KR20130122964A - Anti-glare film, method for producing anti-glare film, anti-glare anti-reflection film, polarizing plate, and image display device - Google Patents

Abstract

The present invention is an antiglare film having an antiglare layer containing an active ray curable resin on a base film, wherein the antiglare layer contains substantially no incompatible resin with respect to the fine particles and the active ray curable resin. Arithmetic mean roughness Ra is 300-1500 nm, The haze resulting from the internal scattering of the said glare-proof layer is 0 to 1.0%, The anti-glare film is provided.

Description

Anti-glare film, manufacturing method of anti-glare film, anti-glare anti-reflection film, polarizing plate and image display device DEVICE}

This invention relates to the liquid crystal display device which has an anti-glare film, the manufacturing method of an anti-glare film, an anti-glare antireflection film, a polarizing plate, an image display apparatus, and a touch panel.

Recently, displays such as cathode ray tube display (CRT) displays, liquid crystal displays, plasma displays, touch panel input devices, organic or inorganic EL (electroluminescence) displays, FED (field emission displays), and the like, When an external light source such as sunlight is projected onto the display surface, the reflected light becomes obstructed, making it difficult to see the screen, and the visibility is remarkably deteriorated. Therefore, various displays blur the outline of the image reflected on the surface. The film (anti-glare film) which has an anti-glare layer which reduces projection is provided in the display surface.

The antiglare treatment has been roughened by chemical etching or the like to give surface irregularities, a surface irregularities are provided by a transfer method using a mold, or a particle is dispersed and contained in the resin layer to give surface irregularities.

In these anti-glare processes, since the method of disperse | distributing microparticles | fine-particles in a resin layer can easily provide surface unevenness, it is generally used.

However, in the anti-glare film which disperse | distributes microparticles | fine-particles and forms surface unevenness | corrugation, microparticles | fine-particles are easy to aggregate and it is difficult to control the surface unevenness | corrugation of the surface, and the freedom of design of surface unevenness was restrict | limited. In addition, unevenness occurred due to aggregation of the fine particles, resulting in a problem of poor appearance. In addition, since the refractive index between the fine particles and the resin forming the antiglare layer is different, haze (internal haze) due to internal scattering due to the difference in refractive index between the two is generated, and the overall haze as a film is increased, so that the entire display is white. As a result, there was a problem of causing a decrease in contrast. Therefore, the anti-glare film of the low internal haze is examined in recent years (for example, refer patent document 1, 2).

Patent Literature 1 discloses an antiglare film having a total haze of 1 to 30%, an internal haze of 0 to 1%, and an average reflectance of 0.001 to 2.5% at 5 ° incidence in a region having a wavelength of 450 to 650 nm. Doing. In addition, the invention described in Patent Literature 1 is a technique in which a curable resin contains an incompatible polymer component (cellulose acetate propionate) to form surface irregularities by spinodal decomposition during coating film drying.

On the other hand, patent document 2 has an anti-glare hard coat layer on a transparent film, and discloses the anti-glare hard coat film whose internal haze of an anti-glare hard coat layer is 0.5% or less, and surface haze / internal haze is 2.0 or more. The invention described in Patent Literature 2 is obtained by spinodal decomposition of two kinds of incompatible resins (resin A; for example, dipentaerythritol hexaacrylate and resin B; for example, methacrylate copolymer). It is a technique of forming surface irregularities using phase separation.

All of these techniques are described as being capable of preventing projection of external light or reflection and obtaining a high quality image with excellent contrast.

In addition, in the anti-glare film which differs in solubility parameters as described in patent documents 1 and 2, and forms in surface unevenness using regular phase separation by mixing incompatible resin and spinoidal decomposition, control of phase separation is controlled. It is difficult to change the size of the phase separation structure due to slight changes in the lot of raw materials, the polymer composition, etc., resulting in unevenness of surface irregularities, and it is difficult to form stable surface irregularities. There was a problem that caused the degradation.

Moreover, the above-mentioned prior art used for an image display apparatus after the durability test assumed outdoor use, such as a digital signage, and as a result, the fall of visibility (projection prevention performance and sharpness) was remarkable. It is estimated that the visibility (projection prevention performance and sharpness) deteriorates under the influence when it is used for an image display apparatus by the occurrence of the micro-white spots and the microcracks of the anti-glare film after the durability test.

Therefore, stable surface irregularities are formed, and the appearance of the anti-glare film excellent in the visibility (projection prevention performance and sharpness) after a durability test is desired.

Japanese Patent Laid-Open No. 2006-106290 (claim 3) Japanese Patent Publication No. 2007-58204

An object of the present invention is to provide excellent visibility (anti-projection performance and sharpness) when stable surface irregularities are formed and there is no occurrence of micro-white spots and micro cracks in the anti-glare film after the durability test, and when used in an image display device. It is to provide a manifest film. Moreover, it is providing the liquid crystal display device which has the manufacturing method of the said anti-glare film, the anti-glare antireflection film using the said anti-glare film, the polarizing plate which has the outstanding visibility, an image display apparatus, and a touch panel.

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

That is, one aspect of this invention is an anti-glare film which has an anti-glare layer containing an active-line curable resin on a base film, and the said anti-glare layer does not contain substantially incompatible resin with respect to microparticles | fine-particles and said active-line curable resin. The arithmetic mean roughness Ra of the said glare-proof layer is 300-1500 nm, and the haze resulting from the internal scattering of the said glare-proof layer is 0 to 1.0%, The anti-glare film is provided.

According to the present invention, when stable surface irregularities are formed and there is no occurrence of micro-white spots and micro cracks of the anti-glare film after the durability test, and it is used in an image display device, the anti-glare property excellent in visibility (projection preventing performance and sharpness) is excellent. Films may be provided. Moreover, the liquid crystal display device which has the manufacturing method of the said anti-glare film, the anti-glare antireflection film using the said anti-glare film, the polarizing plate which has the outstanding visibility, an image display apparatus, and a touch panel can be provided.

1 is an explanatory diagram of a projection.
FIG. 2 is a schematic diagram showing irregular projections of the anti-glare layer of the anti-glare film according to the embodiment of the present invention. FIG. In Fig. 2, reference numeral 1 denotes an antiglare layer, and 2 denotes a projection shape.
3 is an observation diagram of an optical interference surface roughness meter on the surface of an antiglare layer of an antiglare film.
4 shows a cross-sectional view of the polarizing plate produced in the example.
5 is a sectional view of the liquid crystal panel produced in the embodiment.
6 is a schematic view of a liquid crystal cell of a liquid crystal display device.
It is a figure which shows the structural example of the antireflection film provided with an electroconductive film.
8 is a schematic view showing an example of the configuration of a resistive touch panel liquid crystal display device.

EMBODIMENT OF THE INVENTION Hereinafter, although the content for implementing this invention is demonstrated in detail, this invention is not limited to these.

The anti-glare film of this invention is an anti-glare film which has an anti-glare layer containing an active-line curable resin on a base film, and the said anti-glare layer does not contain the resin which is incompatible with microparticles | fine-particles and said active-line curable resin substantially Arithmetic mean roughness Ra of the said glare-proof layer is 300-1500 nm, Haze resulting from the internal scattering of the said glare-proof layer is 0-1.0%, By such a structure, stable surface unevenness | corrugation is formed and after durability test When there is no occurrence of micro-white spots and micro cracks of an anti-glare film, and it is used for an image display apparatus, an anti-glare film excellent in visibility (projection prevention performance and sharpness) can be provided.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining the said subject, generation | occurrence | production of the micro cloudiness unevenness and microcracks of the anti-glare film after a durability test greatly influence the flexibility (flexibility of a film) after a durability test, and also the permeability of permeability. It turns out mad.

According to the present invention, by controlling the arithmetic mean roughness Ra and the internal haze of the antiglare layer to a specific range, and forming an antiglare layer under conditions that are substantially free of incompatible resin with respect to the fine particles and the active ray curable resin, It is estimated that the film elasticity of an anti-glare film does not change even after an endurance test, the generation | occurrence | production of a micro crack can be prevented favorably, and the outstanding flexibility is obtained. In addition, since the non-reacted active line curable resin remains in the antiglare layer, the reaction does not occur in the antiglare layer even when the unreacted active line curable resin remains substantially in the antiglare layer. In addition, it is estimated that a fine cloudy stain does not generate | occur | produce and excellent permeability is obtained even after a durability test.

Moreover, it turns out that using the anti-glare film of this invention for an image display apparatus, the outstanding visibility and also the outstanding sharpness are also acquired, and it is this invention.

EMBODIMENT OF THE INVENTION Hereinafter, specific embodiment of this invention is described in detail.

<Anti-glare film>

The anti-glare film referred to in the present invention includes a liquid crystal display, an organic EL display, and a plasma display by providing a layer (i.e., anti-glare layer) on the surface of the film substrate that blurs the outline of the image or external light reflected on the surface of the film substrate. At the time of use of such an image display apparatus, it is a film which did not mind projection of external light and a reflection image. In addition, in this application, "-" uses the numerical value described before and after that by the meaning included as a lower limit and an upper limit. In addition, "surface haze value" and "internal haze value" are also simply expressed as "surface haze" and "internal haze", respectively.

The anti-glare film of this embodiment is an anti-glare film which has an anti-glare layer containing an active-line curable resin on a base film, and the said anti-glare layer does not substantially contain incompatible resin with respect to microparticles | fine-particles and the said active-line curable resin. The arithmetic mean roughness Ra of the antiglare layer is 300 to 1500 nm, and the haze resulting from the internal scattering of the antiglare layer is 0 to 1.0%.

In addition, in this invention, when it measures and observes melting | fusing temperature (Tm) or glass transition point (Tg) of the melt mixture of two or more types of resins, "incompatibility" is the peak of each resin which comprises the said melt mixture individually. Says what is observed. In addition, it means that each phase is observed substantially in transmission electron microscope observation. On the other hand, "compatibility" means that one or less peaks of the molten mixture are observed when the melting temperature (Tm) or the glass transition point (Tg) of the molten mixture of the same kind or two or more kinds of resins is measured and observed. . Tg and Tm of the said resin are the temperature which the base line based on Tg and Tm of a DSC measurement starts to bias.

In addition, in this application, although it does not contain substantially, it means that content in an anti-glare layer is 0.01 mass% or less except for the extract component from a base film, although it changes with kinds and the properties of microparticles | fine-particles and incompatible resin, More preferably, it does not contain at all.

In this embodiment, as incompatible resin with respect to actinic-ray-curable resin (it mentions later in detail), In resin and polyester resin obtained by superposing | polymerizing or copolymerizing a (meth) acrylic-type or acryl-type monomer, Furthermore, the base film mentioned later The thermoplastic acrylic resin, cellulose ester resin, etc. which are used are mentioned.

As microparticles | fine-particles, microparticles | fine-particles, such as inorganic microparticles | fine-particles and organic microparticles | fine-particles, are mentioned, Specifically, an inorganic fine particle can mention silicon oxide, magnesium oxide, calcium carbonate, etc. Moreover, polymethacrylate methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, polystyrene resin powder, or melamine type resin powder etc. are mentioned as organic particle | grains.

Next, the protrusion shape will be described.

<Surface shape>

The anti-glare film of this embodiment is characterized by one whose arithmetic mean roughness Ra (JIS B0601: 1994) of an anti-glare layer is 300-1500 nm. Arithmetic mean roughness Ra becomes like this. More preferably, it is 350-1300 nm, Especially preferably, it is 500-1300 nm. In the arithmetic mean roughness (Ra) 350-1300 nm, the objective effect of this invention is exhibited more favorable, and in arithmetic mean roughness (Ra) 500-1300 nm, in the hardness test by the pencil hardness evaluation method (The detail of a test method is mentioned later). Since the slipperiness | lubricacy in the anti-glare layer of a scraped pencil increases and it is hard to be damaged, even a thin film is obtained because high hardness (4H or more) is obtained.

In order to make arithmetic mean roughness Ra of the said range, 20 nm-6 micrometers of height of protrusion shape are preferable. Moreover, the width | variety of protrusion shape is 50 nm-300 micrometers, Preferably it is 50 nm-100 micrometers. The height and width of the projection shape can be obtained from cross-sectional observation. In order to make it easier to understand, explanatory drawing for measuring the height of protrusion shape was shown in FIG. As shown in Fig. 1, the center line a is drawn on the image of the cross-sectional observation, and the distance between the two intersections of the lines b and c forming the foot of the mountain and the center line a is the width of the projection size. It was called (t).

As for 10-point average roughness Rz of the anti-glare layer of the anti-glare film of this embodiment, 10-times or less of the center line average roughness Ra, and the average valley distance Sm are 5-150 micrometers, More Preferably, the standard deviation of the height of the convex portion from the deepest uneven portion is 20 to 100 µm, 0.5 µm or less, the standard deviation of the average valley distance Sm based on the center line is 20 µm or less, and the inclination angle 0 to 5 degrees. 10% or more is preferred.

In addition, the kurtosis (Rku) of the antiglare layer is preferably 3 or less. As for the distortion degree Rsk, 1 or less of absolute values are preferable. The arithmetic mean roughness (Ra, Sm, Rz) described above is a value measured by an optical interference surface roughness meter (for example, RST / PLUS, manufactured by WYKO, New View 5030, manufactured by Zygo) according to JIS B0601: 1994. .

The anti-glare film of this embodiment has one characteristic that the haze resulting from internal scattering of an anti-glare layer (hereinafter also described as internal haze) is 0 to 1.0%. When forming the above projection shape, the internal haze of the above range is controlled, and the arithmetic mean roughness Ra of the projection shape is controlled within the above range, so that the antiglare layer is incompatible with the fine particles and the active line curable resin. By not containing substantially, the objective effect of this invention is exhibited favorably. As internal haze, Preferably it is 0 to 0.5%. Internal haze can be measured by the following procedures. A few drops of silicone oil are dripped at the front and back surface of an anti-glare film, and it holds by two sheets of the glass plate (micro slide glass product number S 9111 by MATSUNAMI) of thickness 1mm, and is hold | maintained at the front and back. The anti-glare film which sandwiched the front and back between glass is completely optically stuck with two glass plates, and haze (Ha) is measured according to JIS-K7105 and JIS K7136 in this state. Next, only a few drops of silicone oil is dripped between two glass plates, and glass haze (Hb) is measured. And internal haze (Hi) can be computed by taking out glass haze (Hb) by the haze (Ha) which sandwiched the anti-glare film between glass. Moreover, it is preferable that surface haze (haze resulting from surface scattering of a film) is 3 to 40%. The surface haze can be obtained by subtracting the internal haze from the total haze. The total haze is preferably 3% to 40%.

It is preferable that the anti-glare film of this embodiment has a protrusion shape in which an anti-glare layer forms surface unevenness, the protrusion shape is a protrusion of an irregular shape in a longitudinal direction, and the arrangement is also an irregular arrangement. By having such a protrusion shape, the objective effect of this invention is exhibited favorably.

The "irregular projection" of the antiglare layer of the anti-glare film of the present embodiment means projections of various shapes whose surface irregularities do not have a regular shape regularly in the longitudinal direction formed by stamping, and whose shape and size are not determined. Point. Although not limited to these, for example, projections having different widths and heights shown in FIG. 2 are exemplified as irregularly shaped projections. In addition, "irregular arrangement" means that the projections of the irregular tendency are not arranged regularly (for example, at equal intervals), but are arranged irregularly at arbitrary intervals and may be isotropic or anisotropic. Point.

In addition, although the anti-glare layer which has the characteristics as mentioned above is mentioned later in detail, the surface shape, for example, controls high temperature the treatment temperature of the reduction rate drying period in the drying process of an anti-glare layer coating composition, and coats of resin Convection is generated, a non-uniform state is formed on the surface of the anti-glare layer, and it can be obtained by a method of curing the non-uniform surface state to form a coating film or the like. By forming a coating film in this way, the film strength of an anti-glare layer improves. Moreover, the method of controlling the process temperature of the reduction rate drying period in a drying process of an anti-glare layer coating composition on high temperature conditions is preferable at the point which is excellent also in productivity other than the objective effect of this invention.

<Manufacturing Method>

In addition, the manufacturing method of the said anti-glare film will not be specifically limited, if the thing which has an anti-glare layer which has the characteristics as mentioned above on a base film can be manufactured. Specifically, this production method is an antiglare obtained by diluting an active-line curable resin having a viscosity at 25 ° C in the range of 20 to 3000 mPa · s with at least one solvent selected from esters, glycol ethers or alcohols. The layer coating composition is provided under the conditions which formed the anti-glare layer at least via the application | coating process, a drying process, and a hardening process, and maintained the temperature of the rate reduction drying section in the said drying process within the range of 90-160 degreeC. The manufacturing method to mention is mentioned. According to such a manufacturing method, when stable surface irregularities are formed and there is no occurrence of micro-white spots and micro cracks of the anti-glare film after the durability test, and it is used for an image display device, it is excellent in visibility (projection prevention performance and sharpness). A manifest film is obtained. The said application is not specifically limited if it is a method which can apply | coat an anti-glare layer coating composition on a base film so that the thickness after hardening may become predetermined thickness. Specifically, the coating method as mentioned later is mentioned. If drying and hardening satisfy | fill the said conditions and can form an anti-glare layer on a base film, it will not specifically limit, The method of mentioning later is mentioned.

<Antiglare layer>

The anti-glare layer according to the present embodiment contains an active ray curable resin, that is, a resin which is cured through a crosslinking reaction by irradiation with an active ray (also referred to as an active energy ray) such as an ultraviolet ray or an electron beam as a main component. Layer.

As active ray hardening resin, the component containing the monomer which has an ethylenically unsaturated double bond is used preferably, and it hardens | cures by irradiating an active ray like an ultraviolet-ray or an electron beam, and an active ray hardening resin layer is formed.

Examples of the active ray curable resin include ultraviolet curable resins, electron beam curable resins, and the like, and resins cured by ultraviolet ray irradiation are preferable in terms of excellent mechanical film strength (scratch resistance, pencil hardness).

As ultraviolet curable resin, ultraviolet curable acrylate resin, ultraviolet curable urethane acrylate resin, ultraviolet curable polyester acrylate resin, ultraviolet curable epoxy acrylate resin, ultraviolet curable polyol acrylate resin, or ultraviolet ray, for example Curable epoxy resin etc. are used preferably. Especially, ultraviolet curable acrylate resin is preferable.

As ultraviolet curing acrylate-type resin, polyfunctional acrylate is preferable. The polyfunctional acrylate is selected from the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate. It is preferable to be. Here, polyfunctional acrylate is a compound which has a 2 or more acryloyloxy group or a methacroyloxy group in a molecule | numerator. As a monomer of a polyfunctional acrylate, for example, ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentylglycol diacrylate, trimethylolpropane triacrylate, trimethyl Olethane Triacrylate, Tetramethylolmethane Triacrylate, Tetramethylolmethane Tetraacrylate, Pentaglycerol Triacrylate, Pentaerythritol Diacrylate, Pentaerythritol Triacrylate, Pentaerythritol Tetraacrylate, Penta Erythritol tri / tetraacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, glycerin triacrylate, dipentaerythritol triacrylate, dipentaerythritol tetra Acrylate , Dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, active energy ray-curable isocyanurate derivatives, and the like. The active energy ray-curable isocyanurate derivative may be a compound having a structure in which one or more ethylenically unsaturated groups are bonded to the isocyanuric acid skeleton, and there is no particular limitation, but three or more ethylenically unsaturated groups in the same molecule and Preferred are compounds having at least one isocyanurate ring. More specifically, an isocyanuric-acid triacrylate compound, an isocyanuric-acid diacrylate compound, (epsilon) -caprolactone modified tris- (acryloxyethyl) isocyanurate, etc. are mentioned, for example.

As these commercial items, Adeka Optomer N series, Sunrad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (manufactured by Sanyo Kasei Kogyo Co., Ltd.) ); SP-1509, SP-1507, Aronix M-6100, M-8030, M-8060, Aronix M-215, Aronix M-315, Aronix M-313, Aronix M-327 ), NK-ester A-TMM-3L, NK-ester AD-TMP, NK-ester ATM-35E, NK ester A-DOG, NK ester A-IBD-2E, A-9300, A-9300-1CL (Shinakamura Kagaku Kogyo Co., Ltd.), light acrylate TMP-A, PE-3A (Kyoesha Chemical Co., Ltd.), etc. are mentioned.

Moreover, you may use monofunctional acrylate. As monofunctional acrylate, isoboroyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, isostearyl acrylate, benzyl acrylate, ethylcarbitol acrylate, phenoxyethyl acrylate, la Uryl acrylate, isooctyl acrylate, tetrahydrofurfuryl acrylate, behenyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, cyclohexyl acrylate, etc. Can be mentioned. Such monofunctional acrylate can be obtained from Nihon Kasei Kabushiki Kaisha, Shin-Nakamura Kagaku Kogaku Kaushiki Kaisha, Osaka Yuki Kagaku Kogyo Kakushiki Kaisha, etc.

When monofunctional acrylate is used, it is preferable to contain polyfunctional acrylate: monofunctional acrylate = 70: 30-99: 2 by the content mass ratio of polyfunctional acrylate and monofunctional acrylate. The actinic radiation curable resin may be used singly or in combination of two or more kinds. The viscosity of the actinic radiation curable resin at 25 ° C is preferably 20 mPa · s or more, 3000 mPa · s or less, more preferably 20 mPa · s or more and 2000 mPa · s or less. By using such a low-viscosity actinic curable resin, the above-described protrusion shape and arithmetic mean roughness Ra are easily obtained. Moreover, as long as the viscosity of active ray hardening resin is a viscosity of 20 mPa * s or more, the monomer of high functional water can be used, and sufficient high sclerosis | hardenability is obtained, and if it is a viscosity of 3000 mPa * s or less, sufficient fluidity of active ray hardening resin in a drying process This is easy to get.

