JP2008119867A - Anti-glaring hard coat film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an anti-glaring hard coat film suppressed in whiteness without lowering highly detailed display image quality, capable of imparting excellent anti-glaring properties, preventing that the shape of a fluorescent lamp or the like is projected on a display screen as it is when used in various kinds of displays, good in visibility and suitable as a surface protective film. <P>SOLUTION: The anti-glaring hard coat film is provided with a hard coat layer, which is composed of a cured material formed of a resin composition containing at least first silica particles with an average particle size of 0.2-0.7 μm, second particles with an average particle size of 3.5-5.5 μm, and an active energy ray curable resin, wherein the content ratio of the first and second silica particles is 0.5:1-2.5:1 in the weight ratio of (a first silica particles):(second silica particles) on at least on one side of the base material, and its transmission cleanliness value is 160-250%. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention can suppress whiteness without degrading high-definition display image quality, can impart excellent antiglare properties, has good visibility when used in various displays, and has a surface. The present invention relates to an antiglare hard coat film suitable also as a protective film.

  In a display such as a CRT or a liquid crystal display, light may be incident on the screen from the outside, and this light may be reflected (referred to as glare or glare) to make it difficult to see the displayed image. In particular, with the recent increase in size of displays, solving this problem has become an increasingly important issue.

  In order to solve such a problem, various anti-glare measures have been taken for various displays so far. As one of them, for example, a hard coat film used for a polarizing plate in a liquid crystal display, a hard coat film for protecting various displays, and the like are subjected to an antiglare treatment for roughening the surface.

  Conventionally, a method of mixing a filler such as silica particles in a hard coat agent for forming a hard coat layer is known as an antiglare treatment method for this hard coat film.

  However, in the antiglare hard coat film using silica particles having an average particle diameter of 1 to 2.5 μm alone as a filler, an excellent anti-resistance is obtained without deteriorating the image quality of a liquid crystal display with high definition in recent years. It was difficult to impart glare.

  Therefore, a method of containing a colloidal silica particle aggregate in the hard coat layer (for example, see Patent Document 1), a combination of silica particles having an average particle diameter of 0.5 to 5 μm and fine particles having an average particle diameter of 1 to 60 nm. A method (for example, refer to Patent Document 2) and the like for inclusion in the hard coat layer has been proposed.

  Patent Document 3 has a hard coat layer made of a cured product formed using an active energy ray-curable resin composition containing silica particles on at least one surface of a base film, and the composition The silica particles in the product have peaks in the particle diameter ranges of 0.1 to 1 μm and 1.5 to 5 μm, respectively, and the average particle diameter is 4 μm or less, and the content of the silica particles is 1 to An antiglare hard coat film of 20% by weight is described.

In Patent Documents 2 and 3, the antiglare property of the antiglare hard coat film was evaluated based on a 60-degree specular gloss based on JIS K7105. However, actually, even if the result of this evaluation was good, it did not necessarily reach a level at which the reflection of a fluorescent lamp or the like was not a concern. Therefore, further improvement in visibility has been demanded for high-quality and large-screen displays.
Japanese Patent Laid-Open No. 10-180950 JP 2002-36452 A JP 2006-218798 A

  The present invention has been made in view of such a state of the art, and can impart excellent anti-glare properties without degrading high-definition display image quality, and when used in various displays. Provided is an antiglare hard coat film in which a fluorescent lamp or the like does not appear as it is on a display screen, whiteness is suppressed, visibility is good, and it is also suitable as a surface protective film This is the issue.

  In order to solve the above-mentioned problems, the present inventors diligently studied an antiglare film having a hard coat layer formed using a resin composition containing an active energy ray-curable resin and silica particles. As a result, by using two types of silica particles having a specific average particle diameter as the silica particles used in the resin composition, excellent antiglare properties can be imparted without degrading high-definition display image quality. When used in various displays, fluorescent lamps do not appear as they are on the display screen, whiteness is suppressed, visibility is good, and it is also suitable as a surface protection film The present invention has been completed by finding that an antiglare hard coat film can be obtained.

Thus, according to the present invention, the antiglare hard coat film described in the following (1) to (4) is provided.
(1) First silica particles having an average particle diameter of 0.2 to 0.7 μm and second silica particles having an average particle diameter of 3.5 to 5.5 μm on at least one surface of the base film , And at least an active energy ray-curable resin, and the content ratio of the first silica particles and the second silica particles is (weight ratio of (first silica particles) :( second silica particles)), It has a hard coat layer made of a cured product formed using a resin composition in the range of 0.5: 1 to 2.5: 1, and has a transmission definition value of 160 to 250%. Anti-glare hard coat film.

