JP2012133079A - Hard coat film, production method of the same, antireflection film, polarizing plate and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hard coat film, which is improved in occurrence of irregularity, preventing property against fingerprints, and blocking prevention while maintaining good visibility of the hard coat film, and to provide a method for producing the film, and an antireflection film, and further, a polarizing plate and an image display device having the hard coat film.SOLUTION: The hard coat film has a hard coat layer on one surface or both surfaces of a base film. The surface of the hard coat layer has an arithmetic average roughness Ra ranging from 2 to 20 nm, and a ratio (Ra/RSm) of the arithmetic average roughness Ra to an average interval RSm of projections and recesses on the surface of the hard coat layer ranges from 5×10to 2×10. The surface of the hard coat layer shows an average contact angle of 15 degrees or smaller with hexadecane and an average contact angle of 90 degrees or more with water at 23°C and 55% relative humidity RH.

Description

  The present invention relates to a hard coat film, a production method thereof, an antireflection film, a production method thereof, a polarizing plate provided with the antireflection film, and an image display device.

  In recent years, focusing on the fields of optical lenses, plasma display panels (PDP), cathode ray tube display devices (CRT), liquid crystal display devices for computers and word processors, etc., surface reflection has been performed to improve transmittance and contrast and reduce reflection. There has been proposed an antireflection film having an antireflection layer for reducing the above.

  As the antireflection layer, it is effective to reduce light reflection at the interface between the laminate and the air by laminating several layers having appropriate values of refractive index and optical film thickness as the optical interference layer. As the optical interference layer, at least a low refractive index layer is provided.

  Alternatively, the coated film is generally formed on a film substrate in order to impart mechanical strength.

  Alternatively, a film having a coatability is wound into a roll after applying a hard coat layer from the viewpoint of productivity and handleability.

  Or the roll-shaped film which formed the docoat layer may be stored for several days-dozens of days in a roll state from a viewpoint of production efficiency.

  However, for example, if a film with a roll-shaped hard coat layer is stored in a high temperature and high humidity period such as summer, the surfaces stick to each other (blocking occurs), and the hard coat layer surface There are problems such as scratches and the like, and when a blocked hard coat layer is formed, spotted unevenness occurs. These have led to a decline in the commercial value, and an immediate solution has been desired. In addition, the demand for fingerprint resistance is increasing, and a highly antifouling hard coat film is desired.

  As blocking prevention, for example, in Patent Document 1, a resin composition containing a first component and a second component is applied, and the resin of the first component is precipitated by phase separation to form fine irregularities on the surface of the film. It is disclosed that blocking resistance is obtained.

  However, with this technique, it is difficult to control the phase separation of the first component resin, and it is difficult to stably form fine irregularities. Moreover, the anti-blocking effect after the durability test assuming a high temperature and high humidity period was insufficient, and when an antireflection layer was formed on the phase separation layer, spotted unevenness occurred. In addition, since fine irregularities are formed by phase separation, the materials that can be added are limited, and when an antireflection layer is provided on the phase separated layer, adhesion between the antireflection layer and the phase separation layer cannot be obtained. There was also a problem.

  Concerning stain resistance, for example, Patent Document 2 contains a polyfunctional (meth) acrylate, and is a curable resin composition having an oleic acid contact angle of 10 degrees or less, which is applied to a plastic film and cured. It is disclosed that the stain resistance can be improved so that the haze of the entire film is 1 or less. However, this technique has a problem that the hydrophilicity is increased and the films are adhered to each other, the productivity is deteriorated, and coating unevenness occurs.

JP 2010-163535 A JP 2010-215775 A

  The present invention has been made in view of the above-mentioned problems and situations, and the solution is to prevent the occurrence of unevenness while maintaining good visibility of the hard coat film, to improve fingerprint prevention, It is providing the hard coat film which aimed at blocking prevention, its manufacturing method, and an antireflection film. Moreover, it is providing the polarizing plate and image display apparatus with which the said hard coat film was comprised.

  The above-mentioned problem according to the present invention is solved by the following means.

1. A hard coat film having a hard coat layer on one side or both sides of a base film, the arithmetic average roughness Ra of the surface of the hard coat layer being in the range of 2 to 20 nm, the arithmetic average roughness Ra of the The ratio of the unevenness on the surface of the hard coat layer to the average interval RSm (Ra / RSm) is in the range of 5 × 10 ⁻⁵ to 2 × 10 ⁻³ , and the temperature is 23 ° C. and the relative humidity is 55% RH. A hard coat film having a hexadecane average contact angle of 15 degrees or less and a water average contact angle of 90 degrees or more on the surface of the hard coat layer.

  2. 2. The hard coat film according to item 1, wherein the hard coat layer contains a leveling agent.

  3. 3. The hard coat film according to item 1 or 2, wherein the arithmetic average roughness Ra of the surface of the hard coat layer is in the range of 4 to 20 nm.

  4). The hard coat film according to any one of items 1 to 3, wherein an average contact angle of hexadecane on the surface of the hard coat layer is 10 degrees or less.

  5). The hard coat film according to any one of items 1 to 4, wherein a surface of the hard coat layer has an irregular protrusion shape having no period in the longitudinal direction.

  6). It is a manufacturing method of the hard-coat film which manufactures the hard-coat film as described in any one of said 1st term | claim-5th, Comprising: A hard-coat layer is passed through an application process, a drying process, and a hardening process at least. And a process for producing a hard coat film, wherein the temperature of the decreasing rate drying section in the drying step is maintained within a range of 95 to 120 ° C.

  7). An antireflection film formed by laminating a low refractive index layer on the hard coat film according to any one of items 1 to 5.

  8). 6. A polarizing plate comprising the hard coat film according to any one of items 1 to 5 above.

  9. An image display device comprising the hard coat film according to any one of items 1 to 5 above.

  10. 10. The image display device according to item 9, wherein the polarizing plate according to item 8 is provided on at least one surface of the liquid crystal cell.

  11. The image display device is a liquid crystal display device having a touch panel, and the hard coat film according to any one of items 1 to 5 is provided as a constituent member of the touch panel. Item 10. The image display device according to Item 9 above.

  By the above means of the present invention, while maintaining good visibility of the hard coat film, while maintaining good visibility of the hard coat film, it prevents occurrence of unevenness, improves fingerprint prevention, and further prevents blocking. The hard coat film which aimed at, its manufacturing method, and an antireflection film can be provided. Moreover, the polarizing plate and image display apparatus with which the said hard coat film was comprised can be provided.

  In the present invention, the ratio of the ratio (Ra / RSm) between the arithmetic average roughness Ra of the surface of the hard coat layer and the average interval RSm and the condition that the arithmetic average roughness Ra of the surface of the hard coat layer can be controlled within a specific range. By coating the hard coat layer, irregularities can be stably formed on the surface of the hard coat layer. Thereby, even if the film on which the hard coat layer is formed is wound into a roll and stored in a high temperature and high humidity state, the film is not blocked and unevenness does not occur.

  The irregularities on the surface of the hard coat layer have a fine structure and thus do not affect the transparency and smoothness of the hard coat layer. Also, normally, if the hard coat layer surface has irregularities, the antifouling effect does not show the maximum effect, but because of the optimum irregular shape, the antifouling effect is not impaired and high visibility is obtained. .

Conceptual diagram of an example of irregularly shaped protrusions with different widths and heights Explanatory drawing of protrusion The figure which shows the structural example of an antireflection film with a conductive film Schematic showing an example of the configuration of a resistive touch panel liquid crystal display device Optical interference type surface roughness meter observation figure of hard coat layer surface of antireflection film Schematic diagram of polarizing plate

The hard coat film of the present invention is a hard coat film having a hard coat layer on one side or both sides of the base film, and the arithmetic average roughness Ra of the surface of the hard coat layer is in the range of 2 to 20 nm, The ratio (Ra / RSm) of the arithmetic average roughness Ra to the average spacing RSm of the irregularities on the surface of the hard coat layer is in the range of 5 × 10 ⁻⁵ to 2 × 10 ⁻³ , and the temperature is 23 ° C. The surface of the hard coat layer at a relative humidity of 55% RH has an average hexadecane contact angle of 15 degrees or less and a water average contact angle of 90 degrees or more. This feature is a technical feature common to the inventions according to claims 1 to 11.

  As an embodiment of the present invention, it is preferable that the hard coat layer contains a leveling agent from the viewpoint of manifesting the effects of the present invention. Moreover, it is preferable that arithmetic mean roughness Ra of the surface of the said hard-coat layer exists in the range of 4-20 nm. Furthermore, the average contact angle of hexadecane on the surface of the hard coat layer is preferably 10 degrees or less.

  In the present invention, the surface of the hard coat layer preferably has an irregular protrusion shape having no period in the longitudinal direction.

  As a production method for producing the hard coat film of the present invention, the hard coat layer is formed through at least the coating process, the drying process and the curing process, and the temperature of the rate-decreasing drying section in the drying process is 95 to 120. It is preferable that it is a manufacturing method of the aspect processed in the conditions maintained within the range of (degreeC).

  The hard coat film of the present invention can be formed into an antireflection film by laminating a low refractive index layer on the hard coat film.

  The hard coat film of the present invention can be suitably included in a polarizing plate. Further, the image display apparatus can be suitably provided. In particular, the hard coat film of the present invention can be suitably used in an image display device in which the polarizing plate is provided on at least one surface of a liquid crystal cell.

  Furthermore, the hard coat film of this invention can be comprised suitably as a structural member of the said touch panel in the liquid crystal display device which has a touch panel.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

<Hard coat layer>
<Surface properties of hard coat layer>
<Surface shape>
The hard coat film of the present invention is a hard coat film having a hard coat layer on one side or both sides of the base film, and the arithmetic average roughness Ra of the surface of the hard coat layer is in the range of 2 to 20 nm, The ratio (Ra / RSm) of the arithmetic average roughness Ra to the average interval RSm of the irregularities on the surface of the hard coat layer is in the range of 5 × 10 ⁻⁵ to 2 × 10 ^−3. .

  The arithmetic average roughness Ra of the surface of the hard coat layer is a value measured with a non-contact surface shape measuring instrument (New View 5030 manufactured by ZYGO) based on the standard of JIS B0601: 2001. Moreover, the average interval RSm of the unevenness is synonymous with the average length RSm of the contour curve elements defined in the above standard.

  The arithmetic average roughness Ra of the surface of the hard coat layer according to the present invention is in the range of 2 to 20 nm, and more preferably 4 to 20 nm from the viewpoint of the object effect of the present invention.

  Further, the average interval RSm of the irregularities on the surface of the hard coat layer according to the present invention is also measured by non-contact surface shape measurement (New View 5030 manufactured by ZYGO) based on the provisions of JIS B0601: 2001, similarly to the arithmetic average roughness Ra. It is a measured value. RSm is preferably 3 to 80 μm, more preferably 5 to 70 μm.

By controlling the ratio (Ra / RSm) of the arithmetic average roughness Ra measured as described above and the average interval RSm (Ra / RSm) to a range of 5 × 10 ⁻⁵ to 2 × 10 ⁻³ , the object effect of the present invention is obtained. Good performance.

  The hard coat layer according to the present invention preferably has protrusions on the hard coat layer in order to obtain an arithmetic average roughness Ra (hereinafter also simply referred to as “Ra”) within the above range. The height of the protrusion shape is 1 nm to 1 μm, preferably 10 nm to 0.5 μm. The width is 50 nm to 100 μm, preferably 50 nm to 50 μm.

  In addition, the shape of the protrusion is an irregular shape having no period in the longitudinal direction, and even when the films overlap each other, the protrusion shape does not overlap, and the effect of blocking prevention can be obtained well. The object and effects of the invention are also preferable because they are obtained well.

  Here, the “irregular protrusion shape having no period in the longitudinal direction” is an irregular shape in which the surface unevenness is not determined in shape or size in the width direction of the film, and is formed by a surface transfer roll. Unlike surface irregularities with a periodicity, it refers to protrusions with a shape that does not have a periodicity in the longitudinal direction of the film. Specifically, shapes such as the protrusion shape 12a of the hard coat layer 12 in FIG. 1 are irregularly arranged. Also, “irregular” means that the protrusion shapes are irregularly arranged at random intervals, and may be isotropic or anisotropic.

  The height and width of the protrusion shape can be obtained from cross-sectional observation. Specifically, as shown in FIG. 2, the center line a is drawn on the cross-sectional observation image, and the lines forming the mountain ridges are b and c. The protrusion size width t can be obtained from the distance of the intersection. Further, the distance from the peak to the center line a can be obtained as the height h of the protrusion size.

Alternatively, the number of protrusions in the docoat layer is preferably 500 to 200000 pieces / mm ² . Specifically, it can be measured by the following method.

  For the measurement of the number of protrusions, the hard coat layer was measured with a non-contact surface shape measuring instrument (New View 5030 manufactured by ZYGO), and the number of protrusions in this measurement area (100 μm × 100 μm square) was read from the image. This series of measurements is performed 10 times, and the number of protrusions of the hard coat layer of the hard coat film can be determined from the average value of 10 times. As the number of protrusions, protrusions having a height of 3 nm or more are counted from the average line of the roughness curve.

  As a method of forming the protrusion shape, a method of adding fine particles, a method of forming a protrusion on the surface by pressing a mold, and controlling the processing temperature in the rate-decreasing drying section in the drying process of the hard coat layer coating composition to a high temperature condition The method of doing is mentioned.

  In the present invention, from the viewpoint of productivity and reproducibility, as a method of forming the protrusion shape, it is possible to use a method of controlling the treatment temperature in the drying rate reduction section in the drying process of the hard coat layer coating composition to a high temperature condition. preferable. By controlling the rate-of-decreasing drying section at a high temperature, convection occurs in the resin coating film, resulting in a non-uniform surface state, which is cured in this non-uniform surface state and a coating film is formed. It is believed that surface irregularities can be obtained.

《Contact angle》
In the measurement of the contact angle at a temperature of 23 ° C. and a relative humidity of 55% RH, the surface of the hard coat layer according to the present invention has a hexadecane average contact angle of 15 degrees or less and a water average contact angle of 90 degrees or more. Features.

  In the present invention, it is particularly preferable that the average contact angle of hexadecane on the hard coat layer surface is adjusted to 10 degrees or less.

  In the present invention, the surface of the hard coat layer of the hard coat film was conditioned for 24 hours at a temperature of 23 ° C. and a relative humidity of 55% RH, using a contact angle meter CA-A (Kyowa) using water and n-hexadecane. Measurement was performed at a droplet diameter of 1.0 mm under the above temperature and humidity conditions using Interface Chemical Co., Ltd.

  In addition, 20 samples of a size of 30 mm × 40 mm were sampled randomly from each hard coat film produced, and the contact angle was measured on the surface of each sample by the above-described method, and each 20 hard coat films were measured. The average value of the measured values was adopted as the “average contact angle”.

  The contact angle can be adjusted by optimizing the surface irregularity, the type and composition of the resin constituting the hard coat layer, and additives (for example, leveling agents).

<Constituent components of hard coat layer>
The hard coat layer according to the present invention contains an actinic radiation curable resin, and is a layer mainly composed of a resin that is cured through a crosslinking reaction by irradiation with actinic rays (also referred to as active energy rays) such as ultraviolet rays and electron beams. Preferably there is. As the actinic radiation curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and an actinic radiation curable resin layer is formed by curing by irradiation with actinic radiation such as ultraviolet rays or electron beams. The Typical examples of the actinic radiation curable resin include an ultraviolet curable resin and an electron beam curable resin, but the resin that is cured by ultraviolet irradiation is excellent in mechanical film strength (abrasion resistance, pencil hardness). preferable. As the ultraviolet curable resin, for example, an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, or an ultraviolet curable epoxy resin is preferable. Used. Of these, ultraviolet curable acrylate resins are preferred.

  As the ultraviolet curable acrylate resin, a polyfunctional acrylate is preferable. The polyfunctional acrylate is preferably selected from the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate. Here, the polyfunctional acrylate is a compound having two or more acryloyloxy groups or methacryloyloxy groups in the molecule. Examples of the polyfunctional acrylate monomer include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethane triacrylate. , Tetramethylolmethane tetraacrylate, pentaglycerol triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, glycerol triacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol Lithol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, Tetramethylol methane trimethacrylate, tetramethylol methane tetramethacrylate, pentaglycerol trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerol trimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetramethacrylate Acrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexa methacrylate, and the like preferably. These compounds are used alone or in combination of two or more. Moreover, oligomers, such as a dimer and a trimer of the said monomer, may be sufficient.

  The hard coat layer according to the present invention may contain a monofunctional acrylate. When monofunctional acrylate is used, polyfunctional acrylate: monofunctional acrylate = 80: 20 to 99: 2 is preferable in terms of mass ratio of polyfunctional acrylate to monofunctional acrylate.