In addition, the said viscosity is the value measured on 25 degreeC conditions using the Brookfield viscometer.

It is preferable that an antiglare layer contains a photoinitiator in order to accelerate | stimulate hardening of active line hardening resin. As a photoinitiator amount, it is preferable to contain in a mass ratio as a photoinitiator: active ray hardening resin = 20: 100-0.01: 100. Specific examples of the photopolymerization initiator include alkyl phenones, acetophenones, benzophenones, hydroxybenzophenones, Michler's ketones, α-amyl oxime esters, thioxanthones, and derivatives thereof, but are not particularly limited thereto. It doesn't happen. Such a photopolymerization initiator may be a commercially available product, and examples thereof include IRGACURE 184, IRGACURE 907, IRGACURE 651 manufactured by BASF Japan Ltd., and the like.

Moreover, in order to provide antistatic property, an antiglare layer may contain a electrically conductive agent. As a preferable electrically conductive agent, (pi) conjugated system conductive polymer, an ionic liquid, etc. are mentioned.

The antiglare layer may contain a silicone surfactant, a fluorine-based surfactant, an acrylic surfactant, a fluorine-siloxane graft compound, or a compound having an HLB value of 3 to 18 from the viewpoint of applicability. The compound whose HLB value is 3-18 is demonstrated. An HLB value means Hydrophile-Lipophile-Balance and hydrophilic-lipophilic-balance, and is a value which shows the magnitude | size of the hydrophilicity or lipophilic property of a compound. The smaller the HLB value, the higher the lipophilicity, and the larger the value, the higher the hydrophilicity. In addition, an HLB value can be calculated | required by the following formula.

HLB = 7 + 11.7 Log (Mw / Mo)

In the formula, Mw represents the molecular weight of the hydrophilic group, Mo represents the molecular weight of the lipophilic group, and Mw + Mo = M (molecular weight of the compound). According to the Griffin method, the HLB value = 20 × total food / molecular weight of the hydrophilic part (J. Soc. Cosmetic Chem., 5 (1954), 294). Although the specific compound of the compound whose HLB value is 3-18 is listed below, it is not limited to this. () Shows an HLB value.

Emulsion 102 (6.3), Emergene 103 (8.1), Emergene 104P (9.6), Emergen 105 (9.7), Emergene 106 (10.5), Emergene 108 Emergen 120 (15.3), Emergen 123P (16.9), Emergen 147 (16.3), Emergen 210P (10.7), Emergen 220 (14.2), Emergene 306P (9.4), Emergene 320P (13.9), Emergen 404 (8.8), Emergen 408 (10.0), Emergen 409PV (12.0), Emergen 420 (13.6), Emergen 430 (16.2), Emergene 705 (10.5), Emergene 707 Emergen 2020G-HA (13.0), Emergen 2025G (15.7), Emergene 1118S-70 (16.4) EMULGEN LS-114 (14.0) manufactured by Nisshin Chemical Industry Co., Ltd., Surfynol 104E (4), Surfynol 104H (4) manufactured by Nisshin Chemical Industry Co., , Surfynol 104A (4), Surfynol 104BC (4), Surfynol 104DPM (4), Surfynol 104PA (4), Surfynol 104PG-50 ), Surinol 440 (8), Surinol 465 (13), Surinol 485 (17), Surinol SE (6) ), Shinetsu Kagaku Kogyo Co., Ltd .: X-22-4272 (7), X-22-6266 (8), KF-351 (12), KF-352 (7), KF-353 (10 ), KF-354L (16), KF-355A (12), KF-615A (10), KF-945 (4), KF-618 (11), KF-6011 (12), KF-6015 (4) , KF-6004 (5). Polyether modified silicone etc. are mentioned as silicone type surfactant, The said KF series by Shin-Etsu Chemical Co., Ltd., etc. are mentioned. As acryl-type surfactant, commercial item compounds, such as BYK-350 and BYK-352 by Big Chemi Japan Co., are mentioned. As a fluorine type surfactant, DIC Corporation Megapak RS series, Megapak F-444, Megapak F-556, etc. are mentioned.

A fluorine-siloxane graft compound means the compound of the copolymer obtained by grafting the polysiloxane and / or organopolysiloxane containing siloxane and / or organosiloxane single substance at least in fluorine-type resin. As a commercial item, ZX-022H, ZX-007C, ZX-049, ZX-047-D, etc. made by Fuji Kasei Kogyo Co., Ltd. are mentioned. Moreover, it is preferable to add these components in 0.01-3 mass% with respect to the solid content component in a coating liquid. It is preferable that an anti-glare layer dilutes the component which forms said anti-glare layer with a solvent, and makes it an anti-glare layer coating composition, It is preferable to apply | coat this anti-glare layer coating composition on a film base material by the following method, dry, and harden to form an anti-glare layer. Do. As a solvent, ketones (methyl ethyl ketone, acetone, cyclohexanone, methyl isobutyl ketone, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, etc.), alcohols ( Ethanol, methanol, butanol, n-propyl alcohol, isopropyl alcohol, diacetone alcohol), hydrocarbons (toluene, xylene, benzene, cyclohexane), glycol ethers (propylene glycol monomethyl ether, propylene glycol monopropyl ether, ethylene Glycol monopropyl ether etc.) etc. can be used preferably. Among these solvents, esters, glycol ethers or alcohols are preferable, and glycol ethers or alcohols are particularly preferable. After using at least 1 sort (s) of these preferable solvents in the range of 20-200 mass parts with respect to 100 mass parts of said actinic wire hardening resins, after apply | coating an anti-glare layer coating composition to a base film, the solvent of an anti-glare layer coating composition will evaporate. In the process of forming the antiglare layer, convection of the resin is likely to occur, and as a result, the surface roughness which is irregular in the longitudinal direction in the antiglare layer and also has an irregular protrusion shape on the base film is likely to be expressed, and the arithmetic mean roughness ( It is preferable because it is easy to control with Ra).

The coating amount of the antiglare layer is suitably 0.1 to 40 µm as the wet film thickness, and preferably 0.5 to 30 µm. Moreover, as dry film thickness, average film thickness is 0.1-30 micrometers, Preferably it is 1-20 micrometers, Especially preferably, it is 2-15 micrometers.

As a coating method of an anti-glare layer, well-known methods, such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, the inkjet method, can be used. Using these coating methods, the antiglare layer coating composition forming the antiglare layer is applied, dried after application, and irradiated with active rays (also referred to as UV curing treatment), and, if necessary, formed by heat treatment after UV curing. Can be. As heat processing temperature after UV hardening, 80 degreeC or more is preferable, More preferably, it is 100 degreeC or more, Especially preferably, it is 120 degreeC or more. By performing heat treatment after UV curing at such a high temperature, an antiglare layer excellent in pencil hardness can be obtained.

The drying is preferably carried out by a high-temperature treatment at 90 deg. More preferably, the temperature of the rate reduction drying section is 90 ° C or more and 150 ° C or less. Since the convection of the coating film resin is likely to occur at the time of forming the antiglare layer by using the temperature of the rate-sensitive drying section at high temperature, as a result, irregular surface roughness is likely to appear on the surface of the antiglare layer, and the arithmetic mean roughness Ra It is preferable because it is easy to control.

In general, the drying process is known to change gradually from a constant drying rate to a gradually decreasing state when drying starts, and it is known that a constant drying rate is divided into a constant rate drying rate and a decreasing drying rate, Quot; In the rate drying section, the amount of heat flowing in is consumed for evaporation of the solvent on the surface of the coating film, and when the solvent on the surface of the coating film decreases, the evaporation surface moves from the surface to the inside to enter the rate reduction drying section. After this, the temperature of the coating film surface rises and approaches hot air temperature, and the temperature of active-line curable resin of a coating film rises. Thereby, it is thought that convection of coating film resin arises because the viscosity of active-rays curable resin falls and fluidity increases.

As a light source of UV hardening treatment, if it is a light source which generate | occur | produces an ultraviolet-ray, it can use without limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.

Although irradiation conditions differ with each lamp | ramp, the irradiation amount of an active line is 50-1000mJ / cm <^2> normally, Preferably it is 50-300mJ / cm <^2> .

When irradiating an active line, it is preferable to carry out, providing a tension in the conveyance direction of a film, More preferably, it is performed, giving a tension also in the width direction. As for the tension | tensile_strength to provide, 30-300 N / m is preferable. The method of providing a tension is not specifically limited, You may give tension to a conveyance direction on a back roll, and you may give tension to a width direction or a biaxial direction with a tenter. Thereby, the film further excellent in planarity can be obtained.

In addition, an anti-glare layer may further contain the ultraviolet absorber demonstrated by the base film mentioned later. As a film in the case of containing a ultraviolet absorber, it is preferable that an antiglare layer is comprised from two or more layers, and it contains a ultraviolet absorber in the antiglare layer which contact | connects a base film.

As content of a ultraviolet absorber, it is preferable to contain in a mass ratio as ultraviolet absorber: anti-glare layer constituent resin = 0.01: 100-10: 100. When providing two or more layers, it is preferable that the film thickness of the anti-glare layer which contact | connects a base film is the range of 0.05-2 micrometers. Two or more layers may be formed in a simultaneous intermediate layer. Simultaneous intermediate | middle layer apply | coats two or more anti-glare layers on a base material by wet on wet, without passing through a drying process, and forms an anti-glare layer. In order to laminate | stack a 2nd anti-glare layer by a wet on wet, without going through a drying process on a 1st anti-glare layer, you may laminate | stack in order by an extrusion coater, or you may perform simultaneous middle layer with the slot die which has several slits.

Moreover, the pencil hardness which is an index of hardness of the anti-glare film in this embodiment is H or more, More preferably, it is 3H or more. If it is 3H or more, it is difficult to be scratched in the polarization printing process of the liquid crystal display device, and it is used as a surface protection film of the large size liquid crystal display device or the liquid crystal display device for digital signage which are often used for outdoor use. It also shows excellent mechanical properties. More preferably, pencil hardness is 4H or more.

In addition, pencil hardness is JIS K5400 using the test pencil prescribed | regulated by JIS S6006 on weighted 500g conditions, after adjusting the produced anti-glare film at the temperature of 23 degreeC and the conditions of 55% of the relative humidity for 2 hours or more. It is the value measured according to the pencil hardness evaluation method to prescribe. Subsequently, a base film is demonstrated.

<Base film>

It is preferable that a base film is easy to manufacture, easy to adhere | attach with an anti-glare layer, and optically isotropic. In addition, in this embodiment, a base film is used as a polarizing plate protective film.

Any base film having the above properties may be used, and for example, a cellulose ester-based film such as a triacetyl cellulose film, a cellulose acetate propionate film, a cellulose diacetate film, a cellulose acetate butyrate film, polyethylene terephthalate, or polyethylene naphthalate Polyester film, polycarbonate film, polyarylate film, polysulfone (including polyether sulfone) film, polyethylene film, polypropylene film, cellophane, polyvinylidene chloride film, polyvinyl alcohol Film, ethylene vinyl alcohol film, syndiotactic polystyrene film, norbornene resin film, polymethylpentene film, polyether ketone film, polyether ketoneimide film, polyamide film, fluororesin film, nylon film, cycloolefin Polymer film, Polymethyl methacrylate film, an acrylic film, etc. can be used. Among these, cellulose ester films (for example, Konica Minolta Tack KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC4UE and KC12UR (above, manufactured by Konica Minolta Opto Co., Ltd.)), polycarbonate A film, a cycloolefin polymer film, and a polyester film are preferable, and in this invention, a cellulose-ester film is preferable at the point which is easy to obtain said protrusion shape in an anti-glare layer, manufacturability, and cost. The refractive index of the base film is preferably 1.30 to 1.70, more preferably 1.40 to 1.65. The refractive index is measured by the method of JIS K7142 using Abbe's refractometer 2T manufactured by Atago Co.,

(Cellulose ester film)

Next, the cellulose ester film suitable as a base film is demonstrated in detail. The cellulose ester film is not particularly limited as long as it has the above characteristics, but the cellulose ester resin (hereinafter also referred to as cellulose ester) is preferably a lower fatty acid ester of cellulose. The lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms, for example, cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, or the like, or cellulose acetate propionate. And mixed fatty acid esters such as cellulose acetate butyrate can be used.

Of the above-mentioned base materials, particularly preferred lower-fatty acid esters of cellulose are cellulose diacetate, cellulose triacetate, and cellulose acetate propionate. These cellulose esters can be used individually or in mixture.

As for cellulose diacetate, the thing whose acetyl group substitution degree is 2.0-2.5 is used preferably. Moreover, as a commercial item, die cell company L20, L30, L40, L50, Eastman Chemical company Ca398-3, Ca398-6, Ca398-10, Ca398-30, Ca394-60S are mentioned.

As cellulose triacetate, an acetyl group substitution degree of 2.75-2.95 is used preferably.

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

(I) 2.6? X + Y? 3.0

(II) 0? X? 2.5

In particular, cellulose acetate propionate is preferably used, and among them, 1.9 ≦ X ≦ 2.5 and 0.1 ≦ Y ≦ 0.9 are preferred.

The cellulose ester preferably has a number average molecular weight (Mn) of 125000 or more and less than 180000, and the cellulose ester preferably has a weight average molecular weight (Mw) / number average molecular weight (Mn) ratio of 1.5 to 5.5, Especially preferably, it is 2.0-5.0, More preferably, it is 2.5-5.0, More preferably, the cellulose ester of 3.0-5.0 is used preferably.

The number average molecular weight (Mn) and the molecular weight distribution (Mw) of the cellulose ester can be measured using high performance liquid chromatography. Measurement conditions are as follows.

Solvent: methylene chloride

Column: Shodex K806, K805, K803G

(Connect 3 Showa Denko Co., Ltd. products)

Column temperature: 25 ° C

Sample concentration: 0.1 mass%

Detector: RI Model 504 (manufactured by GL Science)

Pump: L6000 (manufactured by Hitachi Seisakusho Co., Ltd.)

Flow rate: 1.0 ml / min

Calibration curve: Standard polystyrene STK standard A calibration curve with 13 samples of polystyrene (manufactured by Tosoh Corporation) Mw = 1000000 to 500 was used. The 13 samples are preferably used at substantially equal intervals.

Although the wood pulps and cotton linter may be sufficient as the raw material cellulose of the cellulose ester used by this invention, conifers and hardwoods may be wood pulp, but conifers are more preferable. In view of peelability at the time of film forming, a cotton printer is preferably used. The cellulose ester made from these can be mixed suitably, or can be used independently.

For example, the ratio of cellulose ester derived from cotton linter: cellulose ester derived from wood pulp (softwood): cellulose ester derived from wood pulp (softwood) is 100: 0: 0, 90: 10: 0, 85: 15: 0, 50: 50: 0, 20: 80: 0, 10: 90: 0, 0: 100: 0, 0: 0: 100, 80:10:10, 85: 0: 15, and 40:30:30.

In the present embodiment, 1 g of cellulose ester is added to 20 ml of pure water (electric conductivity of 0.1 μS / cm or less, pH 6.8), and the pH is 6 to 7, when stirred at 25 ° C, 1 hr, and nitrogen atmosphere, and electrical conductivity. It is preferable that it is 1-100 microS / cm.

(Cellulose ester resin, thermoplastic acrylic resin containing film)

In addition, the base film contains a thermoplastic acrylic resin and a cellulose ester resin, and also uses the film whose content mass ratio of a thermoplastic acrylic resin and a cellulose ester resin is a thermoplastic acrylic resin: cellulose ester resin = 95: 5-50: 50. desirable.

Methacrylic resin is also contained in acrylic resin. Although it does not restrict | limit especially as an acrylic resin, What consists of 50-99 mass% of methyl methacrylate units and 1-50 mass% of other monomeric units copolymerizable with this is preferable. Examples of the other monomer copolymerizable include alkyl methacrylate having 2 to 18 carbon atoms in alkyl, alkyl acrylate having 1 to 18 carbon atoms in alkyl, alpha, beta -unsaturated acids such as acrylic acid and methacrylic acid, and maleic acid. , Aromatic vinyl compounds such as unsaturated group-containing divalent carboxylic acids such as fumaric acid and itaconic acid, styrene and α-methylstyrene, α, β-unsaturated nitriles such as acrylonitrile and methacrylonitrile, maleic anhydride and maleic acid Mead, N-substituted maleimide, glutaric anhydride, etc. are mentioned, These can be used individually or in combination of 2 or more types of monomers.

Among these, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, etc. are preferable from the viewpoint of the thermal decomposition resistance and fluidity of a copolymer, And methyl acrylate or n-butyl acrylate are particularly preferably used. The weight average molecular weight (Mw) is preferably in the range of 80000 to 500000, and more preferably in the range of 1100000 to 500000.

The weight average molecular weight of an acrylic resin can be measured by gel permeation chromatography including measurement conditions. There is no restriction | limiting in particular as a manufacturing method of an acrylic resin, You may use any of well-known methods, such as suspension polymerization, emulsion polymerization, block polymerization, or solution polymerization. Here, as a polymerization initiator, the thing of normal peroxide type and azo type can be used, and it can also be set as a redox system. About superposition | polymerization temperature, it can implement at 30-100 degreeC in suspension or emulsion polymerization, and 80-160 degreeC in block or solution polymerization. In order to control the reduced viscosity of the obtained copolymer, polymerization may be carried out using alkylmercaptan or the like as a chain transfer agent. Commercially available products may also be used. (Manufactured by Asahi Kasei Chemicals Corporation), Dianal BR52, BR80, BR83, BR85 and BR88 (manufactured by Mitsubishi Rayon Co., Ltd.) and KT75 (manufactured by Denki Kagaku Kogyo Co., Ltd.) And the like. Acrylic resin can also use 2 or more types together. As the acrylic resin, a graft copolymer in which a (meth) acrylic resin is grafted to a copolymer of a (meth) acrylic rubber and an aromatic vinyl compound may be used. The graft copolymer is a graft copolymer in which a copolymer of a (meth) acrylic rubber and an aromatic vinyl compound constitutes a core and a core-shell type graft composed of the (meth) acrylic resin constitutes a shell, Is preferably a copolymer.

The total mass of the acrylic resin and the cellulose ester resin in the base film is preferably 55 mass% or more, more preferably 60 mass% or more, and particularly preferably 70 mass% or more, of the base film. The base film may be comprised containing resin and additives other than a thermoplastic acrylic resin and a cellulose-ester resin.

(Acrylic particles)

The base film may contain acrylic particles in that it is excellent in improvement in brittleness. An acryl particle represents the acryl component which exists in the state of a particle | grain (also called an emergency state) in the base film containing the said thermoplastic acrylic resin and a cellulose ester resin in a compatible state.

Although an acryl particle is not specifically limited, It is preferable that it is a multilayer structure acrylic granular composite. As an example of the commercial item of the acryl-type granular composite_body | complex which is a multilayered structure polymer, for example, "Metablene" by Mitsubishi Rayon, "Kane Ace" by Kanegachichi Kagaku Kogyo Co., Ltd. "Paraloid" by Kureha Kagaku High School, "Acryloid" by Rohm and Haas Corporation, "Staphyloid" by Gantsu Kasei Kogyo Co., Ltd., "Paparat SA" by Kureray Corporation, etc. are mentioned, These can use single or 2 types or more. When acrylic particles are added to the base film, it is preferable that the refractive index of the mixture of the acrylic resin and the cellulose ester resin is close to the refractive index of the acrylic particles, in view of obtaining a film having high transparency. Specifically, the refractive index difference between the acrylic particles and the acrylic resin is preferably 0.05 or less, more preferably 0.02 or less, particularly preferably 0.01 or less.

By containing acrylic fine particles in the range of acrylic fine particles: acrylic resin and cellulose ester resin total mass = 0.5: 100-30: 100 with respect to the total mass of the acrylic resin and cellulose ester resin which comprise the said film, It is preferable at the point which an effect is exhibited more fully, More preferably, it is the range of the total mass of an acrylic microparticle: acrylic resin and a cellulose ester resin = 1.0: 100-15: 100.

(Fine particles)

The base film is, for example, silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, kaolin, talc, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, etc. It is preferable to contain matting agents, such as inorganic fine particles and crosslinked polymers. Among them, silicon dioxide is preferably used since the haze of the film can be reduced.

As primary average particle diameter of microparticles | fine-particles, 20 nm or less is preferable, More preferably, it is 5-16 nm, Especially preferably, it is 5-12 nm.

(Other additives)

To improve the fluidity and flexibility of the composition, a plasticizer may be used in combination with the base film. Phthalic acid ester type, fatty acid ester type, trimellitic acid ester type, phosphate ester type, polyester type, or epoxy type etc. are mentioned as a plasticizer. Among these, polyester plasticizers are preferably used. The polyester plasticizer is excellent in non-migration and extraction resistance compared to phthalic ester plasticizers such as dioctyl phthalate. By selecting or using these plasticizers according to a use, it can apply to a wide range of uses.

The polyester-based plasticizer is a reaction product of a mono- to tetravalent carboxylic acid and a mono- to hexavalent alcohol, which is obtained mainly by reacting a divalent carboxylic acid with a glycol. Representative divalent carboxylic acids include glutaric acid, itaconic acid, adipic acid, phthalic acid, azelaic acid, sebacic acid and the like. The polyester-based plasticizer is preferably an aromatic-terminal ester-based plasticizer. As an aromatic terminal ester plasticizer, the ester compound which has a structure which made phthalic acid, adipic acid, at least 1 sort (s) of benzene monocarboxylic acid, and at least 1 sort (s) of C2-C12 alkylene glycol reacted.

Examples of the benzene monocarboxylic acid component include benzoic acid, para tert-butyl benzoic acid, orthotoluic acid, metatoluic acid, paratoluic acid, dimethylbenzoic acid, ethyl benzoic acid, normal propyl benzoic acid, amino benzoic acid, acetoxy benzoic acid, and the like. It is most preferable that it is benzoic acid. These may be used alone or as a mixture of two or more kinds.

Examples of the alkylene glycol component having 2 to 12 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,2-propanediol, and 2- Methyl 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentylglycol), 2,2-diethyl-1,3- Propanediol (3,3-dimethylol pentane), 2-n-butyl-2-ethyl-1,3 propanediol (3,3-dimethylolheptane), 3-methyl-1,5-pentanediol 1,6 -Hexanediol, 2,2,4-trimethyl 1,3-pentanediol, 2-ethyl 1,3-hexanediol, 2-methyl 1,8-octanediol, 1,9-nonanediol, 1,10-decane Diol, 1, 12- octadecanediol, etc. are mentioned. Among these, 1,2-propylene glycol is particularly preferable. These glycols may be used alone or as a mixture of two or more thereof.

The aromatic terminal ester plasticizer may be in the form of oligoester or polyester, and the molecular weight is preferably in the range of 100 to 10000, but preferably in the range of 350 to 3000. The acid value is 1.5 mgKOH / g or less, the hydroxyl value is 25 mgKOH / g or less, more preferably the acid value is 0.5 mgKOH / g or less, and the hydroxyl value is 15 mgKOH / g or less.

It is preferable to add 0.5-30 mass parts of aromatic terminal ester plasticizers with respect to 100 mass parts of base films. Although the compound (B-1-B-10) etc. which are specifically shown below are mentioned, It is not limited to these.

In addition, the following sugar ester compound may contain in the base film. The sugar ester compound is a compound obtained by esterifying all or part of OH groups of sugars such as the following monosaccharides, disaccharides, trisaccharides, and oligosaccharides, and examples thereof include compounds represented by the formula (1).

(In formula, R1-R8 represents a substituted or unsubstituted C2-C22 alkyl carbonyl group or a substituted or unsubstituted C2-C22 aryl carbonyl group, and R1-R8 may be same or different.)

Although the compound represented by General formula (1) below is shown more specifically (compound 1-1 to compound 1-23), it is not limited to these. In addition, "average substitution degree" in the following table shows substitution degree of R. FIG. For example, when average substitution degree is 6.0, it shows that the number substituted by R among R1-R8 is 6 on average. And R1-R8 in the compound represented by General formula (1) is unsubstituted, ie, a hydrogen atom couple | bonded except having substituted by R.

It is also preferable that a base film contains a ultraviolet absorber, and the thing of a benzotriazole type, 2-hydroxy benzophenone series, or a salicylic acid phenyl ester system etc. is mentioned as a ultraviolet absorber used. For example, there can be mentioned 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5- , Triazole compounds such as 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy- Phenone, and 2,2'-dihydroxy-4-methoxybenzophenone.

In addition, among ultraviolet absorbers, the ultraviolet absorber having a molecular weight of 400 or more is difficult to volatilize at a high boiling point and difficult to scatter even at high temperature molding, so that weather resistance can be effectively improved by the addition of a relatively small amount.

Examples of the ultraviolet absorbent having a molecular weight of 400 or more include 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2-benzotriazole and 2,2-methylene bis [4- (1 , 1,3,3-tetrabutyl) -6- (2H-benzotriazol-2-yl) phenol] and bis (2,2,6,6-tetramethyl-4-piperidyl ) Sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate Hindered amine type, such as 2- (3,5-di-t-butyl-4- Hydroxybenzyl) -2-n-butylmalonic acid bis (1,2,2,6,6-pentamethyl-4-piperidyl), 1- [2- [3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6 The hybrid system which has the structure of a hindered phenol and a hindered amine together in molecule | numerators, such as tetramethyl piperidine, These can be used individually or in combination of 2 or more types. Among them, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2-benzotriazole or 2,2-methylene bis [4- (1,1,3,3 -Tetrabutyl) -6- (2H-benzotriazol-2-yl) phenol] is particularly preferred.

These may use a commercial item, for example, the tinubin 109, the tinubin 171, the tinubin 234, the tinubin 326, the tinubin 327, the tinubin 328, the tinubin 928 etc. made by BASF Japan company, for example. Tinuvin can be used preferably. Moreover, in order to improve the thermal decomposition property and thermal coloring property at the time of shaping | molding process, various antioxidant can also be added to a base film. It is also possible to add an antistatic agent to impart antistatic properties to the base film.

As the base film, a flame retardant acrylic resin composition containing a phosphorus flame retardant may be used. Examples of the phosphorus flame retardant used herein include triaryl phosphate esters, diaryl phosphate esters, monoaryl phosphate esters, aryl phosphonic acid compounds, aryl phosphine oxide compounds, condensed aryl phosphate esters, halogenated alkyl phosphate esters and halogen-containing condensation. 1 type, or 2 or more types of mixtures chosen from a phosphate ester, a halogen containing condensation phosphonic acid ester, a halogen containing phosphite ester, etc. are mentioned.

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

The base film is required to be able to withstand use in a higher temperature environment, and it can be determined that the tensile softening point of the base film exhibits sufficient heat resistance if it is 105 ° C to 145 ° C, and particularly preferably 110 ° C to 130 ° C. Is preferred.

As a specific measuring method of the tension softening point, an optical film is cut out to 120 mm (length) x 10 mm (width) using the Tensilon tester (The product made from Orientec, RTC-1225A), for example, 10N The temperature is continuously increased at a temperature increase rate of 30 ° C./min while tensioning at a temperature of 3 ° C., and the temperature at the time of 9N can be measured three times, and the average value can be obtained.

In addition, the glass transition temperature here is the intermediate point glass transition temperature measured by the temperature increase rate of 20 degree-C / min using a differential scanning calorimeter (DSC-7 type | mold by Perkin Elmer), and calculated | required according to JISK7121 (1987). (Tmg).

When a base film is used as a protective film for polarizing plates of a liquid crystal display device, a nonuniformity and a change of retardation value generate | occur | produce according to the dimensional change by moisture absorption, and produce problems, such as a fall of contrast and a color unevenness. Said problem will become remarkable if it is a polarizing plate protective film used especially for the liquid crystal display device used outdoors. For this reason, the dimensional change rate (%) is preferably less than 0.5%, and more preferably less than 0.3%. It is preferable that the fault of 5 micrometers or more in diameter inside a film plane is 1/10 cm square or less in a base film. More preferably not more than 0.5 / 10 cm square, more preferably not more than 0.1 / 10 cm square. Here, the diameter of the defect refers to the diameter when the defect has a circular shape, and when the defect is not circular, the range of the defect is determined by observing with a microscope by the following method, and the maximum diameter is defined as the diameter of the circumscribed circle.

The range of the defect is the size of the shadow when the defect is observed as the transmitted light of the differential interference microscope when the defect is bubble or foreign matter. When a fault is a change of surface shape, such as transfer of a scratch or a scratch, a fault is observed with the reflected light of a differential interference microscope, and a magnitude | size is confirmed.

In addition, when observing with reflected light, if the magnitude | size of a fault is unclear, it will observe by depositing aluminum or platinum on a surface. In order to obtain a film having excellent durability represented by such defect frequency at a high productivity, it is necessary to perform high-precision filtration of the polymer solution just before bending, to increase the degree of cleanliness around the bubble generator, Thus, it is effective to efficiently and also suppress foaming and dry.

If the number of defects is more than 1/10 cm square, for example, when tension is applied to the film during processing in a subsequent step, the film may break from the defect and the productivity may decrease. Further, when the diameter of the defect is 5 m or more, it can be visually confirmed by observing the polarizing plate and the like, and a bright spot may be generated when used as an optical member.

Moreover, even when it cannot visually confirm, when a hard-coat layer etc. are formed on the said film, a coating agent cannot be formed uniformly and may become a fault (application omission). Here, a fault means the foreign material in a film (foreign defect) resulting from the cavity (foaming defect) in the film which arises from the rapid evaporation of a solvent in the drying process of solution film forming, the foreign material in a film forming undiluted | stock solution, or the foreign material mixed in film forming. Say.

Moreover, in the measurement based on JIS-K7127-1999, it is preferable that the breaking elongation of at least one direction is 10% or more, More preferably, it is 20% or more. The upper limit of the elongation at break is not particularly limited, but is about 250% in reality. In order to enlarge breaking elongation, it is effective to suppress the fault in the film resulting from a foreign material and foaming. It is preferable that the thickness of a base film is 10 micrometers or more. More preferably, it is 20 micrometers or more. Although the upper limit of thickness is not specifically limited, When film-forming by the solution film forming method, an upper limit is about 250 micrometers from a viewpoint of applicability | paintability, foaming, and solvent drying. In addition, the thickness of a film can be suitably selected according to a use.

It is preferable that the total light transmittance of a base film is 90% or more, More preferably, it is 93% or more. In addition, the upper limit is about 99%. In order to achieve excellent transparency expressed by such a total light transmittance, it is necessary not to introduce an additive or a copolymerizing component which absorbs visible light, or to remove foreign substances in the polymer by high precision filtration, thereby preventing diffusion or absorption of light inside the film. It is effective to reduce. Moreover, the surface roughness of the film contact part (cooling roll, calender roll, drum, belt, coating base material, conveyance roll, etc. in solution film forming, etc.) at the time of film forming is made small, and the surface roughness of a film surface is made small, and the refractive index of an acrylic resin It is effective to reduce the diffusion and reflection of light on the film surface by making it small.

(Film forming of base film)

Next, an example of the film-forming method of the substrate film is described, but the present invention is not limited thereto. As a film forming method of a base film, manufacturing methods, such as an inflation method, a T-die method, a calendar method, a cutting method, a casting method, an emulsion method, and a hot press method, can be used.

The method of producing by the melt casting film formation method is preferable at the point of the residual suppression of the solvent which used the cellulose ester resin and the acrylic resin for melt | dissolution. The method of forming by melt casting can be classified into a melt extrusion molding method, a press molding method, an inflation method, an injection molding method, a blow molding method, and a stretching molding method. Among them, the melt extrusion method is preferable in which a film having excellent mechanical strength and surface precision is obtained. Moreover, the solution film forming by the casting | flow_spread method is preferable from a viewpoint of coloring suppression, suppression of a foreign material fault, suppression of optical faults, such as a die line. Moreover, the method of film-forming material heated, expressing the fluidity, and extruded and forming into a film on a drum or an endless belt is also included as a melt casting film forming method.

(Organic solvent)

The organic solvent useful for forming the dope when the base film is prepared by the solution casting method can be used without limitation as long as it dissolves the acrylic resin, the cellulose ester resin and other additives at the same time.

For example, as the chlorine organic solvent, methylene chloride, and the non-chlorine organic solvent, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclo Hexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1 , 3,3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-penta Fluoro-1-propanol, nitroethane, etc. are mentioned, Methylene chloride, methyl acetate, ethyl acetate, acetone can be used preferably.

The dope preferably contains a linear or branched aliphatic alcohol having 1 to 4 carbon atoms in an amount of 1 to 40 mass% in addition to the above-mentioned organic solvent. When the proportion of alcohol in the dope is high, the web is gelled to facilitate peeling from the metal support. When the proportion of alcohol is small, the role of promoting the dissolution of the acrylic resin and the cellulose ester resin in the non-chlorinated organic solvent system have. In particular, the dope composition which melt | dissolved three types of an acrylic resin, a cellulose ester resin, and an acryl particle at least 15-45 mass% in total in the solvent containing methylene chloride and a C1-C4 linear or branched aliphatic alcohol. Is preferably. Examples of the linear or branched aliphatic alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol and tert-butanol. Of these, ethanol is preferable in terms of dope stability, relatively low boiling point, and good drying property.

(Solution softening method)

The base film can be produced by a solution casting method. In the solution casting method, a step of preparing a dope by dissolving a resin and an additive in a solvent, a step of casting the dope on a belt or drum-shaped metal support, a step of drying the flexible dope as a web, a step of peeling from the metal support, It carries out by the process of extending | stretching or holding a width, the process of drying, and the process of winding up the finished film.

The concentration of the cellulose ester and the cellulose ester resin / acrylic resin in the dope is preferable because a high concentration can reduce the dry load after being flexible to the metal support, but when the concentration of the cellulose ester is too high, the load at the time of filtration increases and the filtration The precision worsens. As a density | concentration which makes these compatible, 10-35 mass% is preferable, More preferably, it is 15-25 mass%. It is preferable that the surface of the metal support body in the casting process is mirror-finished, and as a metal support body, the drum which plated the surface with the stainless steel belt or the casting is used preferably.

The width of the cast may be 1 to 4 m. The surface temperature of the metal support of the flexible process is set at -50 캜 to a temperature not exceeding the temperature at which the solvent boils and does not foam. A high temperature is preferable because it can speed up the drying speed of the web. However, if the temperature is too high, the web may foam or the planarity may be degraded.

As preferable support body temperature, it determines suitably at 0-100 degreeC, and 5-30 degreeC is more preferable. Alternatively, it is preferable that the web be gelled by cooling to peel off the drum in a state containing a large amount of residual solvent. The method of controlling the temperature of the metal support is not particularly limited, but there is a method of blowing hot air or cold air hard or a method of bringing hot water into contact with the back side of the metal support. Use of hot water is preferable because heat is efficiently transferred and the time until the temperature of the metal support becomes constant is short.

In the case of using hot wind, in consideration of the temperature decrease of the web due to the latent heat of evaporation of the solvent, the hot wind above the boiling point of the solvent may be used while the wind at a temperature higher than the desired temperature is used while preventing foaming.

Particularly, it is preferable to change the temperature of the support and the temperature of the drying wind during the period from the softening to the peeling, thereby efficiently performing drying.

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

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

Amount of residual solvent (mass%) = {(M-N) / N} 100

M is the mass of the sample taken at any time point during or after the production of the web or film, and N is the mass after heating at 115 DEG C for 1 hour.

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

In the film drying process, generally, the method of drying while conveying a web is employ | adopted by the roll drying method (the method of passing-drying a web to many rolls arrange | positioned up and down) and the tenter system.

(Drawing step)

In an extending process, it can extend | stretch in order or simultaneously with respect to the longitudinal direction (MD direction) and the width direction (TD direction) of a film. The stretching ratio in the biaxial direction perpendicular to each other is preferably in the range of 1.0 to 2.0 times in the MD direction and 1.07 to 2.0 times in the TD direction, respectively, and 1.0 to 1.5 times in the MD direction and 1.07 in the TD direction. It is preferable to carry out in the range of -2.0 times. For example, a circumferential speed difference is provided in a plurality of rolls, and in the meantime, the circumferential speed difference is used to extend in the MD direction. The method of extending | stretching to MD direction, the method of extending | stretching to a TD direction by extending horizontally, or the method of extending | stretching to both directions of MD / TD simultaneously extending | stretching MD / TD direction etc. are mentioned. It is preferable to perform these width retention or extending | stretching of the width direction of a film forming process with a tenter, and a pin tenter or a clip tenter may be sufficient.

Although film conveyance tension in film forming processes, such as in a tenter, also depends on temperature, 120N / m-200N / m are preferable and 140N / m-200N / m are more preferable. Most preferred are 140N / m to 160N / m.

When extending | stretching, when glass transition temperature of a base film is Tg, it is (Tg-30)-Tg + 100) degreeC, More preferably, (Tg-20)-Tg + 80) degreeC, More preferably, it is (Tg-5) ) To Tg + 20) ° C.

Tg of a base film can be controlled by the ratio of the material type which comprises a film, and the material which comprises. In the use of this invention, 110 degreeC or more is preferable and, as for Tg at the time of drying of a film, 120 degreeC or more is preferable. Especially preferably, it is 150 degreeC or more.

Therefore, it is preferable that glass transition temperature is 190 degrees C or less, More preferably, it is 170 degrees C or less. At this time, Tg of a film can be calculated | required by the method of JISK7121, etc.

When extending | stretching temperature is 150 degreeC or more and draw ratio is 1.15 times or more, since the surface becomes moderately rough, it is preferable. Roughening a film surface is preferable because it improves not only sliding property but also surface workability, especially adhesiveness of an anti-glare layer.

(Melt film forming method)

The base film may be formed by a melt film forming method. The melt film-forming method refers to heating and melting a composition including an additive such as a resin and a plasticizer to a temperature at which fluidity is exhibited, and thereafter flexing a melt containing a fluid cellulose ester.

In more detail, the shaping | molding method which heat-melts can be classified into a melt extrusion molding method, a press molding method, an inflation method, an injection molding method, a blow molding method, an extending molding method, etc. Of these molding methods, the melt extrusion method is preferable in terms of mechanical strength and surface precision. It is preferable that a plurality of raw materials used for melt extrusion are usually previously kneaded and pelletized.

Pelletization may be a well-known method, For example, dry cellulose ester, a plasticizer, and other additives are supplied to an extruder by a feeder, it knead | mixes using a single screw or a twin screw extruder, and it extrudes into a strand shape from a die, and is water-cooled or It can do by air-cooling and cutting.

The additives may be mixed before being fed to the extruder or may be fed to individual feeders, respectively.

Small amounts of additives such as particles and antioxidants are preferably mixed in advance in order to mix them uniformly.

The extruder is capable of pelletizing so that the shearing force is suppressed and the resin does not deteriorate (molecular weight decrease, coloring, gel formation, etc.) and is preferably processed at a low temperature as possible. For example, in the case of a twin screw extruder, it is preferable to rotate in the same direction using a screw of a deep groove type. In view of the uniformity of kneading, the engagement type is preferred.

Film formation is carried out using the pellets obtained as described above. Of course, it is also possible to feed the powder of the raw material directly to the extruder by using a feeder, without forming pellets, and to form the film as it is.

After the pellets are extruded using a single screw or twin screw extruder, the melt temperature at the time of extruding is set to about 200 to 300 ° C., filtered through a leaf disk type filter or the like to remove foreign substances, and then cast into a film form from the T die. Thus, the film is nip with the cooling roll and the elastic touch roll to solidify on the cooling roll.

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

The extrusion flow rate is preferably stably performed by introducing a gear pump. In addition, a stainless steel fiber sintered filter is preferably used as the filter used for removing the foreign matter. The stainless fiber sintered filter is a product in which a stainless fiber body is intricately entangled, compressed, and then sintered and integrated into contact points. The density can be changed according to the thickness and the amount of compression of the fiber, and the filtration precision can be adjusted.

Additives, such as a plasticizer and particle | grains, may be previously mixed with resin, and may be thrown in the middle of an extruder. In order to uniformly add it, it is preferable to use a mixing device such as a static mixer.

It is preferable that the film temperature on the touch roll side at the time of nipping a film with a cooling roll and an elastic touch roll shall be Tg or more and Tg + 110 degrees C or less of a film. A well-known roll can be used for the roll which has an elastic body surface used for such an objective.

The elastic touch roll is also referred to as a nip pressurizing rotor. What is marketed can also be used as an elastic touch roll.

When peeling a film from a cooling roll, it is preferable to control tension and prevent deformation of a film.

Moreover, it is preferable to extend | stretch by the said extending | stretching operation, after the film obtained by passing through the process of contact | connecting a cooling roll.

As a method of extending | stretching, a well-known roll stretching machine, a tenter, etc. can be used preferably. The stretching temperature is preferably set in the range of Tg to Tg + 60 占 폚 of the resin constituting the film.

Before winding up, the edge part may be slit and cut off to a width to be a product, and knurling processing (embossing processing) may be performed at both ends in order to prevent sticking or scratching during winding up. A method of knurling can be performed by heating or pressing a metal ring having a concavo-convex pattern on its side surface. In addition, since the film is deformed and cannot be used as a product, the holding | gripping part of the clip of film both ends is cut off and recycled normally.

(Property of base film)

Although the film thickness of the base film in this embodiment is not specifically limited, 10-200 micrometers is used. It is especially preferable that the film thickness is 10-100 micrometers. More preferably, it is 20-60 micrometers.

As for the base film which concerns on this embodiment, the thing of width 1-4m is used. Particularly preferably 1.4 to 4 m in width, and particularly preferably 1.6 to 3 m in width. If it exceeds 4 m, it becomes difficult to transport.

In addition, the arithmetic mean roughness Ra of a base film becomes like this. Preferably it is 2.0 nm-4.0 nm, More preferably, it is 2.5 nm-3.5 nm.

<Functional layer>

The anti-glare film which concerns on this embodiment can form functional layers, such as a backcoat layer and an antireflection layer.

(Back coat layer)

The anti-glare film which concerns on this embodiment may form a backcoat layer in the surface on the opposite side to the side where the anti-glare layer of the base film was formed in order to prevent sticking when the curl and the anti-glare film were stored in a wound shape. .

It is preferable that a backcoat layer contains microparticles | fine-particles for the said objective, As microparticles | fine-particles, a silicon dioxide, titanium dioxide, aluminum oxide, a zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, oxide Tin, indium oxide, zinc oxide, ITO, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. Moreover, in order to disperse | distribute the said fine particle and to melt | dissolve the binder mentioned later to make a coating composition, it is preferable to contain a solvent. As a solvent, the solvent demonstrated by the anti-glare layer is preferable. The content of the particles contained in the back coat layer is preferably from 0.1 to 50 mass% with respect to the binder. When the backcoat layer is provided, the increase in haze is preferably 1.5% or less and 0.5% or less. As the binder, it is preferable to use a cellulose ester resin such as diacetyl cellulose.

(Antireflection layer)

The anti-glare film of this embodiment forms the low-refractive-index layer which is an antireflection layer directly or over another layer on an anti-glare layer, and is excellent in the adhesiveness of a low-refractive-index layer and an anti-glare layer, and also generate | occur | produces spot unevenness of a low-refractive-index layer. It is preferable to use the anti-glare film of this invention for an anti-glare antireflection film from the point which can suppress favorably and the outstanding external appearance is obtained. The antireflection layer including the low refractive index layer may have a single layer configuration only of the low refractive index layer, or may be a multilayer. Specifically, it can be comprised combining the high refractive index layer which has a higher refractive index than a support body, and the low refractive index layer which has a lower refractive index than a support body. Further, three layers having different refractive indices on the support side may be laminated in the order of a medium refractive index layer (a layer having a higher refractive index than the support or the antiglare layer and having a lower refractive index than the high refractive index layer) / high refractive index layer / low refractive index layer. Moreover, the antireflection layer of the four or more layered constitution which laminated | stacked two or more high refractive index layers and two or more low refractive index layers alternately is also used preferably. Examples of preferred layer configurations of the antireflection layer are shown below. Here, / indicates that the layers are stacked.

Base film / antiglare layer / low refractive index layer

Base Film / Antiglare Layer / High Refractive Index Layer / Low Refractive Index Layer

Base film / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer

An antifouling layer may be further provided on the low refractive index layer of the outermost surface so as to easily wipe off dirt and fingerprints. As the antifouling layer, a fluorine-containing organic compound is preferably used.

As long as reflectance can be reduced by optical interference, it is not specifically limited only to these layer structures. In the above layer structure, as appropriate it may be formed an intermediate layer, for example conductive polymer fine particles (for example, cross-linked cationic fine particles) or metal oxide fine particles antistatic layer, etc., including (for example, SnO _2, ITO, etc.) desirable.

<Low Refractive Index Layer>

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

The film thickness of the low refractive index layer is not particularly limited, but is preferably 5 nm to 0.5 µm, more preferably 10 nm to 0.3 µm, and most preferably 30 nm to 0.2 µm. In addition, it is preferable to use hollow spherical silica type microparticles | fine-particles for the low refractive index layer from a viewpoint of refractive index adjustment or mechanical strength.

(Hollow spherical silica-based fine particles)

The hollow spherical fine particles are composite particles comprising (I) porous particles and a coating layer provided on the surface of the porous particles, or (II) hollow particles having a cavity inside and filled with a solvent, a gas or a porous material. . In addition, either the (I) composite particle or the (II) cavity particle should just be included in the low refractive index layer, and both may be included.

Also, the cavity is a particle having a cavity therein, and the cavity is surrounded by the particle wall. The cavity is filled with the contents such as a solvent, a gas or a porous material used in the production. It is preferable that the average particle diameter of such hollow spherical microparticles | fine-particles exists in the range of 5-300 nm, Preferably it is 10-200 nm. The hollow spherical microparticles | fine-particles used are suitably selected according to the thickness of the transparent film formed, and it is preferable to exist in the range of 2/3-1/10 of the film thickness of transparent films, such as the low refractive index layer formed. It is preferable to use these hollow spherical fine particles in the state disperse | distributed to a suitable medium for formation of a low refractive index layer. As a dispersion medium, water, alcohol (for example, methanol, ethanol, isopropyl alcohol), ketone (for example, methyl ethyl ketone, methyl isobutyl ketone), ketone alcohol (for example diacetone alcohol) are preferable. .

The thickness of the coating layer of the composite particles or the thickness of the particle wall of the cavity particles is preferably in the range of 1 to 20 nm, preferably 2 to 15 nm. In the case of the composite particles, when the thickness of the coating layer is less than 1 nm, the particles may not be completely covered, and silicic acid monomers, oligomers, and the like having a low polymerization degree, which are the coating liquid components described later, easily enter the interior of the composite particles. Porosity decreases, and the effect of low refractive index may not be sufficiently obtained. When the thickness of the coating layer exceeds 20 nm, the silicic acid monomers and oligomers do not enter the interior, but the porosity (pore volume) of the composite particles may be lowered, whereby the effect of low refractive index may not be sufficiently obtained. In the case of the cavity particles, when the thickness of the particle wall is less than 1 nm, the particle shape may not be maintained, and even if the thickness exceeds 20 nm, the effect of the low refractive index may not be sufficiently exhibited.

The coating layer of the composite particle or the particle wall of the cavity particle preferably contains silica as a main component. In addition, it is optionally contain a component other than silica, and _{specifically, Al 2 O 3, B 2} O 3, TiO 2, ZrO 2, SnO 2, CeO 2, P 2 O 3, Sb 2 O 3, MoO 3 , ZnO ₂ , WO ₃ , and the like. Examples of the porous particles constituting the composite particles include those containing silica, those containing inorganic compounds other than silica and silica, and those containing CaF ₂ , NaF, NaAlF ₆ , MgF, and the like. Among these, porous particles including a composite oxide of an inorganic compound other than silica and silica are particularly suitable. Examples of inorganic compounds other than silica include Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , MoO ₃ , ZnO ₂ , WO _3, and the like. 1 type, or 2 or more types are mentioned. In such porous particles, the molar ratio (MOX / SiO ₂ ) when silica is represented by SiO ₂ and inorganic compounds other than silica in oxide equivalent (MOX) is in the range of 0.0001 to 1.0, preferably 0.001 to 0.3. It is desirable to have. It is difficult to obtain that the molar ratio (MOX / SiO ₂ ) of the porous particles is less than 0.0001. Even if obtained, the pore volume is small and particles having a low refractive index cannot be obtained. In addition, when the molar ratio (MOX / SiO ₂ ) of the porous particles exceeds 1.0, since the ratio of silica decreases, it may be difficult to obtain a large pore volume and a low refractive index. The pore volume of such porous particles is preferably in the range of 0.1 to 1.5 ml / g, preferably 0.2 to 1.5 ml / g. If the pore volume is less than 0.1 ml / g, particles with sufficiently low refractive index cannot be obtained. If the pore volume is more than 1.5 ml / g, the strength of the fine particles decreases, and the strength of the obtained film may decrease. In addition, the pore volume of such a porous particle can be calculated | required by the mercury porosimetry. Such hollow spherical microparticles | fine-particles can be manufactured from the following 1st-3rd process.

First Step: Production of Porous Particle Precursor

In the first step, an alkali aqueous solution of a silica raw material and an inorganic compound raw material other than silica is produced separately, or a mixed aqueous solution of a silica raw material and an inorganic compound raw material other than silica is prepared, and the aqueous solution is Depending on the complex ratio of the complex oxides, the porous particle precursor is prepared by slowly adding the solution into an aqueous alkali solution having a pH of 10 or more.

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

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

Simultaneously with the addition of these aqueous solutions, the pH value of the mixed aqueous solution changes, but an operation for controlling the pH value in a predetermined range is not particularly necessary. The aqueous solution finally becomes a pH value determined according to the kind of inorganic oxide and its mixing ratio. The rate of addition of the aqueous solution at this time is not particularly limited. It is also possible to use a dispersion of seed particles as a starting material in the production of the composite oxide particles. In the art seed particles is not particularly limited, _{but, SiO 2, Al 2 O 3} , TiO 2 or ZrO _2, etc. of the inorganic oxide or fine particles of a composite oxide of them is used, it is possible to use a normal, these sol. The dispersion of the porous particle precursor obtained by the above production method may be used as a seed particle dispersion. When using a seed particle dispersion, after adjusting the pH of a seed particle dispersion to 10 or more, the aqueous solution of the said compound is added to the said seed particle dispersion, stirring in said aqueous alkali solution. In this case also, it is not necessary to necessarily control the pH of the dispersion. By using the seed particles in this way, it is easy to control the particle diameter of the porous particles to be produced, and it is possible to obtain a sorted particle size.

The above-mentioned silica raw material and inorganic compound raw material have a high solubility on the alkali side. However, when the both are mixed in the pH range where the solubility is large, the solubility of oxo acid ions such as silicate ions and aluminate ions decreases, and these complexes precipitate and grow into fine particles, or precipitate on seed particles. Growth takes place. Therefore, at the time of precipitation and growth of fine particles, the pH control like the conventional method is not necessarily performed.

In the composite ratio of silica and inorganic compounds other than silica in the first step, the inorganic compound to silica is converted into an oxide (MOX), and the molar ratio of MOX / SiO ₂ is in the range of 0.05 to 2.0, preferably 0.2 to 2.0. It is desirable to stay within. Within this range, the smaller the proportion of silica, the larger the pore volume of the porous particles. However, even if the molar ratio exceeds 2.0, the pore volume of the porous particles hardly increases. On the other hand, when the molar ratio is less than 0.05, the pore volume becomes small. When manufacturing a Co particle, the mole ratio of MOX / SiO ₂ is preferably in the range of 0.25 to 2.0.

Step 2: Removal of inorganic compounds other than silica from porous particles

In the second step, at least a part of inorganic compounds (elements other than silicon and oxygen) other than silica are selectively removed from the porous particle precursor obtained in the first step. As a specific removal method, the inorganic compound in a porous particle precursor is dissolved and removed using an inorganic acid or an organic acid, or it is ion-exchange-removed by contacting with a cation exchange resin.

In addition, the porous particle precursor obtained by a 1st process is the particle | grains of the mesh structure which the silicon and the inorganic compound structural element couple | bonded through oxygen. Thus, by removing an inorganic compound (elements other than silicon and oxygen) from a porous particle precursor, the porous particle which is further porous and has a large pore volume is obtained. Further, if the amount of the inorganic oxide (element other than silicon and oxygen) removed from the porous particle precursor is increased, the hollow particles can be produced.

In addition, a silicic acid solution or a valence containing a fluorine-substituted alkyl group-containing silane compound obtained by de-alkali alkali metal salt of silica in the porous particle precursor dispersion liquid obtained in the first step before removing the inorganic compound other than silica from the porous particle precursor. It is preferable to form a silica protective film by adding a decomposable organosilicon compound. The thickness of a silica protective film should just be 0.5-15 nm in thickness. Even if a silica protective film is formed, since the protective film in this step is porous and thin, it is possible to remove inorganic compounds other than the silica from the porous particle precursor.

By forming such a silica protective film, inorganic compounds other than said silica can be removed from a porous particle precursor, maintaining particle shape. In addition, when forming the silica coating layer mentioned later, the pore of a porous particle does not block | block by a coating layer, For this reason, a silica coating layer mentioned later can be formed without reducing pore volume. When the amount of the inorganic compound to be removed is small, the particles are not broken, so it is not necessary to form a protective film.

Further, in the case of producing the hollow particles, it is preferable to form this silica protective film. When preparing the hollow particles, the inorganic compound is removed to obtain a precursor of the hollow particles comprising a silica protective film, a solvent in the silica protective film, and an undissolved porous solid, and a coating layer described later in the precursor of the hollow particles. When formed, the formed coating layer becomes a particle wall, and hollow particles are formed.

The amount of the silica source to be added for forming the silica protective film is preferably as small as possible within the range of maintaining the shape of the particles. If the amount of the silica source is too large, the silica protective film becomes too thick, so it may be difficult to remove inorganic compounds other than silica from the porous particle precursor. Examples of the hydrolyzable organosilicon compound used for forming the silica protective film include a chemical formula RnSi (OR ') _4-n [R, R': a hydrocarbon group such as an alkyl group, an aryl group, a vinyl group, an acryl group, n = 0, 1, 2 or 3] can be used. In particular, tetraalkoxy silanes, such as fluorine-substituted tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane, are used preferably.

As the addition method, an inorganic oxide is obtained by adding a solution in which a small amount of alkali or acid as a catalyst is added to a mixed solution of these alkoxysilanes, pure water and alcohols, in addition to the dispersion liquid of the porous particles, to produce a silicic acid polymer produced by hydrolyzing alkoxysilanes. Deposit on the surface of the particles. At this time, you may add an alkoxysilane, alcohol, and a catalyst in a dispersion liquid simultaneously. As the alkali catalyst, ammonia, hydroxides of alkali metals, and amines can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

When the dispersion medium of the porous particle precursor is high in water alone or in a ratio of water to an organic solvent, it is also possible to form a silica protective film using a silicic acid solution. In the case of using a silicic acid solution, a predetermined amount of the silicic acid solution is added to the dispersion, and an alkali is added at the same time to deposit the silicic acid solution on the surface of the porous particles. In addition, a silica protective film may be produced by using a silicate liquid and the alkoxysilane in combination.

Step 3: Formation of a silica coating layer

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

Examples of the hydrolyzable organosilicon compound used for forming the silica coating layer include hydrocarbon groups such as the above-described formula RnSi (OR ') _4-n [R, R': alkyl group, aryl group, vinyl group, acrylic group, alkoxysilane represented by n = 0, 1, 2 or 3] can be used. Particularly, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane and tetraisopropoxysilane are preferably used.

As the addition method, a solution in which a small amount of alkali or acid as a catalyst is added to a mixed solution of these alkoxysilanes, pure water and alcohol is added to the alkoxysilane in addition to the dispersion of the porous particles (co-particle precursor in the case of co-particles). The silicic acid polymer produced by decomposition is deposited on the surface of the porous particles (cavity precursor in the case of hollow particles). At this time, you may add an alkoxysilane, alcohol, and a catalyst in a dispersion liquid simultaneously. As the alkali catalyst, ammonia, hydroxides of alkali metals, and amines can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

The dispersion medium of the porous particles (co-particle precursor in the case of co-particles) is water alone or a mixed solvent with an organic solvent, and in the case of a mixed solvent having a high ratio of water to the organic solvent, a coating layer may be formed using a silicic acid solution. do. The silicic acid solution is an aqueous solution of a low-polymerized silicic acid solution obtained by ion-exchanging an aqueous solution of an alkali metal silicate such as water glass.

The silicic acid solution is added to the porous particle (co-particle precursor in the case of co-particles) dispersion and at the same time an alkali is added to deposit the silicic acid low-polymers on the surface of the porous particles (co-particle precursor in the case of co-particles). In addition, you may use a silicic acid liquid for the coating layer formation in combination with the said alkoxysilane. The amount of the organosilicon compound or silicic acid solution used for forming the coating layer may be such that the surface of the colloidal particles can be sufficiently covered, and the amount of the finally-coated silica coating layer becomes 1 to 20 nm. In the case of particles are added in a co-particle precursor) dispersion. In addition, when the said silica protective film is formed, an organosilicon compound or a silicic acid solution is added in the quantity in which the sum total thickness of a silica protective film and a silica coating layer becomes 1-20 nm.

Subsequently, the dispersion of the particles in which the coating layer is formed is heat-treated. By the heat treatment, in the case of porous particles, the silica coating layer which coats the porous particle surface is densified, and the dispersion liquid of the composite particle by which the porous particle was coat | covered with the silica coating layer is obtained. Further, in the case of the cavity particle precursor, the formed coating layer is densified to become the cavity particle wall, whereby a dispersion of the cavity particles having a cavity filled with a solvent, a gas or a porous solid is obtained.

There is no restriction | limiting in particular if the heat processing temperature at this time is a grade which can close the micropore of a silica coating layer, The range of 80-300 degreeC is preferable. If the heat treatment temperature is less than 80 ° C., the fine pores of the silica coating layer may be completely blocked and may not be densified, and the treatment time may take a long time. Moreover, when heat processing temperature exceeds 300 degreeC and processing for a long time, it may become a dense particle and the effect of a low refractive index may not be acquired.

The refractive index of the inorganic fine particles thus obtained is low, lower than 1.42. Such inorganic fine particles are estimated to have a low refractive index because the porosity inside the porous particles is maintained or the inside is a cavity. In addition, commercially available SiO ₂ fine particles can be used. As a specific example of the particle | grains marketed, P-4 by Shokubai Kasei Kogyo Co., etc. are mentioned.

10-80 mass% is preferable, and, as for content (mass) in the low refractive index layer coating liquid of the hollow spherical silica-type microparticles | fine-particles which has an outer layer and is porous or hollow inside, More preferably, it is 20-60 mass%.

(The tetraalkoxysilane compound or its hydrolyzate)

It is preferable that the low refractive index layer contains a tetraalkoxysilane compound or its hydrolyzate as a sol-gel raw material. As a raw material for a low refractive index layer, it is also preferable to use the silicon oxide which has organic group other than the said inorganic silicon oxide. These are generally called sol-gel materials, and metal alcoholates, organoalkoxy metal compounds and hydrolyzates thereof can be used. In particular, an alkoxysilane, an organoalkoxysilane, and its hydrolyzate are preferable. Examples of these include tetraalkoxysilanes (tetramethoxysilane, tetraethoxysilane, etc.), alkyltrialkoxysilanes (methyltrimethoxysilane, ethyltrimethoxysilane, etc.), aryltrialkoxysilanes (phenyltrimethoxysilane Etc.), a dialkyl dialkoxysilane, a diaryl dialkoxysilane, etc. are mentioned. In particular, tetraalkoxysilane and its hydrolyzate are preferable.

Furthermore, organoalkoxysilane (vinyl trialkoxysilane, methylvinyl dialkoxysilane, (gamma)-glycidyloxypropyl trialkoxysilane, (gamma)-glycidyloxypropyl methyl dialkoxysilane which has various functional groups, (beta)-(3, 4-epoxycyclohexyl) ethyl trialkoxysilane, γ-methacryloyloxypropyl trialkoxysilane, γ-aminopropyl trialkoxysilane, γ-mercaptopropyl trialkoxysilane, γ-chloropropyl trialkoxysilane, etc.), Perfluoroalkyl group-containing silane compounds (eg, (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane, 3,3,3-trifluoropropyl trimethoxysilane, etc.) It is also preferable to use. It is particularly preferable to use a fluorine-containing silane compound from the viewpoint of lowering the refractive index of the layer and imparting water / oil repellency.

When hydrolyzing the said tetraalkoxysilane, it is preferable to mix the said inorganic fine particle in order to raise a film strength. It is preferable that a low refractive index layer contains the said silicon oxide and the following silane coupling agents.

Examples of specific silane coupling agents include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxy Silane, vinyl trimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyl trimethoxyethoxysilane, phenyltrimethoxysilane, phenyl triethoxysilane, phenyl triacetoxysilane, γ-chloropropyl Trimethoxysilane, γ-chloropropyl triethoxysilane, γ-chloropropyl triacetoxysilane, 3,3,3-trifluoropropyl trimethoxysilane, γ-glycidyloxypropyl trimethoxysilane, γ-glycidyloxypropyl triethoxysilane, γ- (β-glycidyloxyethoxy) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- ( 3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-acryloyl jade Propyl trimethoxysilane, γ-methacryloyloxypropyl trimethoxysilane, γ-aminopropyl trimethoxysilane, γ-aminopropyl triethoxysilane, γ-mercaptopropyl trimethoxysilane, γ-mer And captopropyl triethoxysilane, N-β- (aminoethyl) -γ-aminopropyl trimethoxysilane and β-cyanoethyl triethoxysilane.

Moreover, as an example of the silane coupling agent which has a bisubstituted alkyl group with respect to silicon, dimethyl dimethoxysilane, phenylmethyl dimethoxysilane, dimethyl diethoxysilane, phenylmethyl diethoxysilane, (gamma)-glycidyloxypropylmethyl diethoxy Silane, γ-glycidyloxypropylmethyl dimethoxysilane, γ-glycidyloxypropylphenyl diethoxysilane, γ-chloropropylmethyl diethoxysilane, dimethyl diacetoxysilane, γ-acryloyloxypropylmethyl dimethoxy Oxysilane, γ-acryloyloxypropylmethyl diethoxysilane, γ-methacryloyloxypropylmethyl dimethoxysilane, γ-methacryloyloxypropylmethyl diethoxysilane, γ-mercaptopropyl methyldimethoxysilane , γ-mercaptopropyl methyldiethoxysilane, γ-aminopropyl methyldimethoxysilane, γ-aminopropyl methyldiethoxysilane, methylvinyldimethoxysilane and methylvinyldiethoxysilane.

Among them, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl triacetoxysilane, vinyl trimethoxyethoxysilane, γ-acryloyloxypropyl trimethoxysilane and γ-meta having a double bond in the molecule Cryloyloxypropyl trimethoxysilane, γ-acryloyloxypropylmethyl dimethoxysilane, γ-acryloyloxypropylmethyl diethoxysilane, γ-methacryloyl as having a disubstituted alkyl group for silicon Preferred are oxypropylmethyl dimethoxysilane, γ-methacryloyloxypropylmethyl diethoxysilane, methylvinyldimethoxysilane and methylvinyldiethoxysilane, and γ-acryloyloxypropyl trimethoxysilane and γ-meta Cryloyloxypropyl trimethoxysilane, γ-acryloyloxypropylmethyl dimethoxysilane, γ-acryloyloxypropylmethyl diethoxysilane, γ-methacryloyloxypropylmethyl dimethoxysilane And γ-methacryloyloxypropylmethyl diethoxysilane are particularly preferred.

As a specific example of a silane coupling agent, Shin-Etsu Chemical Co., Ltd. KBM-303, KBM-403, KBM-402, KBM-403, KBM-1403, KBM-502, KBM-503, KBE-502 , KBE-503, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM-802, KBM-803 and the like.

Two or more kinds of coupling agents may be used in combination. In addition to the silane coupling agent shown above, you may use another silane coupling agent. Other silane coupling agents include alkyl esters of ortho silicate (for example, methyl ortho silicate, ortho silicate silica, ortho silicate n-propyl, ortho silicate i-propyl, ortho silicate n-butyl, ortho silicate sec-butyl, ortho silicate) t-butyl) and its hydrolyzate.

Moreover, the low refractive index layer may contain the polymer of the quantity of 5-50 mass%. The polymer has a function of adhering the fine particles to maintain the structure of the low refractive index layer containing voids. The amount of the polymer used is adjusted to maintain the strength of the low refractive index layer without filling the voids. It is preferable that the quantity of a polymer is 10-30 mass% of the whole quantity of a low refractive index layer. In order to adhere the fine particles with the polymer, (1) the polymer is bound to the surface treatment agent of the fine particles, (2) the fine particles are used as a core, a polymer shell is formed around the surface, or (3) the binder is used as a binder between the fine particles. It is preferable to use. It is preferable that the polymer couple | bonded with the surface treating agent of (1) is the shell polymer of (2) or the binder polymer of (3). It is preferable to form the polymer of (2) by a polymerization reaction around microparticles | fine-particles before manufacture of the coating liquid of a low refractive index layer. It is preferable that the polymer of (3) is added by the monomer to the coating liquid of a low refractive index layer, and is formed by a polymerization reaction simultaneously with or after application | coating of a low refractive index layer. It is preferable to carry out combining two or all of said (1)-(3), and it is especially preferable to carry out by the combination of (1) and (3), or the combination of all (1)-(3). . (1) Surface treatment, (2) shell, and (3) binder are demonstrated one by one.

(1) surface treatment

It is preferable to surface-treat microparticles | fine-particles (especially inorganic microparticles | fine-particles) and to improve affinity with a polymer. Surface treatment can be classified into physical surface treatments, such as a plasma discharge treatment and a corona discharge treatment, and the chemical surface treatment using a coupling agent. It is preferable to carry out only chemical surface treatment or a combination of physical surface treatment and chemical surface treatment. As the coupling agent, an organoalkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. When the fine particles comprising an SiO _2, it is possible to perform particularly effective for surface treatment according to the above-described silane coupling agent.

Surface treatment with a coupling agent can be performed by adding a coupling agent to the dispersion of microparticles | fine-particles, and leaving a dispersion for several hours to 10 days at room temperature-60 degreeC. In order to promote the surface treatment reaction, inorganic acids (e.g. sulfuric acid, hydrochloric acid, nitric acid, chromic acid, hypochlorous acid, boric acid, orthosilicic acid, phosphoric acid, carbonate), organic acids (e.g. acetic acid, polyacrylic acid, benzenesulfonic acid, phenol , Polyglutamic acid), or salts thereof (for example, metal salts and ammonium salts) may be added to the dispersion.

(2) shell

It is preferable that the polymer which forms a shell is a polymer which has a saturated hydrocarbon as a principal chain. Polymers containing fluorine atoms in the main chain or side chains are preferred, and polymers containing fluorine atoms in the side chains are more preferred. Polyacrylic acid ester or polymethacrylic acid ester is preferable, and ester of a fluorine-substituted alcohol and polyacrylic acid or polymethacrylic acid is the most preferable. The refractive index of a shell polymer falls with increase of content of the fluorine atom in a polymer. In order to reduce the refractive index of a low refractive index layer, it is preferable that a shell polymer contains 35-80 mass% fluorine atoms, and it is more preferable that 45-75 mass% fluorine atoms are included. It is preferable to synthesize | combine the polymer containing a fluorine atom by the polymerization reaction of the ethylenically unsaturated monomer containing a fluorine atom. Examples of ethylenically unsaturated monomers containing fluorine atoms include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl- 1,3-dioxol), fluorinated vinyl ether, and ester of fluorine-substituted alcohol with acrylic acid or methacrylic acid.

The polymer which forms a shell may be a copolymer including a repeating unit containing a fluorine atom and a repeating unit not containing a fluorine atom. It is preferable to obtain the repeating unit which does not contain a fluorine atom by the polymerization reaction of the ethylenically unsaturated monomer which does not contain a fluorine atom. Examples of ethylenically unsaturated monomers that do not contain fluorine atoms include olefins (e.g. ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride), acrylates (e.g. methyl acrylate, ethyl acrylate, 2-acrylate). Ethylhexyl), methacrylic acid esters (e.g. methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate), styrene and derivatives thereof (e.g. styrene, divinylbenzene , Vinyltoluene, α-methylstyrene, vinyl ether (e.g., methyl vinyl ether), vinyl ester (e.g., vinyl acetate, vinyl propionate, vinyl cinnamate), acrylamide (e.g., N-tert Butyl acrylamide, N-cyclohexyl acrylamide), methacrylamide and acrylonitrile.

When using together the binder polymer of (3) mentioned later, you may introduce | transduce a crosslinkable functional group into a shell polymer, and may chemically bond a shell polymer and a binder polymer by crosslinking. The shell polymer may have crystallinity. If the glass transition temperature (Tg) of the shell polymer is higher than the temperature at the time of formation of the low refractive index layer, the maintenance of the micro voids in the low refractive index layer is easy. However, when Tg is higher than the temperature at the time of formation of a low refractive index layer, microparticles | fine-particles may not fuse and a low refractive index layer may not be formed as a continuous layer (as a result, intensity | strength falls). In that case, it is preferable to use together the binder polymer of (3) mentioned later, and to form a low refractive index layer as a continuous layer with a binder polymer. A polymer shell is formed around the fine particles, whereby core shell fine particles are obtained. It is preferable that 5 to 90 volume% of cores containing inorganic fine particles are contained in the core shell fine particles, and more preferably 15 to 80 volume%. You may use together 2 or more types of core shell microparticles | fine-particles. Moreover, you may use together an inorganic fine particle and core shell particle | grains without a shell.

(3) binder

It is preferable that it is a polymer which has a saturated hydrocarbon or a polyether as a principal chain, and it is more preferable that a binder polymer is a polymer which has a saturated hydrocarbon as a principal chain. It is preferable that the binder polymer is bridge | crosslinking. It is preferable that the polymer which has a saturated hydrocarbon as a principal chain is obtained by the polymerization reaction of an ethylenically unsaturated monomer. In order to obtain the binder polymer which is bridge | crosslinking, it is preferable to use the monomer which has two or more ethylenically unsaturated groups. Examples of the monomer having two or more ethylenically unsaturated groups include esters of polyhydric alcohols with (meth) acrylic acid (for example, ethylene glycol di (meth) acrylate, 1,4-cyclohexane diacrylate, pentaerythritol tetra) (Meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerytate Lithol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexane tetramethacrylate, polyurethane polyacrylate, polyester polyacrylate), vinyl benzene and derivatives thereof ( For example, 1,4-divinylbenzene, 4-vinyl benzoic acid-2-acryloylethyl ester, 1,4-divinyl cyclohexanone), vinyl sulfone (for example, divinyl sulfone), Acrylamide (for example, methylenebisacrylamide) and methacrylamide are mentioned. It is preferable to synthesize | combine the polymer which has a polyether as a principal chain by ring-opening polymerization reaction of a polyfunctional epoxy compound. Instead of or in addition to the monomer having two or more ethylenically unsaturated groups, a crosslinked structure may be introduced into the binder polymer by reaction of the crosslinkable group. Examples of the crosslinkable functional group include an isocyanate group, an epoxy group, an aziridine group, an oxazoline group, an aldehyde group, a carbonyl group, a hydrazine group, a carboxyl group, a methylol group, and an active methylene group. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivatives, melamine, etherified methylol, esters and urethanes can also be used as monomers for introducing the crosslinked structure. Like a block isocyanate group, you may use the functional group which shows crosslinkability as a result of a decomposition reaction. In addition, a crosslinking group may show not only the said compound but reactivity as a result of the decomposition | disassembly of the said functional group. Although a thermal polymerization initiator and a photoinitiator are used as a polymerization initiator used for the polymerization reaction and crosslinking reaction of a binder polymer, a photoinitiator is more preferable. Examples of photopolymerization initiators include acetophenones, benzoin, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyl dione compounds, Disulfide compounds, fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexylphenyl ketone, and 2-methyl-4-methylthio-2- Morpholino propiophenone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone. As an example of benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether are mentioned. Examples of the benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of the phosphine oxides include 2,4,6-trimethylbenzoyl diphenylphosphine oxide.

It is preferable that a binder polymer is added by the monomer to the coating liquid of a low refractive index layer, and is formed by a polymerization reaction (and also a crosslinking reaction if necessary) simultaneously with or after application | coating of a low refractive index layer. A small amount of polymer (for example, polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, alkyd) is applied to the coating liquid of the low refractive index layer. Resin) may be added.

The low refractive index layer may be a low refractive index layer formed of crosslinking of a fluorine-containing resin (hereinafter also referred to as "fluorine-containing resin before crosslinking") crosslinked by heat or ionizing radiation.

As fluorine-containing resin before crosslinking, the fluorine-containing copolymer formed from the fluorine-containing vinyl monomer and the monomer for providing a crosslinkable group is mentioned preferably. As a specific example of the said fluorine-containing vinyl monomer unit, For example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro) Rho-2,2-dimethyl-1,3-diosol and the like, partial or fully fluorinated alkyl ester derivatives of (meth) acrylic acid (e.g., biscot 6FM (manufactured by Osaka Yuka Chemical Co., Ltd.)) M-2020 (made by Daikin Kogyo Co., Ltd.), etc., a complete or partial fluorinated vinyl ether, etc. are mentioned. As a monomer for providing a crosslinkable group, a crosslinkable functional group is previously contained in a molecule such as glycidyl methacrylate, vinyl trimethoxysilane, γ-methacryloyloxypropyl trimethoxysilane, vinyl glycidyl ether and the like. In addition to the vinyl monomer having a vinyl monomer having a carboxyl group, a hydroxyl group, an amino group, a sulfonic acid group and the like (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acryl) Rate, hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether, and the like). The latter is described in Japanese Patent Application Laid-Open Nos. (10) -25388 and (10) -147739 by adding a compound having a group reacting with a functional group in the polymer and another compound having at least one reactive group after copolymerization. It is described. Examples of the crosslinkable group include acryloyl, methacryloyl, isocyanato, epoxy, aziridine, oxazoline, aldehyde, carbonyl, hydrazine, carboxyl, methylol, active methylene group and the like. . When a fluorine-containing copolymer crosslinks by heating with a crosslinking group which reacts by heating, or a combination of an ethylenically unsaturated group and a thermal radical generator or an epoxy group and a thermal acid generator, the fluorine-containing copolymer is thermosetting and ethylenically unsaturated. When crosslinking by irradiation of light (preferably ultraviolet rays, an electron beam, etc.) with the combination of group, an optical radical generator, or an epoxy group and a photo-acid generator, it is ionizing radiation hardening type.

Moreover, in addition to the said monomer, you may use the fluorine-containing copolymer formed by using together the fluorine-containing vinyl monomer and monomers other than the monomer for providing a crosslinkable group as a fluorine-containing resin before crosslinking. There is no restriction | limiting in particular in the monomer which can be used together, For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate), Methacrylic acid esters (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyltoluene, α-methylstyrene, etc.), vinyl Ethers (methyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.), acrylamides (N-tertbutyl acrylamide, N-cyclohexyl acrylamide, etc.), methacrylamides, Acrylonitrile derivatives etc. are mentioned. Moreover, in order to provide slipperiness | lubricacy and antifouling property in a fluorine-containing copolymer, it is also preferable to introduce a poly organosiloxane skeleton and a perfluoro polyether skeleton. This is, for example, polyorganosiloxane or perfluoropolyether having an acryl group, methacryl group, vinyl ether group, styryl group or the like at the terminal and the polyorganosiloxane having a radical generator at the end. Or polymerization of the monomers by perfluoropolyether, polyorganosiloxane having a functional group or perfluoropolyether, and reaction of a fluorine-containing copolymer.

The proportion of each monomer used to form the fluorine-containing copolymer before crosslinking is preferably 20 to 70 mol%, more preferably 40 to 70 mol%, for imparting a crosslinkable group to the fluorine-containing vinyl monomer. The monomer is preferably 1 to 20 mol%, more preferably 5 to 20 mol%, and other monomers used in combination is preferably 10 to 70 mol%, more preferably 10 to 50 mol%.

A fluorine-containing copolymer can be obtained by superposing | polymerizing these monomers by means, such as solution polymerization, block polymerization, emulsion polymerization, suspension polymerization method, in presence of a radical polymerization initiator.

The fluorine-containing resin before crosslinking is commercially available and can be used. Examples of commercially available fluorine-containing resins before crosslinking include Cytop (manufactured by Asahi Glass Co., Ltd.), Teflon (registered trademark) AF (manufactured by DuPont), polyvinylidene fluoride, and LumiFlon (manufactured by Asahi Glass Co., Ltd.). ), Opstar (made by JSR), etc. are mentioned.

It is preferable that the low refractive index layer which consists of bridge | crosslinked fluorine-containing resin has a dynamic friction coefficient in the range of 0.03-0.15, and the contact angle with respect to water is in the range of 90-120 degree | times.

Cationic Polymerizable Compound

The low refractive index layer may contain a cationically polymerizable compound as a binder. As the cationically polymerizable compound, any one can be used as long as it catalyzes polymerization by energy actinic radiation or heat and is resinized. Specifically, an epoxy group, a cyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spirorthoester compound, a vinyl oxo group, etc. are mentioned. Especially, the compound which has functional groups, such as an epoxy group and a vinyl ether group, is used suitably in this embodiment. Examples of the cationic polymerizable compound having an epoxy group or a vinyl ether group include phenylglycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, vinylcyclohexene dioxide, limonene dioxide, and 3,4. -Epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, bis- (6-methyl-3,4-epoxycyclohexyl) adipate, 2- (3,4-epoxycyclohexyl) ethyltri Methoxysilane, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, and the like. Moreover, an oxetane compound is also mentioned. The oxetane compound may be a compound having at least one oxetane ring in the molecule.

Moreover, as a (co) polymer containing the monomer which has a hydrogen bond formation group as needed, the reactive polymer etc. whose number average molecular weight which has an oxetanyl group in a principal chain or a side chain is 20,000 or more can also be used. It is preferable that said cationically polymerizable compound is 15 mass% or more and less than 70 mass% in solid content from a low refractive index layer coating composition from a viewpoint of the stability of a low refractive index layer coating composition.

Cationic Polymerization Accelerator

As a compound which promotes superposition | polymerization of a cationically polymerizable compound, a well-known acid and a photo-acid generator are mentioned. As a photo-acid generator, the well-known compound used for the photoinitiator of cationic polymerization, the photochromic agent of pigment | dye, photochromic agent, micro resist, etc., their mixture, etc. are mentioned. Specifically, an onium compound, an organic halogen compound, a disulfone compound is mentioned, Preferably, it is an onium compound. As an onium compound, the diazonium salt, sulfonium salt, iodonium salt, etc. which are represented by each following formula | equation are used suitably.

ArN ₂ ⁺ Z ^-,

_{^{(R) 3 S + Z -}} ,

(R) ₂ I ⁺ Z ^-

In the formula, Ar represents an aryl group, R represents an aryl group or an alkyl group having 1 to 20 carbon atoms, and when R appears multiple times in one molecule, each may be the same or different, and Z ⁻ is nonbasic and non-nucleophilic. Represents anionic anions.

In each formula, the aryl group represented by Ar or R is typically phenyl or naphthyl, and these may be substituted by a suitable group. In addition, as an anion represented by Z ⁻ , tetrafluoroborate ion (BF ₄ ⁻ ), tetrakis (pentafluorophenyl) borate ion (B (C ₆ F ₅ ) ₄ ⁻ ), hexafluorophosphate ion (PF ₆ ^-), hexafluoro-acetoxy carbonate ion (AsF ₆ ^-), antimonate ion (SbF ₆ ^-) hexafluoropropane, hexachloro antimonate ion (SbCl ₆ ^-), hydrogensulfate ion (HSO ₄ ^-), perchlorate ion (ClO ₄ ^-), and the like.

As another onium compound, an ammonium salt, an iminium salt, a phosphonium salt, an arsonium salt, a selenium salt, a boron salt, etc. are mentioned.

Especially, a diazonium salt, an iodonium salt, a sulfonium salt, and an iminium salt are preferable at the point of material stability of a compound, etc.

Since most of these compounds are commercially available, such a commercial item can be used. Commercially available initiators include, for example, "Sairacure UVI-6990" (trade name) sold by Dow Chemical Nippon Corporation, and "Adeca Optomer sold by Adeka Co., Ltd., respectively. SP-150 "(brand name)," Adeka Optomer SP-300 "(brand name)," RHODORSIL PHOTOINITIAOR2074 "(brand name) etc. which are sold by Rhodia Japan Co., Ltd. are mentioned.

Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, or Bronsted acid such as acetic acid, formic acid, methane sulfonic acid, trifluoromethane sulfonic acid and paratoluene sulfonic acid, dibutyl tin dilaurate, dibutyl, and the like. And Lewis acids such as tin diacetate, dibutyl tin dioctate, triisopropoxy aluminum, tetrabutoxy zirconium and tetrabutoxy titanate.

Aromatic polyhydric carboxylic acids such as pyromellitic acid, pyromellitic anhydride, trimellitic acid, trimellitic anhydride, phthalic acid, and phthalic anhydride or aliphatic polyhydric carboxylic acids such as anhydrides thereof and maleic acid, maleic anhydride, succinic acid and succinic anhydride. Acids or anhydrides thereof and the like.

As an acid, only 1 type may be used and 2 or more types may be used together. The ratio of 0.1-20 mass parts is preferable with respect to 100 mass parts of cationically polymerizable compounds, These acid and a photo-acid generator are added at the ratio of 0.5-15 mass parts more preferably. The addition amount is preferable in the said range from the stability of a curable composition, polymerization reactivity, etc.

(Radical polymerizable compound)

Moreover, the low refractive index layer may contain a radically polymerizable compound as a binder. As a radically polymerizable group, ethylenically unsaturated groups, such as a (meth) acryloyl group, a vinyl oxy group, a styryl group, an allyl group, etc. are mentioned, Especially, the compound which has a (meth) acryloyl group is preferable. Moreover, as a radically polymerizable compound, it is preferable to contain the polyfunctional monomer containing two or more radically polymerizable groups in a molecule | numerator. The polyfunctional acrylate is selected from the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate. It is preferable. It is preferable that the addition amount of a radically polymerizable compound is 15 mass% or more and less than 70 mass% in solid content from a low refractive layer coating composition from a viewpoint of the stability of a low refractive layer coating composition.

(Radical polymerization accelerator)

In order to accelerate hardening of a radically polymerizable compound, it is preferable to use a photoinitiator together with a radically polymerizable compound. When using together and using a photoinitiator and a radically polymerizable compound, it is preferable to contain a photoinitiator and a radically polymerizable compound 20: 100-0.01: 100 by mass ratio.

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

The low refractive index layer is coated with the coating composition for forming the low refractive index layer by using a known method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, or an inkjet method, and after application, heat drying It forms by hardening as needed.

0.05-100 micrometers is suitable as a coating film thickness, Preferably it is 0.1-50 micrometers. Moreover, solid content concentration of a coating composition is adjusted so that dry film thickness may become the said film thickness.

Moreover, after forming a low refractive index layer, you may include the process of heat-processing at the temperature of 50-160 degreeC. What is necessary is just to determine suitably the period of heat processing according to the temperature set, for example, if it is 50 degreeC, the range for 3 days or more and less than 30 days is preferable, and if it is 160 degreeC, 10 minutes or more and 1 day or less are preferable. As a hardening method, the method of thermosetting by heating, the method of hardening by light irradiation, such as an ultraviolet-ray, etc. are mentioned. When heat-hardening, 50-300 degreeC of heating temperature is preferable, Preferably it is 60-250 degreeC, More preferably, it is 80-150 degreeC. If cured by the light irradiation, the irradiation light amount of exposure is 10mJ / cm ² to about 1J / cm ² is not preferable, and more preferably 100mJ / cm ² to 500mJ / cm ^2.

Although it does not specifically limit as a wavelength range of the light irradiated here, The light which has a wavelength of an ultraviolet range is used preferably. Specifically, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.

&Lt; High refractive index layer and medium refractive index layer &

It is preferable that the high refractive index layer and the medium refractive index layer contain metal oxide fine particles. The kind of metal oxide fine particles is not particularly limited, and is selected from Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S. It has at least 1 type of element.

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

The average particle diameter of the primary particles of these metal oxide fine particles is in the range of 10 nm to 200 nm, and particularly preferably 10 to 150 nm. The average particle diameter of metal oxide fine particles can be measured from the electron micrograph by a scanning electron microscope (SEM). You may measure with a particle size distribution meter etc. which use a dynamic light scattering method, a static light scattering method, etc. If the particle diameter is too small, the particles tend to aggregate and the dispersibility is deteriorated. If the particle size is too large, the haze increases markedly, which is not preferable. The shape of the metal oxide fine particles is preferably a particulate, spherical, cubic, fusiform, needle or irregular shape.

The refractive index of a high refractive index layer is specifically higher than the refractive index of a base film, and it is preferable that it is the range of 1.5-2.3 in 23 degreeC and wavelength 550nm measurement. As the means for adjusting the refractive index of the high refractive index layer is dominant in the kind and amount of addition of the metal oxide fine particles, the refractive index of the metal oxide fine particles is preferably 1.80 to 2.60, more preferably 1.85 to 2.50.

The refractive index of the medium refractive index layer is adjusted to be a value between the refractive index of the base film and the refractive index of the high refractive index layer. Specifically, the refractive index of the medium refractive index layer is preferably 1.55 to 1.80.