(2) The arithmetic average roughness (Ra) of the hard coat layer is 0.07 to 0.15 μm, The antiglare hard coat film as described in (1).
(3) The antiglare hard coat film according to (1) or (2), wherein the hard coat layer has a thickness of 3 to 6 μm.

  According to the present invention, it is possible to provide excellent anti-glare properties without degrading high-definition display image quality, and when used in various displays, a fluorescent lamp or the like appears on the display screen as it is. There is provided an anti-glare hard coat film that has a low whiteness, good visibility, and is suitable as a surface protective film.

Hereinafter, the present invention will be described in detail.
The antiglare hard coat film of the present invention has first silica particles having an average particle diameter of 0.2 to 0.7 μm and an average particle diameter of 3.5 to 5.5 on at least one surface of the base film. It has a hard coat layer made of a cured product formed by using a resin composition containing at least an active energy ray-curable resin having a second silica particle of 5 μm, and a transmission definition value is 160 to 250 It is characterized by being.

  There is no restriction | limiting in particular as a base film used for the glare-proof hard coat film of this invention, It can select and use suitably from well-known plastic films as a base material of the hard coat film for conventional optics.

  Examples of such plastic films include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefin films such as polyethylene film, polypropylene film, polymethylpentene film, and ethylene-vinyl acetate copolymer film; Cellulose-based films such as diacetylcellulose film, triacetylcellulose film, acetylcellulose butyrate film; polyvinyl chloride film; polyvinylidene chloride film; polyvinyl alcohol film; polystyrene film; polycarbonate film; polysulfone film; Polyethersulfone film; Polyetherimide film Lum, polyimide film such as a polyimide film; fluororesin film; polyamide films; cycloolefin resin film such as norbornene resin film; acrylic resin film, and the like.

  These base films may be transparent or translucent, may be colored, or may be uncolored. For example, when it is used for protecting a liquid crystal display, a colorless and transparent film is suitable.

  The thickness of the base film to be used is not particularly limited and is appropriately selected depending on the situation, but is usually in the range of 15 to 300 μm, preferably 30 to 200 μm.

  Moreover, as a base film to be used, for the purpose of improving the adhesion with a layer provided on the surface thereof, one or both surfaces are subjected to surface treatment by an oxidation method, a concavo-convex method, or the like as desired. Also good.

Examples of the oxidation method include corona discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like. Examples of the unevenness method include a sand blast method and a solvent treatment method.
These surface treatment methods are appropriately selected depending on the type of the base film, but in general, the corona discharge treatment method is preferable from the viewpoints of effects and operability.

  The antiglare hard coat film of the present invention has first silica particles having an average particle diameter of 0.2 to 0.7 μm and an average particle diameter of 3.5 to 5 on at least one surface of the base film. It has a hard-coat layer which consists of a hardened | cured material formed using the 2nd silica particle which is 0.5 micrometer, and the resin composition containing an active energy ray hardening-type resin at least.

  In the present invention, the silica particles contained in the resin composition are first silica particles having an average particle size of 0.2 to 0.7 μm, and second particles having an average particle size of 3.5 to 5.5 μm. The silica particles are used.

  By using a plurality of types of silica particles having such an average particle diameter, it is possible to impart excellent antiglare properties without deteriorating high-definition display image quality, and to be visually recognized when used in various displays. (The transmission sharpness value described later can be in a specific range).

  As a method for producing silica particles having such a specific particle size distribution, a method for setting synthesis conditions so that particle growth is uniform by a sol-gel method or the like, and a method for performing classification after normal particle synthesis Is mentioned. Further, particles with a more preferable sharp particle size distribution can be obtained by increasing the number of classifications and optimizing the conditions.

  Examples of classification include wind classification, mesh classification, classification using a difference in sedimentation speed, classification using centrifugation, and the like, but there is no limitation on the method as long as a desired particle size distribution is obtained. The most efficient classification method is the wind classification method.

  The average particle diameter of the silica particles can be determined by measuring with a laser diffraction / scattering method.

  The mixing ratio of the first silica particles and the second silica particles is a weight ratio of (first silica particles) :( second silica particles), and 0.5: 1 to 2.5. : 1, and 0.8: 1 to 2: 1 is preferable for obtaining more excellent antiglare properties.

  The content of the silica particles in the resin composition (the total of the first silica particles and the second silica particles) is usually 1 to 20% by weight, preferably 3 to 20% by weight, based on the solid content weight. More preferably, it is 5 to 15% by weight. If the content of silica particles is 1% by weight or more, the effect of imparting good antiglare properties to the hard coat layer can be exhibited, and if it is 20% by weight or less, the scratch resistance of the hard coat layer. The decrease can be suppressed.

