KR20110110000A - Hard coat film, polarizing plate and image display device - Google Patents

Abstract

(식 중, θ₁은 기재 필름의 한쪽면에, 계면활성제를 포함하지 않는 것 이외에는 상기 활성 에너지선 경화성 수지 조성물과 동일 조성의 조성물을 주형과 접촉시키지 않고서 25℃의 기체 중에서 경화시켜 형성한 하드 코팅층의 대수 접촉각을 나타냄)The present invention includes a base film 312 and a hard coating layer 311 laminated on one side of the base film 312, and hard for installing the anti-reflection layer 320 on the surface of the hard coating layer 311. As the coating film 31, the hard coat layer 311 is formed by curing an active energy ray curable resin composition containing an active energy ray curable resin, a polymerization initiator, and a surfactant in contact with a mold, and the hard coat layer 311 The logarithmic contact angle θ of is related to the hard coat film 31 that satisfies the following formula (1).
<Equation 1>

(Wherein θ ₁ is a hard surface formed by curing in a gas at 25 ° C. without contacting the mold with a composition having the same composition as the active energy ray-curable resin composition, except that one surface of the base film does not contain a surfactant) Logarithmic contact angle of the coating layer)

Description

Hard Coating Films, Polarizers and Image Displays {HARD COAT FILM, POLARIZING PLATE AND IMAGE DISPLAY DEVICE}

The present invention relates to a hard coat film for installing an antireflection layer. Moreover, this invention relates to the polarizing plate and the image display apparatus using this hard coat film.

In many cases, hard coating films are provided in image display devices such as liquid crystal displays, plasma display panels, cathode ray tube (CRT) displays, and organic electroluminescent (EL) displays in order to prevent scratches caused by various external forces. It is. And such a hard-coating film is generally subjected to the antiglare treatment which scatters incident light by applying fine concavities and convexities on the surface to apply non-precipitated images.

As the method of the above-mentioned anti-glare treatment, for example, while contacting a resin composition for forming a hard coating layer with a mold such as an embossing roll, the active energy ray is irradiated without adjusting the contact temperature, and the surface of the base film has fine irregularities. A method of forming this transferred hard coat layer is disclosed (see International Publication No. 2008/020613 and Japanese Patent Laid-Open No. 2007-76089).

In the said anti-glare treatment method with the shaping | molding by a mold, it is said that it is essential to mix | blend surfactant with the said resin composition from a viewpoint of raising leveling property. However, after the hard coating layer is formed by such antiglare treatment, and when the antireflection layer is to be formed on the surface of the hard coating layer, liquid dripping of the coating liquid for forming the antireflection layer and nonuniformity of the coating layer are likely to occur. The adhesion to the hard coat layer of the antireflection layer tends to be low. It is therefore an object of the present invention to provide a hard coat film suitable for providing an antireflection layer as a hard coat film subjected to antiglare treatment using a mold.

The present invention includes a base film and a hard coating layer laminated on one side of the base film, wherein the hard coating layer is a hard coating film for providing an anti-reflection layer on the surface of the hard coating layer, wherein the hard coating layer is an active energy ray curable resin or a polymerization agent. It forms by hardening an active-energy-ray-curable resin composition containing an initiator and surfactant, making contact with a mold, and provides the hard coat film which the logarithmic contact angle (theta) of the said hard coat layer satisfy | fills following formula (1).

(Wherein θ ₁ is a hard surface formed by curing in a gas at 25 ° C. without contacting the mold with a composition having the same composition as the active energy ray-curable resin composition, except that one surface of the base film does not contain a surfactant) Logarithmic contact angle of the coating layer)

Moreover, this invention is a manufacturing method of the said hard coat film, Comprising: The process of coating the active energy ray curable resin composition containing an active energy ray curable resin, a polymerization initiator, and surfactant on one side of a base film, and the said active activity Irradiating active energy rays while contacting the energy ray-curable resin composition with a mold of 50 ° C. or higher to cure the active energy ray-curable resin composition to form a hard coating layer; and removing the hard coating layer from the mold. It is to provide a method for producing a hard coat film.

The present invention also provides a laminate including the hard coat film and an antireflection layer laminated on a surface of the hard coat layer of the hard coat film, a polarizing plate using the hard coat film or the laminate, and an image display device. will be.

According to the present invention, as a hard coat film subjected to antiglare treatment by a mold, a hard coat film suitable for providing an antireflection layer can be provided. It is preferable that the said mold has a fine uneven | corrugated shape.

1 is a schematic cross-sectional view showing an example of a basic layer structure of the image display device of the present invention.

<Hard coating film>

The hard coat film of the present invention comprises a base film and a hard coat layer laminated on one side of the base film, wherein the hard coat layer is a hard coat film for providing an antireflection layer on the surface of the hard coat layer, wherein the hard coat layer is an active energy ray. It is formed by hardening an active energy ray curable resin composition containing curable resin, a polymerization initiator, and surfactant, making contact with a mold, and the logarithmic contact angle θ of the hard coat layer satisfies the following formula (1).

&Quot; (1) &quot;

In the formula, θ ₁ is a hard coat layer formed by curing in a gas at 25 ° C. without contacting a mold with a composition having the same composition as the active energy ray-curable resin composition, except that one surface of the base film does not contain a surfactant. It represents the logarithmic contact angle of and is the logarithmic contact angle of the hard coat layer formed under an air atmosphere.

The present invention is suitable for forming an antireflection layer by satisfying the above expression (1).

In addition, it is preferable that the said logarithmic contact angle (theta) satisfies following formula (2) from a viewpoint of providing an antireflection layer in the hard coat film of this invention. When the logarithmic contact angle θ satisfies Equation 2 below, coating defects such as unevenness and splashing when the antireflection layer is laminated, liquid dripping during coating, poor adhesion of the antireflection layer, and the like can be prevented.

In the formula, θ ₀ represents the logarithmic contact angle of the hard coat layer formed by curing the active energy ray-curable resin composition in a gas at 25 ° C. without contacting the mold on one side of the base film, and the number of hard coat layers formed under an air atmosphere. Contact angle.

As a base film, as a film which has optical transparency, if it permeate | transmits the active energy ray which can harden an active energy ray curable resin, it will not specifically limit, Various transparent resin films can be used. Specifically, Cellulose resins, such as cellulose acetates, such as a triacetyl cellulose, a diacetyl cellulose, and a cellulose acetate propionate; Polycarbonate resin; (Meth) acrylic resins such as polyacrylate and polymethyl methacrylate; Polyester-based resins such as polyethylene terephthalate and polyethylene naphthalate; Linear polyolefin resins such as polyethylene and polypropylene; Cyclic polyolefin resins; Styrene resins; Polysulfones; Polyethersulfones; The film which consists of polyvinyl chloride, etc. is illustrated. Among the above, a film made of cellulose acetate, polyethylene terephthalate, polymethyl methacrylate and the like is preferable in terms of transparency, mechanical strength, thermal stability, low moisture permeability, isotropy, and the like. More preferred.

It is preferable that the thickness of a base film is 20 micrometers or more and 250 micrometers or less, More preferably, they are 30 micrometers or more and 150 micrometers or less. When the thickness of a base film is less than 20 micrometers, it may be difficult to acquire sufficient hardness as a hard coat film. Moreover, it is not preferable that the thickness of a base film exceeds 250 micrometers from the viewpoint of the request | requirement, cost, etc. for thickness reduction of the recent image display apparatus. From the viewpoint of reducing the thickness of the entire hard coat film, the thickness of the base film is more preferably 150 μm or less, more preferably 120 μm or less.