It is preferable that the thickness of a high refractive index layer and a medium refractive index layer is 5 nm-1 micrometer, It is more preferable that it is 10 nm-0.2 micrometer, It is most preferable that it is 30 nm-100 nm.

It is preferable that the high refractive index layer and the medium refractive index layer contain metal oxide particles as fine particles, and further contain a binder polymer.

As a binder polymer of a high refractive index layer and a medium refractive index layer, a crosslinked polymer is preferable. As examples of the crosslinked polymers, monomers having two or more ethylenically unsaturated groups are most preferred, and examples thereof include esters of polyhydric alcohols with (meth) acrylic acid (for example, ethylene glycol di (meth) acrylate, 1, 4-cyclohexane diacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipenta Erythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexane tetramethacrylate, polyurethane polyacrylate, poly Ester polyacrylates), vinyl benzene and derivatives thereof (e.g., 1,4-divinylbenzene, 4-vinyl benzoic acid-2-acryloylethyl ester, 1,4-divinyl cycle Hexanone), and the like can be vinyl sulfone (e.g., divinyl sulfone), acrylamides (e.g., methylenebisacrylamide) and methacrylamide. As the polymerization reaction of the polymer, a photopolymerization reaction or a thermal polymerization reaction can be used. Especially photopolymerization reaction is preferable. Preference is given to using a polymerization initiator for the polymerization reaction. For example, the thermal-polymerization initiator and photoinitiator mentioned later used in order to form the binder polymer of a hard-coat layer are mentioned.

You may use a commercially available polymerization initiator as a polymerization initiator. In addition to the polymerization initiator, a polymerization accelerator may be used. It is preferable that the addition amount of a polymerization initiator and a polymerization promoter is the range of 0.2-10 mass% of whole quantity of a monomer. The coating liquid (dispersion liquid of inorganic fine particles containing a monomer) may be heated to promote polymerization of the monomer (or oligomer). Moreover, you may heat after the photopolymerization reaction after application | coating, and may further process the thermosetting reaction of the formed polymer.

The medium and high refractive index layers may be formed by diluting the components forming the above medium and high refractive index layers with a solvent to form a coating layer composition, coated, dried and cured on the antiglare layer. As a light source of hardening, if it is a light source which generate | occur | produces an ultraviolet-ray, it can use without limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp and the like can be used. The amount of irradiation light is preferably 20 mJ / cm ² to 1 J / cm ² , more preferably 100 mJ / cm ² to 500 mJ / cm ² .

(Reflectance of the antireflection layer)

As for the antireflection layer of an anti-glare antireflection film, the average reflectance in 450 nm-650 nm is 1.5% or less, Especially preferably, it is 1.2% or less. Moreover, it is preferable that the minimum reflectance in this range exists in 0.00 to 0.5%.

The refractive index and the film thickness of the antireflection layer can be calculated from the measurement of the spectral reflectance. In addition, the reflective optical characteristic of the anti-glare antireflection film which has the produced antireflection layer can measure a reflectance on the conditions of 5 degree regular reflection using a spectrophotometer. In this measuring method, after roughening the back surface of the side on which the antireflection layer is not applied, the light absorption treatment is performed with a black spray, or the light absorption treatment is performed by attaching a black acrylic plate to reflect the light on the film back surface. Can be prevented, and the reflectance can be measured. In the measurement, the transmittance at transmittance of 550 nm is measured with reference to air using a spectrophotometer.

Moreover, it is preferable that the anti-glare antireflection film of this embodiment has a reflection spectrum of the flat shape in the wavelength range of visible light. In addition, the reflection color is often red or blue because the reflectance of the short wavelength region or the long wavelength region is increased in the visible light region due to the design of the antireflection layer. For surface use, neutral shades are preferred. In this case, the generally preferred reflection color range is 0.17 ≦ x ≦ 0.27, 0.07 ≦ y ≦ 0.17 on the XYZ color system (CIE1931 color system). Moreover, since the distance (DELTA) xy of (x, y) = (0.31, 0.31) on an xy plane is near to neutral which has no color taste, 0.03 or less is more preferable. The color tone can be calculated from the refractive index of each layer in consideration of the reflectance and the color taste of the reflected light, and the film thickness can be calculated according to a conventional method.

<Polarizer>

The polarizing plate of this embodiment using the anti-glare film which concerns on this embodiment is demonstrated.

The polarizing plate which concerns on this embodiment is equipped with the anti-glare film which concerns on this embodiment. Since such a polarizing plate is equipped with the said anti-glare film, it is the thing which made the improvement of visibility and the reduction of a moire fringe both compatible. The said polarizing plate is equipped with a polarizing film and the transparent protective film (polarizing plate protective film) arrange | positioned on the surface of the said polarizing film, for example, and the said transparent protective film is an anti-glare film which concerns on this embodiment. One embodiment thereof is shown in FIG. 4. In FIG. 4, the code | symbol 11 is an anti-glare film, 12 is an anti-glare layer, 13 is a base film, 14 is a polarizing film, 15 is an optical film, and 16 is an adhesive layer, respectively. As shown in FIG. 4, the polarizing plate 10 has an anti-glare film such that the anti-glare layer 12 is on the outside and the base film 13 is on the inside of the polarizing film 14 on the surface of the visible side. (11) is arrange | positioned. In addition, as for the polarizing plate 10, the optical film 15 is arrange | positioned on the surface on the opposite side to the visual side of the polarizing film 14, and the adhesive layer 16 which can be attached to another member is arrange | positioned at the outer side. Can be mentioned. Moreover, although it does not specifically limit as the optical film 15, For example, the polarizing plate protective film mentioned later, etc. are mentioned.

The polarizing plate can be manufactured by a general method. Alkaline saponification treatment of the back surface side of the anti-glare film according to the present invention, using a fully saponified polyvinyl alcohol aqueous solution to at least one surface of the polarizing film produced by dipping and stretching the treated anti-glare film in an iodine solution It is preferable to join.

Moreover, you may use the said anti-glare film on one surface, or may use another polarizing plate protective film. About the anti-glare film which concerns on this invention, the polarizing plate protective film used for one side contains the cellulose triacetate film which is the base film mentioned above, a thermoplastic acrylic resin, and a cellulose ester resin, and the said thermoplastic acrylic resin and the said cellulose ester It is preferable to use the protective film whose content mass ratio of resin is thermoplastic acrylic resin: cellulose-ester resin = 95: 5-50: 50. Details of the configuration are as described above, and specific examples include an unoriented film having a retardation (Ro) of 0 to 5 nm at 590 nm and an Rt of -20 to +20 nm.

The retardation is a sample obtained by adjusting the humidity at 23 ° C and 55% RH environment with an automatic birefringence meter (KOBRA 21DH, Oji Keisoku Co., Ltd.). Can be calculated.

Formula (I): Ro = (nx-ny) × d (nm)

Formula (II): Rt = {(nx + ny) / 2-nz} × d (nm)

[In the above formula, Ro represents an in-plane retardation value in the film, and Rt represents a retardation value in the thickness direction in the film. In addition, d represents the thickness (nm) of an optical film, and nx represents the largest refractive index in the plane of a film. ny represents the refractive index of the direction orthogonal to the slow axis in a film plane, and nz represents the refractive index of a film in the thickness direction.]

In addition, an optical compensation film (retardation film) having a retardation of 20 to 70 nm and Rt of 70 to 400 nm at an in-plane retardation Ro of 590 nm may be used as a polarizing plate capable of expanding the viewing angle. Or it is preferable to use the optical compensation film which has the optically anisotropic layer formed by orienting liquid crystal compounds, such as a discotic liquid crystal, further. Moreover, as a commercially available polarizing plate protective film used preferably, KC8UX2MW, KC4UX, KC5UX, KC4UY, KC8UY, KC12UR, KC4UEW, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC4FR-1, KC4FR-2, KC8UE, KC4UE (Konica Minolta Opto Corporation) etc. are mentioned.

The polarizing film which is a main component of a polarizing plate is an element which passes only the light of the polarization plane of a fixed direction, and the typical polarizing film currently known is a polyvinyl alcohol-type polarizing film, which is the thing which dyed iodine on the polyvinyl alcohol-type film, Although there exist some which dyed a dichroic dye, it is not limited to this. The polarizing film forms a polyvinyl alcohol aqueous solution, uniaxially stretches it, or dyes it, or uniaxially stretches it after dyeing, Preferably, the thing which carried out durability treatment with the boron compound is used. As for the film thickness of a polarizing film, the polarizing film of 5-30 micrometers, Preferably 8-15 micrometers is used preferably. On the surface of the said polarizing film, the single side | surface of the anti-glare film concerning this invention is bonded together, and a polarizing plate is formed. Preferably, it is bonded by an aqueous adhesive mainly composed of fully saponified polyvinyl alcohol or the like.

(Pressure-sensitive adhesive layer)

In order to bond with the board | substrate of a liquid crystal cell, it is preferable that the adhesive layer used for the single side | surface of a protective film shows not only optically transparent but also suitable viscoelasticity and adhesive characteristics.

As a specific adhesive layer, adhesive or adhesives, such as an acrylic copolymer, an epoxy resin, a polyurethane, a silicone polymer, a polyether, butyral resin, a polyamide resin, a polyvinyl alcohol resin, synthetic rubber, etc. Using a polymer, it can form and harden | cure a film by a drying method, the chemical hardening method, the thermosetting method, the hot melt method, the photocuring method, etc. Especially, an acryl-type copolymer is easy to control most adhesive physical property, and excellent in transparency, weather resistance, durability, etc., and can be used preferably.

<Image Display Device>

By using the anti-glare film of this embodiment for an image display apparatus, the performance excellent in visibility is exhibited. As an image display device, a liquid crystal display device of various drive systems, such as a reflection type, a transmissive type, a transflective type liquid crystal display device, or a TN type, STN type, OCB type, VA type, IPS type, ECB type, organic electroluminescence A display apparatus, a plasma display, etc. which have an element are mentioned. It is preferable at the point which is excellent in visibility by using the anti-glare film of this embodiment among these image display apparatuses for the polarizing plate of a liquid crystal display device.

The polarizing plate which is one Embodiment of this invention is shown in FIG. Moreover, as shown in FIG. 5, the use of the polarizing plate comprised from the anti-glare film of this embodiment on the back side (backlight side) of the liquid crystal cell (FIG. 6) of a liquid crystal display device is excellent in preventing generation of moire fringes. Preferred at In addition, in FIG. 5, the code | symbol 20 is a liquid crystal display device, 21 is a liquid crystal cell, 22 is a polarizing film, 23 is an optical film, 24 is a clear hard-coat film, 25 is an anti-glare film, 26 is an adhesive layer, 27 is a polarizing plate, 28 represents a polarizing plate, respectively. In Fig. 6, reference numeral 30 denotes a liquid crystal cell, 31 denotes a liquid crystal, 32 denotes an alignment film, 33 denotes a color filter, 34 denotes a glass substrate, 35 denotes a spacer, 36 denotes a polarizing plate, and 37 denotes a polarizing plate, respectively.

More specifically, for example, as shown in FIG. 5, the liquid crystal panel 20 is formed on the surface of the liquid crystal cell 21 on the back (backlight) side (the side opposite to the viewing side surface). The polarizing plate 28 is arrange | positioned so that 25 may become an outer side. In the liquid crystal panel 20, a polarizer 27 different from the polarizer 28 is disposed on the surface of the liquid crystal cell 21 on the viewing side. As said polarizing plate 27, the polarizing plate equipped with the clear hard-coat film 24 instead of an anti-glare film, etc. are mentioned, for example.

In addition, with a liquid crystal cell, a liquid crystal substance is charged between a pair of electrodes, The orientation state of a liquid crystal changes by applying a voltage to this electrode, and the amount of transmitted light is controlled. Specifically, as shown in FIG. 6, the liquid crystal cell 30 includes two laminates in which the alignment film 32, the color filter 33, and the glass substrate 34 are stacked, via the spacer 35. It is arrange | positioned so that the inside of 32 may be inside, and the liquid crystal 31 was filled between the alignment films 32, etc. are mentioned. In the liquid crystal cell 30, a transparent electrode for applying a voltage to the liquid crystal 31 may be disposed between the alignment film 32 and the color filter 33.

In addition, you may use the anti-glare film which concerns on this embodiment for the member for touch panels. The touch panel member which concerns on this embodiment is equipped with the anti-glare film which concerns on this embodiment. Since such a touch panel member is provided with the said anti-glare film, it is preferable at the point which is excellent also in the character blur and the durability (scratches by sliding) etc. with respect to a pen input. Specifically, an anti-glare film provided with a conductive film as shown in FIG. 7 is mentioned. In FIG. 7, 40 is an anti-glare film provided with the conductive film for touch panels, 41 is a base film, 42 is an anti-glare layer, 43 is a transparent conductive thin film (ITO layer), respectively. The anti-glare film 40 provided with this electroconductive film is a member for touch panels, and is equipped with the anti-glare film provided with the anti-glare layer 42 on the surface of the base film 41. The anti-glare film includes an anti-glare layer 42 on both surfaces of the base film 41. And the anti-glare film 40 provided with the electroconductive film is equipped with the transparent conductive thin film (ITO layer) 43 on one surface of this anti-glare film.

Thus, when the anti-glare film of this invention is used for the touch panel member of the image display apparatus provided with a touch panel, it is preferable at the point which is excellent also in the character blur and the durability (scratches by sliding) etc. to a pen input.

<Touch panel>

Next, an example at the time of using the anti-glare film of this embodiment for a touch panel is shown. 8 is a schematic diagram of a liquid crystal display device 50 including a resistive touch panel using the anti-glare film of the present embodiment in a touch panel. In Fig. 8, reference numeral 50 denotes a resistive touch panel liquid crystal display device, 51 denotes a spacer, 52 denotes a transparent conductive thin film (ITO layer), 53 denotes a glass substrate, and 54 denotes an LCD (liquid crystal display panel). The conductive anti-glare film 40 is opposed to the glass substrate 53 on which the transparent conductive thin film 52 is formed and the transparent conductive thin films face each other at regular intervals (spacer 51) to form a resistive touch panel. can do. Electrodes not shown are arrange | positioned at the edge part of a conductive anti-glare film and a glass substrate. In a resistive touch panel, a user presses a conductive anti-glare film with a finger, a pen, etc., and the transparent conductive thin film of a conductive anti-glare film contacts a transparent conductive thin film on a glass substrate. The pressed position is detected by electrically detecting this contact via the electrode at the end. On the transparent conductive thin film of a glass substrate, a dot-shaped spacer is arrange | positioned as needed. Moreover, by mounting a touch panel on LCD (liquid crystal display device), the liquid crystal display device provided with a touch panel can be comprised.

Although this specification discloses the various forms of technology as mentioned above, the main technique is summarized below.

One aspect of the present invention is an antiglare film having an antiglare layer containing an active ray curable resin on a base film, wherein the antiglare layer does not substantially contain incompatible resins with respect to the fine particles and the active ray curable resin, Arithmetic mean roughness Ra of the said glare-proof layer is 300-1500 nm, The haze resulting from the internal scattering of the said glare-proof layer is 0 to 1.0%, It is an anti-glare film characterized by the above-mentioned.

According to such a structure, when stable surface unevenness | corrugation is formed and there is no generation | occurrence | production of the micro cloudiness unevenness and microcracks of the anti-glare film after a durability test, and it is used for an image display apparatus, it is excellent in visibility (projection prevention performance and sharpness). A manifest film can be provided.

Moreover, in the said anti-glare film, it is preferable that arithmetic mean roughness Ra of the said anti-glare layer is 350-1300 nm. Thereby, the said effect is acquired more reliably.

Moreover, in the said anti-glare film, it is preferable that arithmetic mean roughness Ra of the said anti-glare layer is 500-1300 nm. Thereby, the said effect is acquired more reliably.

Moreover, in the said anti-glare film, it is preferable that the haze resulting from the internal scattering of the said anti-glare layer is 0 to 0.5%. Thereby, the said effect is acquired more reliably.

Moreover, in the said anti-glare film, it is preferable that the surface of the said anti-glare layer has the irregular protrusion shape which does not have a period in a longitudinal direction. Thereby, the said effect is exhibited more favorable.

Moreover, in the said anti-glare film, it is preferable that the viscosity in 25 degreeC of the said actinic-rays curable resin exists in the range of 20-3000 mPa * s. By using such actinic-rays curable resin, the arithmetic mean roughness R of the said protrusion shape and the said range is easy to be obtained.

In addition, a new aspect of the present invention is an anti-glare antireflection film, characterized in that the low refractive index layer is laminated on the anti-glare layer of the anti-glare film directly or through another layer. By setting it as such a structure, the anti-glare antireflection film excellent in visibility can be obtained.

Moreover, one new aspect of this invention is a manufacturing method of the anti-glare film which manufactures the said anti-glare film, It is ester, glycol ether which used the actinic-ray curable resin in the range of 20-3000 mPa * s in the viscosity in 25 degreeC. The antiglare layer coating composition diluted with at least one solvent selected from the group or alcohols is formed at least through an application step, a drying step and a curing step to form an antiglare layer, and furthermore, the temperature of the rate-sensitive drying section in the drying step. It is a manufacturing method of the anti-glare film characterized by processing on conditions maintained in the range of 90-160 degreeC. By such a structure, the excellent anti-glare film mentioned above can be obtained.

One new aspect of the present invention is the polarizing plate, wherein the anti-glare film and the anti-glare antireflection film are provided on at least one surface. According to such a structure, the polarizing plate excellent in visibility can be obtained.

One new aspect of the present invention is the image display apparatus, wherein the anti-glare film and the anti-glare antireflection film are provided. According to such a structure, the image display apparatus excellent in visibility can be obtained.

Moreover, in the said image display apparatus, it is preferable that said polarizing plate is provided in at least one surface of a liquid crystal cell. According to such a structure, the image display apparatus excellent in visibility can be obtained more reliably.

Moreover, in the said image display apparatus, it is preferable to use said polarizing plate on the back side of a liquid crystal cell. According to such a structure, it is also preferable at the point which is excellent in the prevention of a moire fringe.

Moreover, in the said image display apparatus, it is preferable that it is an image display apparatus with a touch panel, and that the said anti-glare film or said anti-glare antireflection film is provided as a structural member of the said touch panel. According to such a structure, it is also preferable at the point which is excellent also in the character blur and durability with respect to pen input (scratches by sliding).

Example

Although an Example is given to the following and this invention is concretely demonstrated to it, this invention is not limited to these.

Example 1

<Production of base film 1>

Preparation of Silicon Dioxide Dispersion

Aerosil R812 (manufactured by Nippon Airzyl Co., Ltd., average diameter of 7 nm 10 parts by mass of primary particles)

90 parts by mass of ethanol

The resulting mixture was stirred with a dissolver for 30 minutes and dispersed with Manton-Gaulin. 88 mass parts methylene chloride was thrown into the silicon dioxide dispersion liquid, stirring and mixing for 30 minutes with the dissolver, and the silicon dioxide dispersion dilution liquid was produced. It filtered with the fine particle dispersion dilution filter (Advantech Toyo Co., Ltd .: polypropylene wind cartridge filter TCW-PPS-1N).

<Production of base film 1>

(Dope composition)

Cellulose triacetate (Mn = 148000, Mw = 310000 acetyl group substitution degree 2.92)

90 parts by mass

10 parts by mass of an aromatic terminal ester plasticizer (B-4)

Tinuvin 900 (manufactured by BASF Japan Co., Ltd.)

4 parts by mass of silicon dioxide dispersion diluent

432 parts by mass of methylene chloride

Ethanol 38 parts by mass

The above was put into an airtight container, and it melt | dissolved fully, heating and stirring, and filtered using Azumi Rossi No.24 by Azumi Rossi Co., Ltd., and prepared the dope liquid.

Subsequently, it casted uniformly on the stainless steel band support body using the belt casting apparatus. In the stainless steel band support, the solvent was evaporated until the amount of residual solvent became 100%, and it peeled on the stainless steel band support. The solvent of the cellulose-ester film was evaporated at 35 degreeC, and it slitted to 1.65 m width, and it dried at 160 degreeC, extending | stretching 1.3 times in the TD direction (width direction of film) and 1.01 times in the MD direction with a tenter. Dried at temperature. The residual solvent amount at the start of drying was 20%. Then, after drying for 15 minutes, conveying the inside of a 120 degreeC drying apparatus with many rolls, it slitted to 1.49 m width, knurled processing of width 15mm and 10 micrometers in height at the both ends of a film, and wound up by a winding core, and a base material Film 1 was obtained. The residual solvent amount of the base film was 0.2%, the film thickness was 40 µm, and the number of windings was 3900 m.

<Production of anti-glare film 1>

The following anti-glare layer coating composition 1 filtered through a polypropylene filter having a pore diameter of 0.4 μm was applied to the prepared substrate film using an extrusion coater, and dried at a constant drying section temperature of 95 ° C. and a reduced drying section temperature of 85 ° C. Nitrogen purge so that the oxygen concentration is 1.0 vol% or less, the irradiated portion is 100 mW / cm ² using an ultraviolet lamp, and the coating layer is cured with an irradiation amount of 0.25 J / cm ² , whereby the dry film thickness 8 An anti-glare layer of 탆 was formed. After forming an anti-glare layer, it wound up in roll shape and produced the anti-glare film 1. As a result of observing the antiglare layer surface of the anti-glare film 1 with an optical interference surface roughness meter (New View 5030, manufactured by Zygo), it was found that irregular protrusion shapes were irregularly arranged in the longitudinal direction and the width direction as shown in FIG. 3.

[Antiglare Layer Coating Composition 1]

The following anti-glare layer coating composition 1 was stirred and mixed with a disper, and the anti-glare layer coating composition 1 was obtained.

(Active wire curable resin)

Pentaerythritol tri / tetraacrylate

90 parts by mass (NK ester A-TMM-3L, manufactured by Shinnakamura Kagaku Kogyo Co., Ltd.)

Trimethylolpropane triacrylate

10 parts by mass (NK ester A-TMPT, manufactured by Shinnakamura Kagaku Kogyo Co., Ltd.)

(Photopolymerization initiator)

Irgacure 184 (manufactured by BASF Japan) 5 parts by mass

(Leveling agent)

2 parts by mass of polyether modified silicone (KF-889, Shin-Etsu Chemical Co., Ltd.)

(solvent)

100 parts by mass of propylene glycol monomethyl ether (PGME)

Only the active-ray-curable resin of the said glare-proof layer coating composition 1 was stirred and mixed with the disper, and it measured using the Brookfield viscometer on 25 degreeC conditions, and the resin viscosity was 550 mPa * s.

<Production of Anti-glare Films 2 to 8>

In preparation of the anti-glare film 1, the anti-glare films 2 to 8 were produced in the same manner as the anti-glare film 1 except that the temperature of the rate-sensitive drying section was changed as shown in Table 1.

<Production of anti-glare film 9>

In preparation of the anti-glare film 1, the anti-glare layer coating composition 1 was made into the following anti-glare layer coating composition 2, and the anti-glare film 9 was similarly carried out except having changed the temperature of the rate reduction drying section to 100 degreeC in a drying process. Produced.

[Antiglare Layer Coating Composition 2]

The following anti-glare layer coating composition 2 was stirred and mixed with the disper, and the anti-glare layer coating composition 2 was obtained.

(Active wire curable resin)

Pentaerythritol tri / tetraacrylate

90 parts by mass (NK ester A-TMM-3L, manufactured by Shinnakamura Kagaku Kogyo Co., Ltd.)

Trimethylolpropane triacrylate

10 parts by mass (NK ester A-TMPT, manufactured by Shinnakamura Kagaku Kogyo Co., Ltd.)

(Photopolymerization initiator)

Irgacure 184 (manufactured by BASF Japan)

(Leveling agent)

2 parts by mass of polyether modified silicone (KF-889, Shin-Etsu Chemical Co., Ltd.)

(solvent)

100 parts by mass of ethanol

Only the active-ray hardening-type resin of the said glare-proof layer coating composition 2 was stirred and mixed with the disper, and it measured using the Brookfield viscometer on 25 degreeC conditions, and the resin viscosity was 550 mPa * s.

<Production of anti-glare film 10>

In preparation of the anti-glare film 1, the anti-glare layer coating composition 1 was made into the following anti-glare layer coating composition 3, and the anti-glare film 10 was similarly performed except having changed the temperature of the rate reduction drying section in a drying process to 100 degreeC. Produced.

[Antiglare Layer Coating Composition 3]

The following anti-glare layer coating composition 3 was stirred and mixed with the disper, and the anti-glare layer coating composition 3 was obtained.

(Active wire curable resin)

Ditrimethylolpropane tetraacrylate

(NK ester AD-TMP, Shinnakamura Kagaku Kogyo Co., Ltd.) 60 parts by mass

Ethoxylated Pentaerythritol Tetraacrylate

(NK ester ATM-35E, Shin-Nakamura Kagaku Kogyo Co., Ltd.) 40 parts by mass

(Photopolymerization initiator)

Irgacure 184 (manufactured by BASF Japan)

(Leveling agent)

2 parts by mass of polyether modified silicone (KF-889, Shin-Etsu Chemical Co., Ltd.)

(solvent)

50 parts by mass of propylene glycol monomethyl ether (PGME)

50 parts by mass of methanol

Only the active-ray hardening-type resin of the said anti-glare layer coating composition 3 was stirred and mixed with the disper, and it measured using the Brookfield viscometer on 25 degreeC conditions, and the resin viscosity was 740 mPa * s.

<Production of Anti-glare Films 11 to 17>

In preparation of the anti-glare film 7, the anti-glare films 11 to 17 were produced in the same manner as in the anti-glare film 7 except that the temperature of the rate-sensitive drying section was changed as described in Table 1.

<Production of anti-glare film 18>

In preparation of the anti-glare film 1, the anti-glare layer coating composition 1 is changed to the anti-glare layer coating composition 4 containing the incompatible resin component produced with reference to Example 1 of JP-A-2006-106290, Moreover, an anti-glare layer was produced similarly except having made drying temperature into 70 degreeC like Example 1 of Unexamined-Japanese-Patent No. 2006-106290. Subsequently, using an extrusion coater, the thermosetting fluorine-containing compound coating liquid (Nissan Chemical Co., Ltd. product, LR-202B, solid content 1 mass%) was apply | coated so that the film thickness after drying might be 100 nm, using 90 degreeC on an anti-glare layer. It thermosetted by drying for 5 minutes, and the anti-glare film 18 was produced.

[Antiglare Layer Coating Composition 4]

The following anti-glare layer coating composition 4 was stirred and mixed with the disper, and the anti-glare layer coating composition 4 was obtained.

(Active wire curable resin)

Cyclomer P (ACA) 320 (unsaturated group-containing acrylic resin mixture, manufactured by Daicel Chemical Industries, Ltd.) 5.04 parts by mass

Dipentaerythritol hexaacrylate (DPHA, manufactured by Daicel Cytec Co., Ltd.)

6.4 parts by mass

(Incompatible resin)

Cellulose acetate propionate (CAP-482-20, produced by Eastman Chemical Co., Ltd.) 0.9 parts by mass

(Photopolymerization initiator)

0.2 mass parts of Irgacure 184 (manufactured by BASF Japan)

(solvent)

20 parts by mass of methyl ethyl ketone (MEK)

5 parts by mass of cyclohexanone (CYC)

Only the active-ray hardening-type resin of the said anti-glare layer coating composition 4 was stirred and mixed with the disper, and it measured using the Brookfield viscometer on 25 degreeC conditions, and the resin viscosity was 10600 mPa * s. Table 1 also shows cellulose acetate propionate as CAP.

<Production of anti-glare film 19>

In preparation of the anti-glare film 1, the anti-glare layer coating composition 1 is changed to the anti-glare layer coating composition 5 containing the incompatible resin component adjusted with reference to Example 1 of JP-A-2008-225195, Moreover, the anti-glare film 19 was produced similarly to the anti-glare film 1 except having set the drying temperature to 70 degreeC similar to Example 1 of Unexamined-Japanese-Patent No. 2008-225195.

[Antiglare Layer Coating Composition 5]

The following anti-glare layer coating composition 5 was stirred and mixed with the disper, and the anti-glare layer coating composition 5 was obtained.

(Active wire curable resin)

5.65 parts by mass of cyclomer P (ACA) 320 (unsaturated group-containing acrylic resin mixture, manufactured by Daicel Chemical Industries, Ltd.)

Dipentaerythritol hexaacrylate (DPHA, manufactured by Daicel Cytec Co., Ltd.)

6.3 parts by mass

(Incompatible resin)

0.9 mass part of polymethyl methacrylate (weight average molecular weight (480000; Mitsubishi Rayon Corporation make, BR88)

(Photopolymerization initiator)

0.5 mass parts of Irgacure 184 (manufactured by BASF Japan)

(solvent)

0.1 parts by mass of methyl ethyl ketone (MEK)

Butanol 5.4 parts by mass

Propylene glycol monomethyl ether (PGME) 1.89 parts by mass

Only the active-ray hardening-type resin of the said glare-proof layer coating composition 5 was stirred and mixed with the disper, and it measured using the Brookfield viscometer on 25 degreeC conditions, and the resin viscosity was 10500 mPa * s. In Table 1, methyl polymethacrylate was represented by PMMA.

<Production of anti-glare film 20>

In preparation of the anti-glare film 1, the anti-glare layer coating composition 1 is changed to the anti-glare layer coating composition 6 containing the incompatible resin component adjusted with reference to Example 3 of JP-A-2007-58204, Moreover, the anti-glare film 20 was produced like the anti-glare film 1 except having changed the drying temperature to 80 degreeC similar to Example 3 of Unexamined-Japanese-Patent No. 2007-58204.

[Antiglare Layer Coating Composition 6]

The following anti-glare layer coating composition 6 was stirred and mixed with a disper, and the anti-glare layer coating composition 6 was obtained.

(Active wire curable resin)

Dipentaerythritol hexaacrylate (DPHA, manufactured by Daicel Cytec Co., Ltd.)

92 parts by mass

(Incompatible resin)

15 parts by mass of methacrylate copolymer (saptomer ST3600, Mitsubishi Chemical Corporation)

(Photopolymerization initiator)

Irgacure 184 (manufactured by BASF Japan Co., Ltd.)

(solvent)

45 parts by mass of ethanol

Toluene 15 parts by mass

Only the active-ray hardening-type resin of the said anti-glare layer coating composition 6 was stirred and mixed with the disper, and it measured using the Brookfield viscometer on 25 degreeC conditions, and the resin viscosity was 6000 mPa * s. In addition, in Table 1, methacrylate copolymer is shown as MACP.

<Production of anti-glare film 21>

In preparation of the anti-glare film 4, the anti-glare film 21 was produced in the same manner as the anti-glare film 4 except that the anti-glare layer coating composition 1 was changed to the anti-glare layer coating composition 7.

[Antiglare Layer Coating Composition 7]

After mixing 5 mass parts of silica microparticles | fine-particles (brand name: high fresh car TS, the product made by Ubenitto Kasei Co., Ltd.) of the average particle diameter of 2 micrometers with the solvent of the following mixture ratio, it stirred for 30 minutes with the air disper, and obtained the particle dispersion liquid. Another raw material was mixed and stirred in this particle dispersion liquid, and the anti-glare layer coating composition 7 was adjusted.

(Active wire curable resin)

Pentaerythritol tri / tetraacrylate

90 parts by mass (NK ester A-TMM-3L, manufactured by Shinnakamura Kagaku Kogyo Co., Ltd.)

Trimethylolpropane triacrylate

10 parts by mass (NK ester A-TMPT, manufactured by Shinnakamura Kagaku Kogyo Co., Ltd.)

(Photopolymerization initiator)

Irgacure 184 (product made by BASF Japan)

(Leveling agent)

2 parts by mass of polyether modified silicone (KF-889, Shin-Etsu Chemical Co., Ltd.)

(Fine particles)

5 parts by mass of silica fine particles having an average particle diameter of 2 μm

(solvent)

100 parts by mass of propylene glycol monomethyl ether (PGME)

Only the active-ray hardening-type resin of the said glare-proof layer coating composition 7 was stirred and mixed with the disper, and it measured using the Brookfield viscometer on 25 degreeC conditions, and the resin viscosity was 450 mPa * s.

<Production of anti-glare film 22>

In preparation of the anti-glare film 4, the anti-glare film 22 was produced in the same manner as the anti-glare film 4 except that the anti-glare layer coating composition 1 was changed to the anti-glare layer coating composition 8.

[Antiglare Layer Coating Composition 8]

The following anti-glare layer coating composition 8 was stirred and mixed with a disper, and the anti-glare layer coating composition 8 was obtained.

(Active wire curable resin)

Pentaerythritol tri / tetraacrylate

90 parts by mass (NK ester A-TMM-3L, manufactured by Shinnakamura Kagaku Kogyo Co., Ltd.)

Trimethylolpropane triacrylate

10 parts by mass (NK ester A-TMPT, manufactured by Shinnakamura Kagaku Kogyo Co., Ltd.)

(Photopolymerization initiator)

Irgacure 184 (product made by BASF Japan)

(Leveling agent)

2 parts by mass of polyether modified silicone (KF-889, Shin-Etsu Chemical Co., Ltd.)

(solvent)

100 parts by mass of ethylene glycol monopropyl ether (EGPE)

Only the active-ray hardening-type resin of the said anti-glare layer coating composition 8 was stirred and mixed with the disper, and it measured using the Brookfield viscometer on 25 degreeC conditions, and the resin viscosity was 450 mPa * s.

<Production of anti-glare film 23>

In preparation of the anti-glare film 1, the anti-glare film 23 was similarly produced except having changed the anti-glare layer composition 1 into the following anti-glare layer composition 9, and changing the rate reduction drying section temperature to 120 degreeC.

[Antiglare Layer Coating Composition 9]

The following anti-glare layer composition 9 was stirred and mixed with a disper, and the anti-glare layer coating composition 9 was obtained.

(Active wire curable resin)

Pentaerythritol tri / tetraacrylate

75 parts by mass (NK ester A-TMM-3L, manufactured by Shinnakamura Kagaku Kogyo Co., Ltd.)

Isocyanuric Acid EO Modified Diacrylate

25 parts by mass (aronix M-215, manufactured by Toagosei Co., Ltd.)

(Photopolymerization initiator)

Irgacure 184 (manufactured by BASF Japan)

(Leveling agent)

2 parts by mass of polyether modified silicone (KF-889, Shin-Etsu Chemical Co., Ltd.)

(solvent)

100 parts by mass of propylene glycol monomethyl ether

Only the active-ray hardening-type resin of the said glare-proof layer coating composition 9 was stirred and mixed with the disper, and it measured using the Brookfield viscometer on 25 degreeC conditions, and the resin viscosity was 2800 mPa * s.

<Production of anti-glare film 24>

In preparation of the anti-glare film 4, the anti-glare film 24 was similarly produced except having changed the anti-glare layer composition 1 into the following anti-glare layer composition 10.

[Antiglare Layer Coating Composition 10]

The following anti-glare layer coating composition 10 was stirred and mixed with a disper, and the anti-glare layer coating composition 10 was obtained.

(Active wire curable resin)

Trimethylolpropane triacrylate

(Light acrylate TMP-A, Kyoesha Chemical Co., Ltd.) 80 parts by mass

4-hydroxybutyl acrylate (4-HBA, Osaka Kagaku Kogyo KK)

20 parts by mass

(Photopolymerization initiator)

Irgacure 184 (manufactured by BASF Japan)

(Leveling agent)

2 parts by mass of polyether modified silicone (KF-889, Shin-Etsu Chemical Co., Ltd.)

(solvent)

100 parts by mass of propylene glycol monomethyl ether

Only the active-ray hardening-type resin of the said glare-proof layer coating composition 10 was stirred and mixed with the disper, and it measured using the Brookfield viscometer on 25 degreeC conditions, and the resin viscosity was 35 mPa * s.

<Production of anti-glare film 25>

In preparation of the anti-glare film 4, the anti-glare film 24 was similarly produced except having changed the anti-glare layer composition 1 into the following anti-glare layer composition 11.

[Antiglare Layer Coating Composition 11]

The following anti-glare layer coating composition 11 was stirred and mixed with a disper, and the anti-glare layer coating composition 11 was obtained.

(Active wire curable resin)

Pentaerythritol tri / tetraacrylate

90 parts by mass (NK ester A-TMM-3L, manufactured by Shinnakamura Kagaku Kogyo Co., Ltd.)

Trimethylolpropane triacrylate

10 parts by mass (NK ester A-TMPT, manufactured by Shinnakamura Kagaku Kogyo Co., Ltd.)

(Photopolymerization initiator)

Irgacure 184 (product made by BASF Japan)

(Leveling agent)

2 parts by mass of polyether modified silicone (KF-889, Shin-Etsu Chemical Co., Ltd.)

(solvent)

100 parts by mass of butyl acetate

Only the active-ray hardening-type resin of the said anti-glare layer coating composition 11 was stirred and mixed with the disper, and it measured using the Brookfield viscometer on 25 degreeC conditions, and the resin viscosity was 550 mPa * s.

<Evaluation>

Haze and arithmetic mean roughness (Ra) measurement

Haze measurement was performed about the produced anti-glare films 1-25, and internal haze (Hi) was calculated | required. In addition, it measured on the following conditions also about arithmetic mean roughness Ra.

The result was shown in Table 1 about obtained internal haze (Hi) and arithmetic mean roughness (Ra).

(Internal haze (Hi))

A few drops of silicone oil were dripped at the front and back of each anti-glare film. Next, the anti-glare film which dripped the silicone oil was buried in front and back with two sheets of 1 mm thick glass plate (micro slide glass product number S 9111, MATSUNAMI), and the two glass plates and the obtained anti-glare film were optically closely adhered. Haze (Ha) of the sample which was made to contact this optically and the surface haze was removed was measured using the measuring instrument (NDH2000) by the Nippon Denshoku Kogyo Co., Ltd. product.

Subsequently, only silicone oil was sandwiched between two glass plates, and glass haze (Hb) was measured. Hb was subtracted from Ha, and internal haze (Hi) of the anti-glare film was calculated.

(Arithmetic mean roughness (Ra) measurement)

Arithmetic mean roughness Ra of the anti-glare layer of each anti-glare film was measured 10 times using an optical interference surface roughness meter (New View 5030 manufactured by Zygo), and the arithmetic mean of each anti-glare film was measured from the average of the measurement results. Roughness Ra was obtained.

<Durability test>

After preserving anti-glare films 1 to 25 for 50 days in a constant temperature / humidity bath at 90% of 70 ° C relative humidity, after further preservation of cycles (-40 ° C for 45 minutes, and then 110 ° C for 45 minutes) 500 cycles were put into an unattended shift.

<Production of Polarizer>

Each anti-glare film 1-25 after an endurance test, and the following polarizer and the optical film 1 produced by the following procedure on the back surface side were bonded by the roll-to-roll so that the longitudinal direction may be matched, and the polarizing plate was produced, respectively. The schematic diagram of a polarizing plate is shown in FIG.

(Production of optical film 1)

<Fine Particle Dispersion 1>

11 parts by mass of fine particles (aerosol R972V Nippon Aerosol Co., Ltd.)

Ethanol 89 parts by mass

The above was stirred and mixed with a dissolver for 50 minutes and then dispersed with Manton-Gaulin.

&Lt; Fine Particle Addition Solution 1 >

Particulate dispersion 1 was slowly added to the dissolution tank containing methylene chloride with sufficient stirring. Further, the particles were dispersed in the attritor so that the particle diameter of the secondary particles became a predetermined value. This was filtered with Fine Mat NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle addition liquid 1.

99 parts by mass of methylene chloride

Particulate dispersion 1 5 parts by mass

To prepare a main dope solution having the following composition. First, methylene chloride and ethanol were added to the pressure-melting tank. It injected | threw-in stirring the cellulose acetate to the pressure dissolution tank containing a solvent. This was dissolved completely with heating and stirring. This was filtered using Azumi Rossi No. 244 manufactured by Azumi Rossi Co., Ltd. to prepare a main dope liquid.

<Composition of main doping solution>

Methylene chloride 340 parts by mass

64 parts by mass of ethanol

100 parts by mass of cellulose acetate (Mn80000) having an acetyl group substitution degree of 2.4

10 parts by mass of a sugar ester compound (1-23)

2.5 mass parts of aromatic terminal ester plasticizers (2-23)

2.3 mass parts of ultraviolet absorbers (tinuvin 928) (BASF Japan)

1.0 parts by mass of fine particle addition liquid

The composition was placed in a sealed container and dissolved with stirring to prepare a dope solution. Subsequently, the dope liquid was uniformly cast on the stainless steel belt support body at the temperature of 33 degreeC, and 2000 mm width using an endless belt casting apparatus. The temperature of the stainless steel belt was controlled at 30 占 폚.

On the stainless steel belt support, the solvent was evaporated until the amount of residual solvent in the cast film became 75%, and then peeled off on the stainless steel belt support with a peeling tension of 130 N / m.

Thereafter, the film was stretched 1.4 times in the width direction by a tenter set at 170 ° C., then conveyed for 30 minutes in a drying zone set at 130 ° C. for drying, trimming at both ends, and further at the end of 1 cm in width and 6 μm in height. The optical film 1 with a film thickness of 40 micrometers which has a knurling of was produced, and it wound up at 1.49 m and 3900 m in width. In-plane retardation value Ro of the optical film 1 was 50 nm, and thickness direction retardation Rt was 130 nm.

<Production of Polarizer>

The polyvinyl alcohol film of thickness 120 micrometers was uniaxially stretched (temperature 110 degreeC, draw ratio 5 times). This was immersed for 60 seconds in the aqueous solution containing 0.075g of iodine, 5g of potassium iodide, and 100g of water, and then immersed in the 68 degreeC aqueous solution which contains 6g of potassium iodide, 7.5g of boric acid, and 100g of water. This was washed with water and dried to obtain a polarizer. Subsequently, in accordance with the following steps 1 to 5, the polarizer, the anti-glare films 1 to 25, and the rear face side were aligned with the optical film 1 in the longitudinal direction, bonded by a roll-to-roll to produce each polarizing plate 1 to 25, In addition, the adhesion layer was bonded to each polarizing plate 1-25 in the process 6.

Process 1: It was immersed in 2 mol / L sodium hydroxide solution of 60 degreeC for 90 second, and then washed with water and dried, and obtained the anti-glare films 1-25 and optical film 1 which saponified the side which joins a polarizer.

Process 2: The said polarizer was immersed for 1-2 second in the polyvinyl alcohol adhesive bath of 2 mass% of solid content.

Process 3: The excess adhesive adhering to the polarizer in process 2 was lightly wiped and removed, and the optical film 1 was arrange | positioned on the anti-glare film 1-25 processed at the process 1, and a back surface side.

Process 4: The film laminated | stacked by the process 3 was bonded by the pressure of 20-30 N / cm <^2> and conveyance speed at about 2 m / min.

Process 5: The polarizer produced by the process 4, the anti-glare films 1-25, and the sample which bonded the optical film 1 were dried for 2 minutes in 80 degreeC dryer, were wound up in roll shape, and the polarizing plates 1-22 were produced, respectively. .

Process 6: The acrylic adhesive currently marketed to the optical film 1 of each polarizing plate produced at the process 5 was apply | coated so that thickness after drying might be set to 25 micrometers, and it dried in 110 degreeC oven for 5 minutes, and forms an adhesion layer, and the adhesive layer The peelable protective film was stuck to it. This polarizing plate was cut out (punching), and polarizing plates 1-25 were produced.

<Fabrication of Liquid Crystal Display Device>

The polarizing plate of the panel front side previously bonded by 32 type display BRAVIA KDL-32EX by Sony was peeled off, and the adhesion layers of each polarizing plate 1-22 produced above were bonded to the front surface of the glass surface of the liquid crystal cell, respectively. . At that time, the bonding direction of the polarizing plate was performed so that the anti-glare layer of the anti-glare film might be on the viewing side, and the absorption axis would be directed in the same direction as the polarizing plate which was previously bonded, thereby producing liquid crystal displays 1 to 25, respectively.

&Quot; Evaluation of liquid crystal display device &

(Evaluation of visibility)

About each liquid crystal display device 1-25 produced above, after leaving at 80 degreeC for 250 hours, it returned to 23 degreeC and 55% RH, and evaluated visibility. 30 evaluators performed the sensory evaluation of the visibility of an image, and calculated | required the average point. 10 points is the best, the projection is small and the sharpness is high. 1 point is the lowest. 7 points or more is an acceptable level.

Film Evaluation

The following items were evaluated about the anti-glare films 1-25 after the said durability test.

Permeability

About each anti-glare film, the permeability on the comb width of 0.25 mm was measured using the filament measuring device ICM-IDP of Suga-Shiki Co., Ltd .. Higher values indicate better permeability.

(Flexibility)

After adjusting each humidity-resistant film for 12 hours in 23 degreeC 55% RH atmosphere, the flexibility was evaluated by the cylindrical mandrel method using the test apparatus of Type 1 by the method based on JISK5600-5-1. . The lower the value of the diameter of the mandrel, the better the flexibility. In addition, in JIS K5600-5-1, since the cylindrical mandrel had only 2 mm in diameter, 1 mm in diameter was started. The smaller the value of the diameter, the better the flexibility (flexibility of the film). The obtained results are shown in Table 1.

As can be seen from the results in Table 1, the antiglare layer does not substantially contain incompatible resin with respect to the fine particles and the active ray curable resin, and the arithmetic mean roughness Ra of the antiglare layer is 300 to 1500 nm, and the antiglare layer It is understood that the anti-glare film of the present invention having an internal haze of 0 to 1.0% is excellent in permeability and flexibility after the durability test. Moreover, it turns out that it is excellent in visibility by using for the liquid crystal display device the polarizing plate produced using the anti-glare film of this invention after durability test.

Especially, the anti-glare film of this invention whose arithmetic mean roughness (Ra) is 350-1300 nm is excellent in the visibility, transparency, and flexibility as a film at the time of using it for a liquid crystal display device.

Application of an antiglare layer obtained by diluting an active line curable resin having a viscosity at 25 ° C. in a range of 20 to 3000 mPa · s with glycol ethers such as PGME or EPGE, alcohols such as ethanol or methanol, or esters such as butyl acetate Arithmetic mean roughness (Ra) of the glare-proof layer and an inside of a glare-proof layer by processing a composition at least via the application | coating process, a drying process, and a hardening process, and processing on the conditions which hold | maintained the temperature reduction interval section of a drying process at 90-150 degreeC. It can be seen that the haze can be easily controlled within the scope of the present invention, and furthermore, it is preferable in that the desired effect of the present invention can be obtained satisfactorily.

Moreover, since the objective effect of this invention is acquired favorably, the anti-glare film of this invention whose internal haze of an anti-glare layer is 0 to 0.5% turns out that it is preferable.

As for the anti-glare film of the present invention, the anti-glare layer was observed with an optical interference surface roughness meter (New View 5030, manufactured by Zygo). As a result, irregular protrusions were irregularly arranged in the longitudinal direction and the width direction, as in the anti-glare film 1. there was.

In addition, about the anti-glare films 1-25, using the pencil for test prescribed by JIS-S6006, and according to the pencil hardness evaluation method prescribed | regulated by JIS-K5400, the anti-glare layer was made with the pencil of each hardness using the weight of 500g. As a result of scraping repeatedly and evaluating pencil hardness, the anti-glare film of this invention was all 3H or more, and had favorable hard coat property. The pencil hardness of the anti-glare film of this invention whose especially arithmetic mean roughness Ra of this invention is 500-1300 nm was 4H, and was especially excellent.

Example 2

<Preparation of anti-glare antireflection films 1 to 7>

In preparation of the anti-glare films 4, 9, 13 and 18 to 21 of Example 1, the irradiance of the irradiated portion was 100 mW / cm ² without using a nitrogen purge, and the irradiation dose was 0.1 J / cm ^2. The anti-glare films 26-32 were produced similarly except having hardened the coating layer as a roll, and wound up in roll shape. Subsequently, each roll-shaped anti-glare film 26 to 32 subjected to the durability test was again released under the conditions described in Example 1, the coating composition 1 for low refractive index layer was applied on the surface of the anti-glare layer, and a low refractive index layer was formed. The anti-reflective films 1-7 were produced. In addition, the refractive index of the low refractive index layer was 1.37.

[Coating composition 1 for low refractive index layer]

(Preparation of Fluorine-containing Polymer 1)

40 ml of ethyl acetate, 14.7 g of hydroxyethyl vinyl ether, and 0.55 g of dilauroyl peroxide were added to an autoclave with a stainless steel stirrer having a capacity of 100 ml, and the reaction system was degassed and replaced with nitrogen gas. Furthermore, 25 g of hexafluoropropylene (HFP) was introduce | transduced in the autoclave, and it heated up to the temperature of 65 degreeC. The pressure at the time the temperature in the autoclave reached 65 ° C was 5.4 kg / cm ² . The temperature in the autoclave was kept as it was, and the reaction was continued for 8 hours, and the heating was stopped and allowed to cool when the pressure reached 3.2 kg / cm ² . At the time when internal temperature fell to room temperature, the unreacted monomer was taken out, the autoclave was opened, and the reaction liquid was taken out.

The obtained reaction liquid was thrown into a large excess of hexane, and the precipitated polymer was taken out by removing the solvent by decantation. The polymer was dissolved in a small amount of ethyl acetate and reprecipitated twice from hexane to completely remove the remaining monomers and to dry to obtain 28 g of the polymer. Next, 20 g of the polymer was dissolved in 100 ml of N, N-dimethylacetamide, 11.4 g of acrylic acid chloride was added dropwise under ice cooling, followed by stirring at room temperature for 10 hours. Ethyl acetate was added to the reaction solution, the mixture was washed with water, the organic layer was extracted and concentrated to obtain 19 g of fluorine-containing polymer 1 by reprecipitation of the obtained polymer with hexane.

The following materials were stirred and mixed to obtain a coating composition 1 for low refractive index layer.

(menstruum)

460 parts by mass of methyl ethyl ketone

300 parts by mass of cyclohexanone

(Radical polymerizable compound)

130 parts by mass of fluorine-containing polymer

20 parts by mass of pentaerythritol triacrylate

Pentaerythritol tetraacrylate 14 parts by mass

(Photopolymerization initiator)

Irgacure 907 (manufactured by BASF Japan Co., Ltd.)

(additive)

6.5 parts by mass of a 10% propylene glycol monomethyl ether solution of a silicone compound (FZ-2207, manufactured by Nihon Unika Co., Ltd.)

(Fine particles)

50 parts by mass of isopropyl alcohol dispersed hollow silica fine particle sol

(20% of solid content, silica sol made by Shokubai Kasei Kogyo Co., Ltd., a brand name: ELCOM V-8209)

Film Evaluation

The following items were evaluated about the obtained anti-glare films 26-32 and anti-glare antireflection films 1-7. The obtained results are shown in Table 2.

1. Anti-glare film

Internal haze (Hi) and arithmetic mean roughness (Ra) of the antiglare films 26 to 32 were measured by the method described in Example 1. The obtained results are shown in Table 2.

2. Anti-glare antireflection film

(Appearance evaluation)

Each anti-glare antireflection film was cut into a size of 150 cm x 150 cm, light absorbing treatment was carried out using a black spray on the back surface, the reflection of fluorescent lamps was observed from the surface, and the following criteria were observed for the appearance (spot spots). Visually evaluated. The obtained results are shown in Table 2.

(Appearance: spot shape stains)

◎: no spot shape appearance

○: Slightly spotty spots appear

(Triangle | delta): The smudge of a spot shape appears a little. There is a practical problem

×: spot shape unevenness appears

(Adhesion)

After 500 cycles of each anti-glare antireflection film was put into a cycle thermostat (-40 degreeC, 30 minutes left, and 85 degreeC and 30 minutes left alternately), a weather resistance tester (the eye super UV tester, the Iwasaki Electric Corporation make) It was irradiated with light for 120 hours.

On the surface of the low-refractive index layer of each anti-glare antireflection film after the durability test, 11 blades were inserted vertically and horizontally at intervals of 1 mm at an angle of 90 ° with respect to the surface, and 100 1mm angle checker eyes were produced. It was. A commercially available cellophane tape was affixed thereon, and one end was grasped by hand and pulled out vigorously vertically to visually observe the ratio of the peeled area of the thin film to the pasted tape area from the sheath line. Evaluated.

◎: not peeled off at all

(Circle): The peeled area ratio is less than 10%

(Triangle | delta): The peeled area ratio is 10% or more and less than 20%.

X: The area ratio which peeled is 20% or more

As can be seen from the results shown in Table 2, the anti-glare antireflection film of the present invention constituted by the anti-glare layer of the present invention has a good performance against spot unevenness (appearance) and adhesion compared to the comparative example. Able to know. Moreover, about the anti-glare antireflection films 1-7, the black acryl plate with an adhesive was affixed on the back-coat surface, light absorption processing was performed, and CM-3700d (Konica Minolta Sensing Co., Ltd. product) was made from the low refractive index layer surface. As a result of measuring the reflectance using ()), the average reflectance of the anti-glare antireflection film of this invention was 1.2% or less, and had favorable antireflection function.

Example 3

<Production of clear hard coat film 1>

The following clear hard coat coating composition 1 filtered on a substrate film 1 produced in Example 1 with a polypropylene filter having a pore diameter of 0.4 μm was applied using a microgravure coater, and the yield drying section temperature was 80 ° C., and the drying rate section was reduced. After drying at 80 ° C., purge the coating layer with an irradiance of 100 mW / cm ² and an irradiation dose of 0.25 J / cm ² using an ultraviolet lamp while purging with nitrogen so that the oxygen concentration is 1.0% by volume or less. And a clear hard coat layer having a dry film thickness of 5 µm were formed. After forming a clear hard-coat layer, it wound up in roll shape and produced the clear hard-coat film 1. The whole haze of the clear hard coat film 1 was measured using the measuring instrument (NDH2000) by the Nippon Denshoku Kogyo Co., Ltd., and was 0.3%, and was excellent in clearability.

[Clear Hard Coat Layer Coating Composition 1]

The following clear hard coat layer coating composition 1 was stirred and mixed with a disper, and the clear hard coat layer coating composition 1 was obtained.

(Active wire curable resin)

Dipentaerythritol polyacrylate

(NK ester A-9550, Shinnakamura Kagaku Kogyo Co., Ltd.) 100 parts by mass

(Photopolymerization initiator)

Irgacure 184 (manufactured by BASF Japan) 5 parts by mass

(Leveling agent)

2 parts by mass of an acrylic copolymer (BYK-350, manufactured by BIC Chemie Japan)

(solvent)

10 parts by mass of propylene glycol monomethyl ether (PGME)

45 parts by mass of methyl ethyl ketone

45 parts by mass of methyl acetate

<Production of Polarizer>

It bonded by the roll-to-roll so that the clear hard coat film 1 and the following polarizer and the optical film 1 produced in Example 1 at the back surface side may be aligned in the longitudinal direction, and the polarizing plate 100 was produced.

<Production of Polarizer>

The polyvinyl alcohol film of thickness 120 micrometers was uniaxially stretched (temperature 110 degreeC, draw ratio 5 times). This was immersed for 60 seconds in the aqueous solution containing 0.075g of iodine, 5g of potassium iodide, and 100g of water, and then immersed in the 68 degreeC aqueous solution which contains 6g of potassium iodide, 7.5g of boric acid, and 100g of water. This was washed with water and dried to obtain a polarizer. Subsequently, according to steps 1 to 5, the polarizer, the clear hard coat film 1 and the back surface side were aligned with the optical film 1 in the longitudinal direction, joined by a roll-to-roll, and a polarizing plate was produced. Splicing.

Process 1: It was immersed in 60 mol of 2 mol / L sodium hydroxide solutions for 90 second, and then washed with water and dried, saponifying the side which adhere | attaches with a polarizer, and the clear hard coat film 1 and the optical film 1 were obtained.

Process 2: The said polarizer was immersed for 1-2 second in the polyvinyl alcohol adhesive bath of 2 mass% of solid content.

Process 3: The excess adhesive adhering to the polarizer in process 2 was lightly wiped and removed, and the optical film 1 was arrange | positioned on the clear hard coat film 1 and back surface which processed this at the process 1.

Process 4: The film laminated | stacked by the process 3 was bonded by the pressure of 20-30 N / cm <^2> and conveyance speed at about 2 m / min.

Process 5: The sample which bonded the polarizer produced by the process 4, the clear hard-coat film 1, and the optical film 1 in 80 degreeC dryer was dried for 2 minutes, it wound up in roll shape, and the polarizing plate 100 was produced.

Process 6: The acrylic adhesive commercially available for the protective film of the polarizing plate produced at the process 5 is apply | coated so that thickness after drying may be set to 25 micrometers, it is dried for 5 minutes in an oven of 110 degreeC, and an adhesive layer is formed, and it is peelable to an adhesive layer A protective film is attached. This polarization was cut out (punched), and the polarizing plate 100 was produced.

<Production of liquid crystal display device 101>

As shown in FIG. 5, the polarizing plate 1 produced in Example 1 peeled the peelable protective film of an adhesive layer, and bonded it to the back (backlight) side through the glass of a liquid crystal cell. Moreover, the peelable protective film of the adhesive layer of the produced polarizing plate 100 is peeled off, and it bonds to the front side, the liquid crystal panel 101 is produced, and this liquid crystal panel 101 is peeled off and inserted in the panel of SONY notebook PC VAIO TYPE B made by SONY. And liquid crystal display device 101 were produced.

<Production of Liquid Crystal Display Devices 102-125>

In the preparation of the liquid crystal display device 101, the liquid crystal display devices 102 to 125 were produced in the same manner except that the polarizing plates 1 on the back side were changed to the polarizing plates 2 to 25, respectively.

About the produced liquid crystal display devices 101-125, moire fringe was observed and the following references | standards evaluated. The obtained results are shown in Table 3.

<< evaluation of display device >>

(Moire stripe evaluation)

◎: no moire stripes at all

○: slightly moire stripes can be observed

△: faint but can easily confirm the presence of moire stripes

×: The presence of moire stripes can be confirmed. Practical problem level

××: The occurrence of moire stripes can be clearly confirmed

As a result of evaluation, in the liquid crystal display device used for the back side using the polarizing plate comprised from the anti-glare film of this invention, no moire fringe was observed and it was excellent in prevention of generation of moire fringe.

Example 4

<Production of Anti-glare Film 1 with Conductive Film>

In the production of the anti-glare film 1, after coating the anti-glare layer coating layer composition 1 on both sides to form an anti-glare layer on both sides, a transparent conductive thin film of indium tin oxide (ITO) having a surface resistivity of about 200 Ω on one side of the anti-glare layer Was installed using the sputtering method, and the anti-glare film 1 provided with the electroconductive film shown in FIG. 7 was produced.

<Production of Anti-glare Films 2 to 25 with Conductive Film>

In the same manner as the preparation of the anti-glare film 1 having the conductive film, after forming an anti-glare layer on both sides, a transparent conductive thin film of ITO having a surface resistivity of about 200 Ω was provided on one side of the anti-glare layer by sputtering, The anti-glare films 2-25 with a film were produced.

<Production of Resistive Touch Panel Liquid Crystal Display 201>

A conductive optical film of a commercially available resistive touch panel liquid crystal display device (product name: LCD-USB10XB-T, manufactured by IO DATA Co., Ltd.) was peeled off, and the anti-glare film 1 having the produced conductive film was bonded as shown in FIG. 8. Thus, a resistive touch panel liquid crystal display device 201 was produced.

<Production of Resistive Touch Panel Liquid Crystal Display Devices 202 to 225>

In the production of the resistive touch panel liquid crystal display device 1, the resistive touch panel liquid crystal display device 202 was similarly applied except that the anti-glare film 1 having the conductive film was changed to the anti-glare films 2 to 25 having the conductive film. To 225 was produced.

<< visibility evaluation >>

In the same manner as in Example 1, the visibility of the resistive touch panel liquid crystal display devices 202 to 225 was evaluated. The obtained results are shown in Table 4.

Film Evaluation

(Npenpen sliding mobility)

About the anti-glare films 2-25 provided with the electroconductive film, evaluation was performed about the pen-resistant sliding property on the following conditions. The obtained results are shown in Table 4.

On the surface of the anti-glare layer of the anti-glare film provided with each conductive film used for the resistive-type touch panel liquid crystal display device, the tip was straightened at a load of 500 g and a pen sliding speed of 100 mm / sec using a pen made of a polyacetal of 0.08 mmφ. Scratches and peeling of the antiglare layer at the sliding part after reciprocating 40 mm of 150,000 times were visually evaluated.

As a result of evaluation, the anti-glare film provided with the electroconductive film of this invention, and the resistive-film type touch panel liquid crystal display device using this film were excellent in visibility and pen sliding resistance.

This application is based on the JP Patent application 2011-058652 of an application on March 17, 2011, The content is contained in this application.

In order to express the present invention, the present invention has been described appropriately and sufficiently through the embodiments with reference to the drawings in the foregoing description, but those skilled in the art recognize that it is easy to change and / or improve the above-described embodiments. Should be. Therefore, unless the form of a change or improvement which a person skilled in the art implements is a level which deviates from the scope of a claim as described in a claim, the said change form or the said improvement is interpreted to be included in the scope of a claim. .

The present invention has wide industrial applicability in the technical fields of anti-glare film, polarizing plate, image display device, and touch panel.

Claims (13)

An antiglare film having an antiglare layer containing an active ray curable resin on a base film, wherein the antiglare layer contains substantially no incompatible resin with respect to the fine particles and the active ray curable resin, and arithmetic mean roughness of the antiglare layer (Ra) is 300-1500 nm, and the haze resulting from the internal scattering of the said anti-glare layer is 0 to 1.0%, The anti-glare film characterized by the above-mentioned. The method of claim 1,
Arithmetic mean roughness Ra of the said glare-proof layer is 350-1300 nm, The anti-glare film characterized by the above-mentioned. 3. The method according to claim 1 or 2,
Arithmetic mean roughness Ra of the said glare-proof layer is 500-1300 nm, The anti-glare film characterized by the above-mentioned. 4. The method according to any one of claims 1 to 3,
The haze resulting from the internal scattering of the said glare-proof layer is 0 to 0.5%, The anti-glare film characterized by the above-mentioned. 5. The method according to any one of claims 1 to 4,
The surface of the said anti-glare layer has an irregular protrusion shape which does not have a period in a longitudinal direction, The anti-glare film characterized by the above-mentioned. The method according to any one of claims 1 to 5,
The viscosity in 25 degreeC of the said actinic-rays curable resin exists in the range of 20-3000 mPa * s, The anti-glare film characterized by the above-mentioned. The low-refractive-index layer was laminated on the anti-glare layer of the anti-glare film of any one of Claims 1-6 through directly or another layer, The anti-glare antireflection film characterized by the above-mentioned. It is a manufacturing method of the anti-glare film which manufactures the anti-glare film of any one of Claims 1-6, The actinic-rays curable resin which has a viscosity in 25 degreeC in the range of 20-3000 mPa * s is ester, glycol ether The antiglare layer coating composition diluted with at least one solvent selected from the group or the alcohols is formed at least through an application step, a drying step and a curing step to form an antiglare layer, and furthermore, the temperature of the rate-sensitive drying section in the drying step. A process for producing an anti-glare film, characterized in that the treatment is carried out under conditions maintained in the range of 90 to 150 ℃. The anti-glare film of any one of Claims 1-6 and the anti-glare antireflection film of Claim 7 are provided in at least one surface, The polarizing plate characterized by the above-mentioned. The anti-glare film of any one of Claims 1-6 and the anti-glare antireflection film of Claim 7 are equipped, The image display apparatus characterized by the above-mentioned. The method of claim 10,
The polarizing plate of Claim 9 is provided in at least one surface of a liquid crystal cell, The image display apparatus characterized by the above-mentioned. The method of claim 10,
The polarizing plate of Claim 9 is used for the back side of a liquid crystal cell, The image display apparatus characterized by the above-mentioned. The method of claim 10,
The said image display apparatus is an image display apparatus provided with a touch panel, The anti-glare film of any one of Claims 1-6, or the anti-glare antireflection film of Claim 7 is provided as a structural member of the said touch panel. There is an image display apparatus characterized by the above-mentioned.

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