  In the present invention, as the silica particles to be used, silica particles having other average particle diameters can be mixed in addition to the first silica particles and the second silica particles.

  Further, the silica particles used in the present invention may have their surfaces treated with an organic surface treating agent or may be untreated. As the organic surface treatment agent, a silane coupling agent, silicone oil, silicone wax, or the like can be used.

  Examples of the silane coupling agent include triethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β- (3,4-epoxy. (Cyclohexyl) ethyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N -Phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane and the like. Among these, aminosilanes such as γ-aminopropyltriethoxysilane and N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane are preferable.

  There is no restriction | limiting in particular about the method of processing this silica particle with a surface treating agent, Arbitrary methods, such as the conventionally used method, for example, the aqueous solution method, the organic solvent method, a spray method, are mentioned.

  The active energy ray-curable resin used in the present invention is a polymerizable compound that crosslinks and cures when irradiated with electromagnetic waves or charged particle beams having chemical activity, that is, ultraviolet rays or electron beams.

  Examples of such an active energy ray-curable resin include an active energy ray-polymerizable prepolymer and / or an active energy ray-polymerizable monomer.

  Examples of the active energy ray polymerizable prepolymer include radical polymerization type active energy ray polymerizable prepolymers and cationic polymerization type active energy ray polymerizable prepolymers.

  Examples of radical polymerization type active energy ray polymerizable prepolymers include polyester acrylate, epoxy acrylate, urethane acrylate, and polyol acrylate.

  Polyester acrylate-based prepolymers are prepared by esterifying the hydroxyl groups of polyester oligomers having hydroxyl groups at both ends obtained by condensation of polyvalent carboxylic acids and polyhydric alcohols with (meth) acrylic acid, or polyvalent carboxylic acids. And a compound obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding alkylene oxide to (meth) acrylic acid. Here, (meth) acrylic acid means acrylic acid or methacrylic acid (the same applies hereinafter).

  Examples of the epoxy acrylate prepolymer include compounds obtained by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it.

  Examples of the urethane acrylate prepolymer include compounds obtained by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid.

Moreover, as a polyol acrylate type prepolymer, the compound obtained by esterifying the hydroxyl group of polyether polyol with (meth) acrylic acid is mentioned.
These active energy ray polymerizable prepolymers can be used singly or in combination of two or more.

  Cationic polymerization type active energy ray polymerizable prepolymers include compounds obtained by epoxidizing polyphenols such as bisphenol resins and novolac resins with epichlorohydrin, linear olefin compounds and cyclic olefin compounds with peroxides, etc. Examples thereof include epoxy resins such as compounds obtained by oxidation.

  Active energy ray polymerizable monomers include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neo Pentyl glycol adipate di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified di (meth) phosphate Acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipenta Erythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipenta Examples include polyfunctional acrylates such as erythritol hexa (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate. Here, (meth) acrylate means acrylate or methacrylate.

  These active energy ray-curable resins can be used singly or in combination of two or more.

  As a photopolymerization initiator used as desired, as an active energy ray-polymerizable prepolymer or an active energy ray-polymerizable monomer, when a radical polymerization type photopolymerizable prepolymer or photopolymerizable monomer is used, benzoin, Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-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-morpholino-propane-1- 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiary -Butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, p-dimethylamine Examples thereof include benzoic acid esters.

When a cationic polymerization type photopolymerizable prepolymer is used, onium such as aromatic sulfonium ion, aromatic oxosulfonium ion, aromatic iodonium ion, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, The compound which consists of anions, such as hexafluoroarsenate, is mentioned.
These can be used individually by 1 type or in combination of 2 or more types.

  The blending amount of the photopolymerization initiator is usually selected in the range of 0.2 to 10 parts by weight with respect to 100 parts by weight of the photopolymerizable prepolymer and / or photopolymerizable monomer.

  In addition to the active energy ray-curable polymerizable resin, silica particles (first silica particles and second silica particles), and a photopolymerization initiator used as desired, the resin composition used in the present invention includes: Known additives such as antioxidants, ultraviolet absorbers, light stabilizers, leveling agents, antifoaming agents and the like can be added. The addition amount of these additives is within a range where the effects of the present invention are not impaired. Thus, it can be set as appropriate.

  The resin composition used in the present invention comprises the above-mentioned active energy ray-curable polymerizable resin, silica particles (first silica particles and second silica particles), and photopolymerization initiation used as desired in a suitable solvent. An agent and various additives can be prepared by adding them at a predetermined ratio and dissolving or dispersing them.

