KR101242778B1 - Anti-reflection film, polarizing plate and liquid crystal display device - Google Patents

Abstract

(Problem) To provide a polarizing plate and a liquid crystal display using the same that the viewing angle is enlarged, the contrast decreases due to the change of vision, the gradation or black and white inversion and color change hardly occurs.
(Solution means) The protective film on one side of the polarizing film has at least one hard coat layer and a low refractive index layer located on the outermost layer on the transparent support, and the hard coat layer has at least one kind of binder and a binder having different refractive index. It is an antireflection film containing permeable particles and having a surface roughness Ra (center line average roughness) of 0.10 µm or less, the other protective film has a Re retardation value of 20 to 70 nm, and a Rth retardation value of 70 to 400 nm. And the ratio (Re / Rth ratio) of Re retardation value and Rth retardation value is 0.2-0.4, and is arrange | positioned so that the slow axis of a retardation film and the transmission axis of a polarizing film may become substantially parallel.

Description

Anti-reflective film, polarizer and liquid crystal display {ANTI-REFLECTION FILM, POLARIZING PLATE AND LIQUID CRYSTAL DISPLAY DEVICE}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal display device for use in image display of a computer, word processor, television, and the like, and more particularly, to an antireflection film, a polarizing plate, and a liquid crystal display device for improving display quality.

Liquid crystal displays have various advantages, such as low voltage, low power consumption, miniaturization, and thinness, and are widely used in PCs, portable devices, monitors, and TVs. The liquid crystal display device has been proposed in various modes based on the arrangement of liquid crystals in the liquid crystal cell. In the related art, the TN mode in which the liquid crystal cell is arranged in a 90 ° twisted direction from the lower substrate to the upper substrate has become mainstream.

In general, a liquid crystal display device includes a liquid crystal cell, an optical compensation sheet, and a polarizing plate. An optical compensating sheet is used to eliminate image coloring or to enlarge a viewing angle, and a film obtained by applying a liquid crystal to a stretched birefringent film or a transparent film is used. For example, Japanese Patent Publication No. 2587398 discloses a technique for widening the viewing angle by applying an optical compensation sheet obtained by applying and orienting a discotic liquid crystal on a triacetylcellulose film to a liquid crystal cell of TN mode. However, a liquid crystal display device for TV use, which is a large screen and can be viewed from various angles, has a strict demand for viewing angle dependence, and cannot be fulfilled even by the above-described method. Accordingly, different liquid crystal displays have been studied, which are different from TN modes such as IPS (In-Plane Switching) mode, OCB (Optically Compensatory Bend) mode, and VA (Vertically Aligned) mode. In particular, VA mode has attracted attention as a liquid crystal display device for TV because of its high contrast and relatively high production yield.

Even in VA mode, in order to achieve a wide viewing angle, it is necessary to combine retardation films, and as a retardation film, Re-retardation of 20-70 nm and Rth retardation of 70-400 nm are needed. Japanese Laid-Open Patent Publication No. 2003-75638 proposes a combination of a retardation film and a light diffusion film for the purpose of further improving the contrast and further improving the gray scale characteristics.

However, in recent years, the environment in which a liquid crystal display is used is very wide, and higher demands have been made on display quality, and even in the above combination, insufficient performance is obtained in terms of the change in left and right color taste peculiar to VA mode and the reproducibility of black in bright places. It was.

In addition, antireflective films are generally used in display devices such as cathode ray tube displays (CRTs), plasma displays (PDPs), electroluminescent displays (ELDs), and liquid crystal displays (LCDs), and have low contrast due to reflection of external light. Since the projection of one image is prevented to improve the visibility of the image, it is disposed on the outermost surface of the display using the principles of light diffusion and optical interference.

As a conventional antireflection film, there is an anti-glare antireflection film which suppresses the specular reflection of external light by diffusing the surface reflected light to prevent projection of the external environment. For example, in the anti-reflection film of JP 2000-338310 A, the hard coat layer contains appropriate fine particles to impart unevenness to the surface and diffuse external light to alleviate the dazzling screen. In addition, in the antireflection films of JP-A-2002-196117 and 2003-161816, one low-refractive-index layer is formed on an anti-glare hard coat layer having a surface microconcavo-convex shape, and in addition to diffusion of external light on the surface. Reflectance is suppressed using the principle of optical interference. In the anti-reflection film of JP-A-2003-121620, a high refractive index layer is formed under the low refractive index layer to effectively reduce light reflection by using optical interference.

However, these anti-glare antireflective films diffuse external light from the fine concavo-convex on the surface, and at the same time, the display screen becomes white (white), the sharpness of the image deteriorates (the image is blurred), and further, due to the lens effect of the fine concave-convex structure. The problem of glittering phenomenon is inevitable. These problems have been tried to improve by controlling the haze, image sharpness, fine concavo-convex shape, and the like of the antiglare layer, but a satisfactory one could not be obtained.

On the other hand, Japanese Laid-Open Patent Publication No. 2003-57415 is an anti-reflection film that has high image clarity, no whitening or glitter, and further expands the viewing angle, and has very small surface fine unevenness and internal scattering property in the hard coat layer. There is proposed an antireflection film containing light transmitting particles.

However, even when using the antireflection film of Unexamined-Japanese-Patent No. 2003-57415, although some improvement effect is acquired, it is still not satisfactory from the viewpoint of black reproducibility when displaying black in a bright place.

These antireflection films are usually used as a protective film on the viewing side of the polarizing plate. A cellulose acylate film and an optical compensation film (retardation film) are used individually or in combination for the other side of a polarizing plate, ie, the protective film on the liquid crystal cell side.

And since a cellulose acylate film has the characteristic of having high optical isotropy (low retardation value) compared with another polymer film, it is normally used for the use which requires optical isotropy, for example, a polarizing plate.

On the other hand, optical anisotropy (high retardation value) is required for the optical compensation sheet (retardation film) of a liquid crystal display device. In such a case, it is common to use a synthetic polymer film having a high retardation value such as a polycarbonate film or a polysulfone film as the optical compensating sheet.

EP 0911656A2 discloses a cellulose acetate film having a high retardation value which can be used in applications which overturn conventional principles and require optical anisotropy. In this patent document, in order to implement | achieve a high retardation value with cellulose triacetate, the compound which has at least 2 aromatic ring, and the compound which has the 1,3,5-triadine ring among these is added and extending | stretching. In general, cellulose triacetate is a difficult polymer material to be stretched, and it is known that it is difficult to increase the birefringence. However, the birefringence can be increased by aligning the additives simultaneously by the stretching treatment, thereby achieving a high retardation value. . Since this film can also serve as a protective film of a polarizing plate, there is an advantage that it can provide a liquid crystal display device which is a thin film at low cost.

Recently, in order to reduce the weight of the liquid crystal display device and reduce the manufacturing cost, thinning of the liquid crystal cell has become an essential requirement. For this reason, the optical compensation sheet is required to have a higher Re retardation value and a lower Rth retardation value. However, in the method of EP 0911656A2, there is a problem that the above-described Re retardation value and Rth retardation value are not compatible when they are individually designated.

In addition, Japanese Patent Laid-Open No. 2001-116926 discloses controlling the Rth value, but the Re value and the Rth value are not compatible.

In order to solve the above problem, the optical compensation sheet which consists of cellulose acetate films like Unexamined-Japanese-Patent No. 2001-249223 is newly proposed. However, the problem mentioned later that the wound of outermost layer was outstanding in the polarizing plate which consists of an optical compensation sheet of Unexamined-Japanese-Patent No. 2001-249223 appeared.

That is, such an optical compensation sheet is a conventional structure of a polarizing plate which is provided in the one side of a polarizing film, and forms a transparent protective film in the other side which interposed the polarizing film. However, when the outermost transparent protective film is made of only a conventional cellulose acylate film having no anti-reflection function, contrast reduction due to reflection of external light, disturbance of viewing by projection of an image, and scratch resistance are deteriorated and are easily visible. There was such a problem.

In addition, in general display devices such as cathode ray tube display (CRT), liquid crystal display (LCD), plasma display (PDP), and electroluminescent display (ELD), reflection which reduces reflectance using the principle of optical interference It is known to arrange the prevention film on the outermost surface of the display.

The polarizing plate having the above-described optical compensatory sheet is effective for thinning the liquid crystal cell. However, when the outermost layer is made of only a normal cellulose acylate film having no antireflective function, the outermost layer is applied to the outermost layer to damage the film. The problem arises that the deformation is strong and noticeable.

In short, a polarizing plate that is compatible with optical compensation and anti-reflection functions, and which is not easily scratched on the surface has not been proposed, and a polarizing plate having these performances in terms of light weight and low cost of a liquid crystal display device has not been proposed. This is what is desired.

In order to improve the visibility of a liquid crystal display, a first object of the present invention is to provide a polarizing plate in which a viewing angle is enlarged and a contrast decrease due to visual change, gradation or black and white inversion, and color change hardly occur, and a liquid crystal display using the same. It is in providing a device.

Moreover, it is providing the polarizing plate which can improve anti-reflective property, and especially improves visibility in bright places, and the liquid crystal display device using the same.

A second object of the present invention is to prevent the projection of external light to improve the visibility of a display such as a liquid crystal display device, so that there is no whitening, blurring or glittering of the image, and further, the reproducibility of black in bright places is improved. One antireflection film is to be provided.

In addition, the object of the present invention is to have a high visibility by the antireflection film, further increase the viewing angle (especially the downward viewing angle), and almost no contrast reduction, grayscale or black and white inversion and color change due to visual change It is providing the polarizing plate which does not generate | occur | produce, and the liquid crystal display device using the same.

A third object of the present invention is a polarizing plate having a functional film made of only a cellulose acylate film provided with an optical compensation function, further providing an antireflection function without increasing the number of constituent members, and further scratching the surface The present invention provides a liquid crystal display device in which a polarizing plate having no visible features is provided, and furthermore, a polarizing plate having these functions is formed.

According to the present invention, in order to improve the visibility of a liquid crystal display, there is provided a polarizing plate in which a viewing angle is enlarged and a contrast deterioration, gradation or black and white reversal, and color change hardly occur due to a visual change, and a liquid crystal display device using the same. can do.

In addition, it is possible to provide a polarizing plate and a liquid crystal display device using the same, which can improve antireflection and improve visibility in particularly bright places.

In addition, in order to improve the visibility of a display such as a liquid crystal display device, by preventing the projection of external light, there is no whitening, image blurring, glittering phenomenon, and further provides an antireflection film that improves the reproducibility of black in bright places can do.

In addition, a polarizing plate having high visibility by the antireflection film, and further expanding the viewing angle (especially the downward viewing angle), and hardly causing a decrease in contrast, gray level or black and white inversion and color change due to visual change, and A liquid crystal display device using the same can be provided.

Moreover, in the polarizing plate which has a functional film which consists only of the cellulose acylate film with which the optical compensation function was provided, the antireflection function is further provided without increasing the number of constituent members, and further, the scratches on the surface are made inconspicuous. By providing a polarizing plate, the liquid crystal display device which further provided the polarizing plate which has these functions can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS Sectional drawing which shows the structural example of the antireflection film of 1st and 2nd aspect of this invention.
FIG. 2 is a cross-sectional view showing a configuration example of an antireflection film of the first and second aspects of the present invention. FIG.
3 is a cross-sectional view showing a configuration example of an antireflection film of the first and second aspects of the present invention.
4 is a cross-sectional view showing a configuration example of a polarizing plate of the first and second aspects of the present invention.
5 is a cross-sectional schematic diagram showing the layer structure of an antireflection film used in a third embodiment of the present invention.
Fig. 6 is a cross-sectional schematic diagram showing the layer structure of an antireflection film used in the third aspect of the present invention.

The said 1st objective of this invention is achieved by the polarizing plates of following (1)-(9) and the liquid crystal display device of following (10).

<1st aspect>

(1) A polarizing plate sandwiching both surfaces of a polarizing film with an antireflection film and a retardation film, wherein the antireflection film has at least one hard coat layer and a low refractive index layer located on the outermost layer on the transparent support, and the hard The coating layer contains a binder and at least one light-transmitting particle having a refractive index different from that of the binder, and the surface roughness (Ra; centerline average roughness) of the antireflection film is 0.10 µm or less, and the retardation film is represented by the following formula (I). The Re retardation value defined by) is 20 to 70 nm, the Rth retardation value defined by the following formula (II) is 70 to 400 nm, and the ratio of the Re retardation value and the Rth retardation value (Re / Rth ratio) is 0.2-0.4, and is arrange | positioned so that the slow axis of this retardation film and the transmission axis of this polarizing film may become substantially parallel.

Formula (I) Re = (nx-ny) × d

Formula (II) Rth = [{(nx + ny) / 2} -nz] × d

[Wherein nx is a refractive index in the slow axis direction in the film plane; ny is the refractive index in the fast axis direction in a film plane; nz is a refractive index in the thickness direction of the film; And d is the thickness of the film].

(2) Transparence image sharpness of an antireflection film is 65% or more, The polarizing plate as described in said (1) characterized by the above-mentioned.

(3) The haze of an antireflection film is 10% or more, The polarizing plate as described in said (1) or (2) characterized by the above-mentioned.

(4) The scattered light intensity of 30 ° to the light intensity of the exit angle of 0 ° of the scattered light profile measured with a goniphotometer of the antireflection film is 0.01% to 0.2%, characterized in that (1) to (3) The polarizing plate in any one of them.

(5) The polarizing plate according to any one of (1) to (4), wherein the low refractive index layer contains hollow silica fine particles having an average particle diameter of 0.5 to 200 nm and a refractive index of 1.17 to 1.40.

(6) The polarizing plate in any one of said (1)-(5) which has at least 1 layer of high refractive index layers whose refractive index is higher than a transparent support body on a hard-coat layer.

(7) The polarizing plate in any one of said (1)-(6) characterized by the retardation film consisting of the cellulose acylate film extended | stretched by 3-100% of draw ratio.

(8) Said retardation film consists of a cellulose acylate film containing 0.01-20 mass parts of rod-shaped compounds which have a linear molecular structure with at least 2 aromatic rings with respect to 100 mass parts of cellulose acylates, The said characterized by the above-mentioned. The polarizing plate as described in (7).

(9) The acetylation degree of cellulose acylate is 59.0 to 61.5%, The polarizing plate as described in said (7) or (8) characterized by the above-mentioned.

(10) A liquid crystal display device comprising a liquid crystal cell and two polarizing plates disposed on both sides thereof, wherein the polarizing plate according to any one of the above (1) to (9) is one of the two polarizing plates, and the low refractive index layer is The liquid crystal display device of VA mode characterized by being used so that it may be arrange | positioned at the outermost layer of a display.

The 2nd object of this invention is achieved by the antireflection film of following (11)-(16), the polarizing plate of following (17), (18), and the liquid crystal display device of following (19).

(11) An antireflection film having at least one hard coat layer and a low refractive index layer positioned on an outermost layer on a transparent support, wherein the haze of the hard coat layer is 40% or more, and the surface roughness (Ra; Center line average roughness) is 0.10 micrometer or less, and the average value of 5 degree specular reflectance with respect to the average value of the integral reflectance in the wavelength range from 450 nm to 650 nm is 65% or more.

(12) The antireflection film according to (11), wherein the average value of the integral reflectance in the wavelength range of 450 nm to 650 nm of the antireflection film is 2.5% or less.

(13) The antireflection film according to (11) or (12), wherein the transmissive image clarity of the antireflection film is 65% or more.

(14) The antireflection film according to any one of (11) to (13), wherein the hard coat layer has a binder and at least one light-transmitting particle having a refractive index different from that of the binder and has internal scattering properties.

(15) In (11) to (14), wherein the scattered light intensity of 30 ° to the light intensity of 0 ° of the scattered light profile measured by the goniphotometer of the hard coat layer is 0.01% to 0.2%. The antireflective film in any one of them.

(16) The antireflection film according to any one of (11) to (15), having at least one high refractive index layer having a higher refractive index than the transparent support on the hard coat layer.

(17) The antireflection film in any one of (11)-(16) was used for one protective film as a polarizing plate which pinched both surfaces of a polarizing film with a protective film. The polarizing plate characterized by the above-mentioned.

(18) Of the two protective films, a protective film in which no antireflection film is used is an optical compensation film having an optically anisotropic layer, the optically anisotropic layer being a layer containing a compound having a discotic structural unit, and a discotic structural unit The disk surface of which inclines with respect to the protective film surface, and the angle which the disk surface of a discotic structural unit and a protective film surface make is changed in the thickness direction of an optically anisotropic layer, The polarizing plate as described in (17) characterized by the above-mentioned.

(19) The liquid crystal display device using the antireflection film as described in any one of (11)-(16) or the polarizing plate as described in (17) and (18) for the outermost layer of a display.

According to the first aspect of the present invention, a polarizing plate capable of improving the visibility of a liquid crystal display and a liquid crystal display using the same as the viewing angle is enlarged, and contrast decrease, gradation or black and white reversal, and color change due to visual change hardly occur. A device can be provided.

In addition, it is possible to provide a polarizing plate and a liquid crystal display device using the same, which have high anti-reflection properties and can improve visibility in particularly bright places.

According to the second aspect of the present invention, the visibility of a display such as a liquid crystal display device is improved, which prevents the projection of external light, prevents whitening, blurring of the image, glare, and further improves the reproducibility of black in bright places. It is possible to provide an antireflection film.

In addition, the antireflection film of this invention can be used as a protective film of a polarizing plate. The antireflection film and the polarizing plate of the present invention have high visibility by being used in a liquid crystal display device, and the viewing angle, in particular, the downward viewing angle is enlarged, and the contrast decrease, the gray scale or the black and white inversion and the color change due to the visual change, etc. It is possible to provide a liquid crystal display device which hardly occurs.

(Best Mode for Carrying Out the Invention)

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of the antireflection film polarizing plate of the 1st, 2nd aspect of this invention is described with reference to drawings.

First, the structural example of the anti-reflective film used for the polarizing plates of the 1st, 2nd aspect of this invention is shown typically in FIGS. 1-3. As shown in FIG. 1, the antireflection film 10 of the present invention includes a transparent support 1, a hard coat layer 2A including translucent particles 4A capable of imparting internal scattering properties, and an outermost layer. The low refractive index layer 3 is laminated on the substrate. The aspect of each layer and the layer structure of a film can be changed suitably, For example, as shown to the anti-reflection film 20 of FIG. 2, another type of translucent particle (further inside the hard-coat layer 2B) 4B), and as shown to the antireflection film 30 of FIG. 3, the medium refractive index layer 5 and the high refractive index layer (for the purpose of improving the antireflection property by optical interference on 2 A of hard-coat layers) 6) may be formed and the low refractive index layer 3 may be disposed in the outermost layer.

Next, the structural example of the polarizing plate of the 1st and 2nd aspect of this invention is shown typically in sectional drawing in FIG.

As for the polarizing plate 60 of this invention, the antireflection film 10, 20, or 30 is used for one of the protective films which pinched the polarizing plate 40, and the retardation film 50 is used for the other one.

Next, each layer which comprises the polarizing plate of this invention is demonstrated in detail. In addition, in this specification, description of "(value A)-(value B)" shows the meaning of "(value A) or more (value B) or less."

(Retardation film)

Re retardation value and Rth retardation value of retardation film are defined by following formula (I) and (II), respectively. The measurement wavelength is 550 nm.

Formula (I) Re = (nx-ny) × d

Formula (II) Rth = [{(nx + ny) / 2} -nz] × d

In Formulas (I) and (II), nx is a refractive index in the slow axis direction (direction in which the refractive index becomes maximum) in the film plane. In formula (I) and (II), ny is the refractive index of the fast-axis direction (direction in which refractive index becomes minimum) in a film plane. In formula (II), nz is the refractive index of the thickness direction of a film. In formula (I) and (II), d is the thickness of the film which makes a unit nm.

In this invention, Re-retardation value of retardation film is adjusted to 20-70 nm, and Rth retardation value is adjusted to 70-400 nm. In the present invention, the Re / Rth ratio is adjusted to 0.2 to 0.4. Preferably, the Re retardation value is adjusted to 40 to 70 nm, the Rth retardation value is set to 90 to 200 nm, and the Re / Rth ratio is adjusted to 0.3 to 0.4. These adjustment can be performed by the kind, addition amount, and draw ratio of the rod-shaped compound which has an aromatic ring.

The birefringence index (nx-ny) of the retardation film is preferably 0.0002 to 0.0009, more preferably 0.00025 to 0.0009, and most preferably 0.00035 to 0.0009. In addition, the birefringence [{(nx + ny) / 2} -nz] in the thickness direction of the retardation film is preferably 0.0006 to 0.005, more preferably 0.0008 to 0.005, and most preferably 0.0012 to 0.005.

As a retardation film, the transparent polymer film is used conventionally. Examples of resin films and polymers include norbornene resins, cellulose esters (e.g., cellulose triacetate, cellulose diacetate, cellulose acetate butyrate), polyesters (e.g., polyethylene terephthalate, polycarbonate), polyether sulfone, polyolefin (Eg, polymethylpentene, polyacrylic acid ester), polyurethane, polysulfone, polyether, polyetherketone, polyacrylonitrile and polymethacrylonitrile. A commercially available norbornene resin (Aton, manufactured by JSR Corporation; Zeonex, Zeonor, Nippon Xeon Corporation) may be used. Especially, it is preferable to use the cellulose acylate film generally used as a protective film of a polarizing plate. That is, in order not to thicken a liquid crystal display device, it is preferable to use one cellulose acetate film which has both a function as a retardation film and a function as a transparent protective film (protective function of a polarizing film).

[Cellulose Acylate Film]

As a raw material surface of the cellulose acylate used for this invention, a well-known raw material can be used (for example, refer the invention association publication method 2001-1745). Synthesis of cellulose acylate can also be carried out by a known method (see, for example, Migita et al. "Wood Chemistry" pages 180 to 190 (Gyoritsu Publication, 1968)). As for the viscosity average polymerization degree of a cellulose acylate, 200-700 are preferable, 250-500 are more preferable, 250-350 are the most preferable. Moreover, it is preferable that the cellulose ester used for this invention has a narrow molecular weight distribution of Mw / Mn (Mw is mass mean molecular weight, Mn is number average molecular weight) by gel permeation chromatography. As specific Mw / Mn value, it is preferable that it is 1.5-5.0, It is more preferable that it is 2.0-4.5, It is most preferable that it is 3.0-4.0.

Although the acyl group of a cellulose acylate film does not have a restriction | limiting in particular, It is preferable to use an acetyl group and a propionyl group, and especially an acetyl group is preferable. 2.7-3.0 are preferable and, as for the substitution degree of all acyl groups, 2.8-2.95 are more preferable. In this specification, the substitution degree of an acyl group is the value computed according to ASTMD817.

It is most preferable that an acyl group is an acetyl group, and when using the cellulose acetate whose acyl group is an acetyl group, it is preferable that it is 59.0-62.5%, and it is more preferable that it is 59.0-61.5%. When the acetylation degree is in this range, Re does not become larger than a desired value by the conveyance tension at the time of casting | flow_spread, there are few in-plane deviations, and the change of retardation value is also small by temperature and humidity.

The substitution degree of the acyl group at the 6-position is preferably 0.9 or more from the viewpoint of suppressing variation in Re and Rth.

[Retardation control agent]

In the present invention, in order to control the retardation, it is preferable to use a rod-shaped compound having at least two aromatic rings as the retardation controlling agent. The rod-shaped compound preferably has a linear molecular structure. The linear molecular structure means that the molecular structure of the rod-shaped compound is linear in the thermodynamic most stable structure. The most thermodynamically stable structure can be obtained by crystal structure analysis or molecular orbital calculation. For example, molecular orbital calculations are performed using molecular orbital calculation software (e.g., WinMOPAC2000, manufactured by Fujitsu Co., Ltd.) to obtain the structure of the molecule in which the heat of production of the compound is the smallest. The linear molecular structure means that in the thermodynamic most stable structure calculated and calculated as described above, the angle formed by the main chain in the molecular structure is 140 degrees or more.

As a rod-shaped compound which has at least two aromatic rings, the compound represented by following General formula (1) is preferable.

General formula (1) Ar ₁ -L ₁ -Ar ₂

Wherein in the formula (1), Ar ₁ and Ar ₂ are, each independently, a substituted or non-carbon atoms of 6-30 optionally substituted aryl groups (e.g., phenyl, naphthyl, anthracenyl), or 2 to 30 carbon atoms An aromatic heterocyclic group is shown. The aromatic heterocycle is preferably a 5-membered ring, a 6-membered ring, or a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring. The hetero atom is preferably a nitrogen atom, an oxygen atom or a sulfur atom, and more preferably a nitrogen atom or a sulfur atom. Examples of aromatic heterocycles include furan rings, thiophene rings, pyrrole rings, oxazole rings, isoxazoles, thiazole rings, isothiazol rings, imidazole rings, pyrazole rings, furazane rings, and triazole rings. , Pyran ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring and 1,3,5-triazine ring.

Examples of the aromatic ring of Ar ₁ and Ar ₂ include a benzene ring, a furango ring, a thiophene ring, a pyrrole ring, an oxazole ring, a thiazole ring, an imidazole ring, a triazole ring, a pyridine ring, a pyrimidine ring and a pyrazine ring. Preference is given, with benzene rings being particularly preferred. Ar ₁ and Ar ₂ are more preferably an aryl group.

Examples of the substituent of the aryl group and the aromatic heterocyclic group include halogen atoms (F, Cl, Br, I), hydroxyl, carboxyl, cyano, amino, alkylamino groups (alkylamino groups having 1 to 20 carbon atoms, for example, Methylamino, ethylamino, butylamino, dimethylamino), nitro, sulfo, carbamoyl, alkylcarbamoyl groups (alkylcarbamoyl groups having 1 to 20 carbon atoms, for example N-methylcarbamoyl, N- Ethylcarbamoyl, N, N-dimethylcarbamoyl), sulfamoyl, alkylsulfamoyl groups (sulfamoyl groups having 1 to 20 carbon atoms, for example, N-methylsulfamoyl, N-ethylsulfamoyl, N, N-dimethyl sulfamoyl), ureido, alkyl ureido group (C1-20 ureido group, for example, N-methylureido, N, N-dimethylureido, N, N, N'-trimethylureido ), An alkyl group (a straight-chain, branched or cyclic alkyl group having 1 to 20 carbon atoms, for example methyl, ethyl, propyl, butyl, pentyl, Heptyl, octyl, decyl, dodecyl, isopropyl, s-butyl, t-amyl, cyclohexyl, cyclopentyl), alkenyl group (straight, branched or cyclic alkenyl group having 2 to 20 carbon atoms), for example, vinyl , Allyl, 2-butenyl, hexenyl), alkynyl group (for example, alkynyl group having 2 to 20 carbon atoms, ethynyl, 2-butyn-1-yl, propargyl), aryl group (6- to 6 carbon atoms) Aryl group of 20, for example, phenyl, 2-naphthyl), acyl group (acyl group having 1 to 20 carbon atoms, for example, formyl, acetyl, butyryl, hexanoyl, lauroyl), acyl Period (it is a C1-C20 acyloxy group, for example, acetoxy, butyryloxy, hexanoyloxy, lauroyloxy), an alkoxy group (It is a C1-C20 alkoxy group, For example, methoxy, Ethoxy, propoxy, isopropoxy, butoxy, 2-butoxy, pentyloxy, heptyloxy, octyloxy, cyclohexyloxy), an aryloxy group (aryloxy group having 6 to 20 carbon atoms), For example, phenoxy, 1-naphthoxy) and alkoxycarbonyl groups (alkoxycarbonyl groups having 2 to 20 carbon atoms), for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentyloxycarbon Carbonyl, heptyloxycarbonyl), an aryloxycarbonyl group (aryloxycarbonyl group having 7 to 20 carbon atoms, for example, phenoxycarbonyl), alkoxycarbonylamino group (alkoxycarbonylamino group having 2 to 20 carbon atoms, for example Methoxycarbonylamino, butoxycarbonylamino, hexyloxycarbonylamino, cyclohexyloxycarbonylamino), alkylthio group (alkylthio group having 1 to 20 carbon atoms, for example, methylthio, ethylthio , Propylthio, butylthio, pentylthio, heptylthio, octylthio, dodecylthio, tetradecylthio), arylthio group (It is an arylthio group having 6 to 20 carbon atoms, for example, phenylthio), alkylsulfonyl group ( Carbon number 1 It is an alkylsulfonyl group of -20, For example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, pentylsulfonyl, heptylsulfonyl, octylsulfonyl), an amide group (amide group of 1-20 carbon atoms) For example, acetamide, butylamide, hexanoylamino, lauroylamino, benzamide, cyclohexanecarbonylamino) and non-aromatic heterocyclic groups (non-aromatic heterocyclic groups having 2 to 20 carbon atoms, for example 4 Morpholinyl, 1-piperidinyl, 2-tetrahydrofuryl).

Examples of the substituent for the aryl group and the aromatic heterocyclic group include a halogen atom, cyano group, carboxyl group, hydroxyl group, amino group, alkylamino group, acyl group, acyloxy group, amide group, alkoxycarbonyl group, alkoxy group, alkylthio group and alkyl group Is preferred.

The alkyl moiety and alkyl group of the alkylamino group, the alkoxycarbonyl group, the alkoxy group and the alkylthio group may further have a substituent. Examples of the substituent of the alkyl moiety and the alkyl group include halogen atom, hydroxyl group, carboxyl group, cyano group, amino group, alkylamino group, nitro group, sulfo group, carbamoyl group, alkylcarbamoyl group, sulfamoyl group, alkylsulfayl group , Ureido, alkylureido, alkenyl, alkynyl, acyl, acyloxy, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, alkoxycarbonylamino, alkylthio, arylthio, alkylsulfo And an aryl group, an amide group, and a non-aromatic heterocyclic group, and the preferred carbon number and specific examples thereof are the same as those mentioned as the substituents for the aryl group and the aromatic heterocyclic group. As a substituent of an alkyl part and an alkyl group, a halogen atom, a hydroxyl group, an amino group, an alkylamino group, an acyl group, an acyloxy group, an acylamino group, an alkoxycarbonyl group, and an alkoxy group are preferable.

In General formula (1), L <_1> is a bivalent coupling group chosen from the group which consists of an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -CO-, and its combination.

The alkylene group may have a cyclic structure. As the cyclic alkylene group, cyclohexylene is preferable, and 1,4-cyclohexylene is particularly preferable. As a linear alkylene group, a linear alkylene group is more preferable than the alkylene group which has a branch.

The number of carbon atoms of the alkylene group is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, still more preferably 1 to 8, and most preferably 1 to 6 carbon atoms.

It is preferable that an alkenylene group and an alkynylene group have a linear structure rather than a cyclic structure, and it is more preferable to have a linear structure rather than a branched chain structure.

The number of carbon atoms of the alkenylene group and the alkynylene group is preferably 2 to 10, more preferably 2 to 8, still more preferably 2 to 6, still more preferably 2 to 4, and most preferably 2 (ethylene or ethynylene).

It is preferable that arylene group has 6-20 carbon atoms, More preferably, it is 6-16, More preferably, it is 6-12.

The example of the bivalent coupling group which consists of combinations is shown.

L-1: -O-CO-alkylene group-CO-O-

L-2: -CO-O-alkylene group-O-CO-

L-3: -O-CO-alkenylene group-CO-O-

L-4: -CO-O-alkenylene group-O-CO-

L-5: -O-CO-alkynylene group-CO-O-

L-6: -CO-O-alkynylene group-O-CO-

L-7: -O-CO-arylene group-CO-O-

L-8: -CO-O-arylene group-O-CO-

L-9: -O-CO-arylene group-CO-O-

L-10: -CO-O-arylene group-O-CO-

In the molecular structure of General formula (1), it is preferable that the angle which Ar <_1> and Ar <_2> form between L <_1> is 140 degree or more.

As a rod-shaped compound, the compound represented by following General formula (2) is more preferable.

Formula (2) Ar ₁ -L ₂ -XL ₃ -Ar ₂

In the formula (2), Ar ₁ and Ar ₂ Represents a group having the same meaning as Ar ₁ and Ar ₂ in General Formula (1).

In General Formula (2), L ₂ and L ₃ each independently represent a divalent linking group selected from a group consisting of an alkylene group, -O-, -CO-, and a combination thereof.

It is preferable that an alkylene group has a chain structure rather than a cyclic structure, and it is more preferable that it has a linear structure rather than a branched chain structure.

The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 8, still more preferably 1 to 6, still more preferably 1 to 4, and 1 or 2 (methylene or ethylene) Most preferred.

L ₂ and L ₃ are particularly preferably -O-CO- or -CO-O-.

In General formula (2), X is 1, 4- cyclohexylene, ethylene, or ethynylene.

Below, the specific example of a compound represented by General formula (1) and (2) is shown.

[Formula 1]

[Formula 2]

(3)

[Formula 4]

[Chemical Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Chemical Formula 9]

[Formula 10]

[Formula 11]

[Chemical Formula 12]

Specific examples (1)-(34), (41), and (42) have two subtitle carbon atoms in the 1-position and 4-position of a cyclohexane ring. However, since specific examples (1), (4) to (34), (41), and (42) have symmetric meso-type molecular structures, there is no optical isomer (optical activity) and geometric isomers (trans and cis type) ) Only exists. As described above, the rod-shaped compound preferably has a linear molecular structure. Therefore, a trans type is more preferable than a sheath type.

In the case where the compound has an optical isomer, the optical isomer is not particularly superior and may be either D, L or racemate.

In specific examples (43)-(45), a trans type and a cis type exist in the center ethylene bond. For the same reason as above, the trans type is more preferable than the cis type.

It is preferable that the molecular weight of a retardation increasing agent is 300-800.

In the ultraviolet absorption spectrum of a solution, you may use together two or more types of rod-shaped compounds whose maximum absorption wavelength ((lambda) max) is shorter than 250 nm.

The rod compound can be synthesized with reference to the method described in the literature. In the literature, mol. Cryst. Liq. Cryst., Vol. 53, p. 229 (1979), p. 89, p. 93 (1982), p. 145, p. 111 (1987), p. 170, p. 43 (1989), J. Am. Chem. Soc., Vol. 113, p. 1349 (1991), p. 118, p. 5346 (1996), p. 92, p. 1582 (1970), J. Org. Chem., 40, 420 (1975), Tetrahedron, 48, 16, 3437 (1992).

The addition amount of the aromatic compound used as a retardation control agent is used in 0.01-20 mass parts with respect to 100 mass parts of cellulose acylate. It is preferable to use an aromatic compound in the range of 0.05-15 mass parts with respect to 100 mass parts of cellulose acylate, and it is more preferable to use in the range which is 0.1-10 mass parts. You may use together 2 or more types of compounds.

[Production of Cellulose Acylate Film]

It is preferable to manufacture a cellulose acylate film by the solvent cast method. In the solvent cast method, a film is manufactured using the solution (dope) which melt | dissolved cellulose acylate in the organic solvent.

The organic solvent preferably includes a solvent selected from ethers having 3 to 12 carbon atoms, ketones having 3 to 12 carbon atoms, esters having 3 to 12 carbon atoms, and halogenated hydrocarbons having 1 to 6 carbon atoms. .

Ethers, ketones and esters may have a cyclic structure. Compounds having two or more of functional groups of ethers, ketones and esters (ie, -O-, -CO- and -COO-) can also be used as the organic solvent. The organic solvent may have other functional groups, such as an alcoholic hydroxyl group. In the case of the organic solvent which has two or more types of functional groups, the carbon atom number should just be in the defined range of the compound which has any one functional group.

Examples of ethers having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, anisole and phentol This includes.

Examples of ketones having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexanone.

Examples of esters having 3 to 12 carbon atoms include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate and pentyl acetate.

Examples of the organic solvent having two or more kinds of functional groups include 2-ethoxyethyl acetate, 2-methoxyethanol and 2-butoxyethanol.

The number of carbon atoms of the halogenated hydrocarbon is preferably 1 or 2, most preferably 1. The halogen of the halogenated hydrocarbon is preferably chlorine. It is preferable that the ratio which the hydrogen atom of a halogenated hydrocarbon is substituted by halogen is 25-75 mol%, It is more preferable that it is 30-70 mol%, It is more preferable that it is 35-65 mol%, It is 40-60 mol% Most preferred. Methylene chloride is a representative halogenated hydrocarbon.

You may mix and use two or more types of organic solvents.

A cellulose acylate solution can be prepared by a general method. A general method means to process at a temperature (normal temperature or high temperature) of 0 degreeC or more. Preparation of the solution can be carried out using a method and apparatus for preparing a dope in a conventional solvent cast method. In addition, in the case of a general method, it is preferable to use a halogenated hydrocarbon (particularly methylene chloride) as an organic solvent.

The amount of cellulose acylate is adjusted to contain 10-40 mass% in the solution obtained. The amount of cellulose acylate is more preferably 10 to 30% by mass. In the organic solvent (main solvent), you may add the arbitrary additive mentioned later.

A solution can be prepared by stirring a cellulose acylate and an organic solvent at normal temperature (0 degreeC-40 degreeC). The high concentration solution may be stirred under pressure and heating conditions. Specifically, the cellulose acylate and the organic solvent are placed in a pressurized container and sealed, and the mixture is stirred while heating to a temperature not lower than the boiling point at normal temperature of the solvent and not boiling the solvent under pressure. Heating temperature is 40 degreeC or more normally, Preferably it is 60-200 degreeC, More preferably, it is 80-110 degreeC.

You may put each component in a container, after mixing previously. Moreover, you may inject into a container one by one. The vessel should be configured to allow stirring. The vessel can be pressurized by injecting an inert gas such as nitrogen gas. Moreover, you may use the vapor pressure rise of a solvent by heating. Or you may add each component under pressure after sealing a container.

When heating, it is preferable to heat outside of the container. For example, a jacket-type heating device can be used. Moreover, the whole container can also be heated by providing a plate heater outside the container, piping, and circulating a liquid.

It is preferable to form a stirring blade inside a container, and to stir using this. The stirring vane is preferably a length reaching the vicinity of the wall of the vessel. It is preferable to form a scratch blade at the end of the stirring blade to update the liquid film of the container wall.

Instruments may be provided with instruments such as pressure gauges and thermometers. Each component is dissolved in a solvent in a container. The prepared dope is taken out of the container after cooling or taken out and cooled using a heat exchanger or the like.

A solution can also be prepared by a cooling solution method. By the cooling dissolution method, cellulose acetate can be dissolved in an organic solvent which is difficult to dissolve by the usual dissolution method. Moreover, even if it is a solvent which can melt | dissolve cellulose acetate by a normal dissolution method, there exists an effect that a uniform solution can be obtained quickly by a cooling dissolution method.

In the cold dissolution method, cellulose acetate is slowly added with stirring in an organic solvent at room temperature.

It is preferable to adjust the amount of cellulose acylate so that it may contain 10-40 mass% in this mixture. The amount of cellulose acylate is more preferably 10 to 30% by mass. In addition, you may add arbitrary additives mentioned later in a mixture.

The mixture is then cooled to -100 to -10 ° C (preferably -80 to -10 ° C, more preferably -50 to -20 ° C, most preferably -50 to -30 ° C). Cooling can be performed, for example in a dry ice methanol bath (-75 degreeC) or the cooled diethylene glycol solution (-30--20 degreeC). This cooling causes the mixture of cellulose acylate and organic solvent to solidify.

The cooling rate is preferably 4 ° C / minute or more, more preferably 8 ° C / minute or more, and most preferably 12 ° C / minute or more. The faster the cooling rate is, the better, but 10000 ° C / sec is the theoretical upper limit, 1000 ° C / sec is the technical upper limit, and 100 ° C / sec is the practical upper limit. The cooling rate is a value obtained by dividing the difference between the temperature at the start of cooling and the final cooling temperature by the time from the start of cooling to the final cooling temperature.

Moreover, when this is heated to 0-200 degreeC (preferably 0-150 degreeC, more preferably 0-120 degreeC, most preferably 0-50 degreeC), a cellulose acetate will melt | dissolve in an organic solvent. An elevated temperature may be left to stand only at room temperature, and may be heated in a warm bath.

The heating rate is preferably 4 ° C / minute or more, more preferably 8 ° C / minute or more, and most preferably 12 ° C / minute or more. The higher the heating rate is, the better, but 10000 ° C / sec is the theoretical upper limit, 1000 ° C / sec is the technical upper limit, and 100 ° C / sec is the practical upper limit. The heating rate is a value obtained by dividing the difference between the temperature at the start of heating and the final heating temperature by the time from the start of heating to the final heating temperature.

A homogeneous solution is obtained as mentioned above. In addition, when melt | dissolution is inadequate, you may repeat operation of cooling and a heating. Whether or not dissolution is sufficient can be judged only by observing the appearance of the solution by visual observation.

In the cooling dissolution method, it is preferable to use a sealed container in order to avoid moisture mixing due to condensation during cooling. In addition, in a cooling heating operation, when it pressurizes at the time of cooling and depressurizes at the time of heating, a dissolution time can be shortened. In order to perform pressurization and pressure reduction, it is preferable to use a pressure-resistant container.

In addition, the 20 mass% solution which melt | dissolved cellulose acylate (degree of acetylation: 60.9%, viscosity average degree of polymerization: 299) in the methyl acetate by the cooling dissolution method is sol-state near 33 degreeC according to differential thermal calorimetry (DSC). The pseudo phase transition point of the gel state exists, and below this temperature, it will become a uniform gel state. Therefore, this solution should be maintained at a temperature above the pseudo phase transition temperature, preferably at a gel phase transition temperature of about + 10 ° C. However, this pseudo phase transition temperature differs depending on the degree of acetylation of the cellulose acylate, the viscosity average polymerization degree, the solution concentration, or the organic solvent to be used.

From the prepared cellulose acylate solution (dope), a cellulose acetate film is manufactured by the solvent cast method.

The dope is flexible on a drum or band and the solvent is evaporated to form a film. It is preferable to adjust concentration so that solid content dope may be 18 to 35% before casting | flow_spread. It is preferable to finish the surface of the drum or the band in a mirror state. Regarding the casting and drying method in the solvent cast method, U.S. Pat.Nos. 2336310, 2367603, 2492078, 2492977, 2492978, 22607704, 2739069, 2739070, and British Patent 640731 And Japanese Unexamined Patent Publication Nos. 45-4554, 49-5614, 60-176834, 60-203430, and 62-115035.

It is preferable that dope is cast on the drum or band whose surface temperature is 10 degrees C or less. It is preferable to air dry for 2 seconds or more after being soft. The obtained film may be peeled off from the drum or the band, and then dried again by hot air whose temperature is sequentially changed from 100 ° C to 160 ° C to evaporate the residual solvent. The above method is described in JP-A-5-17844. According to this method, the time from peeling to peeling off can be shortened. In order to carry out this method, it is necessary to gel dope at the surface temperature of the drum or band at the time of casting.

A plurality of prepared cellulose acylate solutions (dopes) may be used to cast two or more layers by the solvent cast method to produce a film. In this case, the dope is flexible on a drum or band and the solvent is evaporated to form a film. It is preferable to adjust density | concentration so that dope before casting may be 10 to 40% of solid content. It is preferable to finish the surface of a drum or a band in a mirror state.

When plural cellulose acylate liquids of two or more layers are cast, a plurality of cellulose acylate solutions can be cast, and a solution containing cellulose acylate is formed from a plurality of oil studies formed at intervals in the advancing direction of the support. You may produce a film, making it flexible and laminating | stacking, respectively, For example, the method of Unexamined-Japanese-Patent No. 61-158414, Unexamined-Japanese-Patent No. 1-22419, Unexamined-Japanese-Patent No. 11-198285, etc. can be applied. have. Moreover, a cellulose acylate solution may be cast or film-formed from two oil studies, for example, Unexamined-Japanese-Patent No. 60-27562, Unexamined-Japanese-Patent No. 61-94724, and Japan Unexamined-Japanese-Patent No. 61-104813. It can implement by the method of Unexamined-Japanese-Patent No. 61-158413 and Unexamined-Japanese-Patent No. 6-134933. Further, the flow of the high viscosity cellulose acylate solution described in JP-A-56-162617 is wrapped in a low viscosity cellulose acylate solution, and the cellulose acylate film cast which simultaneously extrudes the high viscosity and low viscosity cellulose acylate solution is cast. It may be a method.

Alternatively, the film formed into the support by the first oil study may be peeled off using two oil studies, and a film may be produced by performing a second casting on the side in contact with the support surface. The method described in 44-20235. The flexible cellulose acylate solution may be the same solution, or may be another cellulose acylate solution, and is not particularly limited. In order to provide a function to a some cellulose acylate layer, the cellulose acylate solution according to the function may be extruded from each oil research.

In addition, in the present invention, the cellulose acylate solution is flexible at the same time as a solution for forming another functional layer (for example, an adhesive layer, a dye layer, an antistatic layer, an antihalation layer, a UV absorbing layer, a polarizing layer, etc.) to form a functional layer and a film. May be simultaneously formed.

In the monolayer solution, it is necessary to extrude a high concentration and high viscosity cellulose acylate solution in order to achieve the required film thickness, and in this case, the stability of the cellulose acylate solution is poor, and solids are generated, resulting in protrusion failure or poor planarity. There are many things to be. As this solution, a plurality of cellulose acylate solutions are flexible from dairy research. As a result, a solution having a high viscosity can be extruded onto the support at the same time, thereby producing a planar and excellent planar film, and by using a thick cellulose acylate solution, reduction of dry load can be achieved. Increase production speed

Plasticizers may be added to the cellulose acylate film in order to improve mechanical properties or to improve the drying rate. Phosphoric acid ester or carboxylic acid ester is used as a plasticizer. Examples of the phosphate ester include triphenyl phosphate (TPP), biphenyl diphenyl phosphate and tricredyl phosphate (TCP). Phthalic acid ester and citric acid ester are typical as carboxylic acid ester. Examples of phthalate esters include dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP), diphenyl phthalate (DPP) and diethylhexyl phthalate (DEHP). . Examples of citric acid ester include O-acetyl citrate triethyl (OACTE) and O-acetyl citrate tributyl (OACTB). Examples of the other carboxylic acid esters include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters. Phthalate ester plasticizers (DMP, DEP, DBP, DOP, DPP, DEHP) are preferably used. DEP and DPP are particularly preferred.

It is preferable that the addition amount of a plasticizer is 0.1-25 mass% of the quantity of a cellulose ester, It is more preferable that it is 1-20 mass%, It is most preferable that it is 3-15 mass%.

A deterioration inhibitor (for example, antioxidant, peroxide decomposer, radical inhibitor, metal deactivator, acid trapping agent, and amine) may be added to the cellulose acetate film.

Deterioration inhibitors are described in Japanese Unexamined Patent Publications No. 3-199201, 5-1907073, 5-194789, 5-271471, and 6-107854. It is preferable that the addition amount of a deterioration inhibitor is 0.01-1 mass% of the solution (dope) prepared from a viewpoint of suppressing the effect which a deterioration agent adds and the deterioration agent bleeds out on the film surface. It is more preferable that it is 0.01-0.2 mass%. Examples of particularly preferred deterioration inhibitors include butylated hydroxytoluene (BHT) and tribenzylamine (TBA).

[Extending Treatment of Cellulose Acylate Film]

A cellulose acylate film can adjust retardation by an extending | stretching process. It is preferable that a draw ratio is 3 to 100%.

Although the stretching method can use the existing method in the range which does not deviate from the Claim, in terms of in-plane uniformity, especially tenter stretching is used preferably. It is preferable that the width | variety of the cellulose acylate film of this invention is at least 100 cm or more, It is preferable that the variation of Re value of the full width is +/- 5 nm, It is more preferable that it is +/- 3 nm. In addition, the deviation of the Rth value is preferably ± 10 nm, more preferably ± 5 nm. Moreover, it is preferable that the deviation of Re value and Rth value of a longitudinal direction also exists in the range of the deviation of the width direction.

In addition, an extending | stretching process may be performed in the middle of a film formation process, and the raw material wound by film formation may be extended | stretched. In the former case, you may extend | stretch in the state containing the residual solvent amount, and it can extend | stretch preferably when the residual solvent amount is 2 to 30%. At this time, it is preferable to extend | stretch in the direction orthogonal to a longitudinal direction, conveying a film in a longitudinal direction, and to make the slow axis of the film orthogonal to the elongate direction of the film.

The stretching temperature can be selected according to the residual solvent amount and the film thickness at the time of stretching.

When extending | stretching in the state containing a residual solvent, it is preferable to dry after extending | stretching. The drying method can be carried out in accordance with the method described in the film formation of the film.

The thickness of the cellulose acylate film after stretching is 110 µm or less, preferably 40 to 110 µm, more preferably 60 to 110 µm, and most preferably 80 to 110 µm. This film thickness is corresponded to the film thickness of the retardation film of this invention.

[Surface Treatment of Cellulose Acylate Film]

It is preferable to perform a surface treatment of a cellulose acylate film. Specific methods include corona discharge treatment, glow discharge treatment, flame treatment, acid treatment, alkali treatment or ultraviolet irradiation treatment. Moreover, forming a undercoat layer as described in Unexamined-Japanese-Patent No. 7-333433 is also used preferably.

From the viewpoint of maintaining the planarity of the film, it is preferable to set the temperature of the cellulose acylate film to Tg or less, specifically 150 ° C or less, in these treatments.

When the cellulose acylate film is adhered to the polarizing film as in the case of using the antireflective film of the present invention as a protective film of the polarizing plate, the acid treatment or alkali treatment, that is, the cellulose acylate to the polarizing film, Particular preference is given to performing saponification treatment.

From the viewpoint of adhesiveness, the surface energy of the cellulose acylate film is preferably 55 mN / m or more, more preferably 60 mN / m or more and 75 mN / m or less, and can be adjusted by the surface treatment.

The surface energy of a solid can be calculated | required by the contact angle method, the wet heat method, and the adsorption method, as described in "The basis and application of a wet" (Issue 1989.12.10). In the case of the cellulose acylate film of this invention, it is preferable to use a contact angle method. Specifically, the two angles of known surface energy are added to the cellulose acylate film, and the contact angle including the droplet at the angle between the tangent drawn on the droplet and the film surface at the intersection of the surface of the droplet and the film surface is the contact angle. It defines as this and can calculate the surface energy of a film by calculation.

Hereinafter, the surface treatment will be specifically described by taking an alkali saponification treatment as an example.

Preferably, the film surface is immersed in an alkaline solution, neutralized with an acidic solution, washed with water and dried.

Examples of the alkaline solution include potassium hydroxide solution and sodium hydroxide solution, and the prescribed concentration of the hydroxide ion is preferably 0.1 mol / L to 3.0 mol / L, more preferably 0.5 mol / L to 2.0 mol / L. Do. The alkali solution temperature is preferably in the range of room temperature to 90 ° C, more preferably 40 ° C to 70 ° C.

From the viewpoint of productivity, it is preferable to apply alkali solution to remove alkali from the film surface by water washing after saponification treatment. From the viewpoint of wettability, as the coating solvent, alcohols such as IPA, n-butanol, methanol, ethanol and the like are preferable, and addition of water, propylene glycol, ethylene glycol or the like is preferably used as an alkali dissolving aid.

(Antireflection film)

[Transparent support]

There is no limitation in particular as a transparent support body of the antireflection film of this invention, such as a transparent resin film, a transparent resin board, a transparent resin sheet, and transparent glass. As the transparent resin film, a cellulose acylate film (cellulose triacetate film (refractive index 1.48), cellulose diacetate film, acetate butylate cellulose film, cellulose acetate propionate film), polyethylene terephthalate film, polyether sulfone film, poly Acrylic resin film, polyurethane resin film, polyester film, polycarbonate film, polysulfone film, polyether film, polymethylpentene film, polyether ketone film, (meth) acrylonitrile film and the like can be used.

Especially, the cellulose acylate film which is high in transparency, optically birefringent, easy to manufacture, and generally used as a protective film of a polarizing plate is preferable, and a cellulose triacetate film is especially preferable. In addition, the thickness of a transparent support body is about 25 micrometers-1000 micrometers normally.

The cellulose acylate film described above can be used as the retardation film for the cellulose acylate film of the present invention.

When using as a support body of an antireflection film, it is not necessary to control retardation, and may or may not contain the said retardation control agent.

In addition, although it is not necessary to control retardation by an extending | stretching process, it can extend | stretch in order to improve the film thickness unevenness and surface unevenness which generate | occur | produce by a dry stain and dry shrinkage. The specific method of extending | stretching process is the same as the extending | stretching process of retardation film.

[Hard Coat Layer]

In the antireflection film of the present invention, a hard coat layer is formed on at least one surface of the transparent support to impart physical strength of the film. In the present invention, a low refractive index layer is formed on the hard coat layer, and preferably, a medium refractive index layer and a high refractive index layer are formed between the heart coat layer and the low refractive index layer to constitute the antireflection film of the present invention.

In the antireflection film of the present invention, it is essential to flatten the surface in order to improve whitening, image blurring, and glittering. Specifically, the centerline average roughness Ra is set to 0.10 µm or less among the characteristics showing surface roughness. Ra is more preferably 0.09 µm or less, and still more preferably 0.08 µm or less. In the antireflection film of the present invention, the surface irregularities of the hard coat layer are dominant in the surface irregularities of the film, and it is preferable that the center line average roughness of the hard coat layer is in the above range.

In addition to controlling the surface shape described above, it is also necessary to control the reflectance characteristics. The antireflection film of the present invention is 5 degrees to the average value of the integral reflectance in the wavelength region from 450 nm to 650 nm in order to improve the reproducibility of black in bright places by eliminating whitening, image blurring, and glittering. The average value of the specular reflectance becomes 65% or more. More preferably, it is 70% or more, More preferably, it is 75% or more.

It is also important to control the absolute value of the integral reflectance, and it is preferable that the average value of the integral reflectance in the wavelength range from 450 nm to 650 nm is 2.5% or less, more preferably 2.3% or less, and even more preferably 2.1% or less.

As for the transmission image sharpness of the antireflection film of this invention, 65% or more is preferable. Transmissive image clarity is generally an indicator of the blurred state of an image that penetrates through a film, and the larger this value, the clearer and better the image viewed through the film. The transmission image clarity is preferably 70% or more, and more preferably 80% or more.

Here, the transmission image clarity can be measured using an optical comb with a slit width of 5 mm with a mapping tester (ICM-2D type) manufactured by Suga Tester Co., Ltd. according to JIS K 7105.

It is preferable that the refractive index of the hard-coat layer of this invention exists in the range of 1.48-2.00 from a optical design for obtaining an antireflective film, More preferably, it is 1.50-1.90, More preferably, it is 1.50-1.80. . In the present invention, since there is at least one low refractive index layer on the hard coat layer, when the refractive index is too smaller than this range, the antireflection property is lowered, and when too large, the color taste of the reflected light tends to be strong.

The thickness of the hard coat layer is usually 0.5 µm to 50 µm, preferably 1 µm to 20 µm, and more preferably 2 µm, in terms of imparting sufficient durability and impact resistance to the film. -10 micrometers, Most preferably, they are 3 micrometers-7 micrometers.

In addition, the strength of the hard coat layer is preferably at least H, more preferably at least 2H, and most preferably at least 3H in a pencil hardness test according to JIS K 5400.

In the taper test according to JIS K 5400, the less the amount of wear of the test piece before and after the test, the more preferable.

The hard coat layer is preferably formed by a crosslinking reaction or an polymerization reaction of the ionizing radiation curable compound. For example, it can be formed by crosslinking or polymerizing a polyfunctional monomer or a polyfunctional oligomer by applying a coating composition containing an ionizing radiation curable polyfunctional monomer or a polyfunctional oligomer onto a transparent support.

As a functional group of an ionizing radiation curable polyfunctional monomer and a polyfunctional oligomer, it is preferable that they are light, an electron beam, and a radiation polymerizable, and a photopolymerizable functional group is especially preferable.

As a photopolymerizable functional group, unsaturated polymerizable functional groups, such as a (meth) acryloyl group, a vinyl group, a styryl group, an allyl group, etc. are mentioned, Especially, a (meth) acryloyl group is preferable.

Specific examples of the photopolymerizable polyfunctional monomer having a photopolymerizable functional group include (meth) of alkylene glycols such as neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, and propylene glycol di (meth) acrylate. ) Acrylic acid diesters; (Meth) acryl of polyoxyalkylene glycol, such as a triethylene glycol di (meth) acrylate, a dipropylene glycol di (meth) acrylate, a polyethylene glycol di (meth) acrylate, and a polypropylene glycol di (meth) acrylate Acid diesters; (Meth) acrylic acid diesters of polyhydric alcohols such as pentaerythritol di (meth) acrylate; Ethylene oxide or propylene oxide adducts such as 2,2-bis {4- (acryloxydiethoxy) phenyl} propane and 2-2-bis {4- (acryloxypolypropoxy) phenyl} propane ( And meta) acrylic acid diesters.

Moreover, epoxy (meth) acrylates, urethane (meth) acrylates, and polyester (meth) acrylates are also used suitably as a photopolymerizable polyfunctional monomer.

Especially, ester of polyhydric alcohol and (meth) acrylic acid is preferable. More preferably, the polyfunctional monomer which has three or more (meth) acryloyl groups in 1 molecule is preferable. Specifically, trimethylolpropane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, 1,2,4-cyclohexane tetra (meth) acrylate, pentaglycerol triacrylate, pentaerythritol tetra (meth) ) Acrylate, pentaerythritol tri (meth) acrylate, (di) pentaerythritol triacrylate, (di) pentaerythritol pentaacrylate, (di) pentaerythritol tetra (meth) acrylate, (di) pentaerythritol hexa ( Meta) acrylate, tripentaerythritol triacrylate, tripentaerythritol hexatriacrylate, and the like. In this specification, "(meth) acrylate" represents "acrylate or methacrylate", and "(meth) acryloyl" shows "acryloyl or methacryloyl".

The polyfunctional monomer may use two or more types together.

It is preferable to use a photoinitiator for the polymerization reaction of a photopolymerizable polyfunctional monomer. As a photoinitiator, an optical radical polymerization initiator and a photocationic polymerization initiator are preferable, and an optical radical polymerization initiator is especially preferable.

-아밀옥심에스테르, 테트라메틸티우람모노술파이트 및 티오크산톤류 등을 들 수 있다.As an optical radical polymerization initiator, For example, acetophenones, benzophenones, Michler's benzoyl benzoate,

-Amyl oxime ester, tetramethyl thiuram monosulfite, thioxanthones, etc. are mentioned.

Commercially available photoradical polymerization initiators include KAYACURE (DETX-S, BP-100, BDMK, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, ITX, QTX, BTC, MCA, manufactured by Nippon Kayaku Co., Ltd.). Etc.), Irgacure (651, 184, 500, 907, 369, 1173, 2959, 4265, 4263, etc.) manufactured by Chiba Co., Ltd., Esacure (KIP100F, KB1, EB3, BP, X33, KT046, KT37, KIP150, TZT), etc. are mentioned.

In particular, a photo cleavage type radical photopolymerization initiator is preferable. Photo cleavage type photoradical polymerization initiators are described in the latest UV curing technology (P.159, Publisher; Takasusky Kazuhiro, Issuance; Technical Information Association, Ltd., 1991). Commercially available photo cleavage type optical radical polymerization initiators include Irgacure (651, 184, 907) manufactured by Chiba Co., Ltd., and the like.

It is preferable to use a photoinitiator in 0.1-15 mass parts with respect to 100 mass parts of polyfunctional monomers, More preferably, it is the range of 1-10 mass parts.

In addition to a photoinitiator, you may use a photosensitizer. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone. As a commercial photosensitizer, Nippon Kayaku Co., Ltd. KAYACURE (DMBI, EPA) etc. are mentioned.

It is preferable to perform photopolymerization reaction by ultraviolet irradiation after apply | coating and drying a hard-coat layer.

The crosslinked or polymerized binder of the hard coat layer has a structure in which the main chain of the polymer is crosslinked or polymerized. Examples of the main chain of the polymer include polyolefins (saturated hydrocarbons), polyethers, polyureas, polyurethanes, polyesters, polyamines, polyamides, and melamine resins. Polyolefin backbones, polyether backbones and polyurea backbones are preferred, polyolefin backbones and polyether backbones are more preferred, and polyolefin backbones are most preferred.

The polyolefin backbone consists of saturated hydrocarbons. The polyolefin main chain is obtained by, for example, addition polymerization of an unsaturated polymerizable group. In the polyether main chain, repeating units are bonded by ether bonds (-O-). A polyether main chain is obtained by ring-opening polymerization reaction of an epoxy group, for example. In the polyurea main chain, repeating units are bonded by a urea bond (-NH-CO-NH-). A polyurea main chain is obtained by the polycondensation reaction of an isocyanate group and an amino group, for example. The repeating unit couple | bonds with the polyurethane main chain by the urethane bond (-NH-CO-O-). A polyurethane main chain is obtained by the polycondensation reaction of an isocyanate group and a hydroxyl group (containing N-methylol group, for example). The repeating unit couple | bonds with the polyester main chain by ester bond (-CO-O-). The polyester main chain is obtained by, for example, a polycondensation reaction of a carboxyl group (including an acid halide group) and a hydroxyl group (including an N-methylol group). The repeating unit couple | bonds with the polyamine main chain by imino bond (-NH-). A polyamine main chain is obtained by the ring-opening polymerization reaction of an ethyleneimine group, for example. In the polyamide main chain, repeating units are bonded by an amide bond (-NH-CO-). Polyamide main chain is obtained by reaction of an isocyanate group and a carboxyl group (including an acid halide group), for example. Melamine resin main chain is obtained by the polycondensation reaction of a triazine group (for example, melamine) and an aldehyde (for example, formaldehyde), for example. In addition, the melamine resin has a crosslinked or polymerized structure of the main chain itself.

A high refractive index monomer and / or inorganic fine particles may be added to the binder of the hard coat layer for the purpose of controlling the refractive index of the hard coat layer. In addition to the effect of controlling the refractive index, the inorganic fine particles also have an effect of suppressing hardening shrinkage due to the crosslinking reaction.

Examples of the high refractive index monomers include bis (4-methacryloylthiophenyl) sulfide, vinylnaphthalene, vinylphenyl sulfide, 4-methacryloxyphenyl-4'-methoxyphenylthioether and the like.

Examples of the inorganic fine particles include oxides of at least one metal selected from silicon, zirconium, titanium, aluminum, indium, zinc, tin, antimony, other BaSO ₄ , CaCO ₃ , talc and kaolin, and have a particle diameter of 100 nm or less, Preferably it is 50 nm or less. By miniaturizing the inorganic fine particles to 100 nm or less, a hard coat layer that does not impair transparency can be formed.

For the purpose of high refractive index of the hard coat layer, as the inorganic fine particles, oxide ultrafine particles of at least one metal selected from Al, Zr, Zn, Ti, In, and Sn are preferable, and specific examples thereof include ZrO ₂ and TiO _2. , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ITO and the like. Among them, ZrO ₂ is particularly preferably used.

It is preferable that it is 10-90 mass% of the total mass of a binder, and, as for the addition amount of a high refractive index monomer and an inorganic fine particle, it is more preferable that it is 20-80 mass%. You may use 2 or more types of inorganic fine particles in a hard-coat layer.

The haze value of the hard coat layer is preferably 10% or more, more preferably 20% to 80%, still more preferably 30% to 70%, most preferably 35% to improve the viewing angle characteristic by scattering. 60%.

In particular, the haze value of the hard coat layer of the second embodiment is preferably 40% or more, more preferably 40% to 90%, even more preferably 45% to 80% in order to impart the function of expanding the viewing angle by scattering. And most preferably 50% to 70%.

The antireflection film of the present invention is a film having little or no surface irregularities and little surface haze, and when provided with haze, it is preferable to form it as internal haze. Therefore, it is preferable that the hard coat layer has internal haze, that is, internal scattering property.

In order to impart a viewing angle enlargement function, in addition to adjusting the haze value, it is important to adjust the intensity distribution (scattered light profile) of the scattered light measured by the goniphotometer of the hard coat layer. For example, in the case of a liquid crystal display, the viewing angle characteristic improves as the light emitted from the backlight diffuses by the antireflection film provided on the surface of the polarizing plate on the viewer's side. However, if too diffused, problems such as back scattering increase and front luminance decrease, or scattering becomes excessively large, resulting in deterioration of image clarity. Therefore, the scattered light intensity distribution of the hard coat layer should be controlled to a certain range. In order to achieve the desired viewing characteristics, it is preferable that the scattered light intensity of the outgoing angle 30 ° correlated with the viewing angle improvement effect, in particular with respect to the light intensity of the outgoing angle 0 ° of the scattered light profile, is 0.01% to 0.2%, and 0.02% to 0.15% More preferred, 0.02% to 0.1% are most preferred.

Scattered light profile can be measured using the automatic variable angle photometer GP-5 type by Murakami Color Research Institute Co., Ltd. for the antireflection film in which the hard coat layer was formed.

As a method of imparting internal scattered light or a desired scattering profile to the heart coat layer, it is preferable to contain light-transmitting particles having a different refractive index from the binder in the binder (including the inorganic particles capable of adjusting the refractive index). . The difference in refractive index between the binder and the light transmitting particles is preferably 0.02 to 0.20. This is because when the difference in refractive index is less than 0.02, the difference in refractive index between the two is too small, the light diffusion effect is small, and when the difference in refractive index is larger than 0.20, the light diffusivity is too high and the entire film is whitened. The refractive index difference is more preferably 0.03 to 0.15, and most preferably 0.04 to 0.13.

The combination of the binder and the translucent particles can be appropriately selected for the purpose of adjusting the refractive index difference.

It is preferable that the particle diameter of a light transmissive particle is 0.5 micrometer-5 micrometers. In the case where the particle diameter is 0.5 µm or less, the light diffusion effect is too small or the backscattering is large and the light utilization efficiency is lowered. In the case of 5 micrometers or more, the unevenness | corrugation of a surface becomes large and whitening and a glittering phenomenon generate | occur | produce. In addition, the particle diameter of the light-transmitting particle is preferably 0.7 µm to 4.5 µm, and most preferably 1.0 µm to 4.0 µm.

In the case where the hard coat layer contains translucent particles, it is necessary to adjust the film thickness of the hard coat layer so that surface irregularities due to the particles are not produced. Usually, the film thickness is increased so that the projections of the particles do not protrude from the surface of the hard coat, and the surface roughness (Ra; centerline average roughness) can be 0.10 µm or less.

The light transmitting particles may be organic particles or inorganic particles. As there is no variation in the particle size, the variation in scattering characteristics decreases, making it easier to design haze values. As light-transmitting microparticles | fine-particles, a plastic bead is suitable, It is especially preferable that transparency is high and a refractive index difference with a binder becomes a numerical value as mentioned above.

As organic particles, polymethyl methacrylate beads (refractive index 1.49), acrylic-styrene copolymer beads (refractive index 1.54), melamine beads (refractive index 1.57), polycarbonate beads (refractive index 1.57), styrene beads (refractive index 1.60), crosslinking Polystyrene beads (refractive index 1.61), polyvinyl chloride beads (refractive index 1.60), benzoguanamine melamine formaldehyde beads (refractive index 1.68) and the like are used.

As the inorganic particles, silica beads (refractive index 1.44), alumina beads (refractive index 1.63) and the like are used.

As mentioned above, the particle size of the light-transmitting particle may be selected from 0.5 to 5 µm as appropriate, may be used in combination of two or more kinds, and may be contained in an amount of 5 to 30 parts by mass with respect to 100 parts by mass of the binder.

In the case of the above-mentioned translucent particles, the translucent particles tend to settle in the binder, and an inorganic filler such as silica may be added to prevent sedimentation. In addition, the inorganic filler is effective in preventing sedimentation of the light-transmitting fine particles as the amount added increases, but adversely affects the transparency of the coating film. Therefore, Preferably, you may contain the inorganic filler of 0.5 micrometer or less of particle diameters less than 0.1 mass% so that the transparency of a coating film may not be impaired with respect to a binder.

When the hard coat layer is in contact with the transparent support, the solvent of the coating liquid for forming the hard coat layer is compatible with both the control of the irregularities on the surface of the hard coat layer (reducing the irregularities or flattening) and the adhesion between the transparent support and the hard coat layer. In order to achieve this, it is preferable to comprise at least one or more solvents for dissolving the transparent support (for example, triacetyl cellulose support) and at least one or more solvents for dissolving the transparent support. More preferably, it is preferable that at least 1 type of the solvent which does not melt a transparent support body is higher boiling point than at least 1 type of the solvent which melt | dissolves a transparent support body. More preferably, the boiling point temperature difference between the solvent having the highest boiling point among the solvents which do not dissolve the transparent support and the solvent having the highest boiling point among the solvents dissolving the transparent support is 30 ° C or more, and most preferably 50 ° C or more.

Ethers having 3 to 12 carbon atoms as the solvent for dissolving the transparent support (preferably triacetyl cellulose): specifically dibutyl ether, dimethoxymethane, dimethoxyethane, diethoxyethane, propylene oxide, 1 Ketones having 3 to 12 carbon atoms, such as 4-dioxane, 1,3-dioxolane, 1,3,5-trioxane, tetrahydrofuran, anisole, and phentol: specifically, acetone, methyl ethyl ketone, Esters having 3 to 12 carbon atoms, such as diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, and methylcyclohexanone: specifically ethyl formate, propyl formate, Organic solvents having two or more functional groups, such as n-pentyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, n-pentyl acetate and γ-butylolactone: specifically 2-methoxymethyl acetate, 2-e Methyl oxyacetate, 2-ethoxy acetate, 2-ethoxy propionate, 2-methoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 1,2-diacetoxyacetone, acetylacetone, diacetone alcohol, acetacetic acid Methyl, ethyl acetate, etc. are mentioned.

These can be used individually by 1 type or in combination of 2 or more types. As a solvent which melt | dissolves a transparent support body, a ketone system solvent is preferable.

As a solvent that does not dissolve the transparent support (preferably triacetylcellulose), methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-methyl- 2-butanol, cyclohexanol, isobutyl acetate, methyl isobutyl ketone, 2-octanone, 2-pentanone, 2-hexanone, 2-heptanone, 3-pentanone, 3-heptanone, 4-hep Tannon is mentioned.

These can be used individually by 1 type or in combination of 2 or more types.

As for the mass ratio (A / B) of the total amount (A) of the solvent which melt | dissolves a transparent support, and the total amount (B) of solvent which does not melt a transparent support, 5 / 95-50 / 50 are preferable, More preferably, 10 / 90-40 / 60, More preferably, it is 15 / 85-30 / 70.

[Low refractive index layer]

The antireflection film of this invention has a low refractive index layer in outermost layer. The refractive index of the low refractive index layer is preferably 1.20 to 1.46, more preferably 1.25 to 1.41, and most preferably 1.30 to 1.39. In addition, it is preferable that a low refractive index layer satisfy | fills following formula (1) from the point of low reflectivity.

Formula (1) (m ₁ /4)×0.7<n ₁ d ₁ <(m ₁ /4)×1.3

In formula (1), m ₁ is a positive odd number, n ₁ is the refractive index of the low refractive index layer, and d ₁ is the film thickness (nm) of the low refractive index layer. In addition, (lambda) is a wavelength and is a value of the range of 500-550 nm. In addition, satisfying the above formula (1) means that m ₁ (positive odd number, usually 1) exists in the above wavelength range that satisfies the formula (1).

The low refractive index layer includes a fluorine-containing polymer or a fluorine-containing sol-gel material as a low refractive index binder. As the fluorine-containing polymer or the fluorine-containing sol-gel, a material having a dynamic friction coefficient of 0.03 to 0.15 on the surface of the low refractive index layer formed by crosslinking by heat or ionizing radiation and having a contact angle of 90 to 120 ° to water is preferable. An inorganic filler for improving the film strength may be used for the low refractive index layer of the present invention.

As a fluorine-containing polymer used for a low refractive index layer, the valence of the fluoroalkyl group containing silane compound (for example, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane) In addition to the decomposition and dehydration products, there may be mentioned fluorine-containing copolymers comprising fluorine-containing monomer units and structural units for providing crosslinking reactivity.

Specific examples of the fluorine-containing monomer unit include perfluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1, 3-dioxol, etc.), partial or fully fluorinated alkyl ester derivatives of (meth) acrylic acid (e.g., biscot 6FM (manufactured by Osaka Organic Chemical Co., Ltd.) or M-2020 (manufactured by Daikin)), fully or partially fluorinated vinyl Ethers etc. are mentioned, Preferably they are perfluoro olefins, Especially preferably, it is hexafluoro propylene from a viewpoint of refractive index, solubility, transparency, availability, etc.

Structural units for imparting crosslinking reactivity are structural units obtained by polymerization of monomers having self-crosslinkable functional groups in the molecule, such as glycidyl (meth) acrylate and glycidylvinyl ether, carboxyl groups, hydroxyl groups, amino groups, and sulfides. Monomers having aeration and the like (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, maleic acid, Structural units obtained by the polymerization of crotonic acid, etc., and structural units (eg, chloroacrylate reacting with respect to hydroxy groups) incorporating crosslinking reactive groups such as (meth) acryloyl groups by polymer reaction to these structural units. Can be introduced by a method).

-메틸스티렌 등), 비닐에테르류 (메틸비닐에테르, 에틸비닐에테르, 시클로헥실비닐에테르 등), 비닐에스테르류 (아세트산비닐, 프로피온산비닐, 신남산비피닐 등), 아크릴아미드류 (N-tert 부틸아크릴아미드, N-시클로헥실아크릴아미드 등), 메타크릴아미드류, 아크릴로니트릴 유도체 등을 들 수 있다.In addition to the above-mentioned fluorine-containing monomer units and structural units for imparting crosslinking reactivity, monomers containing no fluorine atoms may be copolymerized appropriately from the viewpoints of solubility in solvents and transparency of the coating. There is no restriction | limiting in particular in the monomer unit which can be used together, For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylate esters (methyl acrylate, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate) Methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyltoluene,

-Methyl styrene), vinyl ethers (methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate, cinnamic acid cinnamic acid, etc.), acrylamides (N-tert butyl Acrylamide, N-cyclohexyl acrylamide, etc.), methacrylamide, an acrylonitrile derivative, etc. are mentioned.

About the said polymer, you may use together a hardening | curing agent suitably as described in each Unexamined-Japanese-Patent No. 10-25388 and Unexamined-Japanese-Patent No. 10-147739.

Particularly useful fluorine-containing polymers in the present invention are random copolymers of perfluoroolefins and vinyl ethers or vinyl esters. In particular, it is preferable to have a crosslinkable reaction group (a radical reactive group, such as a (meth) acryloyl group, ring-opening-polymerizable groups, such as an epoxy group and an oxetanyl group, etc.) which can be independently crosslinked. It is preferable that these crosslinking reactive group containing polymerized units occupy 5-70 mol% of all the polymerized units of a polymer, Especially preferably, it is the case of 30-60 mol%.

Moreover, it is preferable that the polysiloxane structure is introduce | transduced into the fluorine-containing polymer of this invention for the purpose of providing antifouling property. Although there is no restriction | limiting in the method of introduction of a polysiloxane structure, For example, as described in each Unexamined-Japanese-Patent No. 11-l89621, 11-228631, and Unexamined-Japanese-Patent No. 2000-313709, a silicon macroazo initiator is used. The method of introducing a polysiloxane block copolymerization component and the method of introducing a polysiloxane graft copolymerization component using a silicone macromer as described in each of Unexamined-Japanese-Patent No. 2-251555 and 2-308806 are preferable. It is preferable that these polysiloxane components are 0.5-10 mass% in a polymer, Especially preferably, it is 1-5 mass%.

Regarding imparting antifouling properties, in addition to the above, reactive group-containing polysiloxanes (for example, KF-100T, X-22-169AS, KF-102, X-22-3701IE, X-22-164B, X-22-5002, and X- 22-173B, X-22-174D, X-22-167B, X-22-161AS (above brand name, Shin-Etsu Chemical Co., Ltd.), AK-5, AK-30, AK-32 (above brand name, Toagosei Co., Ltd.) (Manufacture), Cyraprene FM0275, Cyraprene FM0721 (above Chisso Corp., etc.) are also preferable. At this time, these polysiloxanes are preferably added in the range of 0.5-10 mass% of the total solid content of the low refractive index layer, Especially preferably, it is the case of 1-5 mass%.

It is preferable to contain hollow silica fine particles for the purpose of making both the low refractive index and scratch resistance compatible in the low refractive index layer of the present invention.

The refractive index of the hollow silica fine particles is preferably 1.17 to 1.40, more preferably 1.17 to 1.35, most preferably 1.17 to 1.30. The refractive index here shows the refractive index as the whole particle | grain, and does not show the refractive index only of the outer-side silica which forms hollow silica microparticles | fine-particles. At this time, if the radius of the voids in the particle is a and the radius of the outer shell of the particle is b, the porosity x is calculated by the following formula (2).

Equation ^{(2) x = (4πa 3} /3) / (4πb 3/3) × 100

The porosity (x) is preferably 10 to 60%, more preferably 20 to 60%, most preferably 30 to 60%. When the hollow silica fine particles are made to have a lower refractive index and a larger porosity, the outer shell becomes thinner and weaker as the particle strength. Therefore, low refractive index particles of less than 1.17 are not established from the viewpoint of scratch resistance.

In addition, the refractive index of these hollow silica microparticles | fine-particles was measured with the Abbe refractive index meter (made by Atago Co., Ltd.).

The manufacturing method of hollow silica microparticles | fine-particles is described, for example in Unexamined-Japanese-Patent No. 2001-233611 and Unexamined-Japanese-Patent No. 2002-79616.

The coating forming amount of the hollow silica fine particles is preferably 1 mg / m 2 to 100 mg / m 2, more preferably 5 mg / m 2 to 80 mg / m 2, still more preferably 10 mg / m 2 to 60 mg / m 2. . When too small, the effect of lowering the refractive index or improving the scratch resistance is reduced. When the amount is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance and the integral reflectance such as black reproducibility deteriorate.

The average particle diameter of the hollow silica fine particles is preferably 30% or more and 150% or less of the thickness of the low refractive index layer, more preferably 35% or more and 80% or less, still more preferably 40% or more and 60% or less. That is, when the thickness of the low refractive index layer is 100 nm, the particle diameter of the hollow silica fine particles is preferably 30 nm or more and 150 nm or less, more preferably 35 nm or more and 80 nm or less, still more preferably 40 nm or more and 60 nm or less. .

If the particle diameter of the hollow silica fine particles is too small, the ratio of the cavity is reduced, so that a decrease in the refractive index cannot be expected. If the particle size is too large, fine irregularities are formed on the surface of the low refractive index layer, resulting in deterioration of appearance and integral reflectance such as black reproducibility. The silica in the outer portion of the hollow silica fine particles may be either crystalline or amorphous. The size distribution of the hollow silica fine particles is preferably monodisperse particles, but may be polydisperse particles or aggregated particles as long as the particle size is satisfied. Although spherical shape is most preferable, even if it is an indefinite shape, there is no problem.

Here, the average particle diameter of the hollow silica fine particles can be obtained from an electron micrograph.

In the present invention, for the purpose of improving the scratch resistance, it may be used in combination with the hollow silica fine particles, and may contain other inorganic fillers.

It is preferable that the inorganic filler is low refractive index from the point of making it contain in a low refractive index layer. For example, magnesium fluoride and silica can be mentioned. In particular, silica fine particles having no voids are preferable in terms of refractive index, dispersion stability, and cost. The preferred particle size of the silica fine particles without voids is 30 nm or more and 150 nm or less, more preferably 35 nm or more and 80 nm or less, most preferably 40 nm or more and 60 nm or less.

Moreover, at least 1 sort (s) of silica microparticles | fine-particles (referred to as "microparticles of small size particle size") whose average particle diameter is less than 25% of the low refractive index layer thickness, and silica microparticles | fine-particles of the said particle size (it is called "micro particle | grains of large size particle size") It is preferable to use together.

Since the silica fine particles having a small size particle size may exist in the gaps between the silica fine particles having a large size particle size, they can contribute as a retainer of the silica fine particles having a large size particle size.

1 nm or more and 20 nm or less are preferable, as for the average particle diameter of the silica fine particle of small size particle size, 5 nm or more and 15 nm or less are more preferable, 10 nm or more and 15 nm or less are especially preferable. The use of such silica fine particles is preferable in view of raw material cost and fat and oil effect.

Silica fine particles are chemically treated by physical surface treatments such as plasma discharge treatment or corona discharge treatment, surfactants or coupling agents, etc. in order to stabilize the dispersion in the dispersion liquid or the coating liquid, or to enhance affinity and binding properties with the binder component. Surface treatment may be given. The use of a coupling agent is particularly preferred. As a coupling agent, an alkoxy metal compound (for example, a titanium coupling agent and a silane coupling agent) is used preferably. Especially, the process by the silane coupling agent which has acryloyl group or a methacryloyl group is especially effective.

Although the said coupling agent may be used as a surface treating agent of the inorganic filler of a low refractive index layer, in order to perform surface treatment before preparation of the layer coating liquid previously, it is added as an additive at the time of preparation of the layer coating liquid, and is contained in the layer. It is preferable to make it.

The silica fine particles are preferably dispersed in the medium before the surface treatment, in order to reduce the load of the surface treatment.

In the present invention, at least one of the hard coat layer and the low refractive index layer contains a hydrolyzate of an organosilane compound and / or a partial condensate thereof and a so-called sol component (hereinafter referred to as above) in terms of scratch resistance. desirable. The organosilane compound used can be represented by following General formula (3).

Formula (3) (R ¹⁰ ) _m -Si (X) _4-m

In General Formula (3), R ¹⁰ is a substituted or unsubstituted alkyl group (a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, for example, methyl, ethyl, propyl, butyl, pentyl, heptyl , Octyl, decyl, dodecyl, isopropyl, s-butyl, t-amyl, cyclohexyl, cyclopentyl), substituted or unsubstituted aryl group (aryl group having 6 to 20 carbon atoms, for example, phenyl, 1- Naphthyl).

X represents a hydrolyzable group, for example an alkoxy group (alkoxy group having 1 to 5 carbon atoms, for example methoxy, ethoxy), halogen (for example Cl, Br, I, etc.), or R ² COO (R ² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. For example, CH ₃ COO, C ₂ H ₅ COO, etc. may be mentioned). X is preferably an alkoxy group, particularly preferably a methoxy group or an ethoxy group.

m represents the integer of 1-3. Or R ¹⁰ X in the presence of the plurality, a plurality of R ¹⁰ or X may be the same or different, respectively. As m, Preferably it is 1 or 2, Especially preferably, it is 1.

The substituent contained in R ¹⁰ is not particularly limited but may be halogen (fluorine, chlorine, bromine, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (methyl, ethyl, i-propyl, propyl, t-butyl, etc.). , Aryl groups (phenyl, naphthyl, etc.), aromatic heterocyclic groups (furyl, pyrazolyl, pyridyl, etc.), alkoxy groups (methoxy, ethoxy, i-propoxy, hexyloxy, etc.), aryloxy (phenoxy C), alkylthio groups (methylthio, ethylthio, etc.), arylthio groups (phenylthio, etc.), alkenyl groups (vinyl, 1-propenyl, etc.), acyloxy groups (acetoxy, acryloyloxy, meta ), Alkoxycarbonyl groups (methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl groups (phenoxycarbonyl, etc.), carbamoyl groups (carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl, etc., acylamino groups (acetylamino, benzoylamino, acrylamino, Tacrylamino etc.) These substituents may be substituted further.

When there are two or more R <^10> , it is preferable that at least one is a substituted alkyl group or a substituted aryl group.

Among the organosilane compounds represented by the general formula (3), an organosilane compound having a vinyl polymerizable substituent represented by the following general formula (4) is preferable.

In general formula (4)

[Chemical Formula 13]

In general formula (4), R <^1> is a hydrogen atom, an alkyl group (methyl group, ethyl group etc.), an alkoxy group (methoxy group, an ethoxy group etc.), an alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group etc.), a cyano group, a halogen The atom (fluorine atom, chlorine atom, etc.) is represented. Especially, a hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom, and a chlorine atom are preferable, and a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom, and a chlorine atom are more preferable, and a hydrogen atom and a methyl group Is particularly preferred.

Y is a single bond, * -COO-, * -OCO-, * -CON (R ²⁰ )-, * -N (R ²⁰ ) CO-, -O-, or * -N (R ²¹ ) CON (R ²² )-. Here, * represents the position which couple | bonds with the double bond in General formula (4), R <^20> , R <^21> and R <^22> represent a hydrogen atom or a C1-C5 alkyl group. Y is preferably a single bond, * -COO-, and * -CON (R ²⁰ )-, more preferably a single bond and * -COO-, and particularly preferably * -CO0-.

L represents a C1-C20 bivalent coupling group. Specifically, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group having a linking group (for example, ether, ester, amide, etc.) therein, having a linking group therein Substituted or unsubstituted arylene group is mentioned. Among them, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, and an alkylene group having a linking group therein are preferable, and an unsubstituted alkylene group, an unsubstituted arylene group, and an ether or ester therein. The alkylene group which has a coupling group which consists of these is further more preferable, The unsubstituted alkylene group and the alkylene group which has a coupling group which consists of an ether or ester inside are especially preferable. As a substituent, a halogen, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, an aryl group, etc. are mentioned, These substituents may further be substituted.

n represents 0 or 1; When there are a plurality of X's, the plurality of X's may be the same or different, respectively. n is preferably 0.

R <^10> is synonymous with general formula (3), and an unsubstituted alkyl group and an unsubstituted aryl group are preferable.

X is the same meaning as General formula (3), A halogen and an unsubstituted alkoxy group are preferable, A chlorine atom and an unsubstituted C1-C5 alkoxy group are more preferable, A C1-C3 alkoxy group is more preferable And methoxy groups are particularly preferred.

As an organosilane compound, you may use together 2 or more types of compounds represented by General formula (3) or (4). Although the specific example of a compound represented by General formula (3) or (4) below is shown, this invention is not limited to these.

[Formula 14]

[Formula 15]

Among these, (M-1), (M-2), and (M-5) are especially preferable.

Although the hydrolysis and condensation reaction of the organosilane can be carried out without solvent or in a solvent, it is preferable to use an organic solvent in order to uniformly mix the components. For example, alcohols, aromatic hydrocarbons, ethers, Ketones, esters, etc. are preferable.

It is preferable that a solvent dissolves organosilane and a catalyst. In addition, it is preferable in the process to use an organic solvent as a coating liquid or a part of coating liquid, and when mixing with other raw materials, such as a fluorine-containing polymer, it is preferable not to impair solubility or dispersibility.

Among these, as alcohols, monohydric alcohol or dihydric alcohol is mentioned, for example, As monohydric alcohol, C1-C8 saturated aliphatic alcohol is preferable. Specific examples of these alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene Glycol monobutyl ether, ethylene glycol monoethyl ether, and the like.

Specific examples of the aromatic hydrocarbons include benzene, toluene and xylene, and specific examples of the ethers include tetrahydrofuran and dioxane. Specific examples of the ketones include acetone, methyl ethyl ketone, and methyl. Isobutyl ketone, diisobutyl ketone, etc. are mentioned as an example of ester, ethyl acetate, propyl acetate, butyl acetate, a propylene carbonate, etc. are mentioned.

These organic solvents may be used individually by 1 type, or may be used in combination of 2 or more type.

Although the concentration of solid content in this reaction is not specifically limited, Usually, it is the range of 1%-90%, Preferably it is the range of 20%-70%.

The hydrolysis and condensation reaction of the organosilane is preferably carried out in the presence of a catalyst. As a catalyst, Inorganic acids, such as hydrochloric acid, a sulfuric acid, nitric acid; Organic acids such as oxalic acid, acetic acid, formic acid, methanesulfonic acid and toluenesulfonic acid; Inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia; Organic bases such as triethylamine and pyridine; Metal alkoxides such as triisopropoxy aluminum and tetrabutoxy zirconium; Although a metal chelate compound etc. can be mentioned, Acid catalysts (inorganic acids, organic acids) and a metal chelate compound are preferable from a manufacturing stability of a sol liquid, and storage stability of a sol liquid. As the inorganic acid, the acid dissociation constant (pKa value (25 ° C)) in water is preferably 4.5 or less, and more preferably an organic acid in hydrochloric acid, sulfuric acid, or organic acid is 3.0 or less. More preferably, an organic acid having an acid dissociation constant of 2.5 or less in water, an organic acid having an acid dissociation constant of 2.5 or less in water, still more preferably methanesulfonic acid, oxalic acid, phthalic acid, and maronic acid, and particularly oxalic acid. desirable.

The hydrolysis / condensation reaction is usually added in an amount of 0.3 to 2 mol, preferably 0.5 to 1 mol, with respect to 1 mol of the hydrolyzable group of the organosilane, in the presence or absence of the solvent, and preferably Is carried out by stirring at 25 to 100 ° C. in the presence of a catalyst.

When the hydrolyzable group is an alkoxide and the catalyst is an organic acid, since the carboxyl group or sulfo group, which is an organic acid, supplies protons, the amount of water added can be reduced, and the amount of water added to 1 mole of the alkoxide group of the organosilane is 0 to 2 mol. , Preferably it is 0-1.5 mol, More preferably, it is 0-1 mol, Especially preferably, it is 0-0.5 mol. When alcohol is used for the solvent, it is also preferable that substantially no water is added.

The amount of the catalyst used is 0.01 to 10 mol%, preferably 0.1 to 5 mol% with respect to the hydrolyzable group when the catalyst is an inorganic acid, and when the catalyst is an organic acid, the optimum amount of use varies depending on the amount of water added, but water is added. 0.01 to 10 mol%, preferably 0.1 to 5 mol% with respect to the hydrolyzable group, and 1 to 500 mol% with respect to the hydrolyzable group, preferably 10 to 200 mol, when substantially no water is added. %, More preferably, it is 20-200 mol%, More preferably, it is 50-150 mol%, Especially preferably, it is 50-120 mol%.

Although reaction is made by stirring at 25-100 degreeC, it is preferable to adjust suitably by the reactivity of organosilane.

The metal chelate compound can be preferably used without particular limitation as long as the metal selected from Zr, Ti or Al is a central metal. If it is this range, you may use 2 or more types of metal chelate compounds together. Specific examples of the metal chelate compound used in the present invention include tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium and n-butoxytris (ethylacetoacetate) zirconium Zirconium chelate compounds such as tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium and tetrakis (ethylacetoacetate) zirconium; Titanium chelate compounds such as diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium and diisopropoxy bis (acetylacetone) titanium; Diisopropoxyethylacetoacetate aluminum, diisopropoxyacetylacetate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetyl Aluminum chelate compounds such as acetonate) aluminum and monoacetylacetonate bis (ethylacetoacetate) aluminum.

Preferred among these metal chelate compounds are tri-n-butoxyethylacetoacetate zirconium, diisopropoxybis (acetylacetonate) titanium, diisopropoxyethylacetoacetate aluminum, and tris (ethylacetoacetate) aluminum. These metal chelate compounds can be used individually by 1 type or in mixture of 2 or more types. Moreover, the partial hydrolyzate of these metal chelate compounds can also be used.

The metal chelate compound of the present invention is preferably from 0.01 to 50% by mass, more preferably from 0.1 to 50% by mass, more preferably from the viewpoint of the rate of condensation reaction and the film strength when the coating film is used. Preferably it is used in the ratio of 0.5-10 mass%.

Although the appropriate content of the sol of organosilane also varies depending on the layer to be added, the addition amount to the low refractive index layer is preferably 0.1 to 50% by mass, more preferably 0.5 to 20% by mass, of the total solids of the low refractive index layer, 1-10 mass% is especially preferable. 0.001-50 mass% of the total solid of a containing layer (addition layer) is preferable, as for the addition amount with respect to layers other than a low refractive index layer, 0.01-20 mass% is more preferable, 0.05-10 mass% is more preferable, 0.1-5 mass% is especially preferable.

5-100 mass% is preferable, as for the usage-amount of the sol of organosilane with respect to a fluorine-containing polymer in a low refractive index layer, 5-40 mass% is more preferable, 8-35 mass% is more preferable, 10 30 mass% is especially preferable. If the amount is small, the effect of the present invention is hardly obtained. If the amount is too large, the refractive index increases or the shape and surface shape of the film deteriorate.

As a solvent composition of the coating liquid used for forming the low refractive index layer which concerns on this invention, it is possible to be single or mixing, and when mixing, it is preferable that the solvent whose boiling point is 100 degrees C or less is 50 to 100%, More preferably, Is 80 to 100%, more preferably 90 to 100%, still more preferably 100%. If the solvent having a boiling point of 100 ° C. or less is 50% or less, the drying speed is very slow, and the shape of the coated surface is deteriorated, and unevenness occurs in the thickness of the coated film. Therefore, optical characteristics such as reflectance are also deteriorated. In this invention, this problem can be solved by using the coating liquid containing many solvents whose boiling point is 100 degrees C or less.

As a solvent whose boiling point is 100 degrees C or less, hydrocarbons, such as hexane (boiling point 68.7 degreeC, hereafter abbreviation "° C"), heptane (98.4), cyclohexane (80.7), benzene (80.1), dichloromethane Halogenated hydrocarbons such as (39.8), chloroform (61.2), carbon tetrachloride (76.8), 1,2-dichloroethane (83.5), trichloroethylene (87.2), diethyl ether (34.6), diisopropyl ether ( Ethers such as 68.5), dipropyl ether (90.5), tetrahydrofuran (66), esters such as ethyl formate (54.2), methyl acetate (57.8), ethyl acetate (77.1), isopropyl acetate (89), Ketones such as acetone (56.1) and 2-butanone (= methylethyl ketone, 79.6), alcohols such as methanol (64.5), ethanol (78.3), 2-propanol (82.4), and 1-propanol (97.2), and aceto And cyano compounds such as nitrile (81.6) and propionitrile (97.4), carbon disulfide (46.2), and the like. Among these, ketones and esters are preferable, and ketones are particularly preferable. Among the ketones, 2-butanone is particularly preferable.

As a solvent whose boiling point is 100 degreeC or more, for example, octane (125.7), toluene (110.6), xylene (138), tetrachloroethylene (121.2), chlorobenzene (131.7), dioxane (101.3), dibutyl Ether (142.4), isobutyl acetate (118), cyclohexanone (155.7), 2-methyl-4-pentanone (= MIBK, 115.9), 1-butanol (117.7), N, N-dimethylformamide (153 ), N, N-dimethylacetamide (166), dimethyl sulfoxide (189), and the like. Preferably, they are cyclohexanone and 2-methyl-4- pentanone.

By diluting the low refractive index layer component with the solvent of the above-mentioned composition, the coating liquid for low refractive index layers is prepared. Although it is preferable to adjust suitably the coating liquid density | concentration in consideration of the viscosity of a coating liquid, specific gravity of a layer raw material, etc., 0.1-20 mass% is preferable, More preferably, it is 1-10 mass%.

(High refractive index layer)

In the antireflective film of this invention, a high refractive index layer and a medium refractive index layer can be formed on a hard-coat layer, and reflection prevention property can be improved. As for the refractive index of the high refractive index layer and the medium refractive index layer of this invention, 1.55-2.40 are preferable. In the following specification, the high refractive index layer and the middle refractive index layer may be referred to collectively as the high refractive index layer. In addition, in this invention, the "high", "medium", and "low" of a high refractive index layer, a medium refractive index layer, and a low refractive index layer show the magnitude relationship of the relative refractive index of layers. In addition, as for the relationship with the transparent support, it is preferable that the refractive index satisfies the relationship between the transparent support> low refractive index layer and the high refractive index layer> transparent support.

[Inorganic fine particles of high refractive index layer]

As the high refractive index layer of the present invention, inorganic fine particles that can be used for the purpose of high refractive index of the hard coat layer described in the hard coat layer can be preferably used. As the inorganic fine particles used in the high refractive index layer of the present invention, inorganic fine particles mainly containing titanium dioxide containing at least one element selected from cobalt, aluminum and zirconium are particularly preferable. A main component means the component with most content (mass%) among the components which comprise particle | grains.

Inorganic fine particles containing titanium dioxide as a main component of the present invention preferably have a refractive index of 1.90 to 2.80, more preferably 2.10 to 2.80, and most preferably 2.20 to 2.80.

The mass average diameter of the primary particles of the inorganic fine particles containing titanium dioxide as a main component is preferably 1 to 200 nm, more preferably 1 to 150 nm, still more preferably 1 to 100 nm, and particularly preferably 1 to 80 nm. Nm.

The particle diameter of the inorganic fine particles can be measured by a light scattering method or an electron micrograph. The specific surface area of the inorganic fine particles is preferably 10 to 400 m 2 / g, more preferably 20 to 200 m 2 / g, and most preferably 30 to 150 m 2 / g.

As for the crystal structure of the inorganic fine particle which has a titanium dioxide as a main component, it is preferable that the mixed crystal of rutile, a rutile / anatase, an anatase, and an amorphous structure are a main component, and especially a rutile structure is a main component. A main component means the component with most content (mass%) among the components which comprise particle | grains.

By containing at least one element selected from Co (cobalt), Al (aluminum), and Zr (zirconium) in the inorganic fine particles mainly composed of titanium dioxide, the photocatalytic activity of titanium dioxide can be suppressed, and the high refractive index of the present invention The weather resistance of the layer can be improved.

Particularly preferred element is Co (cobalt). Moