TWI391251B - A method for manufacturing an anti-glare hard coat film - Google Patents

Description

Method for manufacturing anti-glare hard coating film

The present invention relates to an antiglare hard coating film. More specifically, an anti-glare hard coating film which imparts excellent anti-glare properties without degrading high-precision display image quality, and is used in various displays such as a liquid crystal display (LCD), a plasma display (PDP), Cathode ray tube (CRT), and when used as a touch panel or the like, has good visibility (high photographic brightness), can increase surface hardness, and is suitable as a surface protective film.

In displays such as CRTs and liquid crystal displays, light is incident from the outside of the screen, and this light is reflected (called glare or glare, etc.), and it is difficult to see the displayed image, especially in recent years, with the large size of the display. To solve the above problems has become an increasingly important issue.

In order to solve such a problem, various anti-glare treatments have been performed on various displays so far. For example, in the liquid crystal display, an anti-glare treatment for roughening the surface of the hard coating film used for the polarizer and various hard coating films for display protection is performed. The anti-glare treatment method of such a hard coating film can be generally classified into (1) a method of roughening a surface using a physical method in forming a hard coating layer, and (2) a hard coating agent for forming a hard coating layer. There are two main types of methods for mixing fillers.

Among the two methods, the latter is a mainstream method in which a filler is mixed in a hard coating, and as a filler, vermiculite particles are mainly used. The reason why the vermiculite particles are used is that the whiteness of the obtained hard coating film can be suppressed from being lowered, the hardness is not lowered, and the dispersibility is good when the coating agent is mixed.

However, when the liquid crystal display body is high-precision, for example, when the conventional non-high-precision hard coating film (feeling rough) is used as the anti-glare hard coating film, the liquid crystal display body has a high-definition angle. It also has the problem that its image quality will inevitably fall. Therefore, in order to obtain high image quality of a high-precision liquid crystal display, it is necessary to have a high-precision anti-glare hard coating film.

In the conventional antiglare hard coating film, vermiculite particles having an average particle diameter of about 1 to 2.5 μm are usually used. Such a vermiculite particle is excellent in anti-glare property, but it cannot be adapted to a high-precision liquid crystal display body in recent years, and the display image quality is lowered.

Actually, in such an antiglare hard coating film in which vermiculite particles having an average particle diameter of 1 to 2.5 μm are used as a filler alone, no painting of a highly precise liquid crystal display body in recent years has been found. A hard coating film which is degraded in quality and imparts excellent anti-glare properties.

Therefore, a method of containing a colloidal vermiculite particle agglomerate in a hard coating layer (see, for example, Patent Document 1) has been attempted, and a combination of vermiculite particles having an average particle diameter of 0.5 to 5 μm and an average particle diameter are combined in the hard coating layer. A method of fine particles of 1 to 60 nm (see, for example, Patent Document 2), but it is necessary to further improve the sharpness.

Further, a scratch-resistant antiglare film formed by forming an antiglare layer composed of a resin pellet having a refractive index of 1.40 to 1.60 and an ionizing radiation curable resin composition on a transparent substrate is disclosed (see, for example, Patent Document 3). . In such an anti-glare film, as a preferred resin pellet, polymethyl methacrylate pellets having a particle diameter of 3 to 8 μm, polycarbonate beads, polystyrene beads, and polypropylene styrene are used. In addition, in order to prevent sedimentation of these resin spheres in the coating agent, less than 0.1 part by weight of a crucible having a particle diameter of 0.5 μm or less is added per 100 parts by weight of the ionizing radiation curable resin. Stone ball.

As described above, in the above publication, in order to impart anti-glare property, a typical resin pellet having a relatively large particle diameter is dispersed in the antiglare layer, but the scratch resistance of the antiglare layer is not necessarily sufficiently good.

[Patent Document 1] JP-A-2002-36452 [Patent Document 3] JP-A-6-18706

The present invention has been made in view of the above circumstances, and an object of the invention is to provide an anti-glare hard coating film which can provide excellent anti-glare properties without deteriorating high-precision display image quality, good visibility for various displays, and high surface hardness. Suitable as a surface protection film.

The inventors of the present invention conducted research on the anti-glare hard coating film having excellent properties as described above, and found that it was used by laser diffraction. In the particle size distribution of the particle size distribution measured by the scattering method, the active energy ray-curable resin composition of the vermiculite particles having a peak particle diameter of 4 μm or less in each of the two ranges forms a hard coating film, and the object can be achieved. Based on this finding, the present invention has been completed.

That is, the present invention provides: (1) an anti-glare hard coating film characterized by having a cured film formed of an active energy ray-curable resin composition containing vermiculite particles on at least one side of a substrate film. a hard coating formed by the object, and the vermiculite particles in the above composition are laser diffraction. The particle size distribution in the particle size distribution measured by the scattering method has a peak value and a mean particle diameter of 4 μm or less in the range of 0.1 to 1 μm and 1.5 to 5 μm, respectively, and the content of the vermiculite particles is based on the solid content of the above composition (2) an anti-glare hard coating film characterized in that the photographic brightness of the anti-glare hard coating film according to (1) has a value of 100 or more; (3) The anti-glare hard coating film according to the above item (1) or (2), which contains a laser diffraction. The active energy ray-curable resin composition of the vermiculite particles each having a peak diameter and an average particle diameter of 4 μm or less in the particle size distribution measured by the scattering method in the range of 0.1 to 1 μm and 1.5 to 5 μm by the scattering method The meteorite particles have a large average particle size and are diffracted by a laser. The active energy ray-curable resin composition of vermiculite particles having a peak in the particle size distribution determined by the scattering method has pulverization by utilizing shear force. Dispersing the function of the machine to crush. Dispersion treatment, the average particle size ratio of vermiculite particles is pulverized. (4) The anti-glare hard coating film according to the above item (1), (2) or (3), wherein the arithmetic mean roughness Ra of the hard coating layer is The anti-glare hard coating film according to any one of the above-mentioned (1), wherein the hard coating layer has a thickness of 0.5 to 20 μm.

According to the present invention, it is possible to provide an anti-glare hard coating film which can provide excellent anti-glare properties without deteriorating high-precision display image quality, and has good visibility (high photographic brightness) for various displays, and It has a large surface hardness and is suitable as a surface protective film.

In the anti-glare hard coating film of the present invention, the substrate is not particularly limited, and can be appropriately selected from those conventionally known as optical hard coating film substrates. Examples of such a plastic film include a polyester film such as polyethylene terephthalate, polybutylene terephthalate or polyethylene naphthalate, a polyethylene film, a polypropylene film, and celluloid. Diacetyl cellulose film, triethylene glycol cellulose film, acetonitrile cellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate film, polyphenylene Vinyl film, polycarbonate film, polymethylpentene film, polyfluorene film, polyetheretherketone film, polyether fluorene film, polyether quinone film, polyimine film, fluororesin film, polyfluorene An amine film, an acrylic resin film, a norbornene resin film, a cycloolefin resin film, or the like.

These base material films may be transparent or translucent, and may be colored or colorless, and may be appropriately selected according to the intended use. For example, when used as a protective layer for a liquid crystal display, a colorless and transparent film is suitable.

The thickness of these base film is not particularly limited and may be appropriately selected depending on the case, and is usually in the range of 15 to 300 μm, preferably 30 to 200 μm. Further, the base film is intended to improve the adhesion to the layer provided on the surface thereof, and may be subjected to surface treatment on one or both sides by an oxidation method, a roughening method, or the like as necessary. Examples of the oxidation method include a charge discharge treatment, a chromic acid treatment (wet method), a flame treatment, a hot air treatment, and ozone. For the embossing method, for example, a blasting method, a solvent treatment method, or the like is exemplified. These surface treatment methods can be appropriately selected depending on the type of the base film. Generally, the electric discharge treatment method is preferably used from the viewpoints of effects and workability.