Moreover, you may provide an antistatic layer and an easily bonding layer in the coating surface of the active-energy-ray-curable resin composition of a base film, and / or the surface on the opposite side. An antistatic layer and an easily bonding layer are especially as long as it reduces the coating property and adhesiveness of an active-energy-ray-curable resin composition, or more than necessary causes coloring and thinning, and it does not significantly reduce the transmittance | permeability of an active energy ray. It does not restrict | limit, A conventionally well-known thing can be used.

When using the hard coat film of this invention as an optical member which comprises optical uses, especially a liquid crystal display (LCD), for example, when using it as a protective film of a polarizing plate, other optical members, such as a polarizing film and a liquid crystal cell, are ultraviolet-rays. In order to protect from a base film, it is preferable that a base film contains a UV absorber.

The active energy ray curable resin composition contains an active energy ray curable resin that polymerizes and cures by irradiation of an active energy ray, a polymerization initiator that generates radicals by irradiation of an active energy ray, and a surfactant. Active energy ray curable resin may be a thing containing a polyfunctional (meth) acrylate type compound, for example. A polyfunctional (meth) acrylate type compound is a compound which has at least 2 (meth) acryloyloxy group in a molecule | numerator. A commercial item may be sufficient as an active energy ray curable resin, a polymerization initiator, and surfactant. In most cases, active energy ray-curable resin compositions are marketed as containing additives such as active energy ray-curable resins, polymerization initiators, and surfactants added as necessary.

Specific examples of the polyfunctional (meth) acrylate-based compound include, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Neopentylglycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tetramethylol methane tri (meth) acrylate, tetramethylol methane tetra (meth) acrylic Late, pentaglycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerin tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, Dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris ((meth) acryloyl When ethyl) isocyanurate; Phosphazene (meth) acrylate compounds in which a (meth) acryloyloxy group is introduced into the phosphazene ring of the phosphazene compound; Urethane (meth) acrylate compounds obtained by the reaction of a polyisocyanate having at least two isocyanate groups in a molecule with a polyol compound having at least one (meth) acryloyloxy group and a hydroxyl group; Polyester (meth) acrylate compounds obtained by reaction of at least two carboxylic acid halides with a polyol compound having at least one (meth) acryloyloxy group and a hydroxyl group in a molecule; And oligomers such as dimers, trimers, and the like of the above compounds. These compounds are used individually or in mixture of 2 or more types, respectively.

Active energy ray curable resin may contain monofunctional (meth) acrylate type resin other than the above-mentioned polyfunctional (meth) acrylate type compound. As a monofunctional (meth) acrylate type compound, for example, hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth ) Acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycidyl (meth) acrylate, etc. are mentioned. These compounds are used individually or in mixture of 2 or more types, respectively. It is preferable that content of a monofunctional (meth) acrylate type compound is 10 weight% or less in resin solid content of an active energy ray curable resin composition.

In addition, the active energy ray curable resin may contain a polymerizable oligomer. The hardness of a hard coat layer can be adjusted by containing a polymeric oligomer. As a polymerizable oligomer, terminal (meth) acrylate polymethylmethacrylate, terminal styryl poly (meth) acrylate, terminal (meth) acrylate polystyrene, terminal (meth) acrylate polyethylene glycol, terminal (meth) acrylate acrylic Macromonomers, such as a ronitrile styrene copolymer and a terminal (meth) acrylate styrene-methyl (meth) acrylate copolymer, are mentioned. It is preferable that content of a polymeric oligomer is 5 to 50 weight% in resin solid content of an active energy ray curable composition.

Examples of the polymerization initiator contained in the active energy ray-curable resin composition include acetophenone, acetophenonebenzyl ketal, anthraquinone, 1- (4-isopropylphenyl-2-hydroxy-2-methylpropan-1-one, Carbazole, xanthone, 4-chlorobenzophenone, 4,4'-diaminobenzophenone, 1,1-dimethoxydeoxybenzoin, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone , 2,2-dimethoxy-2-phenylacetophenone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- [4- (methylthio ) Phenyl] -2-morpholinopropane-1-one, triphenylamine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, 1 Hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoisopropyl ether, benzophenone, Michler's ketone , 3-methylacetophenone, 3,3 ', 4,4'-tetra tert-butylperoxycarbonylbenzophenone (BTTB), 2- (dimethylamino) -1- [4- (morpholinyl) phenyl] -2-phenylmethyl) -1-butanone, 4-benzoyl-4 ' -Methyldiphenyl sulfide, benzyl, derivatives thereof, and the like. These polymerization initiators may be used independently, and may mix and use several types as needed. All the polymerization initiators mentioned above are photoinitiators which generate | occur | produce a radical by irradiation of an active energy ray.

A polymerization initiator can also be used in combination with a dye sensitizer. As a dye sensitizer, xanthene, thioxanthene, coumarin, ketocoumarin, etc. are mentioned, for example. Examples of the combination of the polymerization initiator and the dye sensitizer include a combination of BTTB and xanthene, a combination of BTTB and thioxanthene, a combination of BTTB and coumarin, a combination of BTTB and ketocoumarin, and the like. .

The content of the polymerization initiator is preferably in the range of 1 to 10% by weight, more preferably in the range of 3 to 6% by weight based on the active energy ray-curable resin. If content of a polymerization initiator is less than 1 weight%, hardening reaction will not fully advance and an uncured active energy ray curable resin may adhere to a mold, or the hard coat film which has the outstanding hardness may not be obtained. Moreover, when content of a polymerization initiator exceeds 10 weight%, the polymerization degree of active energy ray curable resin falls, and the hard coat film which has the outstanding hardness may not be obtained.

As described above, the base film preferably contains a UV absorber, and usually the UV absorber absorbs ultraviolet rays having a wavelength of less than 360 to 380 nm. Moreover, in the (1st) hardening process of this invention, as above-mentioned, it is preferable to irradiate an active energy ray from the base film side, and to harden an active energy ray curable resin composition. Therefore, it is preferable that at least 1 sort (s) of the polymerization initiator contained in an active energy ray curable resin composition has an absorption wavelength in 380 nm or more. Examples of such a polymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO), phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide and the like. If all of the polymerization initiators contained in the active energy ray-curable resin composition are polymerization initiators having an absorption wavelength only at less than 380 nm, most of the active energy ray-curable resins may remain uncured even after the completion of the (first) curing step described above. If the uncured active energy ray-curable resin remains attached to the mold even after peeling off the base film, it is not preferable because it causes the contamination and prevents the transfer of the mold surface shape accurately.

Here, "having an absorption wavelength in 380 nm or more" means that when irradiating an active energy ray with a wavelength of 380 nm or more, an amount of radicals necessary for initiation of the polymerization reaction is generated to function effectively as a polymerization initiator.

Moreover, as a UV absorber contained in a base film, it becomes possible to use only the polymerization initiator which does not have an absorption wavelength in 380 nm or more by using the UV absorber which has an absorption wavelength in the lower wavelength side. Such a method uses the hard-coating film obtained by the manufacturing method of the present invention in an image display apparatus with respect to an optical member such as a liquid crystal cell on the opposite side to the visual side, that is, the rear side (for example, in a liquid crystal display, It is effective in the case of disposing on the backlight side). However, in the case where the hard coat film is disposed on the viewing side, that is, the front side (for example, the front side of the liquid crystal panel in the liquid crystal display) with respect to optical members such as liquid crystal cells in the image display device, the polarizing film From the viewpoint of protecting optical members such as liquid crystal cells from ultraviolet rays, a UV absorber that absorbs ultraviolet rays having a wavelength of less than 360 to 380 nm is added to the base film, and at least one kind contained in the active energy ray-curable resin is 380 nm. It is preferable to set it as the polymerization initiator which has an absorption wavelength above.

As surfactant contained in active-energy-ray-curable resin composition, the leveling agent for improving smoothness, the mold release agent for improving mold release property with a mold, the antifouling agent for expressing antifouling property or fingerprint adhesion, and charging of a film And a conductive agent for preventing this. These additives are not particularly limited so long as they inhibit the polymerization reaction of the active energy ray-curable resin, and the hardness after the polymerization reaction and the adhesion to the base film are not limited, and conventionally known ones can be used.

As surfactant, it can select suitably from hydrocarbon type surfactant, fluorine type surfactant, silicone type surfactant, etc., and can use these 2 or more types together as needed. Especially, it is more preferable to contain a fluorochemical surfactant, silicone type surfactant, or both from a functional viewpoint.

Examples of the fluorine-based surfactants include perfluoroalkyl group-containing carboxylates, perfluoroalkyl group-containing sulfonates, perfluoroalkyl group-containing phosphates, perfluoroalkyl group-containing carboxylic acid esters, and perfluoroalkyl group-containing sulfonic acid esters. Perfluoroalkyl group-containing phosphate esters, perfluoroalkyl group-lipophilic group-containing oligomers, perfluoroalkyl group-hydrophilic group-lipophilic group-containing oligomers, or the perfluoroalkyl group substituted with a perfluoroalkenyl group And the like.

Examples of silicone surfactants include polyether-modified polysiloxanes, polyester-modified polysiloxanes, alkyl-modified polysiloxanes, aralkyl-modified polysiloxanes, higher fatty acid-modified polysiloxanes, epoxy-modified polysiloxanes, amino-modified polysiloxanes, and carboxy-modified polysiloxanes. And organic modified polysiloxanes such as alcohol-modified polysiloxanes and derivatives thereof.

Moreover, surfactant containing both a fluorine atom and a silicon atom can also be used, The fluorinated modified polysiloxane etc. which substituted one part or all hydrogen of the alkyl group of the said silicone type surfactant with fluorine etc. are mentioned.

An active energy ray curable resin composition may also contain a solvent in order to improve the coating property. As a solvent, For example, Aliphatic hydrocarbons, such as hexane and an octane; Aromatic hydrocarbons such as toluene and xylene; Alcohols such as ethanol, 1-propanol, isopropanol and 1-butanol; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; Esters such as ethyl acetate, butyl acetate and isobutyl acetate; Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; It can select suitably from esterification glycol ethers, such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate. These organic solvents may be used independently, and may mix and use various types as needed. Since it is preferable to evaporate and dry a solvent after a coating process and before a (1st) hardening process, it is preferable that the boiling point of a solvent is 60-160 degreeC. Moreover, it is preferable that the saturated vapor pressure in 20 degreeC is the range of 0.1-20 kPa. The kind and content of a solvent are suitably selected according to the kind and content of the active energy ray curable compound to be used, the material, shape of a base film, a coating method, the thickness of the target hard coat layer, etc.

Light-transmitting microparticles | fine-particles can also be added to active energy ray curable resin composition for the purpose of providing an internal haze for reducing a glare. The light-transmitting fine particles are not particularly limited, and conventionally known ones can be used. For example, organic fine particles containing acrylic resin, melamine resin, polyethylene, polystyrene, organic silicone resin, acrylic-styrene copolymer, and the like, calcium carbonate, silica, aluminum oxide, barium carbonate, barium sulfate, titanium oxide, glass, and the like Inorganic fine particles and the like can be used as the light transmitting fine particles. Balloons or glass hollow beads of organic polymers may also be used. These light-transmitting fine particles may be used individually by 1 type, and may mix and use 2 or more types. The shape of the light-transmitting fine particles may be any of spherical, flat, plate, needle and irregular shapes.

The particle diameter and refractive index of the light-transmitting fine particles are not particularly limited, but the particle diameter is preferably in the range of 0.5 µm to 20 µm in terms of effectively expressing internal haze. Moreover, for the same reason, it is preferable that the difference between the refractive index after hardening of active energy ray curable resin, and the refractive index of translucent microparticles | fine-particles is the range of 0.04-0.15. The content of the light-transmitting fine particles is 3 to 60 parts by weight, preferably 5 to 50 parts by weight based on 100 parts by weight of the active energy ray curable resin. When the content of the light transmitting fine particles is less than 3 parts by weight with respect to 100 parts by weight of the active energy ray curable resin, sufficient internal haze for reducing glare is not obtained. On the other hand, when it exceeds 60 weight part, since transparency of a hard coat film may be impaired, and when a hard coat film is arrange | positioned at the visual recognition side in a liquid crystal display device, since light scattering is too strong, for example, black display may be carried out. In this case, the contrast may be lowered due to the fact that light leaking obliquely with respect to the front direction of the liquid crystal panel is strongly scattered in the front direction by the hard coating layer.

The mold is for imparting a desired shape to the surface of the hard coating layer, and has a surface shape including a transfer structure of the desired shape. The surface shape of a mold may be a smooth surface, such as a mirror surface, and may be uneven | corrugated shape for providing anti-glare property to a hard coat film. The uneven pattern may be a regular pattern, or may be a random pattern or a pseudo-random pattern in which one or more random patterns of a specific size are laid tightly, due to interference of reflected light due to the surface shape of the hard coat film. It is preferable that it is a random pattern or a pseudo random pattern from the point which prevents a reflection image from coloring in rainbow color.

The shape of the mold is not particularly limited, and may be a flat plate or a cylindrical or cylindrical roll, but is preferably a cylindrical or cylindrical mold such as a mirror surface roll or an embossing roll in terms of continuous productivity. In this case, a predetermined surface shape is formed on the side of the columnar or cylindrical mold.

The material of the base material of the mold is not particularly limited and can be appropriately selected from metals, glass, carbon, resins, or composites thereof, and metals are preferred in view of workability and the like. Preferred metal materials include aluminum, iron, or an alloy mainly composed of aluminum or iron in terms of cost.

As a method of obtaining a mold, for example, a method of polishing a substrate, sandblasting, electroless nickel plating and then manufacturing a roll die (Japanese Patent Laid-Open No. 2006-53371); A method of subjecting a substrate to copper plating or nickel plating, followed by polishing, sandblasting, and then chromium plating (Japanese Patent Laid-Open No. 2007-187952); A method of carrying out copper plating or nickel plating, followed by polishing, sandblasting, followed by an etching step or a copper plating step, and then performing chromium plating (Japanese Patent Laid-Open No. 2007-237541); After copper plating or nickel plating was performed on the surface of the base material for a mold, polishing was carried out, and a photosensitive resin film was coated and formed on the polished surface, the pattern was exposed on the photosensitive resin film, and then developed, and the developed photosensitive resin film was used as a mask. A method of performing etching treatment, peeling off the photosensitive resin film, and performing etching treatment to blunt the uneven surface, and then to perform chromium plating on the formed uneven surface; And a method for cutting a substrate to be cast by a cutting tool using a machine tool such as a lathe (International Publication No. 2007/077892).