  Monofunctional acrylates include isobornyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, isostearyl acrylate, benzyl acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, lauryl acrylate, isooctyl acrylate, tetrahydrofurfuryl acrylate, behenyl Examples include acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and cyclohexyl acrylate. Monofunctional acrylates can be obtained from Shin Nakamura Chemical Co., Ltd., Osaka Organic Chemical Industry Co., Ltd., and the like. In the present invention, actinic radiation curable resins other than the above-described polyfunctional acrylates and monofunctional acrylates may be used singly or in combination. The viscosity at 25 ° C. of the actinic radiation curable resin alone or in combination of two or more is preferably 20 mPa · s or more and 2000 mPa · s or less. By using such a low-viscosity resin, sufficient fluidity of the resin composition can be obtained in the drying step, so that a protrusion shape is easily formed on the hard coat layer. Moreover, if it is an actinic radiation curable resin having a viscosity of 20 mPa · s or more, sufficient curability is obtained, and if it is an actinic radiation curable resin having a viscosity of 3000 mPa · s or less, sufficient flow of the resin composition in the drying step. Therefore, it is easy to form an uneven shape on the hard coat layer surface. The viscosity is a value measured using a B-type viscometer at 25 ° C. Examples of the low viscosity resin include glycerin triacrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate.

  By using such a low-viscosity resin, sufficient fluidity of the resin composition can be obtained in the drying step, so that a protrusion shape is easily formed on the hard coat layer. In addition, the said viscosity is the value measured on 25 degreeC conditions using the B-type viscometer.

  The hard coat layer preferably contains a photopolymerization initiator to accelerate the curing of the actinic radiation curable resin. The amount of the photopolymerization initiator is preferably contained in a mass ratio of photopolymerization initiator: active ray curable resin = 20: 100 to 0.01: 100.

  Specific examples of the photopolymerization initiator include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof, but are not particularly limited thereto. .

  The hard coat layer according to the present invention may include fine particles of an inorganic compound or an organic compound.

  As inorganic fine particles, silicon oxide, titanium oxide, aluminum oxide, tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide, magnesium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated silicic acid Mention may be made of calcium, aluminum silicate, magnesium silicate and calcium phosphate. In particular, silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide and the like are preferably used.

  These inorganic fine particles are preferably coated with an organic component having a reactive functional group on a part of the surface because the scratch resistance is improved while maintaining the transparency of the hard coat layer. As a method for coating an organic component having a reactive functional group on a part of the surface, for example, a compound containing an organic component such as a silane coupling agent reacts with a hydroxyl group present on the surface of the metal oxide fine particles, and the surface A mode in which an organic component is bonded to a part of the metal particle, a mode in which an organic component is attached to a hydroxyl group present on the surface of a metal oxide fine particle by an interaction such as a hydrogen bond, or one or more inorganic particles in a polymer particle The aspect containing microparticles | fine-particles etc. are mentioned.

  As organic particles, polymethacrylic acid methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicon resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, melamine resin powder, A polyolefin resin powder, a polyester resin powder, a polyamide resin powder, a polyimide resin powder, a polyfluoroethylene resin powder, or the like can be added.

  Preferred fine particles include crosslinked polystyrene particles (for example, SX-130H, SX-200H, SX-350H manufactured by Soken Chemical), polymethyl methacrylate-based particles (for example, MX150, MX300 manufactured by Soken Chemical), and fluorine-containing acrylic resin fine particles. . Examples of the fluorine-containing acrylic resin fine particles include commercial products such as FS-701 manufactured by Nippon Paint. Examples of the acrylic particles include Nippon Paint: S-4000, and examples of the acrylic-styrene particles include Nippon Paint: S-1200, MG-251.

  The average particle size of these fine particles is not particularly limited, but is preferably 0.01 to 5 μm, and more preferably 0.01 to 1.0 μm. Moreover, you may contain 2 or more types of microparticles | fine-particles from which a particle size differs. The average particle diameter of the fine particles can be measured by, for example, a laser diffraction particle size distribution measuring device.

  The ratio of the ultraviolet curable resin composition and the fine particles is desirably 10 to 400 parts by mass, more preferably 50 to 200 parts by mass with respect to 100 parts by mass of the resin composition.

  Further, the hard coat layer according to the present invention is provided by applying a hard coat layer coating composition diluted with a solvent that swells or partially dissolves the base film, dried, and cured on the base film by the following method. It is preferable from the point that a protrusion shape is easily obtained in the hard coat layer. As a solvent that swells or partially dissolves the base film, a solvent containing a ketone and / or acetate is preferable. Moreover, 0.1-40 micrometers is suitable for an application quantity as a wet film thickness, Preferably, it is 0.5-30 micrometers. The dry film thickness is from 0.1 to 30 μm, preferably from 1 to 20 μm, particularly preferably from 4 to 15 μm.

  The hard coat layer is a hard coat coating composition that forms a hard coat layer using a known coating method such as a gravure coater, dip coater, reverse coater, wire bar coater, die coater, or ink jet method (hereinafter, hard coat layer composition). (Also referred to as a product), and after application, drying, UV curing treatment, and if necessary, heat treatment to UV curing. Drying is preferably performed at a high temperature of 95 ° C. or higher in the decreasing rate drying section. Particularly preferably, the temperature in the decreasing rate drying section is in the range of 95 ° C to 120 ° C. By controlling the temperature of the decreasing rate drying section within this range, the arithmetic average roughness Ra of the hard coat layer can be easily controlled within the range of the present invention, and the object effect of the present invention is exhibited well. It is inferred that convection is positively generated in the resin coating by forming the reduced rate drying section at a high temperature, and as a result, a protrusion shape is formed on the surface of the hard coat layer.

  In general, it is known that the drying process changes from a constant state to a gradually decreasing state when drying starts. The decreasing section is called the decreasing rate drying section. In the constant rate drying section, the amount of heat flowing in is all consumed for solvent evaporation on the coating film surface, and when the solvent on the coating film surface decreases, the evaporation surface moves from the surface to the inside and enters the decreasing rate drying section. Thereafter, the temperature of the coating film surface rises and approaches the hot air temperature, so that the temperature of the ultraviolet curable resin composition rises, the resin viscosity decreases, and the fluidity increases.

  As a light source for UV curing treatment, any light source that generates ultraviolet rays can be used without limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.

Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is usually 50 to 1000 mJ / cm ² , preferably 50 to 500 mJ / cm ² .

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

  The hard coat layer may contain a conductive agent in order to impart antistatic properties, and preferred conductive agents include metal oxide particles or π-conjugated conductive polymers. An ionic liquid is also preferably used as the conductive compound. Alternatively, in the coating layer, from the viewpoint of applicability, a silicone surfactant, a fluorine surfactant, an acrylic surfactant, a nonionic surfactant such as polyoxyether, an anionic surfactant, or fluorine- A siloxane graft polymer may be contained. The fluorine-siloxane graft polymer refers to a copolymer polymer obtained by grafting polysiloxane and / or organopolysiloxane containing siloxane and / or organosiloxane alone on at least a fluorine-based resin. Examples of commercially available products include ZX-022H, ZX-007C, ZX-049, and ZX-047-D manufactured by Fuji Kasei Kogyo Co., Ltd. The silicone-based surfactant is a surfactant obtained by substituting a part of the methyl group of the silicone oil with a hydrophilic group. Examples of the hydrophilic group include polyether, polyglycerin, pyrrolidone, betaine, sulfate, phosphate, and quaternary salt. Specific products of silicone surfactants include, for example, SH200, BY16-873, PRX413 (dimethylsilicone oil; manufactured by Toray Dow Corning Silicone Co., Ltd.), SH203, SH230, SF8416 (alkyl-modified silicone oil; Toray Dow) Corning Silicone Co., Ltd.), SF8417, BY16-208, BY16-209, BY16-849, BY16-872, FZ-2222, FZ-2207 (dimethylpolysiloxane / polyethylene oxide linear block copolymer; Nippon Unicar ( FZ series), KF-101, KF-102, KF-105 (epoxy-modified silicone oil; manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-UV3500, BYK-UV3510, BYK-333, BYK-33 , BYK-337 (polyether-modified silicone oil, Bikkukemi - Japan Ltd.), but like without limitation. Moreover, as an acrylic surfactant, an acrylic copolymer is specifically preferably used, and examples of commercially available products include BYK-350, BYK-352 (manufactured by BYK-Chemical Japan) and ZX-058-A. (Manufactured by Fuji Kasei Kogyo Co., Ltd.) and the like. Moreover, it is preferable to add these components in 0.01-5 mass% with respect to the solid content component in a coating liquid.

  The hard coat layer may be a single layer or a plurality of layers. In order to easily control the hard coat properties, haze, and arithmetic surface roughness Ra of the hard coat layer, the hard coat layer may be divided into two or more layers.

  The thickness of the uppermost layer when two or more layers are provided is preferably in the range of 0.05 to 2 μm. Two or more layers may be formed as a simultaneous multilayer. The simultaneous multi-layer is to form a hard coat layer by applying two or more hard coat layers on a base material without going through a drying step. In order to laminate the second hard coat layer on the first hard coat layer without a drying process, the layers are stacked one after another by an extrusion coater or simultaneously by a slot die having a plurality of slits. Can be done.

  Alternatively, the haze value of the film in a state where the docoat layer is formed is preferably 2% or less, more preferably 1% or less from the viewpoint of clearness. Alternatively, the absolute value | Hh−Hf | of the difference between the haze value (Hh) of the film on which the coated layer is formed and the haze value (Hf) of the base film is set to 1% or less to increase the size of the liquid crystal display device It is preferable because sufficient brightness and high contrast are easily obtained when used outdoors such as digital signage. The haze can be measured according to JIS-K7105 and JIS-K7136.

  In order to control the haze value of the hard coat layer, adjustment of the resin constituting the hard coat layer, the type and amount of the additive, the content ratio of the resin and solvent of the hard coat layer coating composition, and the reduction in the drying process This can be achieved under the processing temperature conditions in the drying section. Alternatively, since the arithmetic average roughness Ra of the docoat layer also affects the haze value as surface haze, it is effective to control the shape and number of the protrusions.

《Leveling agent》
In the present invention, it is preferable to contain a leveling agent in the hard coat layer in order to adjust the contact angle. It is because the surface energy of a hard-coat layer can be adjusted by containing a leveling agent.

  As described above, the curable resin composition according to the present invention needs to have a hexadecane contact angle of 15 degrees or less. When the hexadecane contact angle is 15 degrees or less, even if a fingerprint is attached, it becomes difficult to stand out.

  The (meth) acrylate compound as the main component of the curable resin composition according to the present invention often has an oleic acid contact angle exceeding 40 degrees, and it is necessary to reduce the hexadecanoic acid contact angle to 15 degrees or less by some method. is there.

  As a leveling agent that lowers the contact angle, various conventionally known leveling agents can be used.

  In the present invention, for example, a so-called lipophilic resin is preferably added as a leveling agent. Specific examples of the lipophilic resin include Lumiflon LF200, LF302, LF400, LF600, LF600X, LF800, LF906N, LF910LM, LF916N, LF936, LF9010 (manufactured by Asahi Glass Co., Ltd.) and polysiloxane modified resins that are fluorine-modified resins. ZX-058-A, ZX-214-A, etc. (manufactured by Fuji Kasei Kogyo Co., Ltd.) can be mentioned. Among the oleophilic resins, those having a hexadecane contact angle of 15 degrees or less by adding a small amount are preferable.

  The amount of the oleophilic resin added is preferably determined by examining the optimum amount in consideration of the contact angle, the surface hardness of the hard coat layer, and the like.

  As the leveling agent, the leveling agents described in JP 2010-217504 A, JP 2010-0799099 A, JP 2009-185282 A and the like can also be used within a range that does not inhibit the effects of the present invention. .

<Base film>
The base film according to the present invention is preferably easy to produce, easy to adhere to the hard coat layer, and optically isotropic. Moreover, in this invention, a base film is used as a protective film.

  Any of these may be used, for example, cellulose ester films such as triacetyl cellulose film, cellulose acetate propionate film, cellulose diacetate film, cellulose acetate butyrate film, polyethylene terephthalate, polyethylene naphthalate Polyester film, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyethylene film, polypropylene film, cellophane, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic Tick polystyrene film, norbornene resin film, polymethylpentene film Polyether ketone film, polyether ketone imide film, a polyamide film, a fluororesin film, a nylon film, cycloolefin polymer films, and polymethyl methacrylate film, or an acrylic film.

  Among these, cellulose ester films (for example, Konica Minoltac KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UE, KC4UE, and KC12UR (above, manufactured by Konica Minolta Opto, Polycarbonate Film) Olefin polymer films and polyester films are preferred, and in the present invention, cellulose ester films are particularly preferred from the viewpoint of production, cost, isotropic properties, and adhesiveness (saponification suitability).

  The refractive index of the base film is preferably 1.30 to 1.70, and more preferably 1.40 to 1.65. The refractive index is measured by the method of JIS K7142 using an Abbe refractometer 2T manufactured by Atago Co., Ltd.

<Cellulose ester film>
Next, a cellulose ester film preferable as a substrate film will be described.

  The cellulose ester film is composed of a cellulose ester resin (hereinafter also referred to as “cellulose ester”), and this resin is preferably a lower fatty acid ester of cellulose. The lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms. For example, a mixed fatty acid such as cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate, etc. Esters can be used.

  Particularly preferably used lower fatty acid esters of cellulose are cellulose triacetate and cellulose acetate propionate. These cellulose esters can be used alone or in combination.

  In the case of cellulose triacetate, those having an average degree of acetylation (bound acetic acid amount) of 54.0 to 62.5% are preferably used, and more preferably an average degree of acetylation of 58.0 to 62.5%. Cellulose triacetate.

  When the average degree of acetylation is small, the dimensional change is large, and the polarization degree of the polarizing plate is lowered. When the average degree of acetylation is large, the solubility in a solvent is lowered and the productivity is lowered.

  The cellulose triacetate has an acetyl group substitution degree of 2.80 to 2.95, a number average molecular weight (Mn) of 125,000 or more and less than 155000, a weight average molecular weight (Mw) of 265,000 or more and less than 310,000, Mw Cellulose triacetate A / Mn of 1.9 to 2.1, acetyl group substitution degree of 2.75 to 2.90, number average molecular weight (Mn) of 155,000 or more and less than 180,000, Mw is 290000 or more and less than 360,000 Mw / Mn preferably contains cellulose triacetate B which is 1.8 to 2.0.

  Further, when cellulose triacetate A and cellulose triacetate B are used in combination, it is preferable that the mass ratio is in the range of cellulose triacetate A: cellulose triacetate B = 100: 0 to 20:80.

  Preferred cellulose esters other than cellulose triacetate have an acyl group having 2 to 4 carbon atoms as a substituent, the substitution degree of acetyl group is X, and the substitution degree of propionyl group or butyryl group is Y, It is a cellulose ester containing the cellulose ester which satisfy | fills (I) and (II) simultaneously.

Formula (I) 2.6 ≦ X + Y ≦ 3.0
Formula (II) 0 ≦ X ≦ 2.5
In particular, cellulose acetate propionate is preferably used, and among them, 1.9 ≦ X ≦ 2.5 and 0.1 ≦ Y ≦ 0.9 are preferable.

  The number average molecular weight (Mn) and molecular weight distribution (Mw) of the cellulose ester can be measured using high performance liquid 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 (GL Science Co., Ltd.)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0 ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation)
A calibration curve with 13 samples from Mw = 100000 to 500 was used. The 13 samples are preferably used at approximately equal intervals.

<Acrylic polymer>
For the base film, a mixture of the cellulose ester resin and the acrylic polymer may be used. When used as a mixture, the mass ratio of the acrylic polymer to the cellulose ester resin is preferably acrylic polymer: cellulose ester resin = 95: 5 to 50:50.

  The acrylic polymer is not particularly limited as long as it is a resin obtained by polymerizing a monomer composition containing (meth) acrylic acid ester as a main component. Moreover, what has two or more types of acrylic polymers as a main component may be used. As said (meth) acrylic acid ester, the following general formula (I);

(Wherein, ^{R 1} and ^{R 2} each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms.)
A compound (monomer) having a structure represented by the formula: Acrylic acid esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, benzyl acrylate, etc. Methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate and benzyl methacrylate; May be used alone, or two or more of them may be used in combination. Among these, a compound having a structure represented by the above general formula (2) and methyl methacrylate are more preferable because of excellent heat resistance and transparency. In addition, benzyl (meth) acrylate is preferred in terms of increasing positive birefringence (positive phase difference).

  In addition, when introduce | transducing a methacrylic acid benzyl monomer structural unit, the preferable content of the (meth) acrylic acid benzyl monomer structural unit in an acrylic polymer is 5-50 mass%, More preferably, it is 10-40 mass%, More preferably, it is 15-30 mass%.

  Examples of the compound having a structure represented by the general formula (I) include methyl 2- (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, isopropyl 2- (hydroxymethyl) acrylate, 2- (Hydroxymethyl) normal butyl acrylate, 2- (hydroxymethyl) tert-butyl acrylate, and the like. Among these, methyl 2- (hydroxymethyl) acrylate and 2- (hydroxymethyl) ethyl acrylate are preferable, and methyl 2- (hydroxymethyl) acrylate is particularly preferable in that the effect of improving heat resistance is high. As for the compound represented by general formula (I), only 1 type may be used and 2 or more types may be used together.

  The acrylic polymer may have a structure other than the structure obtained by polymerizing the (meth) acrylic acid ester described above. The structure other than the structure obtained by polymerizing (meth) acrylic acid ester is not particularly limited, but includes a hydroxyl group (hydroxyl group) -containing monomer, an unsaturated carboxylic acid, the following general formula (II);

(Wherein R ¹ represents a hydrogen atom or a methyl group, X represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an —OAc group, a —CN group, a —CO—R ² group, or a C— O—R ³ represents a group, Ac represents an acetyl group, R ² and R ³ represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms.)
The polymer structural unit (repeating structural unit) constructed by polymerizing at least one selected from the monomers represented by

  The hydroxyl group (hydroxyl group) -containing monomer is not particularly limited as long as it is a hydroxyl group (hydroxyl group) -containing monomer other than the monomer represented by formula (I). For example, methallyl alcohol, allyl 2- (hydroxyalkyl) acrylic acid esters such as alcohol, allyl alcohol such as 2-hydroxymethyl-1-butene, α-hydroxymethylstyrene, α-hydroxyethylstyrene, methyl 2- (hydroxyethyl) acrylate; 2- (Hydroxyalkyl) acrylic acid such as (hydroxyethyl) acrylic acid; and the like. These may be used alone or in combination of two or more.

  Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-substituted acrylic acid, α-substituted methacrylic acid and the like. These may be used alone or in combination of two or more. May be. Among these, acrylic acid and methacrylic acid are preferable in that the effects of the present invention are sufficiently exhibited.

  Examples of the compound represented by the general formula (II) include styrene, vinyl toluene, α-methyl styrene, acrylonitrile, methyl vinyl ketone, ethylene, propylene, and vinyl acetate. These may be used alone. Two or more kinds may be used in combination. Among these, styrene and α-methylstyrene are particularly preferable in that the effects of the present invention are sufficiently exhibited.

  The polymerization method is not particularly limited, and a known polymerization method can be used. A suitable method may be employed depending on the type of monomer (monomer composition) to be used, the use ratio, and the like.

  The acrylic polymer used in the present invention has a glass transition temperature (Tg) of preferably 110 ° C to 200 ° C, more preferably 115 ° C to 200 ° C, still more preferably 120 ° C to 200 ° C, and particularly preferably 125 ° C. It is -190 degreeC, Most preferably, it is 130 to 180 degreeC.

  In terms of heat resistance, N-substituted maleimides such as phenylmaleimide, cyclohexylmaleimide, and methylmaleimide may be copolymerized in the molecular chain (also referred to as the main skeleton of the polymer or the main chain). A lactone ring structure, a glutaric anhydride structure, a glutarimide structure, or the like may be introduced. Among them, a monomer that does not contain a nitrogen atom is preferable from the viewpoint of difficulty in coloring (yellowing) the film, and positive birefringence (positive phase difference) is easily expressed in the main chain. Those having a lactone ring structure are preferred. Regarding the lactone ring structure in the main chain, a 4- to 8-membered ring may be used, but a 5- to 6-membered ring is more preferable, and a 6-membered ring is more preferable in view of the stability of the structure. Further, when the lactone ring structure in the main chain is a 6-membered ring, examples include the structure represented by the general formula (III) and Japanese Patent Application Laid-Open No. 2004-168882, and the lactone ring structure is introduced into the main chain. The point of high polymerization yield in the synthesis of the previous polymer, the point that a polymer with a high content of lactone ring structure is easily obtained with high polymerization yield, and (meth) acrylic acid esters such as methyl methacrylate From the viewpoint of good copolymerizability, a structure represented by the general formula (III) is preferable.

<Acrylic polymer having a lactone ring structure>
When the acrylic polymer is a resin obtained by polymerizing a monomer containing a compound having a structure represented by the general formula (I), the acrylic polymer has a lactone ring structure. Is more preferable (hereinafter, an acrylic polymer having a lactone ring structure is referred to as a “lactone ring-containing polymer”).

  Examples of the lactone ring-containing polymerization include compounds represented by the following general formula (III).

(Wherein R ¹ , R ² and R ³ each independently represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms. The organic residue may contain an oxygen atom.)
The structure represented by is mentioned.

  The organic residue in the general formula (III) is not particularly limited as long as it has 1 to 20 carbon atoms. For example, a linear or branched alkyl group, a linear or branched alkylene is used. Group, aryl group, -OAc group, -CN group and the like.

  The content of the lactone ring structure in the acrylic polymer is preferably in the range of 5 to 90% by mass, more preferably in the range of 20 to 90% by mass, and still more preferably in the range of 30 to 90% by mass. More preferably, it is in the range of 35 to 90% by mass, particularly preferably in the range of 40 to 80% by mass, and most preferably in the range of 45 to 75% by mass. If the content of the lactone ring structure is more than 90% by mass, the moldability becomes poor. Moreover, there exists a tendency for the flexibility of the obtained film to fall, and it is not preferable. When the content of the lactone ring structure is less than 5% by mass, it is difficult to obtain a necessary retardation when formed into a film, and heat resistance, solvent resistance, and surface hardness may be insufficient. It is not preferable.

  In the lactone ring-containing polymer, the content ratio of the structure other than the lactone ring structure represented by the general formula (III) is that of a polymer structural unit (repeating structural unit) constructed by polymerizing (meth) acrylic acid ester. In the range of 10 to 95% by mass, more preferably in the range of 10 to 80% by mass, further preferably in the range of 10 to 65% by mass, particularly preferably in the range of 20 to 60% by mass, Preferably it exists in the range of 25-55 mass%. In the case of a polymer structural unit (repeating structural unit) constructed by polymerizing a hydroxyl group (hydroxyl group) -containing monomer, it is preferably in the range of 0 to 30% by mass, more preferably in the range of 0 to 20% by mass. More preferably, it is in the range of 0 to 15% by mass, particularly preferably in the range of 0 to 10% by mass. In the case of a polymer structural unit (repeating structural unit) constructed by polymerizing an unsaturated carboxylic acid, it is preferably in the range of 0 to 30% by mass, more preferably in the range of 0 to 20% by mass, and still more preferably 0. It is in the range of ˜15% by mass, particularly preferably in the range of 0 to 10% by mass. In the case of a polymer structural unit (repeating structural unit) constructed by polymerizing the monomer represented by formula (III), it is preferably in the range of 0 to 30% by mass, more preferably 0 to 20% by mass. Is more preferably in the range of 0 to 15% by mass, particularly preferably in the range of 0 to 10% by mass.

  The method for producing the lactone ring-containing polymer is not particularly limited, but preferably the polymer obtained after obtaining a polymer having a hydroxyl group (hydroxyl group) and an ester group in the molecular chain by a polymerization step. A lactone ring-containing polymer can be obtained by performing a lactone cyclization condensation step of introducing a lactone ring structure into the polymer by heat treatment.

<Alicyclic polyolefin resin>
In this invention, a base film may be comprised from the alicyclic polyolefin resin represented by the cycloolefin polymer. The alicyclic polyolefin resin is an amorphous resin having an alicyclic structure in the main chain and / or side chain. Examples of the alicyclic structure in the alicyclic polyolefin resin include a saturated alicyclic hydrocarbon (cycloalkane) structure and an unsaturated alicyclic hydrocarbon (cycloalkene) structure. From the viewpoint of mechanical strength, heat resistance, and the like. A cycloalkane structure is preferred. The number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually 4 to 30, preferably 5 to 20, more preferably 5 to 15, when the mechanical strength, heat resistance, In addition, the moldability characteristics of the film are highly balanced and suitable.

  The ratio of the repeating unit having an alicyclic structure constituting the alicyclic polyolefin resin is preferably 55% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more. It is preferable from a viewpoint of transparency and heat resistance that the ratio of the repeating unit which has an alicyclic structure in alicyclic polyolefin resin exists in this range.

  Examples of the alicyclic polyolefin resin include a norbornene resin, a monocyclic olefin resin, a cyclic conjugated diene resin, a vinyl alicyclic hydrocarbon resin, and hydrides thereof. Among these, norbornene-based resins can be suitably used because of their good transparency and moldability.

  Examples of the norbornene-based resin include a ring-opening polymer of a monomer having a norbornene structure, a ring-opening copolymer of a monomer having a norbornene structure and another monomer, or a hydride thereof; norbornene structure The addition polymer of the monomer which has this, the addition copolymer of the monomer which has a norbornene structure, and another monomer, those hydrides, etc. can be mentioned. Among these, a ring-opening (co) polymer hydride of a monomer having a norbornene structure is particularly suitable from the viewpoints of transparency, moldability, heat resistance, low hygroscopicity, dimensional stability, lightness, and the like. Can be used.

  As a monomer having a norbornene structure, bicyclo [2.2.1] hept-2-ene (common name: norbornene), tricyclo [4.3.0.12,5] deca-3,7-diene ( Common name: dicyclopentadiene), 7,8-benzotricyclo [4.3.0.12,5] dec-3-ene (common name: methanotetrahydrofluorene), tetracyclo [4.4.0.12, 5.17,10] dodec-3-ene (common name: tetracyclododecene) and derivatives of these compounds (for example, those having a substituent in the ring). Here, examples of the substituent include an alkyl group, an alkylene group, and a polar group. In addition, these substituents may be the same or different and a plurality may be bonded to the ring. Monomers having a norbornene structure can be used singly or in combination of two or more.

  Examples of the polar group include a hetero atom or an atomic group having a hetero atom. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, and a halogen atom. Specific examples of the polar group include a carboxyl group, a carbonyloxycarbonyl group, an epoxy group, a hydroxyl group, an oxy group, an ester group, a silanol group, a silyl group, an amino group, a nitrile group, and a sulfone group. To obtain a film with a small saturated water absorption rate. It is preferable that the amount of polar groups is small, and it is more preferable that there are no polar groups.

  Other monomers capable of ring-opening copolymerization with monomers having a norbornene structure include monocyclic olefins such as cyclohexene, cycloheptene, and cyclooctene and derivatives thereof; cyclic conjugated dienes such as cyclohexadiene and cycloheptadiene; Derivatives thereof; and the like.

  A ring-opening polymer of a monomer having a norbornene structure and a ring-opening copolymer of a monomer having a norbornene structure and another monomer copolymerizable with the monomer have a known ring-opening polymerization catalyst. It can be obtained by (co) polymerization in the presence.

  Examples of other monomers that can be addition copolymerized with a monomer having a norbornene structure include α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, and 1-butene, and derivatives thereof; cyclobutene, cyclopentene, Cycloolefins such as cyclohexene and derivatives thereof; non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, and the like. These monomers can be used alone or in combination of two or more. Among these, α-olefin is preferable and ethylene is more preferable.

  An addition polymer of a monomer having a norbornene structure and an addition copolymer of another monomer copolymerizable with a monomer having a norbornene structure can be used in the presence of a known addition polymerization catalyst. It can be obtained by polymerization.

  Hydrogenated product of ring-opening polymer of monomer having norbornene structure, hydrogenated product of ring-opening copolymer of monomer having norbornene structure and other monomer capable of ring-opening copolymerization, norbornene structure The hydride of an addition polymer of a monomer having a hydride, and the hydride of an addition copolymer of a monomer having a norbornene structure and another monomer capable of addition copolymerization with these cyclization (co-opening) ) A known hydrogenation catalyst containing a transition metal such as nickel or palladium is added to a polymer or addition (co) polymer solution, and brought into contact with hydrogen, so that the carbon-carbon unsaturated bond is preferably 90% or more. It can be obtained by hydrogenation.

  Among norbornene resins, as a repeating unit, X: bicyclo [3.3.0] octane-2,4-diyl-ethylene structure and Y: tricyclo [4.3.0.12,5] decane-7, 9-diyl-ethylene structure, the content of these repeating units is 90% by mass or more based on the entire repeating unit of the norbornene resin, and the content ratio of X and the content ratio of Y The ratio is preferably a mass ratio of X: Y of 100: 0 to 40:60. By using such a resin, it is possible to obtain a film having no dimensional change over a long period of time and having excellent optical property stability.

  The molecular weight of the alicyclic polyolefin resin is appropriately selected depending on the purpose of use, but polyisoprene (solvent is toluene) measured by gel permeation chromatography using cyclohexane (toluene if the resin does not dissolve) as a solvent. In this case, the weight average molecular weight (Mw) in terms of polystyrene is usually 15,000 to 50,000, preferably 18,000 to 45,000, more preferably 20,000 to 40,000. When the weight average molecular weight is in such a range, the mechanical strength and formability of the film are highly balanced and suitable.

  The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the alicyclic polyolefin resin is not particularly limited, but is usually 1.0 to 10.0, preferably 1.1 to 4.0, more preferably. Is in the range of 1.2 to 3.5. The base film may contain a resin other than the resin and additives.

<Acrylic particles>
The base film may contain acrylic particles because it is excellent in improving brittleness. An acrylic particle represents the acrylic component which exists in the state of particle | grains (it is also called an incompatible state) in the base film containing the said thermoplastic acrylic resin and cellulose-ester resin in a compatible state.

  The acrylic particles are not particularly limited, but are preferably acrylic particles having a layer structure of two or more layers, and particularly preferably a multilayer structure acrylic granular composite. Examples of commercially available acrylic granular composites that are multi-layer structured polymers include, for example, “Metablene” manufactured by Mitsubishi Rayon Co., “Kaneace” manufactured by Kaneka Chemical Co., Ltd., “Paralloid” manufactured by Kureha Chemical Co., Ltd., Rohm and Examples include “Acryloid” manufactured by Haas, “Staffyroid” manufactured by Gantz Kasei Kogyo, and “Parapet SA” manufactured by Kuraray, and these may be used alone or in combination of two or more.

  Moreover, when adding an acrylic particle to a base film, it is preferable at the point which obtains a film with high transparency that the refractive index of the mixture of an acrylic resin and a cellulose-ester resin and the refractive index of an acrylic particle are near. Specifically, the refractive index difference between the acrylic particles and the acrylic resin is preferably 0.05 or less, more preferably 0.02 or less, and particularly preferably 0.01 or less.

  The acrylic fine particles are acrylic fine particles: acrylic resin and cellulose ester resin total mass = 0.5: 100 to 30: 100 with respect to the total mass of the acrylic resin and the cellulose ester resin constituting the base film. By making it contain in a range, it is preferable from the point by which a target effect is exhibited more preferable, More preferably, it is the range of 1.0: 100-15: 100 of acrylic fine particles: total mass of acrylic resin and cellulose-ester resin.

<Other additives>
A plasticizer can also be used in combination with the base film in order to improve the fluidity and flexibility of the composition. Examples of the plasticizer include phthalate ester, fatty acid ester, trimellitic ester, phosphate ester, polyester, and epoxy. Of these, polyester and phthalate plasticizers are preferably used. Polyester plasticizers are superior in non-migration and extraction resistance compared to phthalate ester plasticizers such as dioctyl phthalate. It can be applied to a wide range of uses by selecting or using these plasticizers according to the use.

  The polyester plasticizer is a reaction product of a monovalent or tetravalent carboxylic acid and a monovalent or hexavalent alcohol, and is mainly obtained by reacting a divalent carboxylic acid with a glycol. . Representative divalent carboxylic acids include glutaric acid, itaconic acid, adipic acid, phthalic acid, azelaic acid, sebacic acid and the like. The polyester plasticizer is preferably an aromatic terminal ester plasticizer. The aromatic terminal ester plasticizer is preferably an ester compound having a structure obtained by reacting phthalic acid, adipic acid, at least one benzene monocarboxylic acid and at least one alkylene glycol having 2 to 12 carbon atoms. As long as it has an adipic acid residue and a phthalic acid residue as the structure of such a compound, when an ester compound is produced, it may be reacted as an acid anhydride or esterified product of dicarboxylic acid.

  Examples of the benzene monocarboxylic acid component include benzoic acid, para-tert-butylbenzoic acid, orthotoluic acid, metatoluic acid, p-toluic acid, dimethylbenzoic acid, ethylbenzoic acid, normal propylbenzoic acid, aminobenzoic acid, acetoxybenzoic acid and the like. Most preferred is benzoic acid. Moreover, these can each be used as a 1 type, or 2 or more types of mixture.

  Examples of the alkylene glycol component having 2 to 12 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,2-propanediol, 2-methyl 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2-diethyl-1, 3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptane), 3-methyl-1,5-pentanediol 1 , 6-hexanediol, 2,2,4-trimethyl 1,3-pentanediol, 2-ethyl 1,3-hexanediol, - methyl 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecane diol. Among these, 1,2-propylene glycol is particularly preferable. These glycols may be used as one kind or a mixture of two or more kinds.

  The aromatic terminal ester plasticizer may be of an oligoester type or a polyester type, and the molecular weight is preferably in the range of 100 to 10,000, but is preferably in the range of 350 to 3000. The acid value is 1.5 mgKOH / g or less, the hydroxyl group (hydroxyl group) value is 25 mgKOH / g or less, more preferably the acid value is 0.5 mgKOH / g or less, and the hydroxyl group (hydroxyl group) value is 15 mgKOH / g or less. is there. The plasticizer is preferably added in an amount of 0.5 to 30 parts by mass with respect to 100 parts by mass of the base film. Specific examples include the following compounds, but are not limited thereto.

  Furthermore, the base film may contain a sugar ester compound. The sugar ester compound is a compound obtained by esterifying all or part of the OH group of a sugar such as the following monosaccharide, disaccharide, trisaccharide or oligosaccharide, and is specifically represented by the following general formula (1). And the like.

(In the formula, R _{1 to} R ₈ represent a substituted or unsubstituted alkylcarbonyl group or a substituted or unsubstituted arylcarbonyl group, and R _{1 to} R ₈ are the same or different from each other. May be.)
Although the compound shown by General formula (1) below is shown more concretely (compound 1-1-compound 1-23), it is not limited to these.