The antiglare hard coating film of the present invention has a hard coating layer composed of a cured product formed on at least one surface of the base film by using an active energy ray curable resin composition containing vermiculite particles.

The active energy ray-curable resin composition is a composition containing an active energy ray-curable polymerizable compound, vermiculite particles, a photopolymerization initiator as needed, and various other additives.

In addition, the active energy ray-curable polymerizable compound is a polymerizable compound which is crosslinked and cured by irradiation of an ultraviolet ray or an electron beam which is an internal energy ray which is an electromagnetic wave or a charged particle beam.

Examples of such an active energy ray-curable polymerizable compound include an active energy ray-polymerizable prepolymer and/or an active energy ray-polymerizable monomer. The above-mentioned active energy ray-polymerizable prepolymer includes a radical polymerization type and a cationic polymerization type, and examples of the radical polymerization type active energy ray-polymerizable prepolymer include polyester acrylates, cyclochloro acrylates, and amine groups. Formate acrylates, polyol acrylates, and the like.

Here, as the polyester acrylate-based prepolymer, for example, a hydroxyl group of a polyester oligomer having a hydroxyl group at both terminals obtained by condensing a polyvalent carboxylic acid and a polyhydric alcohol can be esterified with (meth)acrylic acid, or The terminal hydroxyl group of the oligomer obtained by adding a carboxylic acid to an alkylene oxide is obtained by esterification with (meth)acrylic acid. The cyclochloroacrylate prepolymer can be obtained, for example, by esterification of an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or a novolac type epoxy resin with (meth)acrylic acid. The polyurethane acrylate type prepolymer can be esterified with (meth)acrylic acid by, for example, a polyurethane oligomer obtained by reacting a polyether polyol or a polyester polyol with a polyisocyanate. And made. Further, the polyol acrylate prepolymer can be obtained by esterifying a hydroxyl group of a polyether polyol with (meth)acrylic acid. These activated energy ray-polymerizable prepolymers may be used alone or in combination of two or more.

On the other hand, as the cationic polymerization type active energy ray-polymerizable prepolymer, an epoxy resin is usually used. Examples of the epoxy resin include a compound in which a polyphenol such as a bisphenol resin or a phenol resin is epoxidized with epichlorohydrin or the like, and a linear olefin compound or a cyclic olefin compound is oxidized with a peroxide or the like. The obtained compound or the like.

Further, examples of the active energy ray-polymerizable monomer include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and neopentyl glycol di(a). Acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, two Cyclopentyl di(meth) acrylate, caprolactone modified dicyclopentenyl di(meth) acrylate, ethylene oxide modified di(meth) acrylate, allylate ring Hexyl bis (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, diisopentaerythritol tri (meth) acrylate, propionic acid Modified diisoprolol tri(meth)acrylate, isoamyl alcohol tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, tris(propylene)醯oxyethyl)isocyanurate, propionic acid modified diisopentaerythritol penta (meth) acrylate, diisopentaerythritol hexa(meth) acrylate, caprolactone modified bis Isopentenol hexa(meth) acrylate, etc. Polyfunctional acrylate. These activated energy ray-polymerizable monomers may be used singly or in combination of two or more kinds, and may be used in combination with the above-mentioned active energy ray-polymerizable prepolymer.

In addition, as the photopolymerization initiator to be used, the photopolymerizable prepolymer or the photopolymerizable monomer of the radical polymerization type in the active energy ray polymerizable prepolymer or the monomer may, for example, be benzoin , benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylamino acetophenone, 2,2-two Methoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholine-propan-1-one, 4-(2-hydroxyethoxy)phenyl- 2-(hydroxy-2-propyl)ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylindole, 2-ethyl hydrazine, 2-tert-butyl fluorene, 2-amino hydrazine, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2 , 4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethylketal, acetophenone dimethylcondensate Ketone, p-dimethylamino benzoate, and the like. In addition, examples of the photopolymerization initiator include a ruthenium ion such as an aromatic ruthenium ion, an aromatic oxonium ion, or an aromatic iodonium ion, and a tetrafluoroborate or a hexafluorophosphoric acid. a compound composed of an anion such as a salt, a hexafluoroantimonate or a hexafluoroarsenate. These may be used singly or in combination of two or more kinds, and the amount thereof is usually in the range of 0.2 to 10 parts by weight based on 100 parts by weight of the photopolymerizable prepolymer and/or the photopolymerizable monomer. select.

In the present invention, the vermiculite particles contained in the active energy ray curable resin composition are used in laser diffraction. The particle size distribution measured by the scattering method has a peak diameter of 0.1 to 1 μm, preferably 0.2 to 1 μm, more preferably 0.3 to 1 μm and 1.5 to 5 μm, and a vermiculite particle having an average particle diameter of 4 μm or less.

By using vermiculite particles having such a particle size distribution and an average particle diameter, high-precision display image quality is not lowered, excellent anti-glare property can be imparted, and visibility is improved when used in various displays (photographic sharpness is increased) ). The average particle diameter is usually 0.3 to 4 μm, preferably 0.5 to 3 μm.

The active energy ray-curable resin composition containing the vermiculite particles having the above particle size distribution and average particle diameter can be, for example, made to have a larger average particle diameter than the target vermiculite particles and is irradiated by a laser. The active energy ray curable resin composition of vermiculite particles having one peak in the particle size distribution determined by the scattering method has pulverization by utilizing shear force. Dispersing the function of the machine to crush. Dispersion treatment, the average particle size ratio of vermiculite particles is pulverized. It is obtained by 0.5 μm or more before the dispersion treatment.

As the above-mentioned shearing force has pulverization. For the dispersing function machine, a machine with high shear force such as a roller honing machine, a bead mill, a jet mill or the like can be used.

By pulverizing with such a machine with high shear. The dispersion treatment causes the vermiculite particles to have the above particle size distribution and average particle diameter. The meteorite particles are diffracted by a laser. The specific surface area measured by the scattering method is usually 20,000 cm ² /cm ³ or more.

In addition, for laser diffraction. The scattering method will be described later.

The vermiculite particles used in the present invention may be treated with an organic surface treatment agent or may be untreated. As the organic surface treatment agent, a decane coupling agent, an anthrone oil, an anthrone wax or the like can be used.

Examples of the decane-based coupling agent include triethoxydecane, vinyltris(β-methoxyethoxy)decane, γ-methylpropenyloxypropyltrimethoxydecane, and γ-epoxy. Propoxypropyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, N-β-(aminoethyl)-γ-aminopropyltrimethoxydecane , N-β-(Aminoethyl)-γ-aminopropylmethyldimethoxydecane, γ-aminopropyltriethoxydecane, N-phenyl-γ-aminopropyltrimethyl Oxydecane, γ-mercaptopropyltrimethoxydecane, γ-chloropropyltrimethoxydecane, and the like. Among them, amino decanes such as γ-aminopropyltriethoxydecane and N-β-(aminoethyl)-γ-aminopropyltrimethoxydecane are preferred.

The method of treating the vermiculite particles with the above surface treatment agent is not particularly limited, and any method can be used as long as it is a conventional method such as an aqueous solution method, an organic solvent method, a spray method or the like.

The content of the above-mentioned vermiculite particles in the active energy ray curable resin composition is selected in the range of 1 to 20% by weight based on the weight of the solid content. When the content of the vermiculite particles is 1% by weight or more, the hard coating layer can have an effect of providing excellent anti-glare properties, and if it is 20% by weight or less, the abrasion resistance of the hard coating layer can be suppressed from being lowered. The preferred content of the vermiculite particles is from 3 to 20% by weight, particularly preferably from 5 to 15% by weight, based on the weight of the solid content of the resin composition.

The active energy ray-curable resin composition used in the present invention may be optionally added with a predetermined ratio of the above-mentioned active energy ray-curable polymerizable compound, vermiculite particles, and photopolymerization as needed, in a suitable solvent. The initiator or various additional components such as an antioxidant, an ultraviolet absorber, a light stabilizer, a leveling agent, an antifoaming agent, and the like are dissolved or dispersed to prepare.

Examples of the solvent to be used in this case include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as dichloromethane and dichloroethane, methanol, ethanol, propanol and butanol. Examples include alcohols such as ketones such as alcohol, acetone, methyl ethyl ketone, 2-pentanone, isophorone, and cyclohexanone; esters such as ethyl acetate and butyl acetate; and cellosolve solvents such as ethyl cellosolve.

The concentration and viscosity of the composition thus prepared are not particularly limited as long as they can be applied, and may be appropriately selected as necessary.

Next, the composition is applied by a conventionally known method such as a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, or the like to form a coating film, and after drying, The active energy ray is irradiated thereon to cure the coating film to form a hard coating layer.

Examples of the active energy ray include ultraviolet rays, electron beams, and the like. The ultraviolet rays may be obtained by a high pressure mercury lamp, a molten H lamp, a xenon lamp or the like, and the irradiation amount is usually 100 to 500 mJ/cm ² . On the other hand, the electron beam can be obtained by an electron beam accelerator or the like, and the irradiation amount is usually 150 to 350 kV. Among these active energy rays, ultraviolet rays are particularly preferred. In addition, when an electron beam is used, a cured film can be obtained without adding a polymerization initiator.

The thickness of the hard coating layer thus formed is preferably in the range of 0.5 to 20 μm. When the thickness is less than 0.5 μm, the scratch resistance of the hard coating film may not be sufficiently exhibited, and if it exceeds 20 μm, the specular gloss of 60° may increase. The hard coating layer preferably has a thickness of from 1 to 15 μm, particularly preferably from 2 to 10 μm, from the viewpoints of scratch resistance and balance of 60° specular gloss.

The surface of the hard coating layer thus formed has an arithmetic mean roughness Ra of usually 0.05 to 0.15 μm, more preferably 0.05 to 0.10 μm. Further, the arithmetic mean roughness Ra is a value measured based on ISO 1997.

Further, the hardness of the hard coating layer is preferably H or more, and if the pencil hardness is H or more, the hard coating film may have necessary scratch resistance, but it is particularly preferable to make the scratch resistance more sufficient. Good pencil hardness is 2H or more.

Further, the above pencil hardness is a value measured by a hand rub method in accordance with JIS K 5400.

In the anti-glare hard coating film of the present invention, the haze value specified in JIS K 7136 and the 60° specular gloss specified in JIS K 5600 are used as the anti-glare property index, and the haze value is preferably 2% or more. The 60° specular gloss is preferably 150 or less. When the haze value is less than 2%, it is difficult to exhibit sufficient antiglare property, and if the specular gloss of 60° exceeds 150, the surface glossiness is large (reflection of light is large), and the antiglare property is deteriorated. The reason for the impact. However, if the turbidity value is too high, the light transmittance is deteriorated, which is not preferable. Further, the anti-glare hard coating film of the present invention preferably has a photographing brightness of 100 or more. The so-called photographic brightness in the present invention is a photographic brightness measuring device prescribed by JIS K 7105, and four kinds of optical combs having widths of 0.125 mm, 0.5 mm, 1.0 mm, and 2.0 mm are used, in accordance with the above specifications 6.6. 4 and 6.6.5 The brightness (%) of each optical comb was obtained by a transmission method, and the total of these four values was obtained. This photographing sharpness is an index for visually displaying the image quality, and when the value is less than 100, a sufficiently good display image quality (visibility) cannot be obtained. Further, the total light transmittance is preferably 90% or more, and when it is less than 90%, the transparency may be lower.

From the viewpoints of the balance of anti-glare property, display image quality (visibility), light transmittance, transparency, etc., the haze value is preferably from 3 to 80%, and the photographic brightness is more preferably 150 or more, all optical transmission. The rate is more preferably 91% or more.

Further, a specific measurement method of the above optical characteristics will be described later.

In the present invention, an antireflection layer for imparting antireflection properties, such as a siloxane oxide film, a fluorine film, or the like, may be provided on the surface of the hard coating layer as needed. At this time, the thickness of the antireflection layer is preferably about 0.05 to 1 μm. Further, the reflectance at a wavelength of 550 nm is preferably 3.5% or less. By providing the anti-reflection layer, it is possible to eliminate the reflection of a screen caused by reflection of sunlight, a fluorescent lamp, or the like, and by suppressing the surface reflectance, it is possible to increase the total optical transmittance and improve the transparency. Further, depending on the type of the antireflection layer, the purpose of improving the antistatic property can be achieved.

In the antiglare hard coating film of the present invention, an adhesive layer which is attached to an adherend such as a liquid crystal display can be formed on the reverse surface of the hard coating layer of the base film. As the binder constituting the binder layer, a binder for optical use such as an acrylic binder, a urethane binder, or an anthrone-based binder is preferably used. The thickness of the adhesive layer is usually in the range of 5 to 100 μm, preferably 10 to 60 μm.

Further, a release film may be provided on the adhesive layer as needed. Examples of the release film include a release film obtained by coating a release agent such as an anthrone resin on paper such as cellophane, coated paper, or laminated paper, and various plastic films. The thickness of the release film is not particularly limited, but is usually about 20 to 150 μm.

Example

The invention is further illustrated by the examples, but the invention is not limited by the examples.

Further, the particle size distribution of the vermiculite particles and the performance of the antiglare hard coating film were evaluated by the following methods.

(1) The particle size distribution and average particle size of vermiculite particles are laser diffraction produced by the company. The scattering type particle size distribution measuring apparatus "LA-920" was measured.

(2) The total light transmittance was measured in accordance with JIS K 7361-1 using "NDH2000" manufactured by Nippon Denshoku Industries Co., Ltd.

(3) The haze value was measured in accordance with JIS K 7136 using "NDH2000" manufactured by Nippon Denshoku Industries Co., Ltd.

(4) 60° specular gloss was measured in accordance with JIS K 5600 using "VG2000" manufactured by Nippon Denshoku Industries Co., Ltd.

(5) Photographic sharpness The expression measuring device "ICM-10P" manufactured by Shikao test machine (share) was used to obtain a width of 0.125 mm and 0.5 mm by a transmission method in accordance with JIS K 7105, 6.6.4 and 6.6.5. The photographic brightness (%) of the four types of optical combs of 1.0 mm and 2.0 mm was obtained by summing these four values.

(6) Surface arithmetic mean roughness (Ra) was measured in accordance with ISO 1997 using "SURFTEST SV-3000" manufactured by Mitutoyo Corporation.

(7) Pencil hardness was measured in accordance with JIS K 5400 using a pencil scratch coating hardness tester "NP-TYPE" manufactured by Toyo Seiki Co., Ltd.

(8) Scratch resistance The surface of the hard coating layer was rubbed back and forth on steel wool #0000 (load 9.8 N) to confirm the presence or absence of damage.

Example 1

7 parts by weight of vermiculite particles treated with an organic surface treatment agent were added to 100 parts by weight of an ultraviolet curable resin [product of Arakawa Chemical Industry Co., Ltd., trade name "Beamset 575CB", solid content concentration 100%] [Fuji Silysia] Chemical (stock) production, trade name "Sylysia 436", average particle size 4.1 μm], the obtained material was dispersed in a bead mill using 2 mm Φ zirconia beads for 90 minutes, after laser diffraction. The particle size distribution of the vermiculite particles was determined by a scattering method. The particle distribution is shown in Fig. 1, and the average particle diameter, the peak value of the particle size distribution, and the specific surface area are shown in Table 1.

Next, the dispersion-treated product was diluted with ethyl cellosolve to have a total solid content concentration of 40% by weight to prepare an active energy ray-curable composition (coating agent). This coating agent was applied to a triacetonitrile cellulose-based film (manufactured by Fuji Photo Film Co., Ltd., trade name "T80UZ") having a thickness of 80 μm by Maiyarba No. 8, and dried at 70 ° C for 1 minute. Ultraviolet rays of an irradiation amount of 250 mJ/cm ^{2 were} irradiated and cured to form a hard coating layer. The thickness of the hard coating layer was 4.5 μm.

The properties of the obtained hard coating film are shown in Table 1.

Example 2

In the first embodiment, the same as in the first embodiment except that "Sylysia 456 RC" (trade name, manufactured by Fuji Silysia Chemical Co., Ltd., average particle diameter: 6.7 μm) was used as the vermiculite particles having the surface treated with the organic surface treatment agent. A hard coating film is produced.

The particle size distribution of the dispersed-treated vermiculite particles is shown in Fig. 2, and the average particle diameter, the peak value of the particle size distribution, and the specific surface area are shown in Table 1. In addition, the properties of the hard coating are shown in Table 1.

Example 3

In Example 1, except that "Nippshel SS-50B" was used, [trade name, Tosoh. Production of vermiculite (having an average particle diameter of 1.5 μm) A hard coating film was produced in the same manner as in Example 1 except that vermiculite particles having a surface treated with an organic surface treatment agent were used.

The particle size distribution of the dispersed-treated vermiculite particles is shown in Fig. 3, and the average particle diameter, the peak value of the particle size distribution, and the specific surface area are shown in Table 1. In addition, the properties of the hard coating are shown in Table 1.

Example 4

In the first embodiment, in addition to the use of "Nippshel E-200A" [trade name, Tosoh. Production of vermiculite (having an average particle diameter of 1.5 μm) A hard coating film was produced in the same manner as in Example 1 except that vermiculite particles were used.

The particle size distribution of the dispersed-treated vermiculite particles is shown in Fig. 4, and the average particle diameter, the peak value of the particle size distribution, and the specific surface area are shown in Table 1. In addition, the properties of the hard coating are shown in Table 1.

Comparative example 1

In the first embodiment, a hard coating film was produced in the same manner as in Example 1 except that the vermiculite particle dispersion treatment was carried out at 10,000 rpm for 30 minutes using a disperser ["T. K uniform disperser manufactured by Special Kogyo Co., Ltd.").

The particle size distribution of the dispersed-treated vermiculite particles is shown in Fig. 5, and the average particle diameter, the peak value of the particle size distribution, and the specific surface area are shown in Table 2. In addition, the properties of the hard coating are shown in Table 2.

Comparative example 2

In the second embodiment, a hard coating film was produced in the same manner as in Example 2 except that the dispersion treatment of the vermiculite particles was carried out using the same dispersing machine as in Comparative Example 1.

The particle size distribution of the dispersed-treated vermiculite particles is shown in Fig. 6, and the average particle diameter, the peak value of the particle size distribution, and the specific surface area are shown in Table 2. In addition, the properties of the hard coating are shown in Table 2.

Comparative example 3

In the third embodiment, a hard coating film was produced in the same manner as in Example 3 except that the dispersion treatment of the vermiculite particles was carried out using the same dispersing machine as in Comparative Example 1.

The particle size distribution of the dispersed-treated vermiculite particles is shown in Fig. 7, and the average particle diameter, the peak value of the particle size distribution, and the specific surface area are shown in Table 2. In addition, the properties of the hard coating are shown in Table 2.

Comparative example 4

In the fourth embodiment, a hard coating film was produced in the same manner as in Example 4 except that the dispersion treatment of the vermiculite particles was carried out using the same dispersing machine as in Comparative Example 1.

The particle size distribution of the dispersed-treated vermiculite particles is shown in Fig. 8, and the average particle diameter, the peak value of the particle size distribution, and the specific surface area are shown in Table 2. In addition, the properties of the hard coating are shown in Table 2.

As can be seen from Tables 1 and 2, the hard coating films in the examples all maintained the anti-glare property while having a high degree of vividness and having a high hardness. On the other hand, although the hard coating film of the comparative example has a high hardness, it indicates that the sharpness is remarkably low, and the total light transmittance is also low.

The antiglare film of the present invention has high surface hardness and is excellent in visibility while being used for various displays such as liquid crystal displays, plasma displays, cathode ray tubes, and even tactile control panels.

Fig. 1 is a graph showing the particle size distribution of vermiculite particles in the active energy ray-curable resin composition of Example 1.

Fig. 2 is a graph showing the particle size distribution of vermiculite particles in the active energy ray-curable resin composition of Example 2.

Fig. 3 is a graph showing the particle size distribution of vermiculite particles in the active energy ray-curable resin composition of Example 3.

Fig. 4 is a graph showing the particle size distribution of vermiculite particles in the active energy ray-curable resin composition of Example 4.

Fig. 5 is a graph showing the particle size distribution of vermiculite particles in the active energy ray-curable resin composition of Comparative Example 1.

Fig. 6 is a graph showing the particle size distribution of vermiculite particles in the active energy ray curable resin composition of Comparative Example 2.

Fig. 7 is a graph showing the particle size distribution of vermiculite particles in the active energy ray curable resin composition of Comparative Example 3.

Fig. 8 is a graph showing the particle size distribution of vermiculite particles in the active energy ray-curable resin composition of Comparative Example 4.

Claims (7)

A method for producing an anti-glare hard coating film, characterized in that the average particle diameter of the target vermiculite particles is larger than the weight of the solid component of the composition by 1 to 20% by weight and is irradiated by a laser. The active energy ray-curable resin composition of vermiculite particles having one peak in the particle size distribution measured by the scattering method, having a pulverization by utilizing shear force. Dispersing the function of the machine to crush. Dispersion treatment, the average particle size ratio of the vermiculite particles is pulverized. It is smaller than 0.5μm before the dispersion treatment, and is obtained by laser diffraction. The particle size distribution measured by the scattering method has peaks in the range of 0.1~1μm and 1.5~5μm, respectively, and the average particle size is 0.3~4μm, which is irradiated by laser. The active energy ray-curable resin composition of the vermiculite particles having a specific surface area ratio of 20,000 cm ² /cm ³ or more of the vermiculite particles measured by the scattering method, and the cured product formed using the obtained active energy ray-curable resin composition The resulting hard coating layer is formed on at least one side of the base film. The method for producing an anti-glare hard coating film according to the first aspect of the invention, wherein the total value of each slit of the photographic brightness of the anti-glare hard coating film is 100 or more. The method for producing an antiglare hard coating film according to claim 1 or 2, wherein the hard coating layer has an arithmetic mean roughness Ra of 0.05 to 0.15 μm. The method for producing an antiglare hard coating film according to claim 1 or 2, wherein the hard coating layer has a thickness of 0.5 to 20 μm. A method for producing an anti-glare hard coating film according to item 3 of the patent application, The thickness of the medium hard coating layer is 0.5 to 20 μm. The method for manufacturing an anti-glare hard coating film according to the first aspect of the patent application, wherein the grinding method utilizes shearing force. The machine with the dispersing function is a bead mill. The method for producing an antiglare hard coating film according to claim 6, wherein the bead mill is a bead mill using zirconia beads.