The surface irregularities of the mold including the random pattern or the pseudo random pattern may be, for example, by an FM screen method, a DLDS (Dynamic Low-Discrepancy Sequence) method, a method using a microphase separation pattern of a block copolymer, a band pass filter method, or the like. The produced random pattern can be formed by exposing and developing on the photosensitive resin film, and performing an etching process using the developed photosensitive resin film as a mask.

In the present invention, as a reference, a hard coat layer formed by curing in a gas at 25 ° C. without contacting a mold with a composition having the same composition as the active energy ray-curable resin composition except that one surface of the base film does not contain a surfactant. the measurement of the contact angle θ number _1, and the θ ₁ and the logarithmic contact angle θ of the hard coating layer of the present invention is formed by curing while contact with the active energy ray curable resin composition and the mold satisfies the equation (1). In addition,, θ-θ ₁ referred to in equation (1) is intended to mean the difference between θ and θ _1. When the value of θ-θ ₁ exceeds 10 °, liquid dripping of the coating solution for forming the antireflection layer and nonuniformity of the coating layer are likely to occur, and adhesion of the antireflection layer to the hard coating layer is likely to be low. .

In order to set the value of θ-θ ₁ to 10 ° or less, for example, a method of controlling the temperature of the mold, a method of using a surfactant having a low deterioration in surface tension, a method of lowering the amount of surfactant added, The temperature of the mold can be controlled by controlling the temperature of the mold from the point that a sufficient effect by the addition of the surfactant such as leveling property can be obtained without excessively lowering the amount of the surfactant added, and the production of the mold or the manufacturing apparatus is relatively easy. The method of adjusting the value of (theta)-(theta) ₁ to 10 degrees or less is preferable. Specifically, the value of θ-θ ₁ can be made 10 ° or less by controlling the temperature of the mold to 50 ° C. or more, for example.

Moreover, in this invention, as a reference | standard, of the said hard coat layer in the hard coat film which has a hard coat layer formed by hardening | curing the said active-energy-ray-curable resin composition on the one surface of the said base film, without contacting a mold. It is preferable that the logarithmic contact angle θ ₀ is measured, and the logarithmic contact angle θ of the hard coat layer of the present invention formed by curing θ ₀ and the active energy ray-curable resin composition in contact with the mold is satisfied. In addition, | θ ₀ -θ | in the formula (2) means the absolute value of the difference between θ ₀ and θ. When the value of | θ ₀ -θ | is 13 ° or more, coating defects such as unevenness and splashing when the antireflection layer is laminated, liquid dripping during coating, poor adhesion of the antireflection layer, and the like can be prevented.

<Method of Manufacturing Hard Coating Film>

Next, the manufacturing method of the hard coat film of this invention is demonstrated. The hard coat film of this invention is applied to the process of apply | coating the active energy ray curable resin composition containing an active energy ray curable resin, a polymerization initiator, and surfactant on one side of a base film, and the said active energy ray curable resin composition to 50 Irradiating an active energy ray while contacting a mold with a temperature of at least C, thereby curing the active energy ray-curable resin composition to form a hard coating layer, and a manufacturing method including a step of peeling the hard coating layer from the mold. have. That is, it contains below [1] coating process, [2] hardening process, and [3] peeling process in this order, and it demonstrates in detail below.

[1] coating process

The above-mentioned active energy ray curable resin is coated on one side of the base film mentioned above, and a coating layer is formed. As such coating method, a well-known method can be selected suitably, Specifically, the wire bar coating method, the roll coating method, the gravure coating method, the knife coating method, the slot die coating method, the spin coating method, the spray coating method, the slide coating method , Curtain coating method, inkjet method and the like. Especially, the slot die coating method is preferable at the point which prevents mixing, such as a foreign material in the active-energy-ray-curable resin composition at the time of coating as much as possible.

[2] curing step (first curing step)

Subsequently, an active energy ray is irradiated while contacting the said coating layer with the above-mentioned mold at 50 degreeC or more, and hardening the said coating layer. In addition, the surface shape of the mold is transferred to the coating layer, thereby forming a hard coating layer. In this way, the desired logarithmic contact angle can be obtained by making the contact temperature, that is, the surface temperature of the mold at 50 ° C. or higher and curing it while being in contact with the mold, thereby making it possible to form a hard coat layer suitable for providing an antireflection layer. In addition, about the upper limit of a contact temperature, it selects suitably according to the kind of resin of the base film to be used. Moreover, although contact temperature should just be 50 degreeC or more, it is preferable in the case of 100 degrees C or less.

In order to make contact temperature mentioned above, a heating mechanism may be provided in the said mold, and the said mold may be made into the above-mentioned contact temperature by the heat | fever which generate | occur | produces from the light source which irradiates an active energy ray, without providing such a heating mechanism. As a heating mechanism provided in a mold, for example, a pipe or the like for circulating a fluid to be a heat medium inside the mold, and a method of circulating the fluid by connecting it with a device for heating a fluid outside the mold, And a method of embedding a heating mechanism such as a heating wire in the interior thereof. This heating mechanism makes it possible to heat the surface of the mold, whereby it is adjusted to reach the above-mentioned contact temperature.

In addition, in order to make the above-mentioned contact temperature or to protect from overheating by irradiation of an active energy ray, it is preferable that the said mold is equipped with a cooling mechanism. As such a cooling mechanism, the structure which circulates a refrigerant | coolant is provided, for example by providing a cooling pipe in the inside of a mold, connecting the chiller unit provided in the outside with the cooling pipe inside a mold. This cooling mechanism makes it possible to cool the surface of the mold, whereby it is adjusted to reach the above-mentioned contact temperature.

Although there is no restriction | limiting in particular in the method of contact | adhering a coating layer and a mold, It is preferable to use crimping apparatuses, such as a nip roll, in order to prevent a bubble from mixing between a coating layer and a mold. When using a nip roll, there is no restriction | limiting in particular in nip pressure, Preferably it is 0.05 MPa or more and 1.0 MPa or less. If the nip pressure is less than 0.05 MPa, bubbles easily enter between the coating layer and the mold. On the other hand, when the nip pressure exceeds 1.0 MPa, the base film may break due to slight deviation during conveyance of the base film, or the coating layer may protrude from the end of the base film, which may cause contamination.

As an active energy ray, it can select suitably from gamma rays, X rays, an ultraviolet-ray, near-ultraviolet ray, visible ray, near-infrared ray, an infrared ray, an electron beam, etc. according to the kind of active energy ray curable resin and a polymerization initiator, Among these, an ultraviolet-ray, an electron beam, It is preferable, and ultraviolet rays are preferable from the viewpoint of excellent curability and productivity because of easy handling and high energy.

As a light source of an ultraviolet-ray, 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 arc lamp, etc. can be used, for example, It is not limited to these, The ultraviolet-ray There is no restriction | limiting in particular if it is a light source which generate | occur | produces. ArF excimer lasers, KrF excimer lasers, excimer lamps or synchrotron radiation can also be used. Especially, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a xenon arc lamp, and a metal halide lamp can be used preferably.

As an example of the combination of an ultraviolet irradiation device and a light source for irradiating an ultraviolet-ray, UV irradiation apparatus "F600" and "LH10" made by Fusion UV SYSTEMS company, H valve (mercury lamp equivalency), D valve or V valve (metal halide lamp) Equivalency), "CS series" made by GS Yuasa Kabusikishisha, combination with mercury lamp and metal halide lamp, "QRM-2288" and "QRM-2300" made by Oak Seisakusho The combination with a UV irradiation apparatus, a metal halide lamp, and a high pressure mercury lamp, and the combination with the "Unicure system" by Ushio Denki Kabushiki Kaisha, a metal halide lamp, and a high pressure mercury lamp are mentioned. The ultraviolet irradiation device and the light source may use the same combination individually or in plurality, and may use a plurality of different combinations.

The accumulated light amount in the UVA of the ultraviolet ray is preferably 40 mJ / cm 2 or more, and more preferably 70 mJ / cm 2 or more. When accumulated light amount is less than 40 mJ / cm <2>, hardening of ultraviolet curable resin will become inadequate and uncured ultraviolet curable resin may adhere to a mold. On the other hand, the upper limit of the accumulated light amount is not particularly limited as long as it is within the range of the above-mentioned contact temperature.

The irradiation of ultraviolet rays may be performed only once or may be performed twice or more. In addition, there is no restriction | limiting in particular in the number of light sources (ultraviolet irradiation apparatus) used at a hardening process, One light may be sufficient and two or more light may be sufficient.

[3] peeling process

After the said hardening process, a hard coat film (laminated body of a base film and a hard coat layer) is peeled from a mold. Although it does not restrict | limit especially as a peeling method, For example, when a mold is a roll shape, a crimping device, such as a nip roll, is provided in the separation point of a hard coat film and a mold, and a film is peeled from a mold by this crimping device as a point. The method of making is used preferably. Thereby, peeling of a film from a mold is prevented effectively during irradiation of an active energy ray, and the contact | adherence state of a mold and a film is maintained, and the film which reached the said point can be peeled efficiently and stably.

Thereby, although the hard coat film of this invention can be obtained, it is preferable to irradiate an active energy ray further from the hard coat layer side for the purpose of further promoting the hardening reaction of a hard coat layer. This process is called a 2nd hardening process and it demonstrates below.

[4] second curing step

The active energy ray used in the second curing step can be appropriately selected from gamma rays, X rays, ultraviolet rays, near ultraviolet rays, visible rays, near infrared rays, infrared rays, electron rays, and the like. Among these, ultraviolet rays and electron rays are preferable, and handling is particularly easy. Since it is easy and high energy is obtained, an ultraviolet-ray is preferable from a viewpoint of excellent sclerosis | hardenability and productivity. In addition, it is preferable to use the thing of the same kind as the active energy ray used at the time of the 1st hardening process mentioned above as an active energy ray. When using another kind of active energy ray, it is necessary to use several resin and a polymerization initiator accordingly, and there exists a possibility that the design of a resin composition may become complicated.

As a light source of the ultraviolet irradiation device used for a 2nd hardening process, 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 arc lamp etc. can be used, for example, It is not limited to these, There is no restriction | limiting in particular if it is a light source which generate | occur | produces an ultraviolet-ray. ArF excimer lasers, KrF excimer lasers, excimer lamps or synchrotron radiation can also be used. Especially, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a xenon arc lamp, and a metal halide lamp can be used preferably. The ultraviolet irradiation device and the light source may use the same combination individually or in plurality, and may use a plurality of different combinations.

In addition, the kind of ultraviolet irradiation device and light source used for a 2nd hardening process may be different from the ultraviolet-ray of a 1st hardening process, if it is an ultraviolet-ray which the polymerization initiator contained in a hard coat layer functions effectively. For example, a metal halide lamp may be used in the first curing step, and a high pressure mercury lamp may be used in the second curing step.

The accumulated light amount in the UVA of the ultraviolet ray of the second curing step is preferably 200 mJ / cm 2 or more, and more preferably 300 mJ / cm 2 or more. There is no restriction | limiting in particular about the upper limit of accumulated light quantity.

Irradiation of the ultraviolet ray in the second curing step may be performed only once or may be performed twice or more. In addition, there is no restriction | limiting in particular in the number of the ultraviolet irradiation device and the light source used in a 2nd hardening process, only one light may be sufficient, and two or more light may be sufficient as it. In addition, when irradiating an ultraviolet-ray twice or more in a 2nd hardening process, the said accumulated light quantity is a total value of the said accumulated light quantity with respect to the ultraviolet-ray of a 2nd hardening process.

In a 2nd hardening process, in order to prevent that hardening of active energy ray curable resin is inhibited by oxygen, it is preferable to fill an inert gas between the laminated body containing a base film and a hard coat layer, and an irradiation apparatus. Although an inert gas is suitably selected from nitrogen, argon, neon, etc., nitrogen is preferable at the point of handling simplicity and cost. In addition, the oxygen concentration at that time is preferably 0.1% or less.

There is no restriction | limiting in particular in the specific irradiation method of the active energy ray in a 2nd hardening process, For example, you may irradiate in the state which adhere | attached the base film on the rolls, such as a backup roll, to the hollow part between a guide roll and a guide roll. An active energy ray irradiation apparatus can also be installed and irradiated. In addition, when irradiating an active energy ray 2 or more times, irradiation methods may be the same respectively and may be different irradiation methods. For example, both the first and second times may irradiate an active energy ray using a backup roll, the first may irradiate an active energy ray using a backup roll, and the second may be a hollow between the guide roll and the guide roll. An active energy ray irradiation device may be provided at the portion to irradiate the active energy ray.

In order to prevent the heat damage to a base film and generation | occurrence | production of a thermal wrinkle by an active energy ray, the irradiation method using a backup roll provided with a cooling mechanism is preferable. The surface temperature of the cooled backup roll is generally in the range of 10 ° C to 70 ° C, preferably in the range of 20 ° C to 60 ° C. When using a backup roll, the wrinkle prevention apparatus for preventing wrinkles in a base film may be provided in the inlet side of a 2nd hardening process, or both an inlet side and an outlet side.

The hard coat film of this invention is suitable for providing an antireflection layer. And the film provided with the antireflection layer is used suitably as a protective film of various optical members, for example, a polarizing plate. Moreover, it is possible to use this polarizing plate for an image display apparatus.

<Formation of Anti-reflective Layer>

After coating the active energy ray curable resin for forming an antireflection layer on the surface of the hard coat layer of the hard coat film of this invention, an antireflection layer can be formed by irradiating an active energy ray.

<Formation / coating process of antireflection layer>

The coating method on the base film of the active energy ray curable resin composition for forming an antireflection layer is not specifically limited, A well-known method can be selected suitably. Specifically, a wire bar coating method, a roll coating method, a gravure coating method, a knife coating method, a slot die coating method, a spin coating method, a spray coating method, a slide coating method, a curtain coating method, an inkjet method, etc. are mentioned. Especially, the slot die coating method is preferable at the point which prevents mixing, such as a foreign material in the active-energy-ray-curable resin composition at the time of coating as much as possible.

The antireflection layer is usually a layer having a lower refractive index than the hard coating layer. The refractive index of the antireflection layer is preferably in the range of 1.2 to 1.45, and more preferably in the range of 1.25 to 1.4. As active energy ray curable resin for forming such an antireflection layer, the thing containing a silica fine particle and a binder is mentioned, for example.

As for the silica fine particles, from the viewpoint of making the refractive index of the antireflection layer lower than the refractive index of the hard coating layer, it is more preferable to use hollow silica fine particles having a cavity inside. Moreover, the range of 50-200 nm is preferable, and, as for the average particle diameter of a silica fine particle, it is more preferable that it is 60-150 nm. When the average particle diameter is less than 50 nm, the effect of lowering the refractive index of the antireflection layer may not be sufficient. On the other hand, if the thickness exceeds 200 nm, the strength of the antireflection layer may decrease, or irregularities may be formed on the surface of the antireflection layer, resulting in a white light.

As the binder included in the antireflection layer, a silane coupling agent which is an organosilane having hydrolyzability is preferably used in view of compatibility of silica fine particles in active energy ray-curable resin and the like. Examples of such a silane coupling agent include, for example, methoxysilane, dimethoxysilane, trimethoxysilane, tetramethoxysilane, methylmethoxysilane, ethylmethoxysilane, propyltrimethoxysilane, dimethylmethoxysilane, dimethyl Methoxysilanes and derivatives thereof, such as dimethoxysilane, diethyldimethoxysilane, and phenyltrimethoxysilane, ethoxysilane, diethoxysilane, triethoxysilane, tetraethoxysilane, methylethoxysilane, ethylethoxy Ethoxysilanes and derivatives thereof such as silane, propyltriethoxysilane, dimethylethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, and phenyltriethoxysilane. Moreover, silanol which is a hydrolyzate of a silane coupling agent, and siloxane which is a condensate of silanol can also be used.

More preferably, the binder is an organosilane having an unsaturated bond which is a polymerizable functional group. As organosilanes which have such a polymerizable functional group, what has vinyl groups, such as vinyl trimethoxysilane, vinyl triethoxysilane, vinyl triacetoxysilane, and vinyl trichlorosilane, 3- (meth) acryloxypropyl trimeth (Meth) acryloyl groups, such as oxysilane, 3- (meth) acryloxypropyl triethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, and 3- (meth) acryloxypropylmethyl diethoxysilane The thing which has (meth) acrylamide groups, such as what has, 3- (meth) acrylamino-propyl trimethoxysilane, and 3- (meth) acrylamide-propyl triethoxysilane, etc. is mentioned.

In addition, in view of lowering the refractive index, one containing fluoroalkylsilanes in which hydrogen of the alkyl group in the binder is substituted with fluorine may be used.

In addition, these organosilanes may be used independently or may be used in mixture of multiple things.

As said active energy ray curable resin composition, it is an active energy ray curable resin composition which forms the hard-coat layer mentioned above, and contains additives, such as active energy ray curable resin, a polymerization initiator, and surfactant added as needed as mentioned above. Can be used.

The said active energy ray curable resin composition may contain a solvent in order to improve the coating property. As a solvent, For example, Aliphatic hydrocarbons, such as hexane and an octane; Aromatic hydrocarbons such as toluene and xylene; Alcohols such as ethanol, 1-propanol, isopropanol and 1-butanol; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; Esters such as ethyl acetate, butyl acetate and isobutyl acetate; Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; It can select suitably from esterification glycol ethers, such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate. These organic solvents may be used independently, and may mix and use various types as needed. Since it is preferable to evaporate and dry a solvent after a coating process and before a (1st) hardening process, it is preferable that the boiling point of a solvent is 60-160 degreeC. Moreover, it is preferable that the saturated vapor pressure in 20 degreeC is the range of 0.1-20 kPa. The kind and content of a solvent are suitably selected according to the kind and content of the active energy ray curable compound to be used, the material of a base film and a hard-coat layer, a shape, a coating method, the thickness of the antireflection layer made into the objective, etc.

<Formation / hardening process of antireflection layer>

In the hardening process at the time of forming an antireflection layer, after apply | coating the above-mentioned active-energy-ray-curable resin composition to the surface of the hard-coat layer of a hard coat film normally, an active energy ray is irradiated from the said coating surface side, hardening a coating layer, and reflecting The prevention layer is formed.

As said active energy ray, it can select suitably from gamma rays, X-rays, an ultraviolet-ray, a near-ultraviolet ray, a visible ray, a near-infrared ray, an infrared ray, an electron beam, etc. according to the kind of active energy ray curable resin and a polymerization initiator, among these, an ultraviolet-ray, an electron beam This is preferable. In particular, ultraviolet rays are preferred from the viewpoint of excellent curability and productivity because of easy handling and high energy.

As a light source of an ultraviolet-ray, 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 arc lamp, etc. can be used, for example, It is not limited to these, The ultraviolet-ray There is no restriction | limiting in particular if it is a light source which generate | occur | produces. ArF excimer lasers, KrF excimer lasers, excimer lamps or synchrotron radiation can also be used. Especially, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a xenon arc lamp, and a metal halide lamp can be used preferably.

As an example of the combination of an ultraviolet irradiation device and a light source for irradiating an ultraviolet-ray, UV irradiation apparatus "F600" and "LH10" made by Fusion UV SYSTEMS company, H valve (mercury lamp equivalency), D valve or V valve (metal halide lamp) Equivalency), "CS series" made by GS Yuasa Kabusikishisha, combination with mercury lamp and metal halide lamp, "QRM-2288" and "QRM-2300" made by Oak Seisakusho The combination with a UV irradiation apparatus, a metal halide lamp, and a high pressure mercury lamp, and the combination with the "Unicure system" by Ushio Denki Kabushiki Kaisha, a metal halide lamp, and a high pressure mercury lamp are mentioned. The ultraviolet irradiation device and the light source may use the same combination individually or in plurality, and may use a plurality of different combinations.

The accumulated light amount in the UVA of the ultraviolet ray is preferably 200 mJ / cm 2 or more, and more preferably 400 mJ / cm 2 or more. If the accumulated light amount is less than 200 mJ / cm 2, the antireflection layer is hardly cured sufficiently, which is not preferable.

In order to prevent the hardening of the said active energy ray curable resin from being inhibited by oxygen, it is preferable to perform the said hardening process in inert gas atmosphere. Although an inert gas is suitably selected from nitrogen, argon, neon, etc., nitrogen is preferable at the point of handling simplicity and cost. In addition, the oxygen concentration at that time is preferably 0.1% or less.

The irradiation of ultraviolet rays may be performed only once or may be performed twice or more. In addition, there is no restriction | limiting in particular in the number of light sources (ultraviolet irradiation apparatus) used at a hardening process, One light may be sufficient and two or more light may be sufficient.

Thereby, the laminated body provided with the antireflection layer in the surface of the hard coat layer of the hard coat film mentioned above can be obtained. In addition, formation of an antireflection layer can also be performed simultaneously with formation of a hard-coat layer.

<Polarizing plate>

The polarizing plate of this invention has the hard coat film of this invention, and the polarizing film laminated | stacked on the other surface of the said base film of the said hard coat film. Moreover, the polarizing plate of this invention is a laminated body provided with the hard coat film of this invention, the reflection prevention layer laminated | stacked on the surface of the said hard coat layer of the said hard coat film, and the other surface of the said base film of the said laminated body. It has a laminated polarizing film.

The polarizing film here has a function which takes out linearly polarized light from incident light, The kind is not specifically limited. As an example of a preferable polarizing film, the polarizing film in which the dichroic dye is adsorption-oriented to polyvinyl alcohol-type resin is mentioned. As polyvinyl alcohol-type resin, in addition to polyvinyl alcohol which is a saponified substance of vinyl acetate, the partially formalized polyvinyl alcohol, the saponified substance of ethylene / vinyl acetate copolymer, etc. are mentioned. As a dichroic dye, iodine or a dichroic organic dye is used. Moreover, the polyene oriented film of the dehydration process of polyvinyl alcohol, and the dehydrochlorination process of polyvinyl chloride can also be a polarizing film. The thickness of a polarizing film is about 5-80 micrometers normally.

The polarizing plate of this invention may laminate | stack the laminated body in which the anti-reflective layer was provided in the surface of the hard coat film of this invention or the hard coat layer of the said hard coat film on one side or both surfaces (usually one side) of the said polarizing film, The transparent protective layer may be laminated on one side of the polarizing film, and the hard coat film or the laminate of the present invention may be laminated on the other side. At this time, a hard coat film or the said laminated body also has a function as a transparent protective layer of a polarizing film. When the surface uneven | corrugated shape is provided to the hard coat film or the hard coat layer of the said laminated body, this hard coat layer also has a function as an anti-glare layer. A transparent protective layer is laminated | stacked by the method of bonding a film using an adhesive agent etc., the method of apply | coating a coating liquid, etc. Similarly, the hard coat film of the present invention can be bonded to a polarizing film using an adhesive or the like.

It is preferable that a transparent protective layer is excellent in transparency, mechanical strength, thermal stability, moisture shielding property, etc. As these, For example, Cellulose resins, such as cellulose acetates, such as a triacetyl cellulose, a diacetyl cellulose, a cellulose acetate propionate; Polycarbonate resin; (Meth) acrylic resins such as polyacrylate and polymethyl methacrylate; Polyester-based resins such as polyethylene terephthalate and polyethylene naphthalate; Linear polyolefin resins such as polyethylene and polypropylene; Cyclic polyolefin resins; Styrene resins; Polysulfones; Polyethersulfones; The film which consists of polyvinyl chloride, etc. is illustrated. These films may be optically isotropic or they may be optically anisotropic for the purpose of compensating for a wide viewing angle when assembled to an image display device.

When manufacturing the liquid crystal panel by arranging the polarizing plate of the present invention on the liquid crystal cell, when the polarizing plate is disposed on one side or both sides of the liquid crystal cell, the polarizing film is more than the hard coating layer (or antiglare layer) of the polarizing plate of the present invention. The polarizing plate is arranged to approach. At this time, the polarizing plate may be disposed on the viewing side, or may be disposed on the backlight side, or both. When arrange | positioning a polarizing plate at the visual recognition side, a hard coat layer prevents the flaw etc. which arises from an external force, and when it also functions as an anti-glare layer, prevents glare and the reflection of external light. On the other hand, when the polarizing plate is disposed on the backlight side, the hard coat layer prevents scratches due to external force that may occur in the assembling process of the liquid crystal panel, for example, a scratch due to contact with a diffusion plate, and also serves as an antiglare layer. In the case of functioning, it serves as a diffusion plate which prevents moire and the like against light incident on the liquid crystal panel from the backlight.

<Image display device>

The image display apparatus of this invention combines the laminated body in which the anti-reflective layer was provided in the surface of the hard coat film or hard coating layer manufactured by the method of this invention, and the image display apparatus which casts various information on a screen. . In the image display device of the present invention, the type of the image display device is not particularly limited, and in addition to the liquid crystal display (LCD) using the liquid crystal panel, a cathode ray tube (cathode ray tube: CRT) display, a plasma display (PDP), an electrolytic emission display ( FED), a surface conduction electron emission element display (SED), an organic electroluminescent display, a laser display, the screen of projector television, etc. are mentioned.

It is preferable that the hard coat film or laminated body which concerns on this invention is arrange | positioned at the visual side of the image display element of these displays, In this case, as an image display apparatus, it comprises a polarizing plate and an image display element, The said polarizing plate is the said hard board It is arrange | positioned at the visual recognition side of the said image display element so that the said polarizing film side may be closer to the said image display element rather than a coating layer. However, the hard coat film according to the present invention may be inserted into the image display device, as in the case of being disposed on the backlight side of the image display element. Since the image display apparatus of the present invention includes the hard coat film according to the present invention, scratches are less likely to occur and have excellent strength.

1 is a schematic cross-sectional view showing an example of a basic layer structure of the image display device of the present invention. The image display device 100 shown in FIG. 1 includes a backlight 10, a light diffusion plate 50, and a liquid crystal panel 60 in this order. The liquid crystal panel 60 visually recognizes the image display element 40, the polarizing plate 20 arranged on the backlight side of the image display element 40 (the negative direction of the z-axis in FIG. 1), and the image display element 40. The polarizing plate 3 arrange | positioned at the side (plus direction of the z-axis in FIG. 1) is provided. The polarizing plate 3 arrange | positioned at the visual recognition side of the image display element 40 is equipped with the laminated body 32 and the polarizing film 33. As shown in FIG. The laminate 32 includes a hard coat film 31 and an antireflection layer 320. The hard coat film 31 includes a base film 312 and a hard coat layer 311 laminated on one side of the base film 312, and a polarizing film 33 is formed on the other side of the base film 312. Are stacked. In the image display apparatus 100, the polarizing plate 3 is disposed on the visual side of the image display element 40 so that the polarizing film 33 is closer to the image display element 40 than the hard coating layer 311. The vertical line of the light exit surface of the backlight 10 is substantially parallel to the Z axis. In addition, the vertical lines of the light incident surface of the light diffusion plate 50, the polarizing plate 20, the image display element 40, and the polarizing plate 3 are substantially parallel to the Z axis.

The hard coat film 31 of this invention used for the polarizing plate 3 of the image display apparatus 100 of this invention is the base film 312 and the hard coat layer 311 laminated | stacked on one side of the base film 312. And the hard coat layer 311 is formed by curing the active energy ray curable resin composition containing the active energy ray curable resin, the polymerization initiator and the surfactant while contacting with the mold, and the logarithmic contact angle θ of the hard coat layer 311 is The above Equation 1 is satisfied. This hard coat film 31 of the present invention is suitable for providing the antireflection layer 320.

In addition, the image display apparatus of this invention is not limited to the structure shown in FIG. 1, A various deformation | transformation can be added. For example, a polarizing plate 30 having a hard coating film 31 and a polarizing film 33 and not having an antireflection layer 320 may be used in place of the polarizing plate 3. Moreover, the polarizing plate 20 arrange | positioned at the backlight side of the image display element 40 may be the polarizing plate 3 or 30 provided with the hard coat film 31 of this invention, In that case, the polarizing plate 3 or The 30 may be disposed on both the viewing side and the backlight side of the image display element 40, or may be disposed only on one side of the backlight side. In the case where the polarizing plate 3 or 30 is disposed on the backlight side, the polarizing film 33 is displayed on the polarizing film 33 rather than the hard coating layer 311 so that the hard coating layer 311 is on the backlight side with respect to the polarizing film 33. It is preferable to arrange the polarizing plate 3 or 30 so as to be close to the element 40. In addition, the light diffusion plate 50 and the backlight 10 are not necessarily required and may be omitted.

EXAMPLES Hereinafter, although an Example is described and this invention is demonstrated further more concretely, this invention is not limited by these examples.

[Measurement of Logarithmic Contact Angle of Hard Coating Film]

About the hard coat film mentioned later, the logarithmic contact angle was measured using the Kyowa Kaimen Chemical Co., Ltd. make, contact angle meter, and CA-X type.

Example 1

The following ultraviolet curable resin composition was used as an active energy ray curable resin composition.

Ultraviolet curable resin: Brand name "NK hardware KCR2803-50A"

(The urethane acrylate resin, the resin solid content concentration: 60 weight%, dilution solvent: ethyl acetate, a polymerization initiator: TPO (chemical name: 2,4, 6- trimethyl benzoyl diphenyl phosphine oxide) by Shin-Nakamura Chemical Co., Ltd. make) ) Is contained 5.0 wt% with respect to the resin solid content of the ultraviolet curable resin composition.)

Surfactant: Trade name "Megapack F-477"

(Added so that it may become 0.5 weight% with respect to the resin solid content of a perfluoroalkyl group, a hydrophilic group, a lipophilic group containing oligomer, and an ultraviolet curable resin composition.)

On a 80-micrometer-thick triacetyl cellulose (TAC) film (trade name "TDY80UL", manufactured by Fuji Film Co., Ltd.), the film after drying with a die coater was applied so as to have a thickness of 5 µm, and 20 in a dryer set at 60 ° C. Dried for seconds. Next, the laminated body of the obtained TAC film and the coating layer of an ultraviolet curable resin composition was pressed to the embossing roll which controlled the surface temperature to 54 degreeC with the nip roll so that a coating layer might become the embossing roll side, and it adhered closely. In this state, an ultraviolet-ray is irradiated once from the TAC film side using an oak-made UV irradiation apparatus as an ultraviolet irradiation apparatus, and a metal halide lamp as a light source so that accumulated light quantity of UVA may be 200 mJ / cm <2>, and coating The layer was cured to form a hard coat layer.

Next, after peeling a TAC film from the embossing roll of a hard-coat layer, it accumulates UVA with respect to a laminated body using the UV irradiation apparatus by Oak Corporation as an ultraviolet irradiation apparatus, and a high pressure mercury lamp as a light source from a hard-coat layer side. Ultraviolet rays were irradiated once so that the light amount was 500 mJ / cm 2, thereby preparing a hard coat film. Table 1 shows the logarithmic contact angle θ of the hard coat layer in the film.

[Examples 2 and 3 and Comparative Example 1]

A hard coat film was prepared in the same manner as in Example 1 except that the surface temperature of the embossing roll was changed as shown in Table 1. Table 1 shows the logarithmic contact angle θ of the hard coat layer in these films.

Antireflection layer

The following ultraviolet curable resin composition was used as an antireflection layer.

Ultraviolet curable resin composition: Brand name "Offstar TU2276"

(JSR Co., Ltd. make and use the above-mentioned ultraviolet curable resin composition by diluting with methyl isobutyl ketone so that a non-volatile component may be 3%)

The ultraviolet curable resin composition which becomes an antireflection layer was apply | coated to the hard coat film manufactured by the Example and the comparative example, and it dried for 1 minute in the drying furnace set to 80 degreeC. Subsequently, with respect to the laminate of the obtained hard coat film and the antireflection layer, the accumulated light amount of UVA was 400 mJ / cm from the antireflection layer side using a UV irradiation device manufactured by Fusion as an ultraviolet irradiation device and a high pressure mercury lamp as the light source. Ultraviolet rays were irradiated once so as to be ² , and the coating layer was cured to form a hard coat layer. Observing the obtained antireflection layer laminated | multilayer film visually, the thing with a weak nonuniformity and the thing with strong nonuniformity were made into x.

[Reference sample 1]

Except the surfactant from the active energy ray-curable resin composition of Example 1, and the resin composition was hard-coated in the same manner as in Example 1 except that the resin composition was cured under room temperature (25 ° C) and in an air atmosphere without contacting the embossing roll. A film was prepared. Table 1 shows the logarithmic contact angle θ ₁ of the hard coat layer in the film.

[Criteria sample 2]

A hard coat film was produced in the same manner as in Example 1, except that the resin was cured in a room temperature (25 ° C.) and air atmosphere without being brought into contact with the embossing roll. Table 1 shows the logarithmic contact angle θ ₀ of the hard coat layer in the film.

Since the hard coat film of this invention satisfy | fills said Formula (1), the liquid dripping of the coating liquid for forming an antireflection layer, the nonuniformity of a coating layer, and the fall of adhesiveness can be suppressed.

10: backlight
3, 20, 30: polarizer
31: hard coated film
32: laminate
311: hard coating layer
312: base film
320: antireflection layer
33: polarizing film
40: image display element
50: light diffuser plate
60: liquid crystal panel
100: liquid crystal display

Claims (11)

A hard coating film comprising a base film and a hard coating layer laminated on one side of the base film, and for providing an antireflection layer on the surface of the hard coating layer,
The hard coating layer is formed by curing an active energy ray curable resin composition containing an active energy ray curable resin, a polymerization initiator, and a surfactant while contacting with a mold,
A hard coat film in which the logarithmic contact angle θ of the hard coat layer satisfies the following formula (1).
<Equation 1>

(Wherein θ ₁ is a hard surface formed by curing in a gas at 25 ° C. without contacting the mold with a composition having the same composition as the active energy ray-curable resin composition, except that one surface of the base film does not contain a surfactant) Logarithmic contact angle of the coating layer) The hard coat film of claim 1, wherein the logarithmic contact angle θ satisfies Equation 2 below.
&Quot; (2) &quot;

(Wherein θ ₀ represents the logarithmic contact angle of the hard coat layer formed by curing the active energy ray-curable resin composition on a surface of the base film in a gas at 25 ° C. without contacting the mold) The hard coat film of claim 1, wherein the surfactant is a fluorine-based surfactant and / or a silicone-based surfactant. A step of coating an active energy ray curable resin composition containing an active energy ray curable resin, a polymerization initiator, and a surfactant on one side of the base film;
Irradiating active energy rays while contacting the coated active energy ray curable resin composition with a mold having a temperature of 50 ° C. or higher to cure the active energy ray curable resin composition to form a hard coating layer;
A method for producing a hard coat film comprising the step of peeling the hard coat layer from the mold. The method according to claim 4, wherein the mold is a mirror roll or an embossing roll. The laminated body provided with the hard coat film as described in any one of Claims 1-3, and the reflection prevention layer laminated | stacked on the surface of the said hard coat layer of the said hard coat film. The laminated body provided with the hard coat film manufactured by the method of Claim 4, and the anti-reflective layer laminated | stacked on the surface of the said hard coat layer of the said hard coat film. The polarizing plate provided with the hard coat film as described in any one of Claims 1-3, and the polarizing film laminated | stacked on the other surface of the said base film of the said hard coat film. The polarizing plate provided with the hard coat film manufactured by the method of Claim 4 or 5, and the polarizing film laminated | stacked on the other surface of the said base film of the said hard coat film. The polarizing plate provided with the laminated body of Claim 6 or 7, and the polarizing film laminated | stacked on the other surface of the said base film of the said laminated body. The polarizing plate of any one of Claims 8-10, and an image display element are provided,
The said polarizing plate is arrange | positioned at the visual recognition side of the said image display element so that the said polarizing film may be closer to the said image display element rather than the said hard coat layer.

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