In addition, as a preferable specific example of a compound represented by General formula (1), the compound shown in the following table is mentioned. In addition, R described in the following table represents any one of R _{1 to} R ₈ . As the substituent for the alkylcarbonyl group and the arylcarbonyl group, substituents such as a phenyl group and an alkoxy group included in the alkylcarbonyl group and the arylcarbonyl group shown in the following table are preferable.

  Furthermore, the base film preferably contains an ultraviolet absorber. Examples of the ultraviolet absorber include benzotriazole, 2-hydroxybenzophenone, and salicylic acid phenyl ester. For example, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3 Triazoles such as 5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone And benzophenones. Here, among ultraviolet absorbers, ultraviolet absorbers having a molecular weight of 400 or more are less likely to volatilize at a high boiling point and are difficult to disperse even during high-temperature molding, so that the weather resistance is effectively improved with a relatively small amount of addition. be able to.

  Examples of the ultraviolet absorber having a molecular weight of 400 or more include 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2-benzotriazole, 2,2-methylenebis [4- (1, 1,3,3-tetrabutyl) -6- (2H-benzotriazol-2-yl) phenol], bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis ( Hindered amines such as 1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonic acid Bis (1,2,2,6,6-pentamethyl-4-piperidyl), 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl L] -4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine and the like, hindered phenol and hindered amine Examples include hybrid systems having both structures, and these can be used alone or in combination of two or more. Among these, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2-benzotriazole and 2,2-methylenebis [4- (1,1,3,3- Tetrabutyl) -6- (2H-benzotriazol-2-yl) phenol] is particularly preferred. Furthermore, various antioxidants can also be added to the base film in order to improve the thermal decomposability and thermal colorability during molding. It is also possible to add an antistatic agent to give the base film antistatic performance.

  A flame retardant acrylic resin composition containing a phosphorus flame retardant may be used for the base film. Phosphorus flame retardants used here include red phosphorus, triaryl phosphate ester, diaryl phosphate ester, monoaryl phosphate ester, aryl phosphonate compound, aryl phosphine oxide compound, condensed aryl phosphate ester, halogenated alkyl phosphorus. Examples thereof include one or a mixture of two or more selected from acid esters, halogen-containing condensed phosphate esters, halogen-containing condensed phosphonate esters, halogen-containing phosphite esters, and the like.

  Specific examples include triphenyl phosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phenylphosphonic acid, tris (β-chloroethyl) phosphate, tris (dichloropropyl). Examples thereof include phosphate and tris (tribromoneopentyl) phosphate.

  In addition, when a base film is used as a protective film for a polarizing plate of a liquid crystal display device, unevenness or a change in retardation value occurs due to a dimensional change due to moisture absorption, causing problems such as a decrease in contrast and uneven color. . In particular, the above problem becomes significant when the polarizing plate protective film is used in a liquid crystal display device used outdoors. For this reason, the dimensional change rate (%) is preferably less than 0.5%, and more preferably less than 0.3%.

  Moreover, it is preferable that the base film has a defect of 5 μm or more in diameter in the film plane of 1 piece / 10 cm square or less. More preferably, it is 0.5 piece / 10 cm square or less, more preferably 0.1 piece / 10 cm square or less.

  Here, the diameter of the defect indicates the diameter when the defect is circular, and when the defect is not circular, it is determined by observing the range of the defect with a microscope according to the following method, and the maximum diameter (diameter of circumscribed circle) is determined. .

  The range of the defect is the size of the shadow when the defect is observed with the transmitted light of the differential interference microscope when the defect is a bubble or a foreign object. When the defect is a change in the surface shape, such as transfer of a roll flaw or an abrasion, the size is confirmed by observing the defect with the reflected light of a differential interference microscope. In addition, when observing with reflected light, if the size of the defect is unclear, aluminum or platinum is deposited on the surface for observation.

  In order to obtain a film having excellent quality expressed by such a defect frequency with high productivity, it is necessary to filter the polymer solution with high precision immediately before casting, to increase the cleanliness around the casting machine, It is effective to set drying conditions after rolling stepwise and to dry efficiently while suppressing foaming.

  When the number of defects is greater than 1/10 cm square, for example, when the film is tensioned during processing in a later process, the film may break with the defects as a starting point, and productivity may decrease. Moreover, when the diameter of a defect becomes 5 micrometers or more, it can confirm visually by polarizing plate observation etc., and when used as an optical member, a bright spot may arise.

  Moreover, even when it cannot be visually confirmed, when a hard coat layer or the like is formed on the film, the coating agent may not be formed uniformly, resulting in a defect (missing coating). Here, the defect is a void in the film (foaming defect) generated due to the rapid evaporation of the solvent in the drying process of the solution casting, a foreign matter in the film forming stock solution, or a foreign matter mixed in the film forming. This refers to foreign matter (foreign matter defect) in the film.

  In addition, the base film preferably has a breaking elongation of at least one direction of 10% or more, more preferably 20% or more, in the measurement based on JIS-K7127-1999.

  The upper limit of the elongation at break is not particularly limited, but is practically about 250%. In order to increase the elongation at break, it is effective to suppress defects in the film caused by foreign matter and foaming.

  The thickness of the base film is preferably 20 μm or more. More preferably, it is 30 μm or more.

  The upper limit of the thickness is not particularly limited, but in the case of forming a film by a solution casting method, the upper limit is about 250 μm from the viewpoint of applicability, foaming, solvent drying, and the like. In addition, the thickness of a film can be suitably selected according to a use.

  The base film preferably has a total light transmittance of 90% or more, more preferably 93% or more. Moreover, as a realistic upper limit, it is about 99%. In order to achieve excellent transparency expressed by such total light transmittance, it is necessary not to introduce additives and copolymerization components that absorb visible light, or to remove foreign substances in the polymer by high-precision filtration. It is effective to reduce the diffusion and absorption of light inside the film.

  Also, reduce the surface roughness of the film surface by reducing the surface roughness of the film contact part (cooling roll, calender roll, drum, belt, coating substrate in solution casting, transport roll, etc.) during film formation. It is also effective to reduce the diffusion and reflection of light on the film surface by reducing the refractive index of the acrylic resin.

<Formation of base film>
Although the example of the film forming method of a base film is demonstrated, it is not limited to this. As a method for forming the base film, a production method such as an inflation method, a T-die method, a calendar method, a cutting method, a casting method, an emulsion method, or a hot press method can be used.

  From the viewpoint of suppressing the residual solvent using a cellulose ester resin or an acrylic resin for dissolution, a method using a melt casting film forming method is preferable. Methods formed by melt casting can be classified into melt extrusion molding methods, press molding methods, inflation methods, injection molding methods, blow molding methods, stretch molding methods, and the like. Among these, the melt extrusion method is preferable, in which a film having excellent mechanical strength and surface accuracy is obtained. From the viewpoints of suppressing coloring, suppressing defects of foreign matters, and suppressing optical defects such as die lines, solution casting by casting is preferred. Moreover, after the film-forming material is heated to exhibit its fluidity, a method of extrusion film formation on a drum or an endless belt is also included as a melt casting film formation method.

(Organic solvent)
The organic solvent useful for forming the dope when the base film is produced by the solution casting method can be used without limitation as long as it dissolves acrylic resin, cellulose ester resin, and other additives simultaneously. .

  For example, as a chlorine organic solvent, methylene chloride, as a non-chlorine organic solvent, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro- Examples include 2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, and nitroethane. Methylene chloride, methyl acetate, ethyl acetate and acetone can be preferably used.

  In addition to the organic solvent, the dope preferably contains 1 to 40% by mass of a linear or branched aliphatic alcohol having 1 to 4 carbon atoms. When the proportion of alcohol in the dope increases, the web gels and peeling from the metal support becomes easy, and when the proportion of alcohol is small, the acrylic resin and cellulose ester resin dissolve in a non-chlorine organic solvent system. There is also a role to promote.

  In particular, in a solvent containing methylene chloride and a linear or branched aliphatic alcohol having 1 to 4 carbon atoms, at least 15 to 45 mass in total of three types of acrylic resin, cellulose ester resin, and acrylic particles. It is preferable that the dope composition is dissolved in%.

  Examples of the linear or branched aliphatic alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, and tert-butanol. Ethanol is preferred because of the stability of these dopes, the relatively low boiling point, and good drying properties.

(Solution casting method)
The base film can be produced by a solution casting method. In the solution casting method, a step of preparing a dope by dissolving a resin and an additive in a solvent, a step of casting the dope on a belt-like or drum-like metal support, and a step of drying the cast dope as a web , Peeling from the metal support, stretching or maintaining the width, further drying, and winding the finished film.

  The concentration of cellulose ester in the dope, and the concentration of cellulose ester resin / acrylic resin is preferably higher because the drying load after casting on a metal support can be reduced. The load increases, and the filtration accuracy deteriorates. As a density | concentration which makes these compatible, 10-35 mass% is preferable, More preferably, it is 15-25 mass%.

  The metal support in the casting (casting) step preferably has a mirror-finished surface, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used as the metal support. The cast width can be 1 to 4 m. The surface temperature of the metal support in the casting step is set to −50 ° C. to a temperature at which the solvent boils and does not foam. A higher temperature is preferred because the web can be dried faster, but if it is too high, the web may foam or the flatness may deteriorate.

  The preferable support temperature is appropriately determined at 0 to 100 ° C, and more preferably 5 to 30 ° C. Alternatively, it is also a preferable method that the web is gelled by cooling and peeled from the drum in a state containing a large amount of residual solvent.

  The method for controlling the temperature of the metal support is not particularly limited, and there are a method of blowing warm air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use warm water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short.

  When using warm air, considering the temperature drop of the web due to the latent heat of vaporization of the solvent, while using warm air above the boiling point of the solvent, there may be cases where wind at a temperature higher than the target temperature is used while preventing foaming. .

  In particular, it is preferable to perform drying efficiently by changing the temperature of the support and the temperature of the drying air during the period from casting to peeling.

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

  The amount of residual solvent is defined by the following formula.

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

  Further, in the drying step of the cellulose ester film or the cellulose ester resin / acrylic resin film, it is preferable that the web is peeled off from the metal support and further dried to make the residual solvent amount 1% by mass or less, more preferably 0. 0.1 mass% or less, particularly preferably 0 to 0.01 mass% or less.

  In the film drying step, generally, a roll drying method (a method in which webs are alternately passed through a plurality of rolls arranged above and below) and a method in which the web is dried while being conveyed by a tenter method are employed.

(Stretching process)
In the stretching step, the film can be sequentially or simultaneously stretched in the longitudinal direction (MD direction) and the width direction (TD direction) of the film. It is preferable that the draw ratios in the biaxial directions perpendicular to each other are finally in the range of 1.0 to 2.0 times in the MD direction and 1.07 to 2.0 times in the TD direction. It is preferable to carry out within a range of 1.0 to 1.5 times and 1.07 to 2.0 times in the TD direction. For example, a method in which peripheral speed differences are applied to a plurality of rolls and a roll peripheral speed difference is used to stretch in the MD direction, both ends of the web are fixed with clips and pins, and the distance between the clips and pins is increased in the traveling direction. And a method of stretching in the MD direction, a method of stretching in the transverse direction and stretching in the TD direction, a method of stretching in the MD / TD direction simultaneously and stretching in both the MD / TD directions, and the like.

  These width maintenance or width direction stretching in the film forming step is preferably performed by a tenter, and may be a pin tenter or a clip tenter.

  The film transport tension in the film forming process such as in the tenter depends on the temperature, but is preferably 120 N / m to 200 N / m, and more preferably 140 N / m to 200 N / m. 140 N / m to 160 N / m is most preferable. When stretching, assuming that the glass transition temperature of the substrate film is Tg, (Tg-30) to (Tg + 100) ° C., more preferably (Tg-20) to (Tg + 80) ° C., and more preferably (Tg-5) to (T Tg + 20) ° C.

  The Tg of the base film can be controlled by the material type constituting the film and the ratio of the constituting materials. In the application of the present invention, the Tg when the film is dried is preferably 110 ° C. or higher, more preferably 120 ° C. or higher.

  Accordingly, the glass transition temperature is preferably 190 ° C. or lower, more preferably 170 ° C. or lower. At this time, the Tg of the film can be determined by the method described in JIS K7121.

  It is preferable that the temperature at the time of stretching is 150 ° C. or more and the stretching ratio is 1.15 times or more because the surface is appropriately roughened. Roughening the film surface is preferable because it improves not only the slipperiness but also the surface processability, particularly the adhesion of the hard coat layer. The arithmetic average roughness Ra is preferably 2.0 nm to 4.0 nm, more preferably 2.5 nm to 3.5 nm.

(Melting method)
The base film may be formed by a melt film forming method. The melt film-forming method refers to heating and melting a composition containing an additive such as a resin and a plasticizer to a temperature exhibiting fluidity, and then casting a melt containing a fluid cellulose ester.

  More specifically, the heat melting molding method can be classified into a melt extrusion molding method, a press molding method, an inflation method, an injection molding method, a blow molding method, a stretch molding method, and the like. Among these molding methods, the melt extrusion method is preferable from the viewpoint of mechanical strength and surface accuracy. It is preferable that a plurality of raw materials used for melt extrusion are usually kneaded in advance and pelletized.

  Pelletization may be performed by a known method. For example, dry cellulose ester, plasticizer, and other additives are fed to an extruder using a feeder, kneaded using a single or twin screw extruder, and extruded from a die into a strand. It can be done by water cooling or air cooling and cutting.

  The additives may be mixed before being supplied to the extruder, or may be supplied by individual feeders.

  A small amount of additives such as particles and antioxidants are preferably mixed in advance in order to mix uniformly.

  The extruder is preferably processed at as low a temperature as possible so as to be able to be pelletized so that the shear force is suppressed and the resin does not deteriorate (decrease in molecular weight, coloring, gel formation, etc.). For example, in the case of a twin screw extruder, it is preferable to rotate in the same direction using a deep groove type screw. From the uniformity of kneading, the meshing type is preferable.

  A film is formed using the pellets obtained as described above. Of course, the raw material powder can be directly fed to the extruder by a feeder without being pelletized to form a film as it is.

  Using a uniaxial or biaxial extruder, the pellets are melted at a temperature of about 200 to 300 ° C., filtered through a leaf disk type filter to remove foreign matter, and then formed into a film from a T die. The film is cast and the film is nipped by a cooling roll and an elastic touch roll, and solidified on the cooling roll.

  When introducing into the extruder from the supply hopper, it is preferable to prevent oxidative decomposition or the like under vacuum, reduced pressure, or inert gas atmosphere.

  The extrusion flow rate is preferably performed stably by introducing a gear pump or the like. Further, a stainless fiber sintered filter is preferably used as a filter used for removing foreign substances.

  The stainless steel fiber sintered filter is a united stainless steel fiber body that is intricately intertwined and compressed, and the contact points are sintered and integrated. The density of the fiber is changed depending on the thickness of the fiber and the amount of compression, and the filtration accuracy is improved. Can be adjusted.

  Additives such as plasticizers and particles may be mixed with the resin in advance, or may be kneaded in the middle of the extruder. In order to add uniformly, it is preferable to use a mixing apparatus such as a static mixer.

  The film temperature on the touch roll side when the film is nipped between the cooling roll and the elastic touch roll is preferably Tg or more and Tg + 110 ° C. or less of the film. A well-known roll can be used for the roll which has the elastic body surface used for such a purpose.

  The elastic touch roll is also called a pinching rotator. As an elastic touch roll, the touch roll currently disclosed by the registration patent 3194904, the registration patent 3422798, Unexamined-Japanese-Patent No. 2002-36332, each Unexamined-Japanese-Patent No. 2002-36333 etc. can be used preferably. These can also use what is marketed. When peeling the film from the cooling roll, it is preferable to control the tension to prevent deformation of the film. Moreover, it is preferable that the film obtained as described above is stretched by the stretching operation after passing through the step of contacting the cooling roll.

  As a method of stretching, a known roll stretching machine or tenter can be preferably used. The stretching temperature is usually preferably performed in the temperature range of Tg to Tg + 60 ° C. of the resin constituting the film.

  Prior to winding, the ends may be slit and cut to the width of the product, and knurling (embossing) may be applied to both ends to prevent sticking or scratching during winding. The knurling method can process a metal ring having an uneven pattern on its side surface by heating or pressing. In addition, since the film has deform | transformed and cannot use as a product normally, the holding | grip part of the clip of both ends of a film is cut out and reused.

<Physical properties of hard coat film>
(Haze)
The haze (hereinafter also referred to as “internal haze”) of the hard coat film of the present invention is preferably 20% or less. Haze can be measured according to JIS K7105 and JIS K7136. As the transmittance, the total light transmittance is preferably 90% or more, and more preferably 91% or more. The total light transmittance can be measured according to JIS K7361-1.

(hardness)
The hard coat film of the present invention has a pencil hardness as an index of hardness of H or higher, more preferably 2H or higher. If it is 2H or more, it is not only difficult to be scratched in the polarizing plate forming step of the liquid crystal display device, but is also used for outdoor applications, and is a surface protective film for large liquid crystal display devices and liquid crystal display devices for digital signage. Excellent mechanical properties when used. The pencil hardness is determined by adjusting the humidity of the produced optical film for 2 hours or more at a temperature of 23 ° C. and a relative humidity of 55%, and then using a test pencil specified by JIS S 6006 under a weight of 500 g. It is the value which measured the antireflection layer according to the pencil hardness evaluation method which JISK5400 prescribes | regulates.