  Solvents used include aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and ethylene chloride; alcohols such as methanol, ethanol, propanol, and butanol Ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone and cyclohexanone; esters such as ethyl acetate and butyl acetate; cellosolves such as ethyl cellosolve; and the like.

  The concentration and viscosity of the resin composition thus prepared are not particularly limited as long as they can be coated, and can be appropriately selected according to the situation.

  The antiglare hard coat film of the present invention has a hard coat layer made of a cured product formed by using the resin composition on at least one surface of a base film.

  The hard coat layer is formed by coating the composition on at least one surface of the base film to form a coating film of the resin composition, and then drying the coating film. It can be formed by curing by irradiation.

  The method for applying the composition to at least one surface of the base film is not particularly limited, and a conventionally known method can be employed. Examples thereof include a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, and a gravure coating method.

  Next, after the formed coating film is dried, the hard coating layer is formed by irradiating the coating with an active energy ray to cure the coating film.

Examples of the active energy rays include ultraviolet rays and electron beams.
When irradiating with ultraviolet rays, an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, or the like can be used. The irradiation amount is usually 100 to 1000 mJ / cm ² .

When irradiating an electron beam, the electron beam emitted from various electron beam accelerators such as Cockrowalton type, Bande graph type, resonance transformation type, insulation core transformation type, linear type, dynamitron type, high frequency type, etc. is used. it can. The irradiation dose is usually 50 to 1000 keV. Among these active energy rays, ultraviolet rays are particularly preferable.
In addition, when using an electron beam, a cured film can be obtained, without adding a polymerization initiator.

  The thickness of the hard coat layer formed as described above is usually 0.5 to 20 μm, preferably 3 to 6 μm. If the thickness of the hard coat layer is too thin, the scratch resistance of the hard coat film may not be sufficiently exhibited, whereas if it is too thick, the 60 ° specular gloss may be increased.

As described above, the antiglare hard coat film of the present invention can be obtained.
The transmission clarity value of the obtained antiglare hard coat film of the present invention is 160 to 250.

  Here, the transmission sharpness value (%) is measured using five types of optical combs in which the width between the dark part and the bright part is 0.125 mm, 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm. This is the total value of transmitted sharpness. The transmission sharpness can be determined according to the image sharpness measurement method by the transmission method specified in JIS K7105. The incident direction of the light to the test piece is a vertical direction in accordance with this JIS standard. In this case, the image definition by the transmission method is measured for each of the above five types of optical combs, and the total value thereof is taken as the total value of the above-described transmission definition.

  In the antiglare hard coat film of the present invention, the arithmetic average roughness (Ra) of the hard coat layer surface is usually 0.01 to 0.5 μm, preferably 0.07 to 0.15 μm. If the Ra is within the above range, high-definition and dense irregularities are obtained, and thus good transmission sharpness can be obtained. The arithmetic average roughness (Ra) is a value measured according to JIS B 0601-1994.

  The antiglare hard coat film of the present invention preferably has a haze of 2 to 20%, more preferably 3 to 15%. The haze value is a value represented by (diffuse transmittance / total light transmittance) × 100 (%). The haze value can be obtained by a method defined in JIS K 7136.

  When the haze value is too high, when the antiglare hard coat film of the present invention is applied to a display device, particularly a liquid crystal display device, the viewing angle characteristics of the liquid crystal display device are inclined from the normal, particularly 60. Since low-contrast light emitted in a direction inclined at an angle of more than ° is scattered and observed in the front direction, there is a risk of lowering the contrast when observed from the front.

  The antiglare hard coat film of the present invention has excellent antiglare properties. The antiglare hard coat film of the present invention has excellent antiglare properties, for example, by visually observing the reflected light on the surface of the hard coat layer under a three-wavelength fluorescent lamp, and the shape of the reflected fluorescent lamp is linear. It can be confirmed by not seeing.

  The antiglare hard coat film of the present invention has excellent visibility. For example, the hard coat layer of the antiglare hard coat film of the present invention is visually observed for transmitted light with respect to three-wavelength fluorescence, and as a result of observing the whiteness of the transmitted light, the antiglare property having a conventional high-definition display image quality The whiteness was suppressed as compared with the hard coat film.

  In the antiglare hard coat film of the present invention, if necessary, an antireflection layer such as a siloxane-based film or a fluorine-based film may be provided on the surface of the hard coat layer for the purpose of imparting antireflection properties. it can.

