrylate difluorobutyrate, Defensor OP (manufactured by Dainippon Ink & Chemicals, Inc.), OPSTAR JN (manufactured by JSR Corporation), OPSTAR JM JSR Co. Ltd.), Light Ester M-3F (manufactured by Kyoeisha Chemical Co.), manufactured by Light Ester FM-108 (manufactured by Kyoeisha Chemical Co.), and the like. In addition, although only 1 type may be used for the fluorine atom containing acrylate compound used here, you may mix and use 2 or more types of fluorine atom containing acrylate compounds in arbitrary ratios as needed. .

The ink composition for a low refractive index layer used in the present invention contains a solid content of 20 to 100% by mass as a whole. More preferably 25 to 85 wt%, more preferably from 30 to 70 wt%.

Viscosity of the low refractive index layer ink composition of the present invention, Ru 6.5 ~15mP · s der at 25 ° C.. When the viscosity is less than 6.5 mP · s, the viscosity is too low to obtain a pattern having a desired shape, and when it exceeds 15 mP · s, the fluidity of the ink is poor, and the ink emission is also lowered.

  The viscosity of the ink composition for the low refractive index layer can be adjusted depending on the type of resin, other additives, solvent, etc., and the ratio of the solid content, particularly the type and amount of the resin, and the solvent described later. It is preferable to adjust by the kind and amount.

  The viscosity of the ink is not particularly limited as long as it is tested with a standard solution for viscometer calibration specified in JIS Z 8809, and a rotary, vibration or capillary type viscometer can be used. . As a viscometer, it can be measured with a Saybolt viscometer, a Redwood viscometer, etc., for example, Tokimec Co., Ltd., conical plate type E type viscometer, Toki Sangyo E Type Viscometer, manufactured by Tokyo Keiki Co., Ltd. No. B type viscometer BL, FVM-80A manufactured by Yamaichi Electronics Co., Ltd., Viscoliner manufactured by Nametore Industries Co., Ltd., VISCO MATE MODEL VM-1G manufactured by Yamaichi Electronics Co., Ltd., and the like.

(Contact angle)
In order to obtain the effect of the present invention, the contact angle (θ) between the ink liquid for a low refractive index layer of the present invention and an antiglare layer, which will be described later, which is a lower layer, or other layers is preferably 45 to 70 °, More preferably, it is 50-60 degrees. If it is 75 ° or more and 40 ° or less, the shape of the ink droplet may not be constant.

  In order to adjust the surface tension of the ink liquid for the low refractive index layer, silicone oil, modified silicone oil, silicone surfactant, fluorine surfactant, fluorine resin, fluorine oligomer, fluorine modified silicone oil, fluorine The active agent such as a silane coupling agent is preferably 0% by mass to 5% by mass. If the addition amount is too large, the height of the convex portion becomes too low, or the low refractive index layer cannot be applied on the unevenness of the antiglare layer due to the water / oil repellent effect. The surfactant does not necessarily need to be added because it also depends on the ink composition, the solvent composition, and the surface energy of the base substrate. The surfactant used in the present invention is described below.

  Silicone oils used in the present invention can be broadly classified into straight silicone oils and modified silicone oils depending on the type of organic groups bonded to silicon atoms. Straight silicone oil refers to those bonded with a methyl group, a phenyl group, or a hydrogen atom as a substituent. A modified silicone oil is one having a component that is secondarily derived from a straight silicone oil. On the other hand, it can be classified from the reactivity of silicone oil. These are summarized as follows.

Silicone oil Straight silicone oil 1-1. Non-reactive silicone oil: dimethyl, methylphenyl substitution, etc. 1-2. Reactive silicone oil: methyl hydrogen substitution, etc. Modified silicone oil Modified silicone oil was born by introducing various organic groups into dimethyl silicone oil 2-1. Non-reactive silicone oil: alkyl, alkyl / aralkyl, alkyl / polyether, 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 phenylalkyl group,
Polyether-modified silicone oil is a silicone-based polymer 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,
Amino-modified silicone oil is a silicone oil having a structure in which a part of methyl group of silicone oil is substituted with aminoalkyl group,
The epoxy-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 epoxy group-containing alkyl group,
The carboxyl-modified or alcohol-modified silicone oil is a silicone oil having a structure in which a part of the methyl group of the silicone oil is substituted with a carboxyl group or a hydroxyl group-containing alkyl group 2-2. Reactive silicone oil: amino, 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. If the number average molecular weight is less than 1,000, the drying property of the coating film decreases, and conversely, the number average molecular weight. When it exceeds 100,000, it tends to be difficult to bleed out to the coating surface.

  As specific products, Nippon Unicar Co., Ltd. L-45, L-9300, FZ-3704, FZ-3703, FZ-3720, FZ-3786, FZ-3501, FZ-3504, FZ-3508, FZ-3705, FZ-3707, FZ-3710, FZ-3750, FZ-3760, FZ-3785, FZ-3785, Y-7499, Shin-Etsu Chemical KF96L, KF96, KF96H, KF99, KF54, KF965, KF968, KF56, KF995, KF351, KF352, KF353, KF354, KF355, KF615, KF618, KF945, KF6004, FL100, and the like.

  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 a side chain of silicone oil, both ends, one end, both end side chains, and the like. Examples of the hydrophilic group include polyether, polyglycerin, pyrrolidone, betaine, sulfate, phosphate, and quaternary salt.

  A nonionic surfactant is a generic term for surfactants that do not have a group capable of dissociating into ions in an aqueous solution. In addition to a hydrophobic group, a hydrophilic group includes a hydroxyl group of a polyhydric alcohol, a polyoxyalkylene chain (poly Oxyethylene) 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.

  When a nonionic surfactant composed of dimethylpolysiloxane with a hydrophobic group and polyoxyalkylene with a hydrophilic group is used, unevenness of the low refractive index layer and antifouling property of the film surface are improved. It is thought that the hydrophobic group made of polymethylsiloxane is oriented on the surface and forms a film surface that is not easily soiled. This effect cannot be obtained by using other surfactants.

  Specific examples of these nonionic surfactants include, for example, Nippon Unicar 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-2120, FZ-2122, FZ-2123, FZ-2130, FZ-2154, FZ-2161, FZ-2162, FZ- 2163, FZ-2164, FZ-2166, FZ-2191 and the like.

  Moreover, SUPERSILWET SS-2801, SS-2802, SS-2803, SS-2804, SS-2805, etc. are mentioned.

  In addition, as a preferable structure of the nonionic surfactant in which the hydrophobic group is composed of dimethylpolysiloxane and the hydrophilic group is composed of polyoxyalkylene, a dimethylpolysiloxane structure portion and a polyoxyalkylene chain are alternately and repeatedly bonded. It is preferably a linear block copolymer. Since the main chain skeleton has a long chain length and a linear structure, it is excellent. This is considered to be due to the fact that one activator molecule can be adsorbed on the surface of the silica fine particle at a plurality of locations so as to cover the surface of the silica fine particle by being a block copolymer in which hydrophilic groups and hydrophobic groups are alternately repeated.

  Specific examples thereof include, for example, silicone surfactants ABN SILWET FZ-2203, FZ-2207, FZ-2208 and the like manufactured by Nippon Unicar Co., Ltd.

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

  A method for measuring the contact angle is shown in FIG. An aqueous solution sample to be measured is placed in a syringe-like droplet regulator (not shown). As shown to (a), the solid sample which adjusted the surface horizontally is mounted on the sample stand which can change a position up and down, right and left, and this solid sample surface is observed with an optical mirror. The optical mirror incorporates a rotatable rotating cloth. Droplets are made at the tip of a drop adjuster placed just above the solid sample.

  Next, as shown in (b), the surface of the solid sample is raised, and the droplet is brought into contact with the surface of the solid sample. Thereafter, as shown in (c), the solid sample is lowered to the original position, the droplet is transferred from the tip of the needle to the surface of the fixed sample, and the droplet is aligned with the center of the rotating cloth.

  Then, as shown in (d), the rotary cloth is rotated to create a tangent line between the droplet and the solid sample surface, and the angle θ is read. This θ is the contact angle.

  Since there is an individual error in this reading method, the contact angle reading method shown in (e) to (g) is performed based on the assumption that the droplet is a part of a circle.

  First, as shown in (e), the rotation cross is set to 45 °, and the sample stage is adjusted so that the cross is in contact with both sides of the droplet symmetrically. Next, as shown in (f), the sample stage is raised and the center of the cloth is aligned with the top of the droplet. Then, as shown in (g), the apex of the droplet, the solid sample, and the contact point of the droplet are connected, and the extension angle is measured. The angle becomes the half value θ / 2 of the contact angle θ. The contact angle of the present invention was measured using DropMaster (manufactured by Kyowa Interface Science Co., Ltd.).

(solvent)
Examples of the solvent that can be used in the ink composition for the low refractive index layer used in the present invention include 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 cellosolve, butyl cellosolve, and ethyl carbitol , Glycol ethers such as butyl carbitol, diethyl cellosolve, diethyl carbitol, propylene glycol monomethyl ether; N-methylpyrrolidone, dimethylformamide, methyl lactate, ethyl lactate, methyl acetate Le, ethyl acetate, esters such as amyl acetate; dimethyl ether, and diethyl ether, water and the like, can be used as a mixture thereof alone or in combination.

  In the ink composition for a low refractive index layer used in the present invention, among the above solvents, at least one kind of solvent having a boiling point of 140 to 250 ° C. and a viscosity of 1 to 15 mPa · s at 25 ° C. has a solid content. It is preferable that 60% by mass or more of the excluded mass is included. More preferably, at least one solvent having a boiling point of 180 to 230 ° C. and a viscosity of 1 to 10 mPa · 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 the low refractive index layer is preferably volatilized and dried as quickly as the desired pattern shape is maintained after transfer printing or landing. This is because the adhesion to the substrate is inferior and the unevenness of drying tends to occur in the formed low refractive index layer.

The boiling point in the present invention is a boiling point under a pressure of 1 atm, that is, 1.013 × 10 ⁵ N / m 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.

Among the solvents satisfying the above boiling point and viscosity, compounds represented by the following general formula (3) are more preferably used.
Formula _{(3) R 1 -O- (C} x H 2x -O) n-R 2
R _1, R _2: a hydrogen atom, an aryl group, an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group, an alkylcarbonyl group. The hydrocarbon chain may be linear or branched. However, at least one of R ₁ and R ₂ is a substituent other than a hydrogen atom.

n: an integer of 1 to 3 x: an integer of 2 to 4 More preferably, x = 2 or 3, and R ₂ is an acetyl group.

  Specific examples of the solvent preferably used in the ink of the present invention include the following solvents, but are not limited thereto.

  Furthermore, specific examples of the compound represented by the general formula (3) include the following solvents, but the present invention is not particularly limited thereto.

  In addition to the above, ethylene glycol monoisopropyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-t-butyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol mono Isopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether, ethylene glycol monoisopropyl ether Tate, ethylene glycol mono-t-butyl ether acetate, diethylene glycol monomethyl ether 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 mono-t-butyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, ethylene glycol monomethoxymethyl ether, Ethylene glycol monoethyl ether acetate (also known as 2- (ethoxyethoxy) ethyl acetate), triethylene glycol dimethyl ether, diethylene glycol diacetate, propylene glycol diacetate (also known as 1,2-diacetoxypropane), dipropylene glycol dimethyl ether, di Propylene glycol monomethyl ether acetate and the like are also preferably used.

  The thickness of the low refractive index layer can also be controlled by mixing solvents having different boiling points and viscosities from these solvents and changing the ratio as appropriate.

  The viscosity of each solvent can be measured using the aforementioned Viscomate VM-1G (manufactured by Yamaichi Electronics Co., Ltd.).

  After the ink liquid for the low refractive index layer is applied, it is irradiated with actinic rays such as ultraviolet rays or electron beams, or is cured by heat treatment. An ink containing the thermosetting resin or actinic ray curable resin is used. After landing on the substrate as fine droplets, the droplets are preferably solidified by heating or irradiation with actinic rays immediately.

  Immediately performing the heating or irradiation with actinic rays means heating or irradiating within 5 minutes immediately after the ink has landed on the substrate, making the film thickness of the low refractive index layer uniform, In order to satisfy the above relational expression, the ratio of the film thickness hd1 of the low refractive index layer formed on the convex portion and the film thickness hd2 of the low refractive index layer formed on the concave portion is 0.1 second to 1 It is preferably performed within minutes, more preferably within 0.1 seconds to 30 seconds, and particularly preferably within 0.1 seconds to 1 second.

  In the present invention, an ink droplet that forms a low refractive index layer is landed by an ink jet method at any time when the antiglare layer applied on the transparent substrate is in an uncured state or after complete curing is completed. May be.

  Forming a low refractive index layer by landing ink droplets when the antiglare layer is half-cured (semi-cured) is not only excellent in productivity but also in close contact between the antiglare layer and the low refractive index layer. Since it can also improve property, it is preferable.

  Thus, the low refractive index layer according to the present invention can impart a concavo-convex shape to the surface without impairing the fine concavo-convex shape that exhibits the antiglare property of the antiglare layer. The arithmetic average surface roughness Ra defined by JIS B 0601 on the surface of the low refractive index layer is preferably in the range of 0.05 μm to 1.00 μm, more preferably in the range of 0.10 μm to 0.50 μm. is there.

<Anti-glare layer>
The antiglare layer according to the present invention reduces the visibility of the reflected image by blurring the outline of the image reflected on the surface, and reflects the reflected image when using an image display device such as a liquid crystal display, an organic EL display, or a plasma display. It is intended to prevent you from worrying about the reflection. By providing appropriate irregularities on the film surface, such properties can be imparted.

  As a method for forming such irregularities, processing to a transparent substrate, processing to a hard coat layer provided on the transparent substrate, processing to an antireflection film after applying an antireflection layer, and the like can be selected. However, since the processing to the antireflection film may damage the antireflection effect by deforming the antireflection layer, such as the concavo-convex convex portion breaks through the antireflection layer, in the present invention, the processing to the transparent substrate, Processing into a hard coat layer is preferred, and in the present invention, processing into a hard coat layer is more preferred.

  Examples of the concavo-convex structure referred to in the present invention include structures selected from right cones, oblique cones, pyramids, oblique pyramids, wedge shapes, convex polygons, hemispheres, and the like, and structures having partial shapes thereof. Note that the hemispherical shape does not necessarily have a true spherical shape, and may be an ellipsoidal shape or a more deformed convex curved shape. Moreover, the prism shape, the lenticular lens shape, and the Fresnel lens shape in which the ridge line of the concavo-convex shape extends linearly can also be mentioned. The slope from the ridge line to the valley line may be flat, curved, or a combination of both.

Examples of a method for forming a concavo-convex shape on the surface of the hard coat layer or the transparent substrate described later include the following methods.
(1) A method in which a negative shape having a desired shape is formed on a roll or master, and the shape is given by embossing.
(2) A method in which a negative mold having a desired shape is formed on a roll or a master, a thermosetting resin is filled into the negative mold, and the film is peeled off from the negative mold after heat curing.
(3) A negative shape of a desired shape is formed on a roll or a master, and after applying ultraviolet rays or electron beam curable resin and filling the concave portions, ultraviolet rays are applied while the transparent support is coated on the intaglio via a resin liquid. Alternatively, a method in which the cured resin and the transparent support to which it is adhered are peeled from the negative mold by irradiation with an electron beam.
(4) A solvent casting method in which a negative shape having a desired shape is formed on a casting belt and the desired shape is imparted during casting.
(5) A method in which a resin that is cured by light or heating is relief-printed on a transparent substrate and is cured by light or heating to form irregularities.
(6) A method in which a resin that is cured by light or heating is printed on the surface of the transparent support by an ink jet method, and is cured by light or heating to make the surface of the transparent support uneven.
(7) A method of cutting the surface with a machine tool or the like.
(8) A method in which particles of various shapes such as spheres and polygons are pressed and integrated so as to be partially buried in the surface of the transparent support to make the surface of the transparent support uneven.
(9) A method in which fine particles of various shapes such as spheres and polygons are dispersed in a small amount of binder and applied to the surface of the transparent support to make the surface of the transparent support uneven.
(10) A method in which a binder is applied to the surface of the transparent support, and particles of various shapes such as spheres and polygons are dispersed thereon to make the surface of the transparent support uneven.

  In the present invention, (6) and (9) are preferably the method for creating a concavo-convex shape on the hard coat layer.

  First, as an example of the antiglare layer constituting the antireflection film of the present invention, the method for producing the uneven shape of (9) will be described.

<Creation of antiglare layer using fine particles>
The antiglare layer used in the present invention can form fine irregularities by containing fine particles in the hard coat layer, and the hard coat layer contains fine particles having an average particle size of 0.01 μm to 4 μm as described below. It is preferable. Hereinafter, the antiglare layer is also referred to as an antiglare hard coat layer.

(Particles contained in the antiglare hard coat layer)
As particles contained in the antiglare hard coat layer, for example, inorganic or organic fine particles are used.

  Examples of the inorganic fine particles include silicon oxide, titanium oxide, aluminum oxide, tin oxide, zinc oxide, calcium carbonate, barium sulfate, talc, kaolin, and calcium sulfate. The organic fine particles include polymethacrylate methyl acrylate resin fine particles, acrylic styrene resin fine particles, polymethyl methacrylate resin fine particles, silicon resin fine particles, polystyrene resin fine particles, polycarbonate resin fine particles, benzoguanamine resin fine particles, and melamine resin. Examples thereof include fine particles, polyolefin resin fine particles, polyester resin fine particles, polyamide resin fine particles, polyimide resin fine particles, and polyfluoroethylene resin fine particles.

  In the present invention, silicon oxide fine particles or polystyrene resin fine particles are particularly preferable.

  The inorganic or organic fine particles described above are preferably used in addition to a coating composition containing a resin or the like used for producing an antiglare hard coat layer. In addition, the average particle size of these fine particles is preferably 0.01 μm to 4 μm, more preferably 0.01 μm to 3 μm.

  In order to impart antiglare properties to the antiglare hard coat layer used in the present invention, the content of the inorganic or organic fine particles is set to 0.000 parts by mass with respect to 100 parts by mass of the resin for preparing the antiglare hard coat layer. 1 mass part-30 mass parts are preferable, More preferably, it is mix | blending so that it may become 0.1 mass part-20 mass parts. In order to give a more preferable antiglare effect, it is preferable to use 1 part by mass to 15 parts by mass of fine particles having an average particle size of 0.1 μm to 1 μm with respect to 100 parts by mass of the resin for preparing the antiglare hard coat layer. . It is also preferable to use two or more kinds of fine particles having different average particle diameters.

(Arithmetic average surface roughness (Ra) of antiglare hard coat layer
The antiglare hard coat layer used in the present invention has a surface with fine irregularities, but as described above, the irregularities on the outermost surface of the antireflection layer provided on the antiglare hard coat layer are as follows: It is preferable that the fine particles described above are appropriately selected, added and adjusted so that the arithmetic average surface roughness (Ra) defined in JIS B 0601 falls within the range of 0.05 μm to 1.00 μm.

(Fine irregularities on the antiglare hard coat layer)
The fine irregularities on the surface of the antiglare hard coat layer used in the present invention can be obtained by adjusting the addition amount, particle size, film thickness, etc. of the fine particles described above to form an antiglare hard coat layer having more preferable irregularities. Can be obtained. Further, the fine irregularities on the surface of the antiglare hard coat layer used in the present invention are fine having 5 to 20 convex portions per 100 μm ² having a height of 0.5 μm to ² μm with reference to the adjacent concave bottom. It is preferably formed as a structure.

Fine irregularities on the surface of the antiglare hard coat layer can be measured by a commercially available stylus type surface roughness measuring machine or a commercially available optical interference type surface roughness measuring machine. For example, the unevenness is measured two-dimensionally in the range of about 4000 μm ² (55 μm × 75 μm) using an optical interference type surface roughness measuring device, and the unevenness is color-coded as a contour line from the bottom side and displayed.

Here, the number of convex portions having a height of 0.5 μm to ² μm with respect to the adjacent bottom portion was counted and represented by the number per 100 μm ² area. The measurement was carried out by measuring 10 arbitrary points per 1 m ² of the antiglare and antireflection film and obtaining the average value.

Further, the surface of the antiglare hard coat layer according to the present invention preferably has a fine structure having 80 or more protrusions per 100 μm ² having a height of 0.2 μm or more based on the average level of the surface. Also for this fine structure, the unevenness is measured two-dimensionally in a range of about 4000 μm ² (55 μm × 75 μm) with an optical interference surface roughness measuring device in the same manner as described above. A portion that is color-coded and displayed in at least three regions, a portion having a height of less than 0.2 μm and a portion having a height of 0.2 μm or more, and a portion having a height of 0.2 μm or more. Can be counted and expressed as a number per 100 μm ² area.

(Average crest and valley spacing of fine irregularities on the surface of the antiglare hard coat layer)
The antiglare hard coat layer used in the present invention preferably has an average crest / valley spacing of 1 μm to 80 μm, and more preferably 10 μm to 40 μm.

  Here, the shape of the fine concavo-convex structure can be measured by a stylus type surface roughness measuring machine or the like. It is possible to obtain knowledge as a surface roughness curve obtained by scanning the surface with a length of 3 mm in a certain direction and measuring the movement change in the vertical direction of the measuring needle in that case. Alternatively, it can be measured by an optical interference type surface roughness measuring machine as described above.

  Here, the average peak-and-valley interval is assumed to be a reference line on which the unevenness change of the surface roughness curve can be evaluated as a protrusion based on a portion where the unevenness change in the surface roughness curve is minute (portion close to flat), Based on the intersection of the surface roughness curve passing from the bottom to the top (or from the top to the bottom) of the surface roughness curve with the average height of the convex part from the reference line as the center line, the distance between the intersections Can be defined as average.

(Refractive index of antiglare hard coat layer)
The refractive index of the antiglare hard coat layer used in the present invention is 1.5 to 2.0, particularly 1.6 to 1.7, from the viewpoint of optical design for obtaining a low-reflective film. Is preferred. The refractive index of the antiglare hard coat layer can be adjusted depending on the refractive index and content of the fine particles or inorganic matrix to be added.

(Film thickness of antiglare hard coat layer)
From the viewpoint of imparting sufficient durability and impact resistance, the dry film thickness of the antiglare hard coat layer is preferably in the range of 0.5 μm to 15 μm, more preferably 3 to 10 μm, more preferably 5 to 5 μm. 10 μm.

(Haze of antiglare hard coat layer)
In order to obtain the effect (contrast improvement) described in the present invention, the haze of the antiglare hard coat layer is preferably 5% to 40%, and more preferably 6% to 30%.

  Here, the haze can be measured according to ASTM-D1003-52.

  As a means for adjusting the haze value of the antiglare hard coat layer used in the present invention to a preferred range, the above-described organic fine particles and / or inorganic fine particles may be contained in the antiglare hard coat layer. Among them, silicon dioxide is preferably used because it is easily dispersed uniformly. In addition, those obtained by surface-treating fine particles such as silicon dioxide with an organic substance are also preferably used.

  The antiglare hard coat layer preferably contains an actinic ray curable resin such as ultraviolet rays used in the low refractive index layer or a thermosetting resin as a binder.

  Similarly, it is also preferable to contain a photopolymerization initiator, a photosensitizer, an ultraviolet absorber, an antioxidant, a surfactant and the like.

  The solvent for coating the antiglare hard coat layer can be appropriately selected from, for example, hydrocarbons, alcohols, ketones, esters, glycol ethers, and other solvents, or can be used by mixing. . Preferably, a solvent containing 5% by mass or more, more preferably 5% by mass to 80% by mass or more of propylene glycol mono (C1-C4) alkyl ether or propylene glycol mono (C1-C4) alkyl ether ester is used.

  As a method for applying the antiglare hard coat layer coating solution, a known method such as a gravure coater, a spinner coater, a wire bar coater, a roll coater, a reverse coater, an extrusion coater, or an air doctor coater can be used.

  The coating amount is suitably 5 μm to 30 μm, preferably 10 μm to 20 μm in terms of wet film thickness. The coating speed is preferably 10 m / min to 60 m / min.

  The antiglare hard coat layer composition is preferably applied and dried and then irradiated with an active energy ray such as an ultraviolet ray or an electron beam to be cured, but the irradiation time of the active energy ray is 0.5 seconds to 5 seconds. Minutes are preferable, and more preferably 1 second to 2 minutes in view of curing efficiency and work efficiency of the ultraviolet curable resin.

<Creation of anti-glare layer using inkjet method>
In this invention, it is preferable to form an uneven | corrugated | grooved part by a inkjet system on a transparent base material, and to make it an anti-glare layer. Furthermore, after forming convex portions on a transparent substrate or other cured resin layer in advance by an inkjet method, it is possible to achieve higher anti-glare properties by forming an anti-glare layer that overcoats the convex portions with a transparent resin. preferable.

  Therefore, the antiglare layer used in the present invention forms fine convex portions on a transparent substrate by an ink jet method, the convex portion has a diameter of 15 to 40 μm, and the convex portion has a height of 2 to 10 μm. In addition, it is preferable that a transparent resin layer is formed so as to cover the convex portion. As described above, the arithmetic average surface roughness Ra of the antiglare layer is preferably in the range of 0.05 μm to 1.00 μm, more preferably in the range of 0.10 μm to 0.50 μm.

  The projections are preferably formed by an ink jet method using the following pattern production method. Next, after the convex portion is cured by actinic rays or heating, it is transparent by a thin film uniform coating method such as a micro gravure method, an extrusion coating method, a wire bar method, a spray coating method, a flexographic printing method, and an ink jet method. It is produced by uniformly applying a resin layer.

  FIG. 6 is a diagram schematically showing the formation of the convex portion and the coating with the transparent resin layer of the present invention.

  FIG. 7 is a schematic diagram of a fine concavo-convex structure preferable for the present invention.

  (A) is sectional drawing which coat | covered the convex part formed on the transparent base film with the transparent resin layer, (b) provided the cured resin layer mentioned later on a transparent base film, and also a convex part and transparent It is sectional drawing which arranged the resin layer.

  As the device used in the ink jet system for forming the convex portion of the antiglare layer, the device described in the section of the low refractive index layer is preferably used.

  In the present invention, in order to form a fine uneven structure, the ink droplet is preferably 0.1 to 20 pl, more preferably 0.5 to 10 pl, and particularly preferably 0.5 to 5 pl. Also, different ink droplet amounts may be ejected from different ink jet head portions, and ink may be ejected from the same ink jet head portion while changing the amount of liquid droplets. It may be.

  The convex part has a convex part major axis of 15 to 40 μm, more preferably 15 to 30 μm, and the convex part has a constant size and height of 2 to 10 μm, more preferably 2 to 8 μm. It is preferable that the convex portions are arranged at random by a method such as FM screening. Here, the diameter of the convex portion represents the diameter when the convex portion is circular, and the diameter converted into the same area when the convex portion is triangular, quadrangular, polygonal, or indefinite. The height of a convex part means the difference of the height of the highest part of a dot from a base film surface.

  The FM screening method is a method for expressing light and shade by modulating the interval between dots, that is, the frequency, and the frequency of hitting the basic dots (dot density). The FM screening method is sometimes called a random screening method or a stochastic screening method. The FM screening method refers to a method of modulating the interval between dots, that is, periodicity. Specifically, the crystal raster screening method (Agfa Gebalt), the diamond screen method (Rhinotype Hell), the class screening method and the full-tone screening method (Cytex), the velvet screening method ( Ugura Cohan), Accutone Screening (Dannery), Megadot Screening (American Color), Clear Screening (Seacolor), Monet Screening (Barco) Yes. Although all of these methods have different dot generation algorithms, it is a method 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 dots on which ink is placed is constant, and the frequency of dot appearance changes according to the density of the image. Since the size of each dot in FM screening is smaller than a so-called halftone dot, a required pattern can be reproduced with high resolution. Unlike so-called halftone dots, dots in FM screening are not periodically arranged. The FM screening has a feature that moire does not occur because the dot arrangement is not periodic.

  For the liquid composition of the convex portion forming ink liquid and the transparent resin layer used for forming the antiglare layer, it is preferable to use the actinic ray curable resin or thermosetting resin described in the section of the low refractive index layer. .

  Similarly, it preferably contains a photopolymerization initiator, a photosensitizer, an ultraviolet absorber, an antioxidant, a surfactant and the like.

  The solid content concentration of the actinic ray curable resin in the liquid composition of the ink liquid and the transparent resin layer is preferably 10 to 95% by mass, and an optimum concentration is selected depending on the coating method and the like.

  Although the dry film thickness of the anti-glare layer by an inkjet system says the average value of the maximum height of an anti-glare layer from a transparent base material, 3-15 micrometers is preferable, More preferably, it is 5-10 micrometers. If it is less than 3 μm, the antiglare property is insufficient, or in some cases, satisfactory hardness cannot be obtained. On the other hand, if it exceeds 15 μm, the bending resistance among the film properties is remarkably deteriorated, and minute breakage is likely to occur during handling such as conveyance and cutting after the formation of the antiglare layer, resulting in lower productivity. The dry film thickness can be measured by a conventional method using a micrometer, a microscopic observation analysis of a film slice, or the like.

  For example, when the transparent resin layer of the present invention is made of an actinic ray curable resin or a thermosetting resin, the dry film thickness can be obtained by adjusting the ratio of the solid content of the resin and the solvent of the resin. be able to.

  The viscosity of the ink droplet forming the convex portion is preferably 2 to 15 mP · s at 25 ° C., more preferably 5 to 10 mP · s. When the viscosity is less than 2 mP · s, the viscosity is too low to obtain a pattern having a desired shape, and when it exceeds 15 mP · s, the fluidity of the ink is poor and the ink output property is also unfavorable. For the ink liquid, the solvent described in the section of the low refractive index layer is preferably used.

  Examples of the solvent that can be used in the transparent resin layer of the present invention include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, and butanol; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; N-methylpyrrolidone, Amides such as dimethylformamide and dimethylacetamide; ketone alcohols such as diacetone alcohol; aromatic hydrocarbons such as benzene, toluene and xylene; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; ethylene glycol, propylene glycol, 2-6 alkylene groups such as butylene glycol, triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol, diethylene glycol Alkylene glycols containing elemental atoms; glycol ethers such as ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethyl cellosolve, diethyl carbitol, propylene glycol monomethyl ether; cellosolve acetate, diethylene glycol monoethyl ether Examples include glycol esters such as acetate; esters such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, and amyl acetate; ethers such as dimethyl ether and diethyl ether, and water. These may be used alone or in combination of two or more. Can be used. Further, those having an ether bond in the molecule are particularly preferred, and glycol ethers are also preferably used.

  Specific examples of glycol ethers include, but are not limited to, the following solvents. Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether Ac, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether Ac, ethylene glycol Examples thereof include diethyl ether, and Ac represents acetate.

  The transparent resin layer of the present invention comprises an active agent such as silicone oil, modified silicone oil, silicone-based surfactant, fluorine-based surfactant, fluorine-based resin, fluorine-based oligomer, fluorine-modified silicone oil, and fluorine-based silane coupling agent. It is preferable to contain 0.1 mass% or more and 5 mass% or less.

In the present invention, both the convex portion and the transparent resin layer can contain an antistatic agent such as conductive fine particles such as SnO ₂ , ITO, ZnO, and crosslinked cationic polymer particles. In the present invention, it is preferable to add an antistatic agent to the transparent resin layer.

  In the present invention, the convex portion and the transparent resin layer can contain fine particles. For example, inorganic fine particles or organic fine particles can be added.

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

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

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

  The organic fine particles include polymethacrylate methyl acrylate resin fine particles, acrylic styrene resin fine particles, polymethyl methacrylate resin fine particles, silicon resin fine particles, polystyrene resin fine particles, polycarbonate resin fine particles, benzoguanamine resin fine particles, and melamine resin. Examples thereof include fine particles, polyolefin resin fine particles, polyester resin fine particles, polyamide resin fine particles, polyimide resin fine particles, and polyfluoroethylene resin fine particles.

  When the fine particles are contained, the average particle diameter is preferably 5 to 300 nm, more preferably 20 to 100 nm. You may contain 2 or more types of microparticles | fine-particles from which a particle size and refractive index differ. Moreover, it is preferable that content is 5-50 mass% with respect to a convex part or a transparent resin layer.

  When the convex portion or the transparent resin layer contains an actinic ray curable resin, it is preferable that the actinic ray is irradiated with actinic rays after the ink is landed on the transparent substrate and the solvent is evaporated. The timing of irradiation can be determined in consideration of the pattern shape to be formed. For example, when the ink is solvent-free, irradiation is performed within 2 minutes after landing, or when the ink contains a solvent, the solvent in the ink It is preferable to irradiate within 2 minutes immediately after evaporating.

  As the actinic ray that can be used, the above-described light source can be used.

  In the antiglare layer of the present invention, the convex portion can be formed directly on the transparent substrate by the ink jet method, but more preferably one or more curable resin layers or a smooth light formed by a coating method. After forming the diffusion layer, it is preferable to form a convex portion on the surface of the curable resin layer or the smooth light diffusion layer. The dry film thickness of these layers is preferably from 0.1 to 10 μm, more preferably from 0.1 to 5 μm.

  For the curable resin layer or the smooth light diffusing layer, the same actinic radiation curable resin or thermosetting resin as that used in the convex portion forming ink composition and the transparent resin layer can be preferably used. In particular, an ultraviolet curable resin is preferable. Further, when forming a curable resin layer or a smooth light diffusing layer, in addition to the above resins, the same photopolymerization initiator, photosensitizer, oxidation agent as those described for the convex portion forming ink composition An inhibitor, an ultraviolet absorber, an antistatic agent, inorganic fine particles, organic fine particles and the like can be appropriately added.

  In the present invention, the curable resin layer or the smooth light diffusing layer may be composed of a plurality of layers, but the outermost layer of the curable resin layer or the smooth light diffusing layer for landing ink droplets. However, it preferably contains a plasticizer.

  It is preferable that a plasticizer contains 0.1-10 mass%. For example, it is preferable to add a plasticizer in advance to the coating composition of the curable resin layer or the smooth light diffusing layer, or the substrate is previously coated before the curable resin layer or the smooth light diffusing layer is coated. A plasticizer can be applied or adhered to the surface. These improve the adhesion of the ink droplets after curing.

  Examples of the plasticizer that can be used in the curable resin layer or the smooth light diffusing layer include a phosphate ester plasticizer, a phthalate ester plasticizer, a trimellitic ester plasticizer, and a pyromellitic acid plasticizer. Agents, glycolate plasticizers, citrate ester plasticizers, polyester plasticizers, and the like can be preferably used.

  Examples of the phosphate ester plasticizer include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, etc. For trimellitic plasticizers such as phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, butyl benzyl phthalate, diphenyl phthalate, dicyclohexyl phthalate For pyromellitic acid ester plasticizers such as tate and triethyl trimellitate, tetrabutyl pyromellitate For glycolate plasticizers such as tetraphenylpyromellitate and tetraethylpyromellitate, triacetin, tributyrin, ethylphthalylethyl glycolate, methylphthalylethyl glycolate, butylphthalylbutyl glycolate, etc., citrate plastics As the agent, triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri-n-butyl citrate, acetyl tri-n- (2-ethylhexyl) citrate and the like can be preferably used. Examples of other carboxylic acid esters include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters. Trimethylolpropane tribenzoate and the like can also be preferably used.

  As the polyester plasticizer, a copolymer of a dibasic acid and a glycol such as an aliphatic dibasic acid, an alicyclic dibasic acid, or an aromatic dibasic acid can be used. The aliphatic dibasic acid is not particularly limited, and adipic acid, sebacic acid, phthalic acid, terephthalic acid, 1,4-cyclohexyl dicarboxylic acid, and the like can be used. As glycol, ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol and the like can be used. These dibasic acids and glycols may be used alone or in combination of two or more.

  In particular, cellulose esters having additives such as epoxy compounds, rosin compounds, phenol novolac type epoxy resins, cresol novolac type epoxy resins, ketone resins, and toluenesulfonamide resins described in JP-A No. 2002-146044 are also preferably used. .

  As the above compounds, KE-604 and KE-610 are commercially available from Arakawa Chemical Industries, Ltd. with acid values of 237 and 170, respectively. Similarly, KE-100 and KE-356 are commercially available from Arakawa Chemical Industries, Ltd. as an esterified product of a mixture of abietic acid, dehydroabietic acid, and parastrinic acid at 8 and 0, respectively. A mixture of abietic acid, dehydroabietic acid, and parastrinic acid is commercially available from Harima Kasei Co., Ltd. under G-7 and Hartle RX with acid values of 167 and 168, respectively.

  Moreover, as an epoxy resin, Araldide EPN1179 and Araldide AER260 are commercially available from Asahi Ciba.

  As a ketone resin, Hilac 110 and Hilac 110H are commercially available from Hitachi Chemical Co., Ltd.

  As para-toluenesulfonamide resin, as a topler, it is commercially available from Fujiamide Chemical Co., Ltd.

  Examples of the solvent for coating the curable resin layer or the smooth light diffusing layer used in the present invention include hydrocarbons, alcohols, ketones, esters, glycol ethers, and other solvents. It can select suitably or can be mixed and used. Preferably, a solvent containing 5% by mass or more, more preferably 5% by mass to 80% by mass or more of propylene glycol mono (C 1-4) alkyl ether or propylene glycol mono (C 1-4) alkyl ether ester. Used.

  Gravure coater, spinner coater, wire bar coater, roll coater, reverse coater, extrusion can be applied as a method of applying a curable resin layer or a smooth light diffusing layer composition coating solution having the above-described composition onto a transparent substrate. A known method such as a coater or an air doctor coater can be used. The coating amount is suitably 5 μm to 30 μm, preferably 10 μm to 20 μm in terms of wet film thickness. The coating speed is preferably 10 m / min to 60 m / min. Moreover, as a dry film thickness, 0.1-10 micrometers is preferable.

  The curable resin layer composition or the smooth light diffusing layer is coated and dried, and then cured by irradiation with actinic rays such as ultraviolet rays and electron beams, or by heat treatment, in the same manner as ink curing. However, the irradiation time of the actinic ray is preferably from 0.1 second to 5 minutes, and more preferably from 0.1 to 10 seconds from the viewpoint of curing efficiency and work efficiency of the ultraviolet curable resin.

  In the present invention, the curable resin layer or smooth light diffusing layer applied on the transparent substrate by the above method is in an uncured state, or at any time after complete curing, by an inkjet method, Ink droplets that form convex portions may be landed and subsequently covered with a transparent resin layer, but preferably after the curable resin layer or smooth light diffusion layer is cured, the ink droplets are landed by an inkjet method. It is preferable to form a convex part. When the curable resin layer or smooth light diffusing layer is half-cured (semi-cured state), ink droplets are landed to form convex portions, which are then covered with a transparent resin layer to form fine irregularities It is preferable because it is easy to do and is excellent in productivity. Furthermore, the adhesion between the convex portion or the transparent resin layer and the curable resin layer or the surface of the smooth light diffusing layer can be improved.

  In the present invention, after forming the projections, it is preferable to form a transparent resin layer so as to cover the projections after the surface is plasma-treated, but the plasma treatment is particularly preferably an atmospheric plasma treatment. , Noble gases such as helium and argon, or discharge gases such as nitrogen and air and oxygen, hydrogen, nitrogen, carbon monoxide, carbon dioxide, nitrogen monoxide, nitrogen dioxide, water vapor, methane, tetrafluoromethane as required A reaction gas containing one or more of these can be used. In Japanese Patent Application Laid-Open No. 2000-356714, the surface of the cured resin layer can be subjected to plasma treatment with reference to a specific plasma treatment method.

  FIG. 8 is a schematic diagram showing an example of a flow for manufacturing an antiglare film in which a convex portion is formed on a transparent substrate by an inkjet method and then a transparent resin layer is formed so as to cover the convex portion. Specifically, after a curable resin layer or a smooth light diffusion layer is coated on a transparent substrate by a coating method, a convex portion is formed by an inkjet method, and then a transparent resin layer is formed so as to cover the convex portion. An example of a flow for producing an antiglare antireflection film by providing an antiglare layer with a low refractive index layer by an ink jet method is shown.

  In FIG. 8, the transparent base material 102 fed out from the laminating roll 101 is conveyed, and a curable resin layer or a smooth light diffusion layer is applied by the first coater 103 of the extrusion method at the first coater station A. To do. At this time, the curable resin layer or the smooth light diffusing layer may be a single layer structure or a layer composed of a plurality of layers combined with each other. The transparent substrate 102 on which the curable resin layer or the smooth light diffusion layer is applied is then dried in the drying zone 105A. Drying is performed from both surfaces of the transparent substrate 102 by warm air with controlled temperature and humidity. After drying, when an actinic ray curable resin is used as a binder in the curable resin layer or the smooth light diffusing layer, the actinic ray irradiating unit 106A is irradiated with actinic rays such as ultraviolet rays to be cured. In addition, the amount of irradiation and irradiation conditions can be controlled to achieve a half-cure state, or it can be directly conveyed to the inkjet emitting unit 109 without being cured.

  Subsequently, although it conveys to the 2nd coater station B which provides a convex part using an inkjet system, it is preferable that a curable resin layer is a half-cure state. Alternatively, the surface treatment may be performed by the plasma processing unit 107 before forming the convex portion. An ink supply tank 108 is connected to the ink jet emitting portion 109, and ink liquid is supplied therefrom. The ink jet emitting unit 109 has a plurality of ink jet nozzles as shown in FIG. 3B arranged in a staggered manner, preferably in multiple stages, across the entire width of the transparent substrate, and the ink droplets are made of a curable resin layer or a smooth type. The light is emitted onto the light diffusion layer, and a convex portion is formed on the surface. In addition, when ejecting two or more types of ink droplets, each ink droplet may be ejected from two or more rows of inkjet nozzles, or randomly from any inkjet nozzle. It may be emitted. Further, a plurality of ink jet emitting portions may be arranged, and different ink droplets may be emitted from each ink emitting portion. In the present invention, since fine droplets of 0.1 to 100 pl and in some cases 0.1 to 10 pl are emitted, the flying property of the ink droplets is easily affected by the airflow of the outside air. It is preferable that the entire coater station B and the fourth coater station D are covered with a partition wall or the like to perform windproof treatment. In addition, in order to fly an extremely fine droplet of 1 pl or less with high accuracy, a voltage is applied between the ink jet emitting portion 109 and the transparent base material 102 or the back rolls 104B and 104D to give an electric charge to the ink droplet to electrically A method of assisting the flying stability of the ink droplet is also preferable. In order to prevent deformation of the landed ink droplets, it is also preferable to use a method in which the transparent substrate is cooled to quickly reduce the flow of the ink droplets after landing. Alternatively, it is possible to volatilize the solvent contained during the flight until the ink droplets are landed after the ink droplets are ejected, and land the ink droplets in a state where the amount of the solvent contained in the ink droplets is reduced, thereby forming a finer convex portion. Preferred above. Therefore, a method of increasing the temperature of the ink flying space or controlling the atmospheric pressure to 1 atm or lower, for example, 20 to 100 kPa is also preferable. It is also preferable to lower the atmospheric solvent concentration in the ink flying space, and it is 50% or less, more preferably 1 to 30% of the saturation concentration.

  Ink droplets that have landed on the surface of the curable resin layer or the smooth light diffusing layer, when an actinic ray curable resin is used, are generated by the actinic ray irradiation unit 106B disposed immediately after the inkjet emitting unit 109. Then, it is cured by irradiation with actinic rays such as ultraviolet rays. Further, when the ink droplet uses a thermosetting resin, the ink droplet is heated and cured by the heating unit 110, for example, a heat plate. A method of heating the back roll 104B as a heat roll is also preferable.

  In the second coater station B, the actinic ray irradiation unit 106B and the inkjet emission unit 109 are arranged at an appropriate interval so that the irradiation light of the actinic ray irradiation unit 106B does not directly affect the inkjet nozzle of the inkjet emission unit 109. Alternatively, it is preferable to install a light shielding wall or the like between the actinic ray irradiation unit 106B and the inkjet emission unit 109. Further, in order to prevent the heat of the heating unit 110 from directly affecting the ink jet nozzles of the ink jet emitting unit 109, the ink jet emitting unit 109 is covered with a heat insulating cover, or the heating unit 110 is made transparent as shown in FIG. It is preferable to arrange on the back side of the material 102 so as not to affect the ink jet emitting portion 109.

  The transparent substrate 102 that has been cured to such an extent that the convex portions formed by the landed ink droplets can be maintained is evaporated in the drying zone 105B after the unnecessary organic solvent or the like is evaporated, and further by the actinic ray irradiation unit 106C. Irradiation with actinic rays and curing may be completed, or a half-cured state may be used, but a half-cured state is preferred.

  The transparent base material 102 provided with the convex portions is then transported to the third coater station C where the transparent resin layer covering the convex portions is coated, but before the convex portions are covered with the transparent resin layer, the plasma processing unit A surface treatment is preferably performed at 107.

  The transparent substrate 102 on which the transparent resin layer is applied is then dried in the drying zone 105C. Drying is performed from both surfaces of the transparent substrate 102 by warm air with controlled temperature and humidity. Further, the actinic ray irradiation unit 106D irradiates actinic rays to complete the curing.

  The transparent base material 102 provided with the antiglare layer having the convex portion is then coated with a low refractive index layer by the ink jet emitting portion 109 in the fourth coater station D, and cured at the active light irradiation portion 106E and the drying zone 105D. It is also preferable to subject the surface of the transparent resin layer to a surface treatment by the plasma treatment unit 107 before coating the low refractive index layer.

  Further, when a plurality of antireflection layers and antifouling layers are provided, a necessary coater station may be installed (not shown), and in the same manner as the first coater station A, coating, drying, and curing are performed to prevent glare. The antireflective film is produced, and then taken up by a take-up roll 113. The transparent substrate 102 may be appropriately wound up by a winding roll after coating, drying, and curing treatment at each coater station.

<Transparent substrate>
The transparent substrate used in the present invention is easy to manufacture, has good adhesion to the actinic ray curable resin layer, is optically isotropic, is optically transparent, etc. Is preferable, and a transparent film is preferable.

  The term “transparent” as used in the present invention means that the visible light transmittance is 60% or more, preferably 80% or more, and particularly preferably 90% or more.

  Although it will not specifically limit if it has said property, For example, cellulose ester-type films, such as a cellulose diacetate film, a cellulose triacetate film, a cellulose acetate propionate film, a cellulose acetate butyrate film, a polyester-type film, a polycarbonate Film, polyarylate film, polysulfone (including polyethersulfone) film, polyester film such as polyethylene terephthalate and polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol Film, syndiotactic polystyrene film, polycarbonate film, nor Runen resin film, a polymethylpentene film, a polyether ketone film, polyether ketone imide film, a polyamide film, a fluororesin film, a nylon film, polymethyl methacrylate film, acrylic film or a glass plate or the like. Among these, a polycarbonate film, a polyester film, a norbornene resin film, and a cellulose ester film are preferable.

  The norbornene-based resin film preferably used in the present invention is an amorphous polyolefin film having a norbornene structure, such as APO manufactured by Mitsui Petrochemical Co., Ltd., ZEONEX manufactured by Nippon Zeon Co., Ltd., manufactured by JSR Co., Ltd. ARTON etc.

  In the present invention, it is particularly preferable to use a cellulose ester film. As the cellulose ester, cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate are preferable. Among them, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose acetate propionate are preferably used. Examples of commercially available cellulose ester films include Konica Minoltak KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC12UR, KC4FR (manufactured by Konica Minolta Opto Co., Ltd. It is preferably used from the viewpoints of transparency and adhesion. These films may be films produced by melt casting film formation or films produced by solution casting film formation.

  Moreover, the transparent base film in which uneven | corrugated shape is formed in the surface by embossing etc. may be sufficient.

<< Preparation of antireflection film >>
In this invention, it is preferable to manufacture an antireflection layer by the process of forming an anti-glare layer on a base film and coating sequentially using a high refractive index layer composition and a low refractive index layer composition. It is also preferable to coat an antifouling layer and a backcoat layer.

  Although the structure of the anti-reflective film which has preferable anti-glare property is shown below, it is not limited to these.

Transparent substrate / antiglare layer / low refractive index layer Transparent substrate / antiglare layer / high refractive index layer / low refractive index layer Transparent substrate / antistatic layer / antiglare layer / low refractive index layer Transparent substrate / charge Prevention layer / Anti-glare layer / High refractive index layer / Low refractive index layer Transparent substrate / Anti-glare layer / Low refractive index layer / Anti-fouling layer Transparent substrate / Anti-glare layer / High refractive index layer / Low refractive index layer / Antifouling layer Transparent substrate / antistatic layer / antiglare layer / low refractive index layer / antifouling layer Transparent substrate / antistatic layer / antiglare layer / high refractive index layer / low refractive index layer / antifouling layer Backcoat Layer / transparent substrate / antiglare layer / low refractive index layer backcoat layer / transparent substrate / antiglare layer / low refractive index layer / antifouling layer backcoat layer / transparent substrate / antiglare layer / high refractive index layer / Low refractive index layer / Anti-fouling layer <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.

  The high refractive index layer preferable for the present invention preferably contains metal oxide fine particles having an average particle diameter of 10 to 200 nm, a metal compound, and an actinic ray curable resin.

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

  The average particle diameter of the primary particles of these metal oxide fine particles is in the range of 10 nm to 200 nm, particularly preferably 10 to 150 nm. The average particle diameter of the metal oxide fine particles may be measured from an electron micrograph by a scanning electron microscope (SEM) or the like, or measured by a particle size distribution meter using a dynamic light scattering method or a static light scattering method. May be. 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 grain shape, a spherical shape, a cubic shape, a spindle shape, a needle shape, or an indefinite shape.

  Specifically, the refractive index of the high refractive index layer is higher than the refractive index of the transparent substrate as a support, and is preferably in the range of 1.50 to 1.90 at 23 ° C. and a wavelength of 550 nm. The means for adjusting the refractive index of the high refractive index layer is that the kind and addition amount of the metal oxide fine particles are dominant, so that the refractive index of the metal oxide fine particles is preferably 1.80 to 2.60, More preferably, it is 1.85 to 2.50.

  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. . For this reason, the surface modification amount with a preferable organic compound is 0.1 mass%-5 mass% with respect to metal oxide particle, More preferably, it is 0.5 mass%-3 mass%. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Among these, the silane coupling agent mentioned later is preferable. Two or more kinds of surface treatments may be combined.

  The thickness of the high refractive index layer containing the metal oxide fine particles is preferably 5 nm to 1 μm, more preferably 10 nm to 0.2 μm, and most preferably 30 nm to 0.1 μm.

  The ratio of the metal oxide fine particles to be used and a binder such as actinic ray curable resin, which will be described later, varies depending on the type and particle size of the metal oxide fine particles, but the volume ratio of the former 1 to the latter 2 to the former 2 The latter one is preferable.

  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, and most preferably 20% to 75% by mass. preferable. 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.

  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 (eg, diacetone alcohol). , Esters (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene) Chloride, chloroform, carbon tetrachloride), aromatic hydrocarbons (eg, benzene, toluene, xylene), amides (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ethers (eg, diethyl ether, dioxane, Tiger hydrofuran), ether alcohols (e.g., 1-methoxy-2-propanol). Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

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

  In the present invention, metal oxide fine particles having a core / shell structure may be further contained. One layer of the 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.

  For the core, titanium oxide (rutile type, anatase type, amorphous type, etc.), zirconium oxide, zinc oxide, cerium oxide, indium oxide doped with tin, tin oxide doped with antimony, etc. can be used. Titanium may be the main component.

  The shell is preferably formed of a metal oxide or sulfide containing an inorganic compound other than titanium oxide as a main component. For example, an inorganic compound mainly composed of silicon dioxide (silica), aluminum oxide (alumina) zirconium oxide, zinc oxide, tin oxide, antimony oxide, indium oxide, iron oxide, zinc sulfide, or the like is used. Of these, alumina, silica, and zirconia (zirconium oxide) are preferable. A mixture of these may also be used.

  The coating amount of the shell with respect to the core is 2 to 50% by mass as an 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. Two or more kinds of metal oxide fine particles may be used in combination.

  The titanium oxide used as a core can use what was produced by the liquid phase method or the gaseous-phase method. As a method for forming the shell around the core, for example, U.S. Pat. No. 3,410,708, JP-B-58-47061, U.S. Pat. No. 2,885,366, and U.S. Pat. No. 1, British Patent No. 1,134,249, US Pat. No. 3,383,231, British Patent No. 2,629,953, No. 1,365,999, etc. Can do.

(Metal compound)
As the metal compound used in the present invention, a compound represented by the following general formula (4) or a chelate compound thereof can be used.

General formula (4) AnMBx-n
In the formula, M represents a metal atom, A 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.

  Examples of the hydrolyzable functional group A include halogens such as alkoxyl groups and chloro atoms, ester groups and amide groups. 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 alkoxide, zirconium alkoxide, or 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 a large amount. Zirconium alkoxide has a high refractive index but tends to become cloudy, so care must be taken in dew point management during coating. Moreover, since titanium alkoxide has the effect of promoting the reaction between the ultraviolet curable resin and the metal alkoxide, the physical properties of the coating film can be improved even by adding a small amount.

  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, and the like. Is mentioned.

  Examples of the zirconium alkoxide include tetramethoxy zirconium, tetraethoxy zirconium, tetra-iso-propoxy zirconium, tetra-n-propoxy zirconium, tetra-n-butoxy zirconium, tetra-sec-butoxy zirconium, tetra-tert-butoxy zirconium and the like. Is mentioned.

  Preferred chelating agents for forming a chelate compound by coordination with a free metal compound include alkanolamines such as diethanolamine and triethanolamine, glycols such as ethylene glycol, diethylene glycol and propylene glycol, acetylacetone and acetoacetic acid. Examples thereof include ethyl 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 that is stable against water mixing and is excellent in the effect of reinforcing the coating film.

  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. If it is less than 0.3% by mass, the scratch resistance is insufficient, and if it exceeds 5% by mass, the light resistance tends to deteriorate.

(Actinic ray curable resin)
The actinic ray curable resin is added as a binder for the metal oxide fine particles in order to improve the film formability and physical properties of the coating film. As the actinic ray curable resin, a monomer or oligomer having two or more functional groups that undergo a polymerization reaction directly by irradiation with 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) acryloyloxy group, an epoxy group, and a silanol group. Among these, radically polymerizable monomers and oligomers having two or more unsaturated double bonds can be preferably used. You may combine a photoinitiator as needed. Examples of such actinic ray curable resins include polyfunctional acrylate compounds and the like, and the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate. It is preferable that it is a compound chosen from these. Here, the polyfunctional acrylate compound is a compound having two or more acryloyloxy groups and / or methacryloyloxy groups in the molecule.

  Examples of the monomer of the polyfunctional acrylate compound include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethanetriacrylate. Acrylate, tetramethylol methane tetraacrylate, pentaglycerol triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, glycerin triacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, Dipen Erythritol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetra Methylol methane trimethacrylate, tetramethylol methane tetramethacrylate, pentaglycerol trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerol trimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol te La methacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexa methacrylate preferred. These compounds are used alone or in admixture of two or more. Moreover, oligomers, such as a dimer and a trimer of the said monomer, may be sufficient.

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

  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 are in a mass ratio of 3: 7 to 1: 9. It is preferable to contain.

  Specific examples of the photopolymerization initiator include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof.

(solvent)
Examples of the organic solvent used for coating the high refractive index layer used in the present invention include alcohols (for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol). , Hexanol, cyclohexanol, benzyl alcohol, etc.), polyhydric alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin) , Hexanetriol, thiodiglycol, etc.), polyhydric alcohol ethers (for example, ethylene glycol mono Chill ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol Monoethyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, etc.), amines (eg, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylene) Lumorpholine, ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide) Etc.), heterocyclic rings (for example, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc.), sulfoxides (for example, dimethyl sulfoxide, etc.) ), Sulfones (for example, sulfolane, etc.), urea, acetonitrile, acetone and the like, and alcohols, polyhydric alcohols, and polyhydric alcohol ethers are particularly preferable.

<Anti-fouling layer>
The antireflection film having an antiglare property of the present invention preferably has an antifouling layer on the outermost layer.

  The antifouling layer preferable for the present invention preferably contains a fluorine-containing silane compound in the antifouling layer forming composition, and is prepared by coating a silane compound solution having a fluoroalkyl group or a fluoroalkyl ether group. In particular, the fluorine-containing silane compound is preferably silazane or alkoxysilane.

  In addition, among the silane compounds having the fluoroalkyl group or the fluoroalkyl ether group, the fluoroalkyl group in the silane compound is bonded to Si atoms at a ratio of 1 or less to one Si atom, and the remaining Is preferably a silane compound which is a hydrolyzable group or a siloxane bond group.

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

  For example, the silane compound is usually reacted with water (in the presence of an acid catalyst if necessary) in the range of room temperature to 100 ° C. while distilling off by-produced alcohol. 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 adjusted as appropriate depending on the amount of water to be reacted. However, in the present invention, water is not positively added to the silane compound solution used for the antifouling treatment. It is preferable to dilute and use the solid content concentration of the solution in order to cause a hydrolysis reaction with moisture in the air during drying.

  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 diluted to 0.01 to 5% by mass. Use antifouling treatment.

Formula _{(5) CF 3 (CF 2} ) m (CH 2) n-Si- (ORa) 3
Here, m is an integer of 1-10. n is an integer of 0-10. Ra represents the same or different alkyl group.

  In the compound represented by the general formula (5), Ra has 3 or less carbon atoms and is preferably an alkyl group consisting of only carbon and hydrogen, for example, a group such as methyl, ethyl, isopropyl and the like.

Examples of the silane compound having a fluoroalkyl group or fluoroalkyl ether group preferably used in the present invention include CF ₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CH ₂ ) ₂ Si (OC ₂ H ₅ ). ₃ , CF ₃ (CH ₂ ) ₂ Si (OC ₃ H ₇ ) ₃ , CF ₃ (CH ₂ ) ₂ Si (OC ₄ H ₉ ) ₃ , CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₃ H ₇ ) ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC _{3 H 7) 3, CF 3} (CF 2) 7 (CH 2) 2 Si (OCH 3) (OC 3 H 7) 2, CF 3 (CF 2) 7 _{CH 2) 2 Si (OCH 3} ) 2 OC 3 H 7, CF 3 (CF 2) 7 (CH 2) 2 SiCH 3 (OCH 3) 2, CF 3 (CF 2) 7 (CH 2) 2 SiCH 3 ( OC ₂ H ₅ ) ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiCH ₃ (OC ₃ H ₇ ) ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₈ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , C ₇ F ₁₅ CONH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , C ₈ F ₁₇ SO ₂ NH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , C ₈ F ₁₇ (CH ₂ ) ₂ OCONH (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₂ H ₅ ) ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₃ H ₇ ) ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (C ₂ H ₅ ) (OCH ₃ ) ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (C ₂ H ₅ ) (OC ₃ H ₇ ) ₂ , CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂ , CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₂ H ₅ ) ₂ , CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₃ H ₇ ) ₂ , CF ₃ (CF ₂ ) ₅ ( _{CH 2) 2 Si (CH 3} ) (OCH 3) 2, CF 3 (CF 2) 5 (CH 2) 2 Si (CH 3) (OC 3 H 7) 2, CF 3 (CF 2) 2 O (CF ₂ ) ₃ (CH ₂ ) ₂ Si (OC ₃ H ₇ ), C ₇ F ₁₅ CH ₂ O (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , C ₈ F ₁₇ SO ₂ O (CH ₂ ) ₃ Si Examples include (OC ₂ H ₅ ) ₃ , C ₈ F ₁₇ (CH ₂ ) ₂ OCHO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , but not limited thereto.

  Examples of the fluorine-based silane compound include KP801M and X-24-9146 manufactured by Shin-Etsu Chemical Co., Ltd., GE Toshiba Silicones Co., Ltd. XC98-A5382, XC98-B2472, Daikin Industries Co., Ltd. As the compound for surface treatment, perfluoroalkylsilazane, perfluoroalkylsilane, or perfluoropolyether group-containing silane compound, particularly perfluoroalkyltrialkoxysilane, perfluoropolyethertrialkoxysilane, Examples include perfluoropolyether ditrialkoxysilane.

  When these silane compounds are used, they are diluted to 0.01 to 10% by mass, preferably 0.03 to 5% by mass, more preferably 0.05 to 2% by mass with an organic solvent not containing fluorine. It is preferable to use in.

  In the present invention, an organic solvent containing no fluorine is preferably used to prepare the silane compound solution, and the following may be mentioned.

  As a solvent of the coating composition for the antifouling layer used in the present invention, propylene glycol mono (C1-C4) alkyl ether and / or propylene glycol mono (C1-C4) alkyl ether ester, propylene glycol mono (C1-C4). Specific examples of the alkyl ether include propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether and the like. The propylene glycol mono (C1 to C4) alkyl ether ester includes propylene glycol monoalkyl ether acetate, specifically, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and the like. Propylene glycol mono (C1-C4) alkyl ether and / or propylene glycol mono (C1-C4) alkyl ether ester, etc., alcohols such as methanol, ethanol, propanol, n-butanol, 2-butanol, t-butanol, cyclohexanol , Ketones such as methyl ethyl ketone, methyl isobutyl ketone and acetone, esters such as ethyl acetate, methyl acetate, ethyl lactate, isopropyl acetate, amyl acetate and ethyl butyrate, hydrocarbons such as benzene, toluene and xylene, 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.

  Particularly preferred solvents are one or more organic solvents selected from ethanol, isopropyl alcohol, propylene glycol, and propylene glycol monomethyl ether.

  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 of 100 ° C. or more such as propylene glycol monomethyl ether and n-butyl alcohol. (Boiling point solvent) is preferably used in combination, and in particular, those having a boiling point of 60 to 98 ° C. and those having a boiling point of 100 to 160 ° C. are preferably used in combination. The ratio of the low boiling point solvent and the high boiling point solvent when used in combination is preferably 98.0% by mass or more and the high boiling point solvent is 0.5 to 2% by mass in the composition.

  In the antifouling layer forming composition used in the present invention, it is preferable to add an acid to adjust the pH to 5.0 or less. 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 substrate, and the antifouling property can be enhanced. The pH is preferably in the range of 1.5 to 5.0. If the pH is 1.5 or less, the acidity of the solution is too strong, and the container or the piping may be damaged. If the pH is 5 or more, the reaction does not proceed easily. Preferably it is the range of pH2.0-4.0.

  In the present invention, it is preferable not to positively add water to the silane compound solution used for the antifouling treatment, but to cause a hydrolysis reaction with moisture in the air mainly after drying after preparation. Therefore, it is used when the solid content concentration of the solution is diluted. If too much water is added to the treatment liquid, the pot life is shortened accordingly.

  In the present invention, sulfuric acid, hydrochloric acid, nitric acid, hypochlorous acid, boric acid, hydrofluoric acid, preferably an inorganic acid such as hydrochloric acid and nitric acid, an organic acid having a sulfo group (also referred to as a sulfonic acid group) or a carboxyl group, For example, 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, a hydroxydicarboxylic acid such as citric acid or tartaric acid is used. The organic acid is more preferably a water-soluble acid. For example, in addition to the citric acid and tartaric acid, levulinic acid, formic acid, propionic acid, malic acid, succinic acid, methyl succinic acid, fumaric acid, oxaloacetic acid, pyruvin. Acid, 2-oxoglutaric acid, glycolic acid, D-glyceric acid, D-gluconic acid, malonic acid, maleic acid, oxalic acid, isocitric acid, lactic acid and the like are preferably used. Also, benzoic acid, hydroxybenzoic acid, atorvaic acid and the like can be used as appropriate.

  The addition amount is 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the partial hydrolyzate of the silane compound. Further, the amount of water added is not limited as long as the partial hydrolyzate can theoretically be hydrolyzed by 100%, and an amount equivalent to 100% to 300%, preferably an amount equivalent to 100% to 200% is added. Good.

  By using a fluorine-containing silane compound, it is not only preferable in terms of lowering the refractive index of the antifouling layer and imparting water and oil repellency, but also has an effect of being highly scratch resistant and particularly excellent in blocking between films. .

<Back coat layer>
In the antireflection film of the present invention, it is preferable to provide a backcoat layer on the surface opposite to the side on which the active energy ray-curable resin layer of the cellulose ester film serving as the transparent substrate is provided. The back coat layer is provided in order to correct curl caused by providing an active energy ray-curable resin layer or other layers. That is, the degree of curling can be balanced by imparting the property of being rounded with the surface on which the backcoat layer is provided facing inward. The back coat layer is preferably applied also as an anti-blocking layer. In this case, it is preferable that fine particles are added to the back coat layer coating composition in order to provide an anti-blocking function.

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

  These fine particles are commercially available under the trade names of, for example, Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, and TT600 (manufactured by Nippon Aerosil Co., Ltd.). . Zirconium oxide fine particles are commercially available, for example, under the trade names Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) and can be used. Examples of the polymer include silicone resin, fluororesin, and acrylic resin. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120, and 240 (manufactured by Toshiba Silicone Co., Ltd.) It is marketed by name and can be used.

  Among these, Aerosil 200V and Aerosil R972V are particularly preferably used because they have a large anti-blocking effect while keeping haze low. The antireflection film used in the present invention preferably has a dynamic friction coefficient on the back side of the active energy ray-curable resin layer of 0.9 or less, particularly 0.1 to 0.9.

  The fine particles contained in the backcoat layer are 0.1 to 50% by weight, preferably 0.1 to 10% by weight, based on the binder. When the back coat layer is provided, the increase in haze is preferably 1% or less, more preferably 0.5% or less, and particularly preferably 0.0 to 0.1%.

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

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

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

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

  The order of coating the backcoat layer may be before or after coating the active energy ray-curable resin layer of the cellulose ester film, but when the backcoat layer also serves as an antiblocking layer, it is desirable to coat it first. . Alternatively, the backcoat layer can be applied in two or more steps.

  The surfactant BYK series manufactured by Big Chemie Japan Co., Ltd. and the dimethyl silicone series manufactured by GE Toshiba Silicone Co., Ltd. described in the low refractive index layer can be preferably used for an antireflection layer other than the low refractive index layer.

<surface treatment>
After the antiglare layer according to the present invention is formed, the surface of the antiglare layer is subjected to surface treatment, and an antireflection layer (low refractive index layer or high refractive index layer) is formed on the surface of the antiglare layer subjected to the surface treatment. It is preferable to do. It is also preferable to perform a surface treatment on the low refractive index layer 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, atmospheric pressure glow discharge plasma methods, and the like. An alkali treatment method and a corona treatment method are preferable, and an alkali treatment method can be used particularly preferably. The corona treatment is a treatment performed by applying a high voltage of 1 kV or more between the electrodes under atmospheric pressure and discharging it. An apparatus commercially available from Kasuga Electric Co., Ltd. or Toyo Electric Co., Ltd. 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. As one electrode (A electrode) of the corona treatment apparatus, a commercially available one can be used, but the material can be selected from aluminum, stainless steel and the like. The other is an electrode (B electrode) for holding a plastic film, and is a roll electrode installed at a certain distance from the A electrode so that the corona treatment is carried out stably and uniformly. A commercially available one can also be used, and the material is preferably a roll made of aluminum, stainless steel, or a metal thereof, and a roll lined with ceramics, silicon, EPT rubber, hyperon rubber, or the like. It is done. The frequency used for the corona treatment used in the present invention is a frequency of 20 kHz to 100 kHz, 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. In addition, when the frequency is increased, there is no particular problem when performing high-output corona treatment, but when performing low-output corona treatment, it is difficult to perform stable processing, resulting in uneven processing. Will occur. The output of the corona treatment is 1 to 5 w · min. / M ² but ² to 4 w · min. An output of / m ² is preferred. The distance between the electrode and the film is 5 mm or more and 50 mm or less, preferably 10 mm or more and 35 mm or less. When the gap is opened, 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.

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

  As the aqueous alkali solution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous ammonia solution or the like can be used, and an aqueous sodium hydroxide solution is particularly preferable.

  The alkali concentration of the aqueous alkali solution, for example, sodium hydroxide concentration is preferably 0.1 to 25% by mass, and more preferably 0.5 to 15% by mass.

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

  The alkali treatment time is 5 seconds to 5 minutes, preferably 30 seconds to 3 minutes. The film after the alkali treatment is preferably neutralized with acidic water and then thoroughly washed with water.

  In the present invention, after the antiglare layer is formed, the surface is preferably subjected to plasma treatment to form an antireflection layer (a low refractive index layer or a high refractive index layer). In particular, the plasma treatment is an atmospheric plasma treatment. Preferably, a rare gas such as helium or argon or a discharge gas such as nitrogen or air and, if necessary, oxygen, hydrogen, nitrogen, carbon monoxide, carbon dioxide, nitrogen monoxide, nitrogen dioxide, water vapor, methane, 4 A reaction gas containing one or more kinds of fluorinated methane or the like can be used. In Japanese Patent Application Laid-Open No. 2000-356714, the surface of the cured resin layer can be subjected to plasma treatment with reference to a specific plasma treatment method.

  For high refractive index layer, back coat layer and antifouling layer, dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, micro gravure coating method and extrusion coating method are used. And can be formed by coating. At the time of application, the base film is preferably wound up in a roll shape after being unwound from a state wound in a roll shape with a width of 1.4 to 4 m, performing the above-described application, drying and curing treatment. .

  Furthermore, the antireflection film of the present invention can be produced by a production method in which heat treatment is carried out in the range of 50 to 150 ° C. and 1 to 30 days in the state of being wound in a roll. The period of the heat treatment may be appropriately determined depending on the set temperature. For example, if it is 50 ° C, it is preferably a period of 3 days or more and less than 30 days, and if it is 150 ° C, a range of 1 to 3 days is preferable. Usually, it is preferable to set it at a relatively low temperature so that the heat treatment effect on the outside of the winding, the center of the winding, and the core is not biased, and it is preferable to carry out at around 50 to 80 ° C. for about 3 to 7 days.

  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.

  When winding the antireflection film into a roll, the winding core may be any material as long as it is a cylindrical core, preferably a hollow plastic core, Can be any heat-resistant plastic that can withstand the heat treatment temperature, and examples thereof include resins such as phenol resins, xylene resins, melamine resins, polyester resins, and epoxy resins. A thermosetting resin reinforced with a filler such as glass fiber is preferable.

  The number of windings on these winding cores is preferably 100 windings or more, more preferably 500 windings or more, and the winding thickness is preferably 5 cm or more.

  In this way, when the heat treatment is performed in a state where the functional thin film is coated on the long base film and the roll wound around the plastic core is wound, it is preferable to rotate the roll, The rotation is preferably performed at a speed of 1 rotation or less per minute, and may be continuous or intermittent. Moreover, it is preferable to perform rewinding of the roll once or more during the heating period.

"Polarizer"
The polarizing plate can be produced by a general method. The back side of the antiglare antireflection film of the present invention is subjected to alkali saponification treatment and bonded to at least one surface of a polarizing film prepared by immersing and stretching in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution. preferable. 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, Konica Minoltak KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC12UR, KC4FR, and the above manufactured by Konica Minolta Opto Co., Ltd. are also preferably used). In contrast to the antiglare antireflection film of the present invention, the polarizing plate protective film used on the other surface has an in-plane retardation Ro of 590 nm, a phase difference of 30 to 300 nm, and Rt of 70 to 400 nm. Preferably it is. 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 antireflection film having the antiglare property of the present invention, a polarizing plate having excellent flatness and a stable viewing angle expansion effect can be obtained.

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

  In addition, the reflection hue on the surface of the polarizing plate that has undergone antireflection treatment is often colored red or blue due to the high reflectance in the short wavelength region and long wavelength region in the visible light region due to the design of the antireflection film. The color tone of the reflected light varies depending on the application, and when used on the outermost surface of an FPD television or the like, a neutral color tone is desired. In this case, generally preferred reflection hue ranges are 0.17 ≦ x ≦ 0.27 and 0.07 ≦ y ≦ 0.17 on the XYZ color system (CIE1931 color system).

<Display device>
By incorporating the polarizing plate of the present invention into a display device, the display device of the present invention having various visibility can be manufactured. The anti-glare anti-reflection film of the present invention is a reflection type, transmission type, transflective LCD or TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS type, etc. It is preferably used in LCDs. Further, the antiglare antireflection film of the present invention is excellent in flatness and is 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. In particular, in a large-screen display device having a screen of 30 or more types, particularly 30 to 54 types, there is no white spot at the periphery of the screen, and the effect is maintained for a long period of time. MVA liquid crystal display device, IPS liquid crystal display A noticeable effect is observed in the device. In particular, there was little color unevenness, glare and wavy unevenness, and the eyes were not tired even during long viewing.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1
[Production of Cellulose Ester Film 1]
<Synthesis of Polymer X>
In a glass flask equipped with a stirrer, two dropping funnels, a gas introduction tube and a thermometer, 40 g of a monomer Xa and Xb mixed solution of the types and ratios (molar composition ratio) described in Table 3, and 2 g of mercaptopropionic acid as a chain transfer agent And 30 g of toluene were charged, and the temperature was raised to 90 ° C. Thereafter, 60 g of a mixture of monomers Xa and Xb having the types and ratios (molar composition ratios) shown in Table 3 was dropped from one dropping funnel over 3 hours, and at the same time, azobis dissolved in 14 g of toluene from the other funnel. 0.4 g of isobutyronitrile was added dropwise over 3 hours. Thereafter, 0.6 g of azobisisobutyronitrile dissolved in 56 g of toluene was added dropwise over 2 hours, and the reaction was further continued for 2 hours to obtain polymer X. The obtained polymer X was solid at room temperature. The weight average molecular weight of the polymer X is shown in Table 3 by the following measurement method.

  In Table 3, MMA and HEA are abbreviations for the following compounds, respectively.

MMA: methyl methacrylate HEA: 2-hydroxyethyl acrylate (weight average molecular weight measurement)
The weight average molecular weight was measured using gel permeation chromatography.

  The measurement conditions are as follows.

Solvent: Methylene chloride Column: Shodex K806, K805, K803G (Used by connecting three Showa Denko Co., Ltd.)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (manufactured by GL Sciences)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corp.) Mw = 100000-500 calibration curves with 13 samples were used. Thirteen samples are used at approximately equal intervals.

<Synthesis of polymer Y>
Bulk polymerization was performed by the polymerization method described in JP-A No. 2000-128911. That is, the following methyl acrylate (MA) as monomer Ya was introduced into a flask equipped with a stirrer, nitrogen gas inlet tube, thermometer, inlet, and reflux condenser, and nitrogen gas was introduced to replace the inside of the flask with nitrogen gas. The following thioglycerol was added with stirring. After the addition of thioglycerol, the temperature of the contents was appropriately changed and polymerization was performed for 4 hours. The contents were returned to room temperature, and 20 parts by mass of a 5% by weight benzoquinone tetrahydrofuran solution was added thereto to stop the polymerization. The contents were transferred to an evaporator, and tetrahydrofuran, residual monomer and residual thioglycerol were removed under reduced pressure at 80 ° C. to obtain polymer Y shown in Table 3. The obtained polymer Y was liquid at room temperature. The weight average molecular weight of the polymer Y is shown in Table 3 by the above measurement method.

Methyl acrylate 100 parts by weight Thioglycerol 5 parts by weight

<Dope composition>
(Silicon dioxide dispersion)
Aerosil 972V (manufactured by Nippon Aerosil Co., Ltd.) 12 parts by mass (average diameter of primary particles 16 nm, apparent specific gravity 90 g / liter)
88 parts by mass of ethanol or more was stirred and mixed with a dissolver for 30 minutes, and then dispersed with Manton Gorin. The liquid turbidity after dispersion was 200 ppm. 88 parts by mass of methylene chloride was added to the silicon dioxide dispersion while stirring, and the mixture was stirred and mixed with a dissolver for 30 minutes to prepare a silicon dioxide dispersion dilution.

(Dope additive)
Methylene chloride 50 parts by weight Polymer X 12 parts by weight Polymer Y 7 parts by weight Silicon dioxide dispersion diluent 10 parts by weight Tinuvin 109 (manufactured by Ciba Specialty Chemicals) 1.2 parts by weight Tinuvin 171 (Ciba Specialty Chemicals) Manufactured) 0.8 parts by mass The methylene chloride, the polymer X, and the polymer Y were completely dissolved while stirring, and then a silicon dioxide dispersion was added and mixed by stirring to prepare a dope additive solution.

(Preparation of main dope solution)
Cellulose ester (cellulose triacetate synthesized from linter cotton, acetyl group substitution degree 2.92) 100 parts by weight Methylene chloride 380 parts by weight Ethanol 30 parts by weight Dope additive liquid The above preparation parts by weight are charged into a sealed container, and heated. While stirring, it completely dissolved, and Azumi Filter Paper No. 24 was used to prepare a main dope solution.

  The main dope solution was filtered with Finemet NF manufactured by Nippon Seisen Co., Ltd., and uniformly cast on a stainless steel band support at a temperature of 22 ° C. and a width of 2 m using a belt casting apparatus. With the stainless steel band support, the solvent was evaporated until the residual solvent amount became 105%, and the film was peeled from the stainless steel band support with a peeling tension of 162 N / m. The peeled cellulose ester web was evaporated at 35 ° C., slit to 1.6 m width, and then dried at a drying temperature of 135 ° C. while stretching 1.1 times in the width direction with a tenter. At this time, the residual solvent amount when starting stretching with a tenter was 10%. After stretching with a tenter and releasing the width retention by releasing the width tension at 130 ° C., the drying is finished while conveying the drying zone of 120 ° C. and 130 ° C. with a number of rolls, and slitting to a width of 1.5 m, Both ends of the film were subjected to a knurling process having a width of 10 mm and a height of 7 μm, and wound on a core having an inner diameter of 6 inches with an initial tension of 220 N / m and a final tension of 110 N / m, whereby a cellulose ester film 1 was obtained. The draw ratio in the MD direction calculated from the rotational speed of the stainless steel band support and the operating speed of the tenter was 1.1 times. The residual solvent amount of the cellulose ester film 1 was less than 0.1%, respectively, and the film thickness was 40 μm.

[Preparation of antiglare film 1]
On the surface of the cellulose ester film 1 (B surface side; surface in contact with a support mirror surface such as a stainless steel band used in the casting film forming method; support side), the following coating solution 1 for hard coat layer has a pore diameter of 20 μm. A coating solution for hard coat layer is prepared by filtering with a polypropylene filter, coated with a micro gravure coater, dried at 90 ° C., and then irradiated with an ultraviolet lamp with an illuminance of 0.1 W / cm. ² , the coating layer was cured with an irradiation dose of 0.1 J / cm ² , and an antiglare hard coat layer having a thickness of 5 μm was formed to produce an antiglare film 1. It was 133 nm as a result of measuring the arithmetic mean surface roughness (Ra) about the formed anti-glare film using the optical interference type surface roughness measuring machine by WYKO. The average center distance of the convex portions was 37 μm.

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

Acrylic monomer; KAYARAD DPHA (dipentaerythritol hexaacrylate, Nippon Kayaku) oxaacrylate, Nippon Kayaku 200 parts by weight Photopolymerization initiator (Irgacure 184 (Ciba Specialty Chemicals))
25 parts by mass Propylene glycol monomethyl ether 110 parts by mass Ethyl acetate 110 parts by mass Synthetic silica fine particles Average particle size 1.8 μm 40 parts by mass Surfactant (silicone surfactant; FZ2207 (Nihon Unicar)) 10% by mass propylene glycol monomethyl ether Solution) 0.6 parts by mass in solid content [Preparation of antiglare film 2 (antiglare film by inkjet method)]
(Preparation of the first layer)
The following cured resin layer coating composition 1 is applied to the surface of the cellulose ester film 1 (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) with a slit die. Then, the temperature and speed of the hot air were gradually increased and finally dried at 85 ° C., followed by irradiation with ultraviolet rays at an irradiation intensity of 115 mJ / cm ² from the actinic ray irradiation part to form a cured resin layer, thereby producing a first layer. . The dry film thickness by the following composition was 5 micrometers.

(Solid content)
Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 70 parts by mass Trimethylolpropane triacrylate 30 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
4 parts by mass (solvent)
Propylene glycol monomethyl ether 75 parts by weight Methyl ethyl ketone 25 parts by weight On the first layer, the following convex coating liquid 1 is ejected as ink droplets by an ink jet method at 2 to 16 pl, and irradiated with actinic rays 0.2 seconds after drying From the part, it was cured at an illuminance of ultraviolet light of 0.1 W / cm ² and an irradiation amount of 100 mJ / cm ² to form a convex part.

  As the inkjet emitting device, a line head system (FIG. 4A) was used, and 10 inkjet heads having 256 nozzles having a nozzle diameter of 3.5 μm were prepared. An ink jet head having the structure shown in FIG. 3 was used. The ink supply system is composed of an ink supply tank, a filter, a piezo-type ink jet head, and piping. The ink supply tank to the ink jet head section is insulated and heated (40 ° C.), and the emission temperature is 40 ° C. The driving frequency was 20 kHz.

  After forming the protrusions, the surface of the film was subjected to surface treatment by plasma discharge at a high frequency voltage of 100 KHz under atmospheric pressure of nitrogen atmosphere containing 1% oxygen, and then the following coating solution 1 for transparent resin layer was applied by a reduced pressure extrusion method. An antiglare film 2 was produced.

  It was 127 nm as a result of measuring the arithmetic average surface roughness Ra about the formed anti-glare film using the optical interference type surface roughness measuring machine by WYKO. The average center distance of the convex portions was 28 μm.

(Convex coating solution 1)
Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 70 parts by mass Trimethylolpropane triacrylate 30 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
4 parts by mass Propylene glycol monomethyl ether 20 parts by mass Diethylene glycol monobutyl ether acetate 180 parts by mass The above composition was mixed and stirred to prepare a convex coating solution.

(Transparent resin layer coating solution 1)
Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 100 parts by mass Trimethylolpropane triacrylate 40 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
6 parts by mass Propylene glycol monomethyl ether 50 parts by mass Methyl ethyl ketone 50 parts by mass The above composition was mixed and stirred to prepare a transparent resin layer coating solution.

[Preparation of antiglare film 3]
An antiglare film 3 was produced in the same manner as the antiglare film 2 except that the following convex coating solution 2 was used.

(Convex coating solution 2)
Acrylic monomer: KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 70 parts by mass Trimethylolpropane triacrylate 30 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
4 parts by mass Propylene glycol monomethyl ether 20 parts by mass Diethylene glycol monobutyl ether acetate 80 parts by mass The above composition was mixed and stirred to prepare a convex coating solution.

  It was 146 nm as a result of measuring average surface roughness (Ra) about the produced anti-glare film 3 using the optical interference type surface roughness measuring machine by WYKO. The average center distance of the convex portions was 33 μm.

[Formation of back coat layer]
On the opposite side of the surface on which the hard coat layer was applied, the following back coat layer coating solution was die-coated so as to have a wet film thickness of 14 μm, dried at 85 ° C. and wound to provide a back coat layer.

(Coating solution for back coat layer)
Acetone 30 parts by mass Ethyl acetate 45 parts by mass Isopropyl alcohol 10 parts by mass Diacetyl cellulose 0.6 parts by mass Ultrafine silica 2% acetone dispersion (Aerosil 200V manufactured by Nippon Aerosil Co., Ltd.)
0.2 parts by mass <Atmospheric pressure plasma treatment>
The atmospheric pressure plasma treatment apparatus described in FIG. 7 of Japanese Patent Application No. 2005-351829 was used, and the following atmospheric pressure plasma treatment was performed on the hard coat layer surface.

The electrode gap is 0.5 mm, the discharge gas shown below is supplied to the discharge space, and a high frequency power source manufactured by Shinko Electric Co., Ltd. is used, the frequency is 13.5 MHz, the applied voltage Vp = 9.5 kV, and the output density is 1.5 W / Surface treatment was performed by forming a discharge as cm ² .

(Discharge gas)
Nitrogen gas 80.0% by volume
Oxygen gas 20.0% by volume
(Formation of high refractive index layer)
The surface of the hard coat layer is die-coated with the following high refractive index layer coating solution, dried at 80 ° C., and then irradiated with 120 mJ / cm ² of ultraviolet light with a high-pressure mercury lamp so that the cured film thickness becomes 110 nm. A high refractive index layer was provided. The refractive index of the high refractive index layer was 1.60.

(High refractive index layer coating solution)
PGME (propylene glycol monomethyl ether) 40 parts by mass Isopropyl alcohol 25 parts by mass Methyl ethyl ketone 25 parts by mass Pentaerythritol triacrylate 0.9 parts by mass Pentaerythritol tetraacrylate 1.0 part by mass Urethane acrylate (trade name: U-4HA, Shin Nakamura Chemical) (Manufactured by Kogyo)
0.6 parts by mass Particle dispersion A (below) 20 parts by mass 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals) 0.4 parts by mass 2-methyl-1- [4- (Methylthio) phenyl] -2-monoforinopropan-1-one (Irgacure 907, manufactured by Ciba Specialty Chemicals)
0.2 parts by mass FZ-2207 (10% propylene glycol monomethyl ether solution, manufactured by Nihon Unicar) 0.4 parts by mass (Preparation of particle dispersion A)
While stirring 12.0 kg of isopropyl alcohol in 6.0 kg of methanol-dispersed antimony double oxide colloid (solid content 60%, manufactured by Nissan Chemical Industries, Ltd., zinc antimonate sol, trade name: CELNAX CX-Z610M-F2) Gradually added to prepare a particle dispersion A.

[Preparation of antiglare antireflection film 1]
On the anti-glare film 1, the following low refractive index layer coating solution 1 is applied by an extrusion coater, dried at 100 ° C. for 1 minute, then irradiated with ultraviolet rays at 0.1 J / cm ² and an irradiation amount of 100 mJ / Cured at cm ² and further heat cured at 120 ° C. for 5 minutes to produce an antiglare antireflection film 1. The viscosity of the coating solution for the low refractive index layer was 1.8 mPa · s, and the refractive index of the obtained low refractive index layer was 1.37.

  The viscosity was measured at 25 ° C. using a VISCO MATE MODEL VM-1G manufactured by Yamaichi Electronics Co., Ltd., and the refractive index was measured with an Abbe refractometer.

(Low refractive index layer coating solution 1)
Propylene glycol monomethyl ether 500 parts by mass Isopropyl alcohol 500 parts by mass Tetraethoxysilane hydrolyzate A (the following, solid content 21% conversion) 120 parts by mass γ-methacryloxypropyltrimethoxysilane (trade name: KBM503, Shin-Etsu Chemical Co., Ltd.) Product) 3.0 parts by mass Isopropyl alcohol-dispersed hollow silica fine particles 1 (below, solid content 20%, average particle size 45 nm, particle size variation coefficient 30%) 40 parts by mass Aluminum ethyl acetoacetate diisopropylate (Kawaken Fine Chemical) ALCH) 3.0 parts by mass FZ-2207 (10% propylene glycol monomethyl ether solution, manufactured by Nihon Unicar) 3.0 parts by mass (Preparation of tetraethoxysilane hydrolyzate A)
After mixing 230 g of tetraethoxysilane (trade name: KBE04, manufactured by Shin-Etsu Chemical Co., Ltd.) and 440 g of ethanol and adding 120 g of a 2% aqueous acetic acid solution thereto, the mixture is stirred for 28 hours at room temperature (25 ° C.). Silane hydrolyzate A was prepared.

(Preparation of isopropyl alcohol-dispersed hollow silica fine particles 1)
A mixture of 100 g of silica sol having an average particle diameter of 5 nm and a SiO ₂ concentration of 20% by mass and 1900 g of pure water was heated to 80 ° C. The pH of this reaction mother liquor was 10.5, and 9000 g of 0.98 mass% sodium silicate aqueous solution as SiO ₂ and 9000 g of 1.02 mass% sodium aluminate aqueous solution as Al ₂ O ₃ were simultaneously added to the mother liquor. did. 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 hardly changed thereafter. After completion of the addition, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a SiO ₂ .Al ₂ O ₃ core particle dispersion having a solid content concentration of 20% by mass. (Process (a))
1700 g of pure water is added to 500 g of this core particle dispersion and heated to 98 ° C., and while maintaining this temperature, a silicic acid solution (SiO ₂₎ obtained by dealkalizing a sodium silicate aqueous solution with a cation exchange resin. A dispersion of core particles in which 3000 g (concentration of 3.5% by mass) was added to form a first silica coating layer was obtained. (Process (b))
Next, 1125 g of pure water is added to 500 g of the core particle dispersion liquid that has been washed with an ultrafiltration membrane to form a first silica coating layer having a solid concentration of 13% by mass, and concentrated hydrochloric acid (35.5%) is further added dropwise. The pH was adjusted to 1.0 and dealumination was performed. Next, the aluminum salt dissolved in the ultrafiltration membrane was separated while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, and SiO ₂ · Al from which some of the constituent components of the core particles forming the first silica coating layer were removed. A dispersion of ₂ O ₃ porous particles 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 is heated to 35 ° C., and then 104 g of ethyl silicate (SiO ₂ 28 mass%) is added. The surface of the porous particles on which the first silica coating layer was formed was coated with a hydrolyzed polycondensate of ethyl silicate to form a second silica coating layer. Next, a dispersion of hollow silica-based fine particles 1 having a solid content concentration of 20% by mass was prepared by replacing the solvent with isopropyl alcohol using an ultrafiltration membrane.

The thickness of the first silica coating layer of the hollow silica-based fine particles was 3 nm, the average particle size was 45 nm, MOx / SiO ₂ (molar ratio) was 0.0017, and the refractive index was 1.28. Here, the average particle diameter and the coefficient of variation of the particle diameter were measured by a dynamic light scattering method.

[Preparation of antiglare antireflection film 2]
An antiglare antireflection film 2 was produced in the same manner as the antireflection film 1 except that the following low refractive index layer coating composition 2 was applied onto the antiglare film 3 by an extrusion coater. The viscosity of the low refractive index layer coating solution was 3.2 mPa · s, and the refractive index of the obtained low refractive index layer was 1.38.

(Low refractive index layer coating solution 2)
Acrylic monomer; OP-38Z (fluorinated acrylic resin, manufactured by Dainippon Ink & Chemicals, Inc.) 3.3 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
0.17 parts by mass γ-methacryloxypropyltrimethoxysilane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.17 parts by mass ethylene glycol monobutyl ether acetate 77 parts by mass propylene glycol monomethyl ether 20 parts by mass [antiglare reflection Preparation of prevention film 3]
On the antiglare film 3, the low refractive index layer coating solution 2 is ejected as ink droplets at 2 to 16 pl by an ink jet method so as to have an average dry film thickness (hd) shown in Table 4, and after drying After 0.2 seconds, the actinic ray irradiation part was cured at an ultraviolet illuminance of 0.1 W / cm ² and an irradiation amount of 100 mJ / cm ² to prepare an antiglare antireflection film 3.

  As the inkjet emitting device, a line head method (FIG. 4A) was used, and 10 inkjet heads having 256 nozzles having a nozzle diameter of 10.5 μm were prepared. An ink jet head having the structure shown in FIG. 3 was used. The ink supply system is composed of an ink supply tank, a filter, a piezo-type ink jet head, and piping. The ink supply tank to the ink jet head section is insulated and heated (40 ° C.), and the emission temperature is 40 ° C. The driving frequency was 20 kHz.

[Preparation of antiglare antireflection films 4 to 19]
Antiglare antireflection, except that the following low refractive index layer coating solutions 3 to 14 are applied on the antiglare films 1 to 3 by the inkjet method so as to have an average dry film thickness (hd) shown in Table 4. Antiglare antireflection films 4 to 19 were produced in the same manner as film 3.

(Low refractive index layer coating solution 3)
Acrylic monomer: OP-38Z (fluorinated acrylic resin, manufactured by Dainippon Ink & Chemicals, Inc.) 10 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
0.5 parts by mass γ-methacryloxypropyltrimethoxysilane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass ethylene glycol monobutyl ether acetate 72 parts by mass propylene glycol monomethyl ether 17 parts by mass Low refractive index The viscosity of the layer coating solution was 5.1 mPa · s, and the refractive index of the obtained low refractive index layer was 1.38.

(Low refractive index layer coating solution 4)
Acrylic monomer; OP-38Z (fluorinated acrylic resin, manufactured by Dainippon Ink & Chemicals, Inc.) 25 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
1.3 parts by mass γ-methacryloxypropyltrimethoxysilane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.3 parts by mass ethylene glycol monobutyl ether acetate 60 parts by mass propylene glycol monomethyl ether 15 parts by mass Low refractive index The viscosity of the layer coating solution was 6.2 mPa · s, and the refractive index of the obtained low refractive index layer was 1.38.

(Low refractive index layer coating solution 5)
Ethylene glycol monobutyl ether acetate 150 parts by mass Isopropyl alcohol 70 parts by mass Tetraethoxysilane hydrolyzate A (the following solid content 21% conversion) 120 parts by mass γ-methacryloxypropyltrimethoxysilane (trade name: KBM503, Shin-Etsu Chemical Co., Ltd.) 3.0 parts by mass Isopropyl alcohol-dispersed hollow silica fine particles 1 (below, solid content 20%, average particle size 45 nm, particle size variation coefficient 30%) 40 parts by mass Aluminum ethyl acetoacetate diisopropylate (Kawaken) ALCH manufactured by Fine Chemical Co., Ltd.) 3.0 parts by mass FZ-2207 (10% propylene glycol monomethyl ether solution, manufactured by Nippon Unicar Co., Ltd.) 3.0 parts by mass The viscosity of the low refractive index layer coating solution is 3.8 mPa · s. The refractive index of the obtained low refractive index layer is 1.3. It was 8.

(Low refractive index layer coating solution 6)
Acrylic monomer: OP-38Z (fluorinated acrylic resin, manufactured by Dainippon Ink & Chemicals, Inc.) 50 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
2.5 parts by mass γ-methacryloxypropyltrimethoxysilane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) 2.5 parts by mass ethylene glycol monobutyl ether acetate 38 parts by mass propylene glycol monomethyl ether 10 parts by mass Low refractive index The viscosity of the layer coating solution was 8.3 mPa · s, and the refractive index of the obtained low refractive index layer was 1.38.

(Low refractive index layer coating solution 7)
Acrylic monomer: OP-38Z (fluorinated acrylic resin, manufactured by Dainippon Ink & Chemicals, Inc.) 50 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
2.5 parts by mass γ-methacryloxypropyltrimethoxysilane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) 2.5 parts by mass Isopropyl alcohol-dispersed hollow silica fine particles 1 25 parts by mass Ethylene glycol monobutyl ether acetate 14 parts by mass Propylene Glycol monomethyl ether 9 parts by mass The viscosity of the low refractive index layer coating solution was 4.6 mPa · s, and the refractive index of the obtained low refractive index layer was 1.37.

(Low refractive index layer coating solution 8)
Acrylic monomer: OP-38Z (fluorinated acrylic resin, manufactured by Dainippon Ink & Chemicals, Inc.) 50 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
2.5 parts by mass γ-methacryloxypropyltrimethoxysilane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) 2.5 parts by mass Isopropyl alcohol-dispersed hollow silica fine particles 1 25 parts by mass Ethylene glycol monobutyl ether acetate 14 parts by mass Propylene Glycol 9 parts by weight The viscosity of the low refractive index layer coating solution was 18 mPa · s, and the refractive index of the obtained low refractive index layer was 1.37.

(Low refractive index layer coating solution 9)
Acrylic monomer: OP-38Z (fluorinated acrylic resin, manufactured by Dainippon Ink & Chemicals, Inc.) 50 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
2.5 parts by mass γ-methacryloxypropyltrimethoxysilane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) 2.5 parts by mass ethylene glycol monobutyl ether acetate 24 parts by mass propylene glycol monomethyl ether 24 parts by mass The refractive index of the refractive index layer was 1.38, and the viscosity was 7.6 mPa · s.

(Low refractive index layer coating solution 10)
Acrylic monomer: OP-38Z (fluorinated acrylic resin, manufactured by Dainippon Ink & Chemicals, Inc.) 50 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
2.5 parts by mass γ-methacryloxypropyltrimethoxysilane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) 2.5 parts by mass ethylene glycol 38 parts by mass propylene glycol monomethyl ether 10 parts by mass Low refractive index layer coating solution The viscosity of was 14.8 mPa · s, and the refractive index of the obtained low refractive index layer was 1.38.

(Low refractive index layer coating solution 11)
Acrylic monomer; Opstar JM5010 (manufactured by JSR Corporation) 130 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals Co., Ltd.))
2.5 parts by mass γ-methacryloxypropyltrimethoxysilane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) 2.5 parts by mass ethylene glycol monobutyl ether acetate 38 parts by mass propylene glycol monomethyl ether 10 parts by mass Low refractive index The viscosity of the layer coating solution was 6.6 mPa · s, and the refractive index of the obtained low refractive index layer was 1.41.

(Low refractive index layer coating solution 12)
Acrylic monomer; Light Ester FM-108 (manufactured by Kyoeisha Chemical Co., Ltd.)
100 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
2.5 parts by mass γ-methacryloxypropyltrimethoxysilane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) 2.5 parts by mass ethylene glycol monobutyl ether acetate 38 parts by mass propylene glycol monomethyl ether 10 parts by mass Low refractive index The viscosity of the layer coating solution was 5.2 mPa · s, and the refractive index of the obtained low refractive index layer was 1.41.

(Low refractive index layer coating solution 13)
Acrylic monomer; Light ester M-3F (manufactured by Kyoeisha Chemical Co., Ltd.) 90 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals Co., Ltd.))
2.5 parts by mass γ-methacryloxypropyltrimethoxysilane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) 2.5 parts by mass ethylene glycol monobutyl ether acetate 38 parts by mass propylene glycol monomethyl ether 10 parts by mass The refractive index of the refractive index layer was 1.35, and the viscosity was 6.1.

(Low refractive index layer coating solution 14)
Acrylic monomer; Defensor FH800ME (Dainippon Ink Chemical Co., Ltd.)
300 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
2.5 parts by mass γ-methacryloxypropyltrimethoxysilane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) 2.5 parts by mass ethylene glycol monobutyl ether acetate 38 parts by mass propylene glycol monomethyl ether 10 parts by mass Low refractive index The viscosity of the layer coating solution was 9.8 mPa · s, and the refractive index of the obtained low refractive index layer was 1.47.

[Preparation of antiglare antireflection films 20 to 23]
On the anti-glare film 3, the following low refractive index layer coating solution 15 is applied by an ink jet method so as to have an average film thickness (hd) shown in Table 4, and the time required for irradiating ultraviolet rays is determined as anti-glare reflection. Anti-glare antireflection, except for anti-glare film 20 for 0.1 second, anti-glare anti-reflection film 21 for 2 seconds, anti-glare anti-reflection film 22 for 45 seconds, anti-glare anti-reflection film 23 for 2 minutes Antiglare antireflection films 20 to 23 were produced in the same manner as film 3.

(Low refractive index layer coating solution 15)
Acrylic monomer; pentaerythritol diacrylate difluorobutyrate
50 parts by mass Photopolymerization initiator (Irgacure 184 (manufactured by Ciba Specialty Chemicals))
3.0 parts by mass γ-methacryloxypropyltrimethoxysilane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) 3.0 parts by mass ethylene glycol monobutyl ether acetate 38 parts by mass propylene glycol monomethyl ether 10 parts by mass Low refractive index The viscosity of the layer coating solution was 9.6 mPa · s, and the refractive index of the obtained low refractive index layer was 1.37.

<Evaluation of antiglare antireflection film>
About the produced anti-glare antireflection film, arithmetic average surface roughness, film thickness, anti-glare property, reflectance and scratch resistance were evaluated as follows.

(Arithmetic mean surface roughness)
According to JIS B 0601: 2001, using an optical interference type surface roughness meter RST / PLUS (manufactured by WYKO), each surface of the transparent support (b surface), the hard coat layer and the antireflection film is 1.2 mm. The arithmetic average surface roughness was determined for an area of × 0.9 mm.

(Film thickness)
Using the Hitachi Scanning Transmission Electron Microscope HD-2700, the tomographic photograph was taken at a magnification of 100,000 times, and the film thicknesses of 10 portions of the convex part and the concave part confirmed visually were obtained. The values measured and averaged using the scales were defined as the respective film thicknesses hd1 and hd2. The average value of hd1 and hd2 was defined as the average film thickness.

(Anti-glare)
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.

5: The outline of the fluorescent lamp and the external light are blurred and I don't care about the reflection at all 4: Between 5 and 3 3: The outline of the fluorescent lamp and the reflection of the external light are slightly recognized 2: 3: 1 Middle of 1: The outline of the fluorescent lamp and the external light are understood and the reflection is anxious (reflectance)
About the produced anti-glare antireflection film, a spectral reflectance at an incident angle of 5 ° was measured in a wavelength region of 380 to 780 nm using a spectrophotometer (manufactured by JASCO Corporation). Since the antireflection performance is better as the reflectance is smaller in a wide wavelength region, the minimum reflectance at 450 to 650 nm is obtained from the measurement result. In the measurement, the back surface on the observation side was roughened, and then light absorption processing was performed using a black spray to prevent reflection of light on the back surface of the film, and the reflectance was measured.

(Abrasion)
A sample was subjected to a load of 250 g / cm ^{2 on} # 0000 steel wool (SW) in an environment of 23 ° C. and 55% RH, and the number of scratches per 1 cm width was measured after 10 reciprocations. In addition, the number of scratches is measured at a place where the number of scratches is the largest among the portions where the load is applied. If it is 10 / cm or less, there is no practical problem, but 5 / cm or less is preferable, and 3 / cm or less is more preferable.

  From Table 4, it was found that the sample of the present invention was superior in antiglare property, reflectance, and scratch resistance as compared with the comparative example. Further, the shorter the time from application of the low refractive index layer to irradiation with ultraviolet rays, the better the antiglare property, reflectance, and scratching properties, and 0.1 seconds was the best.

Example 2
Using the antiglare antireflection films 1 to 23 prepared in Example 1, a polarizing plate was prepared as follows, and the polarizing plate was incorporated into a liquid crystal display panel (image display device) to evaluate visibility.

  According to the following method, a polarizing plate was prepared using an antiglare antireflection film and a cellulose triacetate film used as a support for the film as a polarizing plate protective film.

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

(B) Production of Polarizing Plate Next, according to the following Steps 1 to 5, the polarizing film and the polarizing plate protective film were bonded together to produce a polarizing plate.

  Step 1: The cellulose triacetate film was immersed in a 2 mol / L sodium hydroxide solution at 60 ° C. for 90 seconds, then washed with water and dried. A surface of the antiglare antireflection film provided with the antireflection layer was previously protected with a peelable protective film (PET).

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

  Step 3: Excess adhesive adhered to the polarizing film in Step 2 was lightly removed, and it was sandwiched between an alkali-treated cellulose triacetate film and an antireflection film and laminated.

Process 4: It bonded together at the speed | rate of about 2 m / min with the pressure of 20-30 N / cm < ² > with the two rotating rollers. At this time, care was taken to prevent bubbles from entering.

  Step 5: The sample prepared in Step 4 in a dryer at 80 ° C. was dried for 2 minutes to prepare a polarizing plate.

  The polarizing plate on the outermost surface of a commercially available liquid crystal display panel (NEC color liquid crystal display MultiSync LCD1525J: model name LA-1529HM) was carefully peeled off, and a polarizing plate with the polarization direction was attached thereto to produce a liquid crystal display device.

(Evaluation)
Visibility in moving images was confirmed as a display device. The display device using the anti-glare anti-reflection film for comparison has a concern about reflection and color unevenness depending on the scene, whereas the display device using the anti-glare anti-reflection film of the present invention has high contrast and visibility. It was good without any problem.

Claims (4)

A method for producing an antireflection film comprising at least one antiglare layer having a fine uneven structure on a transparent substrate, and forming a low refractive index layer directly or via another layer on the antiglare layer. The low refractive index layer is formed by an ink jet method, and the low refractive index layer is formed of a coating solution containing a solid content of 20 to 100% by mass and a viscosity at 25 ° C. of 6.5 to 15 mPa · s. The manufacturing method of the antireflection film characterized by these. The low refractive index layer is formed of a coating liquid containing 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. of 60% or more of the mass excluding the solid content. The method for producing an antireflection film according to claim 1. The coating solution is an ink containing a thermosetting resin or an actinic ray curable resin, and after landing the coating solution on a substrate, it is heated or irradiated with actinic rays within 0.1 seconds to 1 minute. The method for producing an antireflection film according to claim 1, wherein the film is solidified. The layer thickness hd1 of the low refractive index layer formed on the convex portion of the antiglare layer and the layer thickness hd2 of the low refractive index layer formed on the concave portion satisfy the following relational expression. Item 4. The method for producing an antireflection film according to any one of Items 3 to 3.
(Formula) hd1 / hd2 ≧ 0.4