<Functional layer>
The hard coat film of the present invention may be provided with a functional layer such as an antireflection layer or a back coat layer.

<Antireflection layer>
The hard coat film of this invention can be made into the antireflection film of the aspect which has a low-refractive-index layer directly or through another layer on a hard-coat layer.

  The antireflection layer composed of the low refractive index layer may have a single layer configuration consisting of only the low refractive index layer, but may also be a multilayer. Specifically, a high refractive index layer having a higher refractive index than the support and a low refractive index layer having a lower refractive index than the support can be combined.

  Further, the three layers having different refractive indexes from the support side are divided into a medium refractive index layer (a layer having a higher refractive index than the support or hard coat layer and a lower refractive index than the high refractive index layer) / high refractive index layer / low. You may laminate | stack in order of a refractive index layer. Further, an antireflection layer having a layer structure of four or more layers in which two or more high refractive index layers and two or more low refractive index layers are alternately laminated is also preferably used. An example of a preferable layer configuration of the antireflection layer is shown below. Here, / indicates that the layers are arranged in layers.

Base film / hard coat layer / low refractive index layer Base film / hard coat layer / high refractive index layer / low refractive index layer Base film / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index Layer An antifouling layer may be further provided on the outermost low refractive index layer so that dirt and fingerprints can be easily wiped off. As the antifouling layer, fluorine-containing organic compounds are preferably used.

As long as the reflectance can be reduced by optical interference, it is not limited to these layer configurations. In the above layer structure, an intermediate layer may be provided as appropriate. For example, an antistatic layer containing conductive polymer fine particles (for example, crosslinked cation fine particles) or metal oxide fine particles (for example, SnO ₂ , ITO) is preferable. .

<Low refractive index layer>
The hard coat film of the present invention can be an antireflection film in which a low refractive index layer is laminated on a base film directly on the hard coat layer and the hard coat layer or through another layer.

  In the low refractive index layer, a layer lower than the refractive index of the base film is formed, and the refractive index is preferably in the range of 1.30 to 1.45 when measured at 23 ° C. and a wavelength of 550 nm.

  The film thickness of the low refractive index layer is not particularly limited, but is preferably 5 nm to 0.5 μm, more preferably 10 nm to 0.3 μm, and 30 nm to 0.2 μm. Most preferred. The low refractive index layer preferably uses hollow spherical silica-based fine particles from the viewpoint of refractive index adjustment and mechanical strength.

(Hollow spherical silica-based fine particles)
The hollow spherical fine particles are (I) composite particles comprising porous particles and a coating layer provided on the surface of the porous particles, or (II) having a cavity inside, and the content is a solvent, gas or porous Cavity particles filled with a substance. Note that the low refractive index layer only needs to contain either (I) composite particles or (II) hollow particles, or 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 diameter of such hollow spherical fine particles is in the range of 5 to 300 nm, preferably 10 to 200 nm. The hollow spherical fine particles used are appropriately selected according to the thickness of the transparent film to be formed, and are in the range of 2/3 to 1/10 of the film thickness of the transparent film such as the low refractive index layer to be formed. Is desirable. These hollow spherical fine particles are preferably used in a state of being dispersed in an appropriate medium in order to form a low refractive index layer. As the dispersion medium, water, alcohol (for example, methanol, ethanol, isopropyl alcohol), ketone (for example, methyl ethyl ketone, methyl isobutyl ketone), and ketone alcohol (for example, diacetone alcohol) are preferable.

  The thickness of the coating layer of the composite particles or the thickness of the particle walls of the hollow particles is desirably in the range of 1 to 20 nm, preferably 2 to 15 nm. In the case of composite particles, if the thickness of the coating layer is less than 1 nm, the particles may not be completely covered, and it is easy to use a silicate monomer or oligomer having a low polymerization degree, which is a coating liquid component described later. The inside of the composite particles may enter and the internal porosity may decrease, and the low refractive index effect may not 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. Moreover, components other than silica may be contained, and 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 and WO _3. 1 type or 2 types or more can be mentioned. In such porous particles, the molar ratio MO _X / SiO ₂ when the silica is expressed by SiO ₂ and the inorganic compound other than silica is expressed in terms of oxide (MO _X ) is 0.0001 to 1.0, Preferably it is in the range of 0.001 to 0.3. It is difficult to obtain a porous particle having a molar ratio MO _X / SiO ₂ of less than 0.0001. Even if it is obtained, a pore volume is small and particles having a low refractive index cannot be obtained. In addition, when the molar ratio MO _X / SiO _{2 of} the porous particles exceeds 1.0, the ratio of silica decreases, so that the pore volume increases and it is difficult to obtain a material having a lower refractive index. is there. 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. In addition, the pore volume of such porous particles can be determined by a mercury intrusion method. Such hollow spherical fine particles can be produced from the following first to third steps.

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

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

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

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

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

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

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

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

  In addition, prior to removing inorganic compounds other than silica from the porous particle precursor, fluorine-substituted, obtained by dealkalizing an alkali metal salt of silica into the porous particle precursor dispersion obtained in the first step. It is preferable to add a silicic acid solution containing an alkyl group-containing silane compound or a hydrolyzable organosilicon compound to form a silica protective film. The thickness of the silica protective film may be 0.5 to 15 nm. Even if the silica protective film is formed, the protective film in this step is porous and thin, so that it is possible to remove inorganic compounds other than silica described above from the porous particle precursor.

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

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

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

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

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

Third step: Formation of silica coating layer In the third step, the porous particle dispersion prepared in the second step (in the case of hollow particles, the hollow particle precursor dispersion) contains a fluorine-substituted alkyl group-containing silane compound. By adding a hydrolyzable organosilicon compound or silicic acid solution, the surface of the particles is coated with a polymer such as a hydrolyzable organosilicon compound or silicic acid solution to form a silica coating layer.

The hydrolyzable organic silicon compound used for the silica coating layer formed, the above-mentioned such general formula _{R n Si (OR ') 4} -n [R, R': an alkyl group, an aryl group, a vinyl group, An alkoxysilane represented by a hydrocarbon group such as an acryl group, n = 0, 1, 2, or 3] can be used. In particular, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

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

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

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

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

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

The refractive index of the inorganic fine particles thus obtained is as low as less than 1.42. Such inorganic fine particles are presumed to have a low refractive index because the porosity inside the porous particles is maintained or the inside is hollow. Further, it is possible to use commercially available the SiO ₂ particles. Specific examples of commercially available particles include P-4 manufactured by Catalytic Chemical Industry Co., Ltd.

  The content (mass) of the hollow spherical silica-based fine particles A having an outer shell layer and having a porous or hollow interior in the low refractive index layer coating solution is preferably 10 to 80% by mass, and more preferably 20 to 60% by mass. % By mass.

(Tetraalkoxysilane compound or hydrolyzate thereof)
The low refractive index layer preferably contains a tetraalkoxysilane compound or a hydrolyzate thereof as a sol-gel material. As the material for the low refractive index layer, it is also preferable to use a silicon oxide having an organic group in addition to the inorganic silicon oxide. These are generally called sol-gel materials, but metal alcoholates, organoalkoxy metal compounds and hydrolysates thereof can be used. In particular, alkoxysilane, organoalkoxysilane and its hydrolyzate are preferable. Examples of these include tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, etc.), alkyltrialkoxysilane (methyltrimethoxysilane, ethyltrimethoxysilane, etc.), aryltrialkoxysilane (phenyltrimethoxysilane, etc.), dialkyl. Examples thereof include dialkoxysilane and diaryl dialkoxysilane. Tetraalkoxysilane and its hydrolyzate are particularly preferable.

  In addition, organoalkoxysilanes having various functional groups (vinyl trialkoxysilane, methylvinyl dialkoxysilane, γ-glycidyloxypropyltrialkoxysilane, γ-glycidyloxypropylmethyl dialkoxysilane, β- (3,4-epoxy) Dicyclohexyl) ethyltrialkoxysilane, γ-methacryloyloxypropyltrialkoxysilane, γ-aminopropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, γ-chloropropyltrialkoxysilane, etc.), perfluoroalkyl group-containing silane compounds ( For example, it is also preferable to use (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, etc.). In particular, the use of a fluorine-containing silane compound is preferable in terms of lowering the refractive index of the layer and imparting water and oil repellency.

  When hydrolyzing the tetraalkoxysilane, it is preferable to mix the inorganic fine particles in order to increase the film strength. The low refractive index layer preferably contains the silicon oxide and the following silane coupling agent.

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

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

  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.

  Specific examples of the silane coupling agent include: Shin-Etsu Chemical Co., Ltd. KBM-303, KBM-403, KBM-402, KBM-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE- 503, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM-802, KBM-803 and the like.

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

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

(1) Surface treatment It is preferable that the fine particles (particularly inorganic fine particles) are subjected to a surface treatment to improve the affinity with the polymer. The surface treatment can be classified into physical surface treatment such as plasma discharge treatment and corona discharge treatment, and chemical surface treatment using a coupling agent. It is preferable to carry out by chemical surface treatment alone or a combination of physical surface treatment and chemical surface treatment. As the coupling agent, an organoalkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. When the fine particles are made of SiO _{2, the} surface treatment with the above-described silane coupling agent can be carried out particularly effectively.

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

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

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

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

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

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

  Further, the low refractive index layer may be a low refractive index layer formed by crosslinking a fluorine-containing resin that is crosslinked by heat or ionizing radiation (hereinafter also referred to as “fluorine-containing resin before crosslinking”).

  Preferred examples of the fluorine-containing resin before crosslinking include a fluorine-containing copolymer formed from a fluorine-containing vinyl monomer and a monomer for imparting a crosslinkable group. Specific examples of the fluorine-containing vinyl monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3 -Dioxoles, etc.), (meth) acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (manufactured by Osaka Organic Chemicals) and M-2020 (manufactured by Daikin)), fully or partially fluorinated vinyl ethers, etc. Is mentioned. As monomers for imparting a crosslinkable group, glycidyl methacrylate, vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, vinyl glycidyl ether, and other vinyl monomers having a crosslinkable functional group in advance in the molecule. , Vinyl monomers having a carboxyl group, hydroxyl group, amino group, sulfonic acid group, etc. (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyalkyl vinyl ether, hydroxyalkyl allyl) Ether, etc.). The latter can introduce a cross-linked structure by adding a compound having a group that reacts with a functional group in the polymer and one or more reactive groups after the copolymerization, as disclosed in JP-A-10-25388 and 10-147739. In the issue. Examples of the crosslinkable group include acryloyl, methacryloyl, isocyanate, epoxy, aziridine, oxazoline, aldehyde, carbonyl, hydrazine, carboxyl, methylol, and active methylene group. When the fluorine-containing copolymer is crosslinked by heating with a crosslinking group that reacts by heating, or a combination of an ethylenically unsaturated group and a thermal radical generator or an epoxy group and a thermal acid generator, it is a thermosetting type. In the case of crosslinking by irradiation with light (preferably ultraviolet rays, electron beams, etc.) by a combination of an ethylenically unsaturated group and a photo radical generator, or an epoxy group and a photo acid generator, the ionizing radiation curable type is used.

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

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

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

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

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

(Cationically polymerizable compound)
The low refractive index layer may contain a cationically polymerizable compound as a binder. Any cationically polymerizable compound can be used as long as it undergoes cationic polymerization by irradiation with energy active rays or heat to form a resin. Specific examples include an epoxy group, a cyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester compound, and a vinyloxo group. Among them, a compound having a functional group such as an epoxy group or a vinyl ether group is preferably used in the present invention. Examples of the cationically polymerizable compound having an epoxy group or a vinyl ether group include phenyl glycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, vinylcyclohexene dioxide, limonene dioxide, 3,4-epoxycyclohexylmethyl-3 ′. , 4'-epoxycyclohexanecarboxylate, bis- (6-methyl-3,4-epoxycyclohexyl) adipate, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, 1 , 4-cyclohexanedimethanol divinyl ether and the like.

  Moreover, an oxetane compound can also be mentioned. The oxetane compound may be a compound having at least one oxetane ring in the molecule.

  Furthermore, if necessary, a (co) polymer containing a monomer having a hydrogen bond-forming group and a reactive polymer having an oxetanyl group in the main chain or side chain and having a number average molecular weight of 20,000 or more can also be used. From the viewpoint of stability of the low refractive index layer coating composition, the above cationic polymerizable compound is preferably 15% by mass or more and less than 70% by mass in the solid content in the low refractive layer coating composition.

(Cationic polymerization accelerator)
Examples of the compound that accelerates the polymerization of the cationic polymerizable compound include known acids and photoacid generators. Examples of the photoacid generator include a cationic polymerization photoinitiator, a dye photodecoloring agent, a photochromic agent, a known compound used in a microresist, and a mixture thereof. Specific examples include onium compounds, organic halogen compounds, and disulfone compounds, and onium compounds are preferable. As the onium compound, diazonium salts, sulfonium salts, iodonium salts and the like represented by the following formulas are preferably used.

ArN ₂ ⁺ Z ⁻ ,
(R) ₃ S ⁺ Z ⁻ ,
(R) ₂ I ⁺ Z ⁻
In the formula, Ar represents an aryl group, R represents an aryl group or an alkyl group having 1 to 20 carbon atoms, and when R appears multiple times in one molecule, they may be the same or different, and Z ⁻ Represents a non-basic and non-nucleophilic anion.

In each of the above formulas, the aryl group represented by Ar or R is also typically phenyl or naphthyl, and these may be substituted with an appropriate group. Specific examples of the anion represented by Z ⁻ include tetrafluoroborate ion (BF ₄ ⁻ ), tetrakis (pentafluorophenyl) borate ion (B (C ₆ F ₅ ) ₄ ⁻ ), and hexafluorophosphate ion. (PF ₆ ⁻ ), hexafluoroarsenate ion (AsF ₆ ⁻ ), hexafluoroantimonate ion (SbF ₆ ⁻ ), hexachloroantimonate ion (SbCl ₆ ⁻ ), hydrogen sulfate ion (HSO ₄ ⁻ ), perchloric acid Ion (ClO ₄ ⁻ ) and the like.

  Examples of other onium compounds include ammonium salts, iminium salts, phosphonium salts, arsonium salts, selenonium salts, and boron salts.

  Of these, diazonium salts, iodonium salts, sulfonium salts, and iminium salts are preferable from the viewpoint of the material stability of the compound.

  Since many of these compounds are commercially available, such commercially available products can be used. Commercially available initiators include, for example, “Syracure UVI-6990” (trade name) sold by Dow Chemical Japan Co., Ltd., and “Adekaoptomer SP-150” (available from ADEKA Corporation) Product name), “Adekaoptomer SP-300” (trade name), “RHODORSIL PHOTOINITIAOR 2074” (trade name) sold by Rhodia Japan Co., Ltd., and the like.

  As the acid, Bronsted acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or the like, or organic acid such as acetic acid, formic acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, dibutyltin dilaurate, Examples thereof include Lewis acids such as dibutyltin diacetate, dibutyltin dioctate, triisopropoxyaluminum, tetrabutoxyzirconium, and tetrabutoxytitanate.

  Aromatic polycarboxylic acids such as pyromellitic acid, pyromellitic anhydride, trimellitic acid, trimellitic anhydride, phthalic acid, phthalic anhydride, or anhydrides thereof, maleic acid, maleic anhydride, succinic acid, succinic anhydride Aliphatic polyvalent carboxylic acid or anhydride thereof such as

  As an acid, only 1 type may be used and 2 or more types may be used together. These acids and photoacid generators are preferably added in a proportion of 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, with respect to 100 parts by mass of the cationic polymerizable compound. is there. When the addition amount is in the above range, it is preferable from the viewpoint of stability of the curable composition, polymerization reactivity and the like.

(Radically polymerizable compound)
The low refractive index layer can also contain a radical polymerizable compound as a binder. Examples of the radical polymerizable group include ethylenically unsaturated groups such as a (meth) acryloyl group, a vinyloxy group, a styryl group, and an allyl group, and among them, a compound having a (meth) acryloyl group is preferable. Moreover, as a radically polymerizable compound, it is preferable to contain the polyfunctional monomer which contains a 2 or more radically polymerizable group in a molecule | numerator. The polyfunctional acrylate is preferably selected from the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate. The addition amount of the radical polymerizable compound is preferably 15% by mass or more and less than 70% by mass in the solid content in the low refractive layer coating composition from the viewpoint of the stability of the low refractive layer coating composition.

(Radical polymerization accelerator)
In order to accelerate the curing of the radical polymerizable compound, it is preferable to use a photopolymerization initiator in combination with the radical polymerizable compound. When the photopolymerization initiator and the radical polymerizable compound are used in combination, it is preferable to contain the photopolymerization initiator and the radical polymerizable compound in a mass ratio of 20: 100 to 0.01: 100.

  Specific examples of the photopolymerization initiator include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof, but are not particularly limited thereto.

  The low refractive index layer is a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, a known method such as an inkjet method, and the above coating composition for forming the low refractive index layer is applied, and after coating, It is formed by heat drying and curing treatment as necessary.

  The coating amount is suitably 0.05 to 100 μm, preferably 0.1 to 50 μm, as the wet film thickness. Further, the solid content concentration of the coating composition is adjusted so that the dry film thickness becomes the above film thickness.

Moreover, you may include the process of heat-processing at the temperature of 50-160 degreeC after forming a low-refractive-index layer. 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 160 ° C., a range of 10 minutes or more and 1 day or less is preferable. . Examples of the curing method include a method of thermosetting by heating, a method of curing by irradiation with light such as ultraviolet rays, and the like. When thermosetting, the heating temperature is preferably 50 to 300 ° C, preferably 60 to 250 ° C, and more preferably 80 to 150 ° C. When curing by light irradiation, exposure of the irradiation light is preferably from ^{10mJ / cm 2 ~1J / cm 2} , 80mJ / cm 2 ~500mJ / cm 2 is more preferable.

  Here, the wavelength range of the irradiated light is not particularly limited, but light having a wavelength in the ultraviolet region is preferably used. Specifically, 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.

<High refractive index layer and medium refractive index layer>
The high refractive index layer and the middle refractive index layer preferably contain 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 Having at least one element selected from

  A metal oxide can be used, and these metal oxide fine particles may be doped with a trace amount of atoms such as Al, In, Sn, Sb, Nb, a halogen element, and Ta. A mixture of these may also be used. Among them, the main component is at least one metal oxide fine particle selected from organic titanium compounds, zirconium oxide, antimony oxide, tin oxide, zinc oxide, indium tin oxide (ITO), antimony doped tin oxide (ATO), and zinc antimonate. It is particularly preferable to use as In particular, it is preferable to contain zinc antimonate particles.

  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, from the viewpoint of dispersibility and haze. The average particle diameter of the metal oxide fine particles can be measured from an electron micrograph taken with a scanning electron microscope (SEM) or the like. You may measure by the particle size distribution meter etc. which utilize a dynamic light scattering method, a static light scattering method, etc. 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 preferably higher than the refractive index of the obliquely stretched film, and is preferably in the range of 1.5 to 2.3 when measured 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 refractive index of the middle refractive index layer is adjusted to be an intermediate value between the refractive index of the obliquely stretched film and the refractive index of the high refractive index layer. Specifically, the refractive index of the middle refractive index layer is preferably 1.55 to 1.80.

  The thickness of the high refractive index layer and the medium refractive index layer is preferably 5 nm to 1 μm, more preferably 10 nm to 0.2 μm, and most preferably 30 to 100 nm.

  The high refractive index layer and the medium refractive index layer preferably contain metal oxide particles as fine particles, and further contain a binder polymer.

  As the binder polymer of the high refractive index layer and the medium refractive index layer, a crosslinked polymer is preferable. As an example of the crosslinked polymer, a monomer having two or more ethylenically unsaturated groups is most preferable. Examples thereof include esters of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate). 1,4-dichlorohexane diacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate Relate), vinylbenzene and its derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide (eg, , Methylenebisacrylamide) and methacrylamide. For the polymerization reaction of the polymer, a photopolymerization reaction or a thermal polymerization reaction can be used. A photopolymerization reaction is particularly preferable.

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

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

  The medium and high refractive index layers can be provided by coating, drying and curing on the hard coat layer as a coating layer composition by diluting the above-described components forming the medium and high refractive index layers with a solvent.

As a light source for curing, any light source that generates ultraviolet rays can be used without limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. Irradiation dose is preferably ^{20mJ / cm 2 ~1J / cm 2} , and more preferably from 80~500mJ / cm ^2.

(Reflectivity of antireflection layer)
The antireflection layer preferably has an average reflectance at 450 to 650 nm of 1.5% or less, particularly preferably 1.2% or less. Moreover, it is preferable that the minimum reflectance in this range exists in 0.00 to 0.5%.

  The refractive index and film thickness of the antireflection layer can be calculated and calculated by measuring the spectral reflectance. Moreover, the reflection optical characteristic of the produced optical film having the antireflection layer can be measured for reflectance under the condition of regular reflection at 5 degrees using a spectrophotometer. In this measurement method, after roughening the back surface on the side where the antireflection layer is not applied, the light absorption treatment is performed with a black spray, or the light absorption treatment is performed by attaching a black acrylic plate or the like. The reflectance can be measured by preventing reflection of the back light of the film. In the measurement, the transmittance at a transmittance of 550 nm is measured using a spectrophotometer with reference to air.

  The hard coat film of the present invention preferably has a flat reflection spectrum in the visible light wavelength region. Reflective hues are often colored red and blue due to the high reflectance in the short-wavelength and long-wavelength regions in the visible light region due to the design of the antireflection layer. In contrast, when used on the surface of an image display device or the like, a neutral color tone is preferred. 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). Further, the range in which the distance Δxy of (x, y) = (0.31, 0.31) on the xy plane is 0.05 or less is preferable because it is closer to neutral with no color, and 0.03 or less is preferable. Further preferred. The color tone can be calculated from the refractive index of each layer in accordance with a conventional method in consideration of the reflectance and the color of reflected light.

<Back coat layer>
The back coat layer may be provided on the surface of the base film opposite to the side on which the hard coat layer is provided to prevent curling and sticking.

  As 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.

  The particles contained in the backcoat layer are preferably 0.1 to 50% by mass with respect to the binder. When the back coat layer is provided, the increase in haze is preferably 1.5% or less, more preferably 0.5% or less, and particularly preferably 0.1% or less. As the binder, a cellulose ester resin such as diacetylcellulose is preferable.

<Polarizing plate>
A polarizing plate using the hard coat film of the present invention is excellent in visibility when used in an image display device such as a liquid crystal display device.

  The polarizing plate can be produced by a general method. The back surface side of the hard coat film of the present invention is subjected to alkali saponification treatment, and a completely hardened polyvinyl alcohol aqueous solution is used on at least one surface of a polarizing film prepared by immersing and stretching the treated hard coat film in an iodine solution. It is preferable to bond them together.

  The hard coat film may be used on the other surface, or another polarizing plate protective film may be used. The polarizing plate protective film used on the other side of the hard coat film of the present invention contains the cellulose triacetate film, which is the base film described above, a thermoplastic acrylic resin, and a cellulose ester resin. It is preferable to use a protective film in which the mass ratio of the resin and the cellulose ester resin is thermoplastic acrylic resin: cellulose ester resin = 95: 5 to 50:50. Details of the configuration are as described above. Specifically, an example is a non-oriented film having a retardation Ro of 590 nm of 0 to 5 nm and an Rt of -20 to +20 nm described in JP-A No. 2003-12859.

  In addition, an optical compensation film (retardation film) having a retardation of in-plane retardation Ro of 590 nm, 20 to 70 nm, and Rt of 70 to 400 nm may be used as a polarizing plate capable of widening the viewing angle. it can. These can be produced, for example, by the method of JP-A-2002-71957. Alternatively, it is preferable to use an optical compensation film having an optical 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.

  Moreover, as a commercially available polarizing plate protective film preferably used, KC8UX2MW, KC4UX, KC5UX, KC4UY, KC8UY, KC12UR, KC4UEW, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC4FR-1, KC4FR-2, KC4FR-2, KC8FR-2 KC4UE (manufactured by Konica Minolta Opto), Zeonore Film (manufactured by Nippon Zeon Co., Ltd.), Arton Film (manufactured by JSR Co., Ltd.) and the like can be mentioned.

  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 ones in which iodine is dyed on a system film and ones in which a dichroic dye is dyed, but it is not limited to this.

  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. A polarizing film having a thickness of 5 to 30 μm, preferably 8 to 15 μm, is preferably used.

  On the surface of the polarizing film, one side of the hard coat 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.

<Adhesive layer>
The pressure-sensitive adhesive layer used on one side of the protective film to be bonded to the substrate of the liquid crystal cell is preferably optically transparent and exhibits moderate viscoelasticity and adhesive properties. Specific examples of the adhesive layer include adhesives or adhesives such as acrylic copolymers, epoxy resins, polyurethane, silicone polymers, polyethers, butyral resins, polyamide resins, polyvinyl alcohol resins, and synthetic rubbers. A film such as a drying method, a chemical curing method, a thermal curing method, a thermal melting method, a photocuring method, or the like can be formed and cured using a polymer such as the above. Among them, the acrylic copolymer can be preferably used because it is most easy to control the physical properties of the adhesive and is excellent in transparency, weather resistance, durability and the like.

<Image display device>
When the hard coat film of the present invention is used in an image display device, performance with excellent visibility is exhibited. As an image display device, a reflection type, a transmission type, a semi-transmission type liquid crystal display device, a liquid crystal display device of various drive systems such as a TN type, STN type, OCB type, VA type, IPS type, ECB type, etc., organic electroluminescence Examples thereof include a display device having an element, a plasma display, and a stereoscopic image display device. Among these image display devices, a liquid crystal display device is preferable because the liquid crystal display device easily exhibits the above characteristics. Moreover, when the hard coat film of this invention is used for the member for touch panels of the liquid crystal display device containing a touch panel, it is preferable at the point which is excellent in a letter blur and pen-proof sliding property.

(Touch panel)
Next, an example at the time of using the hard coat film of this invention for a touch panel is shown. First, FIG. 3 shows a configuration example of the antireflection film 201 with a conductive film. In the antireflection film 201 with the conductive film, the hard coat layer 12 is formed on the surface of the antireflection film 11 where the antireflection layer 10 is not provided, and the transparent conductive thin film 13 is further formed on the hard coat layer. ing.

  Next, a schematic diagram of a resistive touch panel liquid crystal display device 301 using the antireflection film of the present invention for a touch panel is shown in FIG. The antireflection film 201 with a conductive film is opposed to the glass substrate 14 on which the transparent conductive thin film 15 is formed at a predetermined interval so that the transparent conductive thin films face each other. Can be configured. Electrodes (not shown) are disposed at the ends of the antireflection film 201 with the conductive film and the glass substrate 14. In the resistive touch panel, the transparent conductive thin film of the antireflection film with a conductive film is formed on the glass substrate 14 by pressing the antireflection film 201 with the conductive film with a finger or a pen. Contact the thin film 15. This is a mechanism in which the pressed position is detected by electrically detecting this contact through the electrode at the end. On the transparent conductive thin film 15 of the glass substrate 14, dot-like spacers 16 are arranged as necessary. In addition, by mounting the touch panel 11 on an LCD (liquid crystal display panel) 17, it is possible to configure a liquid crystal display device 301 with a resistive touch panel.

  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
<Preparation of base film>
<Preparation of ester compound 1>
251 g of 1,2-propylene glycol, 278 g of phthalic anhydride, 91 g of adipic acid, 610 g of benzoic acid, 0.191 g of tetraisopropyl titanate as an esterification catalyst, 2 L four-neck equipped with a thermometer, stirrer, and slow cooling tube The flask is charged and gradually heated with stirring until it reaches 230 ° C. in a nitrogen stream. The ester compound 1 was obtained by making it dehydrate-condense for 15 hours and distilling unreacted 1, 2- propylene glycol under reduced pressure at 200 degreeC after completion | finish of reaction. The acid value was 0.10 and the number average molecular weight was 450.

<Preparation of base film 1>
(Silicon dioxide dispersion)
Aerosil R812 (Nippon Aerosil Co., Ltd., average primary particle diameter of 7 nm)
10 parts by mass Ethanol 90 parts by mass The above was stirred and mixed with a dissolver for 30 minutes, and then dispersed with Manton Gorin. 88 parts by mass of methylene chloride was added to the silicon dioxide dispersion while stirring, and the mixture was stirred and mixed for 30 minutes with a dissolver to prepare a silicon dioxide dispersion dilution. It filtered with the fine particle dispersion | distribution dilution liquid filter (Advantech Toyo Co., Ltd .: Polypropylene wind cartridge filter TCW-PPS-1N).

(Dope composition)
Cellulose triacetate (cellulose triacetate synthesized from linter cotton,
Acetyl group substitution degree 2.88, Mn = 14000) 90 parts by mass Ester compound 1 10 parts by mass Tinuvin 928 (manufactured by BASF Japan Ltd.) 2.5 parts by mass Silicon dioxide dispersion diluent 4 parts by mass Methylene chloride 432 parts by mass Ethanol 38 parts by mass or more was put into a sealed container, heated and stirred, and completely dissolved. Azumi filter paper No. 3 manufactured by Azumi Filter Paper Co., Ltd. No. 24 was used for filtration to prepare a dope solution.

  Next, the belt casting apparatus was used to uniformly cast on a stainless steel band support. With the stainless steel band support, the solvent was evaporated until the residual solvent amount reached 100%, and the stainless steel band support was peeled off. The cellulose ester film web was evaporated at 35 ° C., slit to 1.65 m width, and stretched 1.3 times in the TD direction (film width direction) with a tenter, and the MD direction draw ratio was 1.01 times. While stretching, the film was dried at a drying temperature of 160 ° C. The residual solvent amount at the start of drying was 20%. Then, after drying for 15 minutes while transporting the inside of a drying device at 120 ° C. with a number of rolls, slitting to a width of 1.49 m, applying a knurling process with a width of 15 mm and a height of 10 μm at both ends of the film, and winding it around a winding core The base film 1 was obtained. The residual solvent amount of the base film was 0.2%, the film thickness was 40 μm, and the number of turns was 5500 m.

<Preparation of hard coat film 1>
(Preparation of hard coat film 1)
On the base film 1 produced above, the following hard coat layer composition 1 filtered through a polypropylene filter having a pore size of 0.4 μm was applied to the surface of the cellulose triacetate film 1 using a microgravure coater. After drying at a rate drying interval temperature of 95 ° C. and a decreasing rate drying interval temperature of 95 ° C., the illuminance of the irradiated part is 100 mW / cm ² using an ultraviolet lamp, the irradiation amount is 0.1 J / cm ² , and the coating layer is cured, A hard coat layer 1 having a dry film thickness of 6.7 μm was formed, wound up, and a roll-shaped hard coat film 1 was produced. Or, as a result of observing the surface of the hard coat layer of the coated film 1 with an optical interference type surface roughness meter (New View 5030, manufactured by Zygo), irregular projection shapes irregularly in the longitudinal direction and width as shown in FIG. It turns out that it is arranged in the direction.

[Hard Coat Layer Composition 1]
The following materials were stirred and mixed to obtain hard coat layer composition 1.

(Actinic radiation curable resin)
Pentaerythritol tri / tetraacrylate (NK ester A-TMM-3L, manufactured by Shin-Nakamura Chemical Co., Ltd.) 95 parts by mass (photopolymerization initiator)
Irgacure 184 (BASF Japan) 5 parts by mass (additive: leveling agent)
ZX-214-A (Fuji Kasei Kogyo Co., Ltd.) 0.5 parts by mass (solvent)
Propylene glycol monomethyl ether 10 parts by weight Methyl acetate 45 parts by weight Methyl ethyl ketone 45 parts by weight In the description of Table 1, pentaerythritol tri / tetraacrylate is shown as PETTA.

(Durability test of hard coat film 1)
The roll-shaped hard coat film 1 (5500 m) produced above was wrapped in an aluminum moisture-proof sheet and stored for 20 days in a constant temperature and humidity chamber at 70 ° C. and 90% relative humidity.

<Preparation of hard coat film 2>
In the production method of the hard coat film 1, the hard coat layer composition 1 is changed to the following hard coat layer composition 2 and the reduction drying temperature in the drying process of the hard coat layer is changed to 95 ° C. in the same manner. Thus, a hard coat film was produced.

[Hard coat layer composition 2]
The following materials were stirred and mixed to obtain hard coat layer composition 2.

(Actinic radiation curable resin)
Trimethylolpropane triacrylate (Light acrylate TMP-A, manufactured by Kyoeisha Chemical Co., Ltd.) 80 parts by mass 4-hydroxybutyl acrylate (4-HBA, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
19 parts by weight (photopolymerization initiator)
Irgacure 184 (BASF Japan) 5 parts by mass (additive: leveling agent)
ZX-058-A (Fuji Kasei Kogyo Co., Ltd.) 1 part by mass (solvent)
Propylene glycol monomethyl ether 10 parts by mass Methyl acetate 45 parts by mass Methyl ethyl ketone 45 parts by mass <Preparation of hard coat film 3>
The production method of the hard coat film 1 was the same as that of the hard coat layer composition 3 and the hard coat layer, except that the decreasing rate drying section temperature in the drying step was changed to 95 ° C.

[Hard coat layer composition 3]
The following materials were stirred and mixed to obtain hard coat layer composition 3.

(Actinic radiation curable resin)
Trimethylolpropane triacrylate (Light acrylate TMP-A, manufactured by Kyoeisha Chemical Co., Ltd.) 79.5 parts by mass 4-hydroxybutyl acrylate (4-HBA, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
20 parts by mass (photopolymerization initiator)
Irgacure 184 (BASF Japan) 5 parts by mass (additive: leveling agent)
ZX-214-A (Fuji Kasei Kogyo Co., Ltd.) 1 part by mass (solvent)
Propylene glycol monomethyl ether 10 parts by mass Methyl acetate 45 parts by mass Methyl ethyl ketone 45 parts by mass <Preparation of hard coat film 4>
The manufacturing method of the hard coat film 1 was the same except that the decreasing drying interval temperature in the drying process of the hard coat layer composition 4 and the hard coat layer was changed to 100 ° C.

[Hard coat layer composition 4]
The following materials were stirred and mixed to obtain hard coat layer composition 4.

(Actinic radiation curable resin)
Ethoxylated glycerin triacrylate (NK ester A-GLY-9E, manufactured by Shin-Nakamura Chemical Co., Ltd.) 60 parts by mass Ethoxylated isocyanuric acid triacrylate (NK ester A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.) 39. 3 parts by mass (photopolymerization initiator)
Irgacure 184 (manufactured by BASF Japan) 5 parts by mass (additive: leveling agent)
ZX-058-A (Fuji Kasei Co., Ltd.) 1.5 parts by mass (solvent)
Propylene glycol monomethyl ether 10 parts by mass Methyl acetate 45 parts by mass Methyl ethyl ketone 45 parts by mass <Preparation of hard coat film 5>
The production method of the hard coat film 1 was the same except that the reduced drying interval temperature in the drying process of the hard coat layer composition 5 and the hard coat layer was changed to 105 ° C.

[Hard Coat Layer Composition 5]
The following materials were stirred and mixed to obtain hard coat layer composition 5.

(Actinic radiation curable resin)
Ethoxylated glycerin triacrylate (NK ester A-GLY-9E, manufactured by Shin-Nakamura Chemical Co., Ltd.) 58 parts by mass Ethoxylated isocyanuric acid triacrylate (NK ester A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.) 40 mass Part (photopolymerization initiator)
Irgacure 184 (manufactured by BASF Japan) 5 parts by mass (additive: leveling agent)
ZX-214-A (Fuji Kasei Co., Ltd.) 2 parts by mass (solvent)
Propylene glycol monomethyl ether 10 parts by mass Methyl acetate 45 parts by mass Methyl ethyl ketone 45 parts by mass <Preparation of hard coat film 6>
The manufacturing method of the hard coat film 1 was the same except that the decreasing drying interval temperature in the drying process of the hard coat layer composition 6 and the hard coat layer was changed to 95 ° C.

[Hard Coat Layer Composition 6]
The following materials were stirred and mixed to obtain hard coat layer composition 6.

(Actinic radiation curable resin)
Ethoxylated pentaerythritol tetraacrylate (NK ester ATM-4E, manufactured by Shin-Nakamura Chemical Co., Ltd.) 50 parts by mass Pentaerythritol tri / tetraacrylate (NK ester A-TMM-3L, manufactured by Shin-Nakamura Chemical Co., Ltd.) 50 Parts by mass (photopolymerization initiator)
Irgacure 184 (manufactured by BASF Japan) 5 parts by mass (additive: leveling agent)
ZX-214-A (Fuji Kasei Kogyo Co., Ltd.) 0.5 parts by mass (solvent)
Propylene glycol monomethyl ether 10 parts by mass Methyl acetate 45 parts by mass Methyl ethyl ketone 45 parts by mass <Preparation of hard coat film 7>
The manufacturing method of the hard coat film 1 was the same except that the drying rate in the drying process of the hard coat layer composition 7 and the hard coat layer was changed to 90 ° C.

[Hard Coat Layer Composition 7]
The following materials were stirred and mixed to obtain hard coat layer composition 7.

(Actinic radiation curable resin)
Dipentaerythritol hexaacrylate (NK ester A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.) 99.4 parts by mass (photopolymerization initiator)
Irgacure 184 (manufactured by BASF Japan) 5 parts by mass (additive: leveling agent)
ZX-058-A (Fuji Kasei Kogyo Co., Ltd.) 0.6 parts by mass (solvent)
Propylene glycol monomethyl ether 10 parts by mass Methyl acetate 45 parts by mass Methyl ethyl ketone 45 parts by mass In the description of Table 1, dipentaerythritol penta / hexaacrylate was shown as DPHA.

<Preparation of hard coat film 8>
The manufacturing method of the hard coat film 1 was the same except that the decreasing drying interval temperature in the drying process of the hard coat layer composition 8 and the hard coat layer was changed to 120 ° C.

[Hard Coat Layer Composition 8]
The following materials were stirred and mixed to obtain hard coat layer composition 8.

(Actinic radiation curable resin)
Dipentaerythritol hexaacrylate (NK ester A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.) 50 parts by mass Pentaerythritol tri / tetraacrylate (NK ester A-TMM-3L, manufactured by Shin-Nakamura Chemical Co., Ltd.) 49. 5 parts by mass (photopolymerization initiator)
Irgacure 184 (manufactured by BASF Japan) 5 parts by mass (additive: leveling agent)
ZX-214-A (Fuji Kasei Kogyo Co., Ltd.) 0.5 parts by mass (solvent)
Propylene glycol monomethyl ether 10 parts by mass Methyl acetate 45 parts by mass Methyl ethyl ketone 45 parts by mass <Preparation of hard coat film 9>
The method for producing the hard coat film 1 was the same except that the reduced drying interval temperature in the drying process of the hard coat layer composition 9 and the hard coat layer was changed to 120 ° C.

[Hard Coat Layer Composition 9]
The following materials were stirred and mixed to obtain hard coat layer composition 9.

(Actinic radiation curable resin)
Dipentaerythritol hexaacrylate (NK ester A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.) 50 parts by mass Pentaerythritol tri / tetraacrylate (NK ester A-TMM-3L, manufactured by Shin-Nakamura Chemical Co., Ltd.) 48 masses Part (photopolymerization initiator)
Irgacure 184 (manufactured by BASF Japan) 5 parts by mass (additive: leveling agent)
KF-352 (manufactured by Toray Dow Corning) 2 parts by mass (solvent)
Propylene glycol monomethyl ether 10 parts by mass Methyl acetate 45 parts by mass Methyl ethyl ketone 45 parts by mass <Preparation of hard coat film 10>
The method for producing the hard coat film 1 was the same as the hard coat layer composition 10, except that the decreasing drying interval temperature in the drying process of the hard coat layer was changed to 90 ° C.

[Hard Coat Layer Composition 10]
The following materials were stirred and mixed to obtain a hard coat layer composition 10.

(Actinic radiation curable resin)
49.5 parts by mass of ethoxylated pentaerythritol tetraacrylate (NK ester ATM-4E, manufactured by Shin-Nakamura Chemical Co., Ltd.)
4-hydroxybutyl acrylate 50 parts by mass (4-HBA, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
(Photopolymerization initiator)
Irgacure 184 (manufactured by BASF Japan) 5 parts by mass (additive: leveling agent)
ZX-214-A (Fuji Kasei Kogyo Co., Ltd.) 0.5 parts by mass (solvent)
Propylene glycol monomethyl ether 10 parts by mass Methyl acetate 45 parts by mass Methyl ethyl ketone 45 parts by mass <Preparation of hard coat film 11>
In the production method of the hard coat film 1, the same procedure was performed except that the hard coat layer composition 11 and the reduced drying interval temperature in the drying process of the hard coat layer were changed to 100 ° C.

[Hard Coat Layer Composition 11]
The following materials were stirred and mixed to obtain a hard coat layer composition 10.

(Actinic radiation curable resin)
Mixture of urethane prepolymer and pentaerythritol tetraacrylate (UA-306H, manufactured by Kyoeisha Chemical Co., Ltd.) 98.5 parts by mass (photopolymerization initiator)
Irgacure 184 (manufactured by BASF Japan) 5 parts by mass (additive: leveling agent)
ZX-214-A (Fuji Kasei Kogyo Co., Ltd.) 1.5 parts by mass (solvent)
Propylene glycol monomethyl ether 10 parts by mass Methyl acetate 45 parts by mass Methyl ethyl ketone 45 parts by mass <Preparation of hard coat film 12>
In the production method of the hard coat film 1, the same procedure was performed except that the hard coat layer composition 12 and the drying rate in the drying process of the hard coat layer were changed to 80 ° C.

  The following materials were stirred and mixed to obtain hard coat layer composition 12.

(Actinic radiation curable resin)
Triethylene glycol-trimethylolpropane triacrylate (SP value: 11.6) 20 parts by mass Dipentaerythritol hexaacrylate (SP value: 12.1)
(NK ester A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.) 39 parts by mass Pentaerythritol triacrylate (SP value: 12.7) 38 parts by mass (photopolymerization initiator)
Irgacure 184 (manufactured by BASF Japan) 5 parts by mass (additive: leveling agent)
ZX-214-A (Fuji Kasei Kogyo Co., Ltd.) 1 part by mass (solvent)
Methyl isobutyl ketone 105 parts by mass In the description of Table 1, triethylene glycol-trimethylolpropane triacrylate is described as TETPA and pentaerythritol triacrylate as PETA.

<Preparation of hard coat film 13>
In the manufacturing method of the hard coat film 1, the constant rate drying zone temperature and the decreasing rate drying zone temperature in the drying process of the hard coat layer composition 13 and the hard coat layer were changed to 80 ° C., and the irradiation amount of the ultraviolet lamp was set to 0.3 J A hard coat film was prepared in the same manner except that the coating layer was cured at / cm ² , and then a durability test was performed.

[Hard Coat Layer Composition 13]
Preparation of reactive silica particles X To a solution consisting of 23 parts of mercaptopropyltrimethoxysilane and 0.5 parts of dibutyltin dilaurate, 60 parts of isophorone diisocyanate was added dropwise at 50 ° C. over 1 hour and then stirred at 80 ° C. for 3 hours. did. To this, 202 parts of NK ester A-TMM-3LM-N (a solution comprising 60% by mass of pentaerythritol triacrylate and 40% by mass of pentaerythritol tetraacrylate) made by Shin-Nakamura Chemical Co., Ltd. was added dropwise at 30 ° C. over 1 hour. The specific organic compound (S1) was obtained by heating and stirring at 3 ° C for 3 hours. In the infrared absorption spectrum of the product, the absorption peak at 2550 cm −1 characteristic for the mercapto group in the raw material and the absorption peak at 2260 cm −1 characteristic for the isocyanate group disappeared, and [−O—C (= O) —NH—] and [—S—C (═O) —NH—] groups, a peak at 1660 cm −1 characteristic for the carbonyl and a peak at 1720 cm −1 characteristic for the acryloyl group are observed, A specific organic compound having both an acryloyl group as a polymerizable unsaturated group, a [—S—C (═O) —NH—] group, and a [—O—C (═O) —NH—] group has been generated. Showed that. 9.5 parts of the composition produced (including 7.3 parts of an organic compound having a polymerizable unsaturated group), 62.7 parts of methyl ethyl ketone, silica particles (average particle diameter: 250 nm, trade name: KEP-250 ( (Made by Nippon Shokubai Co., Ltd.)) 35.3 parts, 0.13 parts of ion-exchanged water, and 0.01 part of p-hydroxyphenyl monomethyl ether were stirred at 60 ° C. for 5 hours, and then methyl orthoformate 1.45. A reactive silica particle dispersion X was obtained by adding 1 part and further heating and stirring at the same temperature for 1 hour.

  2 g of this dispersion was weighed on an aluminum dish, dried on a hot plate at 175 ° C. for 1 hour, and weighed to determine the solid content, which was 36%. The average particle size of the silica particles was 300 nm.

  Here, the average particle diameter was measured with a transmission electron microscope.

  The following materials were stirred and mixed to obtain a hard coat layer coating composition 13.

(Actinic radiation curable resin)
Dipentaerythritol hexaacrylate (NK ester A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.) 16.6 parts by mass (photopolymerization initiator)
Irgacure 184 (manufactured by BASF Japan Ltd.) 0.85 parts by mass (additive: leveling agent)
ZX-058-A (Fuji Kasei Kogyo Co., Ltd.) 0.7 parts by mass (additive: fine particles)
Reactive silica particle dispersion (reactive silica particles (X) 36%) 115 parts by mass (solvent)
5 parts by mass of propylene glycol monomethyl ether <Preparation of hard coat film 14>
In the production method of the hard coat film 1, after applying the hard coat layer, the drying temperature of the constant rate drying zone temperature and the decreasing rate drying zone temperature is changed to 80 ° C. and dried, and then the examples of JP 2008-276198 A A hard coat film was prepared in the same manner except that it was pressed with a mold roll prepared with reference to, and then cured using an ultraviolet lamp, and then a durability test was performed.

[Hard Coat Layer Composition 14]
The following materials were stirred and mixed to obtain a hard coat layer composition 14.

(Actinic radiation curable resin)
Pentaerythritol tri / tetraacrylate (NK ester A-TMM-3L, manufactured by Shin-Nakamura Chemical Co., Ltd.) 99.2 parts by mass (photopolymerization initiator)
Irgacure 184 (manufactured by BASF Japan) 5 parts by mass (additive: leveling agent)
ZX-214-A (Fuji Kasei Kogyo Co., Ltd.) 0.8 parts by mass (solvent)
Propylene glycol monomethyl ether 10 parts by mass Methyl acetate 45 parts by mass Methyl ethyl ketone 45 parts by mass <Preparation of hard coat film 15>
In the production method of the hard coat film 1, after applying the hard coat layer, the drying temperature of the constant rate drying zone temperature and the decreasing rate drying zone temperature is changed to 95 ° C. and dried, and then the example of JP 2008-276198 A A hard coat film was prepared in the same manner except that it was pressed with a mold roll prepared with reference to, and then cured using an ultraviolet lamp, and then a durability test was performed.

[Hard Coat Layer Composition 15]
The following materials were stirred and mixed to obtain hard coat layer composition 15.

(Actinic radiation curable resin)
Pentaerythritol tri / tetraacrylate (NK ester A-TMM-3L, manufactured by Shin-Nakamura Chemical Co., Ltd.) 99 parts by mass (photopolymerization initiator)
Irgacure 184 (manufactured by BASF Japan) 5 parts by mass (additive: leveling agent)
ZX-214-A (Fuji Kasei Kogyo Co., Ltd.) 1 part by mass (solvent)
Propylene glycol monomethyl ether 10 parts by mass Methyl acetate 45 parts by mass Methyl ethyl ketone 45 parts by mass <Preparation of hard coat film 16>
In the production method of the hard coat film 1, after applying the hard coat layer, the drying temperature of the constant rate drying zone temperature and the decreasing rate drying zone temperature is changed to 95 ° C. and dried, and then the example of JP 2008-276198 A A hard coat film was prepared in the same manner except that it was pressed with a mold roll prepared with reference to, and then cured using an ultraviolet lamp, and then a durability test was performed.

[Hard Coat Layer Composition 16]
The following materials were stirred and mixed to obtain hard coat layer composition 16.

(Actinic radiation curable resin)
Pentaerythritol tri / tetraacrylate (NK ester A-TMM-3L, manufactured by Shin-Nakamura Chemical Co., Ltd.) 99.8 parts by mass (photopolymerization initiator)
Irgacure 184 (manufactured by BASF Japan) 5 parts by mass (additive: leveling agent)
ZX-214-A (Fuji Kasei Kogyo Co., Ltd.) 1.2 parts by mass (solvent)
Propylene glycol monomethyl ether 10 parts by weight Methyl acetate 45 parts by weight Methyl ethyl ketone 45 parts by weight (Preparation of antireflection film 1)
The roll-shaped hard coat film 1 prepared above is drawn out again, and the antireflective layer is applied on the hard coat layer surface in the order of the high refractive index layer and then the low refractive index layer as follows. Was made.

(Application of high refractive index layer)
The following coating composition with a high refractive index layer is die-coated on the hard coat layer, dried at 80 ° C., and then irradiated with an ultraviolet lamp while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0% by volume or less. The coating layer was cured with an illuminance of the part of 100 mW / cm ² and an irradiation amount of 0.15 J / cm ² , and a high refractive index layer was provided so that the film thickness after curing was 120 nm. The refractive index was 1.60.

[High refractive index layer coating composition]
Preparation of particle dispersion A Methanol-dispersed antimony double oxide colloid (solid content 60%, zinc antimonate sol manufactured by Nissan Chemical Industries, Ltd., trade name: Cellnax CX-Z610M-F2) 6.0 kg with isopropyl alcohol 12 0.0 kg was gradually added with stirring to prepare the particle dispersion A.

  The following materials were stirred and mixed to obtain a high refractive index layer coating composition.

(solvent)
PGME (propylene glycol monomethyl ether) 40 parts by mass Isopropyl alcohol 25 parts by mass Methyl ethyl ketone 25 parts by mass (Actinic radiation curable resin)
Pentaerythritol tri / tetraacrylate (NK ester A-TMM-3L, manufactured by Shin-Nakamura Chemical Co., Ltd.) 1.9 parts by mass Urethane acrylate (trade name: U-4HA manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.6 parts by mass (Fine particles)
Particle dispersion A 20 parts by mass (photopolymerization initiator)
Irgacure 184 (manufactured by BASF Japan) 1.5 parts by mass Irgacure 907 (manufactured by BASF Japan) 0.2 parts by mass (leveling agent)
10% FZ-2207, propylene glycol monomethyl ether solution (Nihon Unicar Co., Ltd.) 0.4 parts by mass (application of low refractive index layer)
Next, after forming the high refractive index layer, the following low refractive index layer coating composition 1 is die-coated on the high refractive index layer without being wound, dried at 80 ° C., and then irradiated with an ultraviolet lamp. The low refractive index layer 1 was provided so that the film thickness was 85 nm by irradiation with an illuminance of 100 mW / cm ² and an irradiation amount of 0.3 J / cm ² , and wound into a roll. Next, the produced roll-shaped antireflection film 1 was wrapped in an aluminum moisture-proof sheet and subjected to an aging treatment at 50 ° C. for 5 days to produce an antireflection film 1. The refractive index of the low refractive index layer 1 was 1.37.

[Low refractive index layer coating composition 1 (sol-gel binder)]
-Preparation of tetraethoxysilane hydrolyzate A Tetraethoxysilane 230g (trade name: KBE04, manufactured by Shin-Etsu Chemical Co., Ltd.) and ethanol 440g were mixed, and after adding 120% of 2% aqueous acetic acid solution to this, room temperature (25 ° C) The tetraethoxysilane hydrolyzate A was prepared by stirring for 26 hours.

  The following materials were stirred and mixed to obtain a low refractive index layer coating composition.

(solvent)
Propylene glycol monomethyl ether 430 parts by mass Isopropyl alcohol 430 parts by mass (sol-gel binder)
Tetraethoxysilane hydrolyzate A 120 parts by mass γ-methacryloxypropyltrimethoxysilane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) 3.0 parts by mass (fine particles)
Isopropyl alcohol-dispersed hollow silica sol (solid content 20%, silica sol manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name: ELCOM V-8209) 45.0 parts by mass (additive)
Aluminum ethyl acetoacetate diisopropylate (ALCH manufactured by Kawaken Fine Chemical Co., Ltd.) 3.0 parts by mass (leveling agent)
10% FZ-2207, propylene glycol monomethyl ether solution (manufactured by Nihon Unicar) 3.0 parts by mass <Preparation of antireflection films 2 to 16>
In the same manner as the production of the antireflection film 1, an antireflection layer was formed on the hard coat films 2 to 16, and reflection films 2 to 16 were produced.

<Evaluation>
The following evaluation was performed about the produced hard coat films 1-16.

1. Evaluation of hard coat layer composition a. Resin viscosity measurement About hard coat layer compositions 1-16, only the actinic radiation curable resin of each composition was stirred and mixed with a disper, and the viscosity was measured using a B-type viscometer at 25 ° C. . The obtained results are shown in Table 1.

2. Evaluation of hard coat film a. Measurement of Arithmetic Average Roughness Ra and Average Length RSm of Contour Curve Element The hard coat layer of each hard coat film produced above was measured 10 times using a non-contact surface shape measuring machine (New View 5030 manufactured by ZYGO), and From the average of the measurement results, the arithmetic average roughness Ra of each hard coat layer and the average length RSm of the contour curve elements were determined. The obtained results are shown in Table 2.

b. Measurement of Contact Angle About the surface of the hard coat layer such as each of the hard coat films prepared above, contact angle meter CA using water and n-hexadecane for a sample conditioned at a temperature of 23 ° C. and a relative humidity of 55% RH for 24 hours. Using -A (manufactured by Kyowa Interface Chemical Co., Ltd.), the measurement was performed under the temperature and humidity conditions with a droplet diameter of 1.0 mm.

  In addition, 20 samples of a size of 30 mm × 40 mm were sampled randomly from each hard coat film produced, and the contact angle was measured on the surface of each sample by the above-described method, and each 20 hard coat films were measured. The average value of the measured values was adopted.

3. Evaluation of hard coat film a. Appearance evaluation Each anti-hard coat film produced above was cut into a size of 150 cm x 50 cm, light-absorbing treatment was performed using a black spray on the back surface, and reflection of a fluorescent lamp was observed from the front surface. ) Was visually evaluated according to the following criteria. The obtained results are shown in Table 2.

(Spotted unevenness)
A: Spot-like unevenness is not observed at all. ○: Spot-like unevenness is slightly observed. Δ: Spot-like unevenness is slightly recognized. There is a problem in practical use ×: Spotted unevenness is observed.

b. Adhesiveness After storing the antireflection films 1 to 16 at 90 ° C. and 95% for 200 hours, after putting them in a cycle thermo (500 ° C. and 30 minutes standing at -40 ° C. for 30 minutes), The sample was irradiated with light for 100 hours using a weather resistance tester (eye super UV tester, manufactured by Iwasaki Electric Co., Ltd.)

  On the surface of the antireflection layer of the antireflection film subjected to the above durability test, 11 razor blades are cut at an angle of 90 ° with respect to the surface, and 11 cuts are made vertically and horizontally at intervals of 1 mm. Produced. A commercially available cellophane tape is affixed on this, holding one end by hand and pulling it forcefully vertically, and visually observing the ratio of the area where the thin film was peeled off to the tape area affixed from the score line, Evaluation was made according to the following criteria.

A: Not peeled at all ○: The peeled area ratio was less than 10% Δ: The peeled area ratio was 10% or more and less than 20% ×: The peeled area ratio was 20% or more (Anti-fingerprint: fingerprint adhesion and wiping)
Press the finger against the surface of the hard coat film in an atmosphere of 23 ° C and 55% RH, and wipe the attached fingerprint three times with Bencott (M-3, manufactured by Asahi Kasei Co., Ltd.). Thereafter, the state was observed and evaluated according to the following criteria.

Evaluation criteria ○: Fingerprints are difficult to adhere or are inconspicuous and can be wiped off completely. △: Fingerprints are less attached, but traces of wiping remain. ×: Fingerprints are clearly attached and cannot be wiped off. Are shown in Tables 1 and 2.

As can be seen from the results shown in Tables 1 and 2, Ra of the hard coat layer is 2 to 20 nm, and the ratio of Ra to RSm (Ra / RSm) is 5 × 10 ⁻⁵ to 2 × 10 ^−3. The hard coat film and the antireflection film of the present invention composed of the hard coat layer within the range of the above, compared with the comparative example, improved the occurrence of unevenness while maintaining the visibility, and good fingerprint prevention property, Moreover, it can be seen that even if a fingerprint is attached, the performance is inconspicuous.

  It turns out that the hard coat film of this invention comprised from the hard coat layer whose Ra is 4-20 nm among this invention has the especially outstanding performance with respect to visibility, contrast, and antifouling property.

  Further, the hard coat film and antireflection film of the present invention composed of a hard coat layer whose projection shape is irregular in the longitudinal direction, and a book having a configuration in which the projection shape produced by embossing has regularity in the longitudinal direction. It can be seen that spot unevenness and adhesion are more excellent than the hard coat film and the antireflection film of the invention.

  Alternatively, the hard coat film formed by controlling the temperature of the decreasing rate drying section in the drying process of the coat coat layer in the range of 95 ° C. to 120 ° C. can control the Ra and Ra / RSm of the hard coat layer well within the range of the present invention. It can be seen that it is preferable.

  Or when Ra of a docoat film was measured using the non-contact surface shape measuring machine (New View5030 by ZYGO), Ra of the hard-coat layer was maintained favorable. In addition, the anti-fingerprinting property was improved in addition to the good unevenness formation.

Example 2
<Preparation of polarizing plate>
A 120 μm-thick polyvinyl alcohol film was uniaxially stretched (temperature: 110 ° C., stretch ratio: 5 times).

  This was immersed in an aqueous solution composed of 0.075 g of iodine, 5 g of potassium iodide and 100 g of water for 60 seconds, and then immersed in an aqueous solution of 68 ° C. composed of 6 g of potassium iodide, 7.5 g of boric acid and 100 g of water. This was washed with water and dried to obtain a polarizer.

Next, in accordance with the following steps 1 to 5, the polarizer, the antireflection films 1 to 16 and the back surface side are aligned with the protective film (1) in the longitudinal direction, and bonded together with a roll-to-roll to produce a polarizing plate. Further, in Step 6, an adhesive layer was bonded.
Step 1: After attaching a protective film (made of PET) to the antireflection layers of the antireflection films 1 to 16, it was immersed in a 2 mol / L sodium hydroxide solution at 60 ° C. for 90 seconds, then washed with water and dried. Anti-reflective films 1-16 and the protective film (1) which saponified the side bonded with a polarizer were obtained.
Process 2: The said polarizer was immersed in the polyvinyl alcohol adhesive tank of 2 mass% of solid content for 1-2 seconds.
Step 3: Excess adhesive adhered to the polarizer in Step 2 was gently wiped off, and this was placed on the optical film 1 on the antireflection films 1 to 15 treated in Step 1 and the back side.
Step 4: the antireflection film 1 to 16 laminated in step 3, the polarizer and the protective film (1) the pressure 20-30 N / cm ^2, the conveyance speed was pasted at approximately 2m / min.
Step 5: A sample obtained by bonding the polarizer, the antireflection films 1 to 16 and the protective film (1) prepared in Step 4 in a dryer at 80 ° C. is dried for 2 minutes, wound into a roll, and polarizing plate Each was produced. After bonding, the protective films (made of PET) of the antireflection films 1 to 16 were peeled off.
Step 6: Apply a commercially available acrylic pressure-sensitive adhesive to the protective film of the polarizing plate prepared in Step 5 so that the thickness after drying is 25 μm, and dry in an oven at 110 ° C. for 5 minutes to form an adhesive layer. A peelable protective film was attached to the adhesive layer. This polarized light was cut (punched) to produce a polarizing plate 1. After producing the polarizing plate, the protective films (made of PET) of the antireflection films 1 to 16 were peeled off.

<Production of liquid crystal display device>
A liquid crystal panel was produced as follows, and the visibility and front contrast as a liquid crystal display device were evaluated. First, peel off the previously bonded front plate of SONY KDL-32EX, remove the filler between the polarizing plate on the front of the panel and the front plate, and peel off the previously bonded polarizing plate on the front side of the panel Then, the prepared adhesive layer of each polarizing plate was bonded to the front surface of the glass surface of the liquid crystal cell. At that time, the direction of bonding of the polarizing plate is such that the surface of the antireflection layer of the antireflection film is on the viewing side, and the absorption axis is oriented in the same direction as the polarizing plate previously bonded. Then, liquid crystal display devices 101 to 116 were produced.

<Evaluation of liquid crystal display device>
a. Visibility evaluation About the produced liquid crystal display devices 101-116, it has arrange | positioned on the desk of the height of 80 cm from a floor. Next, a set of 40W x 2 daylight straight tube fluorescent lamps (FLR40S • D / MX Panasonic Corporation) on the ceiling 3m high from the floor, 10 sets at 1.5m intervals Arranged. In this case, when the evaluator is in front of the display surface of the liquid crystal display panel, the fluorescent lamp is arranged so that the fluorescent lamp comes to the ceiling portion from the evaluator's overhead to the rear. Next, the visibility of the liquid crystal display devices 101 to 116 was evaluated according to the following criteria. The obtained results are shown in Table 3.

◎: Fluorescent light is clearly visible ○: Fluorescent light is slightly whitish ×: Fluorescent light is blurred and appears whitish

b. Measurement was performed after the backlight of each liquid crystal display device was lit continuously for 100 hours in an environment with a front contrast of 23 ° C. and 55% RH. For measurement, EZ-Contrast 160D manufactured by ELDIM was used to measure the luminance from the normal direction of the display screen of white display and black display with a liquid crystal display device, and the ratio was defined as the front contrast.

Front contrast = (brightness of white display measured from normal direction of display device) / (brightness of black display measured from normal direction of display device)
The front contrast at any five points of the liquid crystal display device was measured and evaluated according to the following criteria.

○: 1100-1200
Δ: 1000 to less than 1100 ×: less than 1000

  As can be seen from the results shown in Table 3, when the antireflection film using the hard coat film of the present invention is used in an image display device, it can be seen that excellent visibility and brightness (front contrast) can be obtained.

Example 3
<Preparation of Antireflection Film 201 with Conductive Film>
In the production of the antireflection film 1, the hard coat layer composition 1 was applied on both sides and the hard coat layer was provided on both sides, and then the durability test of the hard coat film was performed. Next, an antireflection film 101 was produced in the same manner except that an antireflection layer was coated only on one side of the double-sided hard coat layer. A transparent conductive thin film of indium tin oxide (ITO) having a surface resistivity of about 400Ω is provided on one side of the hard coat layer, which is not provided with the antireflection layer of the antireflection film 101, using a sputtering method. The antireflection film 201 with the conductive film shown was produced.

<Preparation of Antireflection Films 202 to 216 with Conductive Film>
Similarly to the production of the antireflection film 201 with the conductive film, in the production of the antireflection films 2 to 16, the hard coat layer composition was applied on both sides and the hard coat layer was provided on both sides. A durability test was conducted. Next, an antireflection layer was coated only on one side of the double-sided hard coat layer to prepare antireflection films 202 to 216. An anti-reflection film 202 to 216 is not provided with an anti-reflection layer, and a transparent conductive thin film of ITO having a surface resistivity of about 400Ω is provided on one side of the hard coat layer using a sputtering method. Films 202 to 216 were produced.

<Preparation of Resistive Touch Panel Liquid Crystal Display 301>
The conductive optical film of a commercially available resistive film type touch panel liquid crystal display device (model name: LCD-USB10XB-T, manufactured by I-O DATA) is peeled off, and the produced antireflection film 201 with the conductive film is as shown in FIG. The resistance film type touch panel liquid crystal display device 301 was manufactured by pasting together so that the antireflection layer was on the viewing side.

<Preparation of Resistive Touch Panel Liquid Crystal Display Devices 302 to 316>
Resistive touch panel liquid crystal display devices 302 to 316 are manufactured in the same manner except that the antireflection film 201 with a conductive film is changed to the antireflective films 202 to 216 with a conductive film in the fabrication of the resistive touch panel liquid crystal display device 301. did.

  About the resistive film type touch panel liquid crystal display devices 301 to 316 using the antireflection films 201 to 216 produced above, the following character blur and pen sliding resistance were evaluated.

<Evaluation>
a. Character blur The resistive film system is used in a room where 10 sets are arranged at 1.5 m intervals, with one set of 40 W x 2 daylight straight tube fluorescent lamps (FLR40S • D / MX manufactured by Panasonic Corporation) on the ceiling. The touch panel liquid crystal display device was observed from various angles, and character blur was evaluated according to the following criteria.

○: You don't mind the reflection of fluorescent light and can clearly read characters with a font size of 8 or less. ×: You don't care about reflection of fluorescent light, but the font size of 8 or less is blurred. Is difficult.

b. Pen sliding resistance A polyacetal pen with a tip of 0.08 mmφ is used on the surface of the hard coat layer of each conductive optical film used in the resistive film type touch panel liquid crystal display device, the load is 250 g, the pen sliding speed The hard coat layer was scratched and peeled off visually at the sliding part after reciprocating 150,000 times on a straight line 40 mm at 100 mm / second.

  The above evaluation results are shown in Table 4.

  As is apparent from the results shown in Table 4, the resistive touch panel liquid crystal display device using the antireflection film with a conductive film of the present invention is excellent in letter blur and pen sliding resistance.

a Center line a
b, c Lines forming the foot of the mountain h Projection size height h (distance between the summit and the center line a)
t Protrusion size width t (distance between two intersections of lines b and c forming a mountain ridge and center line a)
DESCRIPTION OF SYMBOLS 1 Base film 2 Polarizing film 3 Protective film 4 Adhesive layer 5 Polarizing plate 10 Antireflection layer 11 Antireflection film 12 Hard coat layer 12a Protrusion 13 Transparent conductive thin film 14 Glass substrate 15 Transparent conductive thin film 16 Dot-shaped spacer 17 Liquid crystal Display panel (LCD)
101 resistance film type touch panel 201 antireflection film 20 with conductive film
301 Liquid Crystal Display Device with Resistive Touch Panel

Claims (11)

A hard coat film having a hard coat layer on one side or both sides of a base film, the arithmetic average roughness Ra of the surface of the hard coat layer being in the range of 2 to 20 nm, the arithmetic average roughness Ra of the The ratio of the unevenness on the surface of the hard coat layer to the average interval RSm (Ra / RSm) is in the range of 5 × 10 ⁻⁵ to 2 × 10 ⁻³ , and the temperature is 23 ° C. and the relative humidity is 55% RH. A hard coat film having a hexadecane average contact angle of 15 degrees or less and a water average contact angle of 90 degrees or more on the surface of the hard coat layer.   The hard coat film according to claim 1, wherein the hard coat layer contains a leveling agent.   The hard coat film according to claim 1 or 2, wherein the arithmetic average roughness Ra of the surface of the hard coat layer is within a range of 4 to 20 nm.   The hard coat film according to any one of claims 1 to 3, wherein an average contact angle of hexadecane on the surface of the hard coat layer is 10 degrees or less.   The hard coat film according to any one of claims 1 to 4, wherein the surface of the hard coat layer has an irregular protrusion shape having no period in the longitudinal direction.   It is a manufacturing method of the hard coat film which manufactures the hard coat film as described in any one of Claim 1- Claim 5, Comprising: A hard coat layer is passed through an application process, a drying process, and a hardening process at least. A method for producing a hard coat film, characterized in that the treatment is carried out under a condition of forming and maintaining the temperature of the decreasing rate drying section in the drying step within a range of 95 to 120 ° C.   An antireflection film formed by laminating a low refractive index layer on the hard coat film according to any one of claims 1 to 5.   A polarizing plate comprising the hard coat film according to any one of claims 1 to 5.   An image display device comprising the hard coat film according to any one of claims 1 to 5.   The image display device according to claim 9, wherein the polarizing plate according to claim 8 is provided on at least one surface of the liquid crystal cell.   The image display device is a liquid crystal display device having a touch panel, and the hard coat film according to any one of claims 1 to 5 is provided as a constituent member of the touch panel. The image display device according to claim 9.