  In this case, the thickness of the antireflection layer is suitably about 0.05 to 1 μm. By providing this anti-reflective layer, the reflection of the screen resulting from reflection by sunlight, fluorescent lamps, etc. is eliminated, and by suppressing the reflectance of the surface, the total light transmittance is increased and the transparency is improved. . Depending on the type of the antireflection layer, the antistatic property can be improved.

  In the antiglare hard coat film of the present invention, an adhesive layer for adhering to an adherend such as a liquid crystal display can be formed on the surface of the base film opposite to the hard coat layer. . As an adhesive which comprises this adhesive layer, the thing for optical uses, for example, an acrylic adhesive, a urethane type adhesive, and a silicone type adhesive, are used preferably. The thickness of this pressure-sensitive adhesive layer is usually 5 to 100 μm, preferably 10 to 60 μm.

  Furthermore, a release film can be provided on the pressure-sensitive adhesive layer as necessary. Examples of the release film include paper such as glassine paper, coated paper, and laminated paper, and various plastic films coated with a release agent such as silicone resin. Although there is no restriction | limiting in particular about the thickness of this peeling film, Usually, it is about 20-150 micrometers.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
The average particle size of the silica particles and the physical properties and performance of the antiglare hard coat film were evaluated according to the following methods.

(1) Average particle diameter of silica particles Measured under the following conditions using a particle size distribution meter (LA-920, manufactured by HORIBA, Ltd.), and the median diameter is read as the average particle diameter (hereinafter referred to as “particle diameter”). It was.
Dispersion solvent: PGM (propylene glycol monomethyl ether)
Batch type relative refractive index setting: 110A0001

(2) Arithmetic average surface roughness (Ra)
According to ISO4287, it measured using the contact-type surface roughness meter (SV3000S4, Mitutoyo Corporation).
(3) Total light transmittance It measured using the haze meter (NDH-2000, Nippon Denshoku Co., Ltd.) according to JISK7361-1.
(4) Haze Measured according to JIS K 7136 using a haze meter (NDH-2000, Nippon Denshoku Co., Ltd.).

(5) Transmission clarity Based on JIS K7105, using TM type image clarity measuring device (ICM-1T, manufactured by Suga Test Instruments Co., Ltd.), the transmission measurement is performed, and the total value of the measured values is determined as the transmission clarity value ( %).
(6) Film thickness Create cross-section data of hard coat film with electron microscope data preparation device (EMUC6, manufactured by Leica Microsystem) and measure film thickness with digital microscope (VHX-500, manufactured by Keyence). did.

(7) Evaluation of antiglare property An antiglare hard coat surface is placed on a black plate, and the reflected light of the hard coat layer surface is visually observed at an angle of 70 to 80 ° from the surface under a three-wavelength fluorescent lamp. Observing and evaluating the antiglare property by the shape of the fluorescent light of the reflected light. The case where the fluorescent lamp did not appear to be a straight line was evaluated as ◯, and the case where the fluorescent lamp appeared to be a straight line was evaluated as x.
(8) Transmission inspection (Evaluation of visibility)
The antiglare hard coat surface is placed on a black plate, and the reflected light of the hard coat layer surface is visually observed at an angle of 70 to 80 ° from the surface under a three-wavelength fluorescent lamp. (Whiteness) was observed. The case where the whiteness was slight and it did not cause a problem in use was evaluated as ◯, and the case where it was extremely white and the visibility was deteriorated was evaluated as ×.

(9) Evaluation of Steel Wool Hardness The surface of the hard coat layer was scratched 100 times with steel wool # 0000 (loading 200 g / cm ² (19.6 kN / m ² )) and then visually observed. The case where no scratch was observed on the surface of the hard coat layer was evaluated as ◯, and the case where a scratch was observed was evaluated as ×.

(Example 1)
Mixture of urethane acrylate and polyfunctional monomer (Beamset 575CB, manufactured by Arakawa Chemical Industries, solid content concentration 100%, containing photopolymerization initiator), 100 parts by weight, silica particle dispersed UV curable resin (Seika Beam EXF-01L (BS) Manufactured by Dainichi Seika Kogyo Co., Ltd., silica particle content 10% by weight, silica particle diameter 4.7 μm, solid content 100%, photopolymerization initiator included) 50 parts by weight, silica particle dispersed UV curable resin ( Seika Beam EXF-01L (MB), manufactured by Dainichi Seika Kogyo Co., Ltd., silica particle content 10% by weight, silica particle diameter 0.4 μm, solid content concentration 85%, photopolymerization initiator included) 59 parts by weight, leveling 0.2 parts by weight of an agent (SH28, manufactured by Toray Dow Silicone Co., Ltd., solid content concentration: 100%) was mixed and diluted with ethyl cellosolve to prepare a 40% by weight coating solution. Prepared.

A PET (polyethylene terephthalate) film (Cosmo Shine 188A4100, manufactured by Toyobo Co., Ltd., thickness 188 μm, single-sided easy with an easy-adhesion layer so that the film thickness after drying this coating solution with a Mayer bar # 12 is 5.5 μm. After coating at 70 ° C. for 1 minute, irradiation with ultraviolet rays (light quantity: 200 mJ / cm ² , high-pressure mercury lamp) gave an antiglare hard coat film.

  About the obtained anti-glare hard coat film, the arithmetic average surface roughness (Ra), total light transmittance, haze, and transmission sharpness value are measured, and further, anti-glare property, transmission specimen, and steel wool hardness are evaluated. did. The measurement results and the evaluation results are shown by comparing the particle diameter of silica particles (in the table, the smaller particle diameter is (small) and the larger particle diameter is (large). The same applies hereinafter). Table 1 summarizes the mixing ratio and film thickness (HC layer film thickness) of silica particles having a small particle diameter and silica particles having a relatively large particle diameter.

(Example 2)
Mixture of urethane acrylate and polyfunctional monomer (Beam Set 575CB, manufactured by Arakawa Chemical Industries, 100% solid content, containing photopolymerization initiator), 100 parts by weight of silica particle-dispersed UV curable resin (Seika Beam EXF-01L (MB) Manufactured by Dainichi Seika Kogyo Co., Ltd., 10% by weight of silica particles, 4.7 μm silica particle size, 100% solid content, containing photopolymerization initiator), 40 parts by weight of silica particle-dispersed UV curable resin ( Seika Beam EXF-01L (MB), manufactured by Dainichi Seika Kogyo Co., Ltd., content of silica particles 10% by weight, silica particle diameter 0.4 μm, solid content concentration 85%, photopolymerization initiator included) 70 parts by weight, leveling 0.2 parts by weight of an agent (SH28, manufactured by Toray Dow Silicone Co., Ltd., solid content concentration: 100%) was mixed and diluted with ethyl cellosolve to prepare a 40% by weight coating solution. Prepared.

Easy to apply PET film with easy-adhesion layer (Cosmo Shine 188A4100, manufactured by Toyobo Co., Ltd., thickness 188 μm, single-sided easy-adhesion) so that the film thickness after drying this coating solution with Meyer bar # 10 is 4.0 μm It was applied onto the adhesive surface, dried at 70 ° C. for 1 minute, and then irradiated with ultraviolet rays (light quantity 200 mJ / cm ² , high-pressure mercury lamp) to obtain an antiglare hard coat film.

  About the obtained anti-glare hard coat film, the arithmetic average surface roughness (Ra), total light transmittance, haze, and transmission sharpness value are measured, and further, anti-glare property, transmission specimen, and steel wool hardness are evaluated. did. The measurement results and evaluation results are shown together with the particle size of the silica particles, the mixing ratio of the silica particles having a relatively small particle size and the silica particles having a relatively large particle size, and the film thickness (HC layer film thickness). The results are summarized in Table 1.

(Comparative Example 1)
Mixture of urethane acrylate and polyfunctional monomer (Beamset 575CB, manufactured by Arakawa Chemical Industries, solid content concentration 100%, containing photopolymerization initiator), 100 parts by weight, silica particle dispersed UV curable resin (Seika Beam EXF-01L (BS) Manufactured by Dainichi Seika Kogyo Co., Ltd., 10% by weight of silica particles, 4.7 μm silica particle size, 100% solid content, containing photopolymerization initiator), 40 parts by weight of silica particle-dispersed UV curable resin ( Seika Beam EXF-01L (MB), manufactured by Dainichi Seika Kogyo Co., Ltd., content of silica particles 10% by weight, silica particle diameter 0.4 μm, solid content concentration 85%, photopolymerization initiator included) 141 parts by weight, leveling 0.2 parts by weight of an agent (SH28, manufactured by Toray Dow Silicone Co., Ltd., solid content concentration: 100%) was mixed, diluted with ethyl cellosolve, and coated with 40% by weight. Was prepared.

Easy to apply PET film with easy-adhesion layer (Cosmo Shine 188A4100, manufactured by Toyobo Co., Ltd., thickness 188 μm, single-sided easy-adhesion) so that the film thickness after drying this coating solution with Meyer bar # 10 is 4.0 μm It was applied onto the adhesive surface, dried at 70 ° C. for 1 minute, and then irradiated with ultraviolet rays (light quantity 200 mJ / cm ² , high-pressure mercury lamp) to obtain an antiglare hard coat film.

  About the obtained anti-glare hard coat film, the arithmetic average surface roughness (Ra), total light transmittance, haze, and transmission sharpness value are measured, and further, anti-glare property, transmission specimen, and steel wool hardness are evaluated. did. The measurement results and evaluation results are shown together with the particle size of the silica particles, the mixing ratio of the silica particles having a relatively small particle size and the silica particles having a relatively large particle size, and the film thickness (HC layer film thickness). The results are summarized in Table 1.

(Comparative Example 2)
Mixture of urethane acrylate and polyfunctional monomer (Beamset 575CB, manufactured by Arakawa Chemical Industry Co., Ltd., solid content concentration 100%, containing photopolymerization initiator), 100 parts by weight, silica particle-dispersed UV curable resin (Seika Beam EXF-01L (BS2) Manufactured by Dainichi Seika Kogyo Co., Ltd., 10% by weight of silica particles, 6.9 μm particle size of silica particles, 100% solid content, containing a photopolymerization initiator), 20 parts by weight of silica particle-dispersed ultraviolet curable resin ( Seika Beam EXF-01L (MB), manufactured by Dainichi Seika Kogyo Co., Ltd., content of silica particles 10% by weight, silica particle diameter 0.4 μm, solid content concentration 85%, photopolymerization initiator included) 47 parts by weight, leveling 0.2 parts by weight of an agent (SH28, manufactured by Toray Dow Silicone Co., Ltd., solid content concentration: 100%) was mixed, diluted with ethyl cellosolve, and coated with 40% by weight. Was prepared.

Easy coating of PET film with an easy-adhesion layer (Cosmo Shine 188A4100, manufactured by Toyobo Co., Ltd., thickness 188 μm, single-sided easy adhesion) so that the film thickness after drying this coating solution with Meyer bar # 12 is 4.8 μm It was applied onto the adhesive surface, dried at 70 ° C. for 1 minute, and then irradiated with ultraviolet rays (light quantity 200 mJ / cm ² , high-pressure mercury lamp) to obtain an antiglare hard coat film.

  About the obtained anti-glare hard coat film, the arithmetic average surface roughness (Ra), total light transmittance, haze, and transmission sharpness value are measured, and further, anti-glare property, transmission specimen, and steel wool hardness are evaluated. did. The measurement results and evaluation results are shown together with the particle size of the silica particles, the mixing ratio of the silica particles having a relatively small particle size and the silica particles having a relatively large particle size, and the film thickness (HC layer film thickness). The results are summarized in Table 1.

(Comparative Example 3)
Mixture of urethane acrylate and polyfunctional monomer (Beamset 575CB, Arakawa Chemical Industries, solid content concentration 100%, containing photopolymerization initiator), 100 parts by weight, silica particle dispersed UV curable resin (Seika Beam EXF-01L (BS) Manufactured by Dainichi Seika Kogyo Co., Ltd., silica particle content 10% by weight, silica particle particle size 4.7 μm, solid content concentration 100%, containing photopolymerization initiator), silica particle dispersion (IPA-ST) -ZL, manufactured by Nissan Chemical Industries, Ltd., silica particle content (solid content concentration) 30% by weight, silica particle diameter 0.1 μm) 16.7 parts by weight, leveling agent (SH28, manufactured by Toray Dow Silicone Co., Ltd.) (Partial concentration 100%) 0.2 part by weight was mixed and diluted with ethyl cellosolve to prepare a 40% by weight coating solution.

Easy to apply PET film with easy-adhesion layer (Cosmo Shine 188A4100, manufactured by Toyobo Co., Ltd., thickness 188 μm, single-sided easy adhesion) so that the film thickness after drying this coating liquid with Meyer bar # 10 is 5.0 μm It was applied onto the adhesive surface, dried at 70 ° C. for 1 minute, and then irradiated with ultraviolet rays (light quantity 200 mJ / cm ² , high-pressure mercury lamp) to obtain an antiglare hard coat film.

  About the obtained anti-glare hard coat film, the arithmetic average surface roughness (Ra), total light transmittance, haze, and transmission sharpness value are measured, and further, anti-glare property, transmission specimen, and steel wool hardness are evaluated. did. The measurement results and evaluation results are shown together with the particle size of the silica particles, the mixing ratio of the silica particles having a relatively small particle size and the silica particles having a relatively large particle size, and the film thickness (HC layer film thickness). The results are summarized in Table 1.

(Comparative Example 4)
Silica particle-dispersed UV curable resin (LH-73C (NO), manufactured by Jujo Chemical Co., Ltd., solid content concentration 70%, no photopolymerization initiator, silica particle content 8% by weight (particle diameter: 0.5 μm / 3 μm = 1: 2)) 100 parts by weight, UV curable resin (LH-52X (NO), manufactured by Jujo Chemical Co., Ltd., solid content concentration 80%, no photopolymerization initiator), 20 parts by weight, photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd., solid concentration 100%) 2 parts by weight and leveling agent (SH28, manufactured by Toray Dow Silicone Co., Ltd., solid content concentration 100%) 0.2 parts by weight were mixed and ethyl cellosolve was used. Dilution was performed to prepare a 40% by weight coating solution.

Easy to apply PET film with an easy-adhesion layer (Cosmo Shine 188A4100, manufactured by Toyobo Co., Ltd., thickness 188 μm, single-sided easy adhesion) so that the film thickness after drying this coating solution with Meyer bar # 12 is 5.0 μm It was applied onto the adhesive surface, dried at 70 ° C. for 1 minute, and then irradiated with ultraviolet rays (light quantity 200 mJ / cm ² , high-pressure mercury lamp) to obtain an antiglare hard coat film.

  About the obtained anti-glare hard coat film, the arithmetic average surface roughness (Ra), total light transmittance, haze, and transmission sharpness value are measured, and further, anti-glare property, transmission specimen, and steel wool hardness are evaluated. did. The measurement results and evaluation results are shown together with the particle size of the silica particles, the mixing ratio of the silica particles having a relatively small particle size and the silica particles having a relatively large particle size, and the film thickness (HC layer film thickness). The results are summarized in Table 1.

(Comparative Example 5)
Mixture of urethane acrylate and polyfunctional monomer (Beamset 575CB, Arakawa Chemical Industries, solid content concentration 100%, containing photopolymerization initiator), 100 parts by weight, silica particle dispersed UV curable resin (Seika Beam EXF-01L (BS) Manufactured by Dainichi Seika Kogyo Co., Ltd., 10% by weight of silica particles, 4.7 μm silica particle diameter, 100% solid content, containing photopolymerization initiator), 50 parts by weight of silica gel (Tospearl 120, GE Toshiba Silicone) 5.0 parts by weight, silica particle diameter 1.9 μm) and leveling agent (SH28, manufactured by Toray Dow Silicone Co., Ltd., solid content 100%) 0.2 parts by weight are mixed and diluted with ethyl cellosolve. A 40 wt% coating solution was prepared.

Easy to apply PET film with easy-adhesion layer (Cosmo Shine 188A4100, manufactured by Toyobo Co., Ltd., thickness 188 μm, single-sided easy adhesion) so that the film thickness after drying this coating liquid with Meyer bar # 10 is 5.0 μm It was applied onto the adhesive surface, dried at 70 ° C. for 1 minute, and then irradiated with ultraviolet rays (light quantity 200 mJ / cm ² , high-pressure mercury lamp) to obtain an antiglare hard coat film.

  About the obtained anti-glare hard coat film, the arithmetic average surface roughness (Ra), total light transmittance, haze, and transmission sharpness value are measured, and further, anti-glare property, transmission specimen, and steel wool hardness are evaluated. did. The measurement results and evaluation results are shown together with the particle size of the silica particles, the mixing ratio of the silica particles having a relatively small particle size and the silica particles having a relatively large particle size, and the film thickness (HC layer film thickness). The results are summarized in Table 1.

From Table 1, the antiglare hard coat films of Examples 1 and 2 have high transmission clarity, low whiteness, good visibility, and excellent hardness and antiglare properties. there were.
On the other hand, the antiglare hard coat film of Comparative Examples 1 and 4 is inferior in antiglare property and visibility, and the antiglare hard coat film in Comparative Examples 2 and 5 is inferior in transmission clarity. The antiglare hard coat film of Comparative Example 3 was inferior in visibility.

Claims (3)

  A first silica particle having an average particle diameter of 0.2 to 0.7 μm, a second silica particle having an average particle diameter of 3.5 to 5.5 μm, and activity on at least one surface of the base film It contains at least an energy ray curable resin, and the content ratio of the first silica particles and the second silica particles is 0.5 by weight ratio of (first silica particles) :( second silica particles). Having a hard coat layer made of a cured product formed using a resin composition in the range of 1 to 2.5: 1, and having a transmission sharpness value of 160 to 250% Dazzling hard coat film.   2. The antiglare hard coat film according to claim 1, wherein an arithmetic average roughness (Ra) of the hard coat layer is 0.07 to 0.15 μm.   The antiglare hard coat film according to claim 1 or 2, wherein the hard coat layer has a thickness of 3 to 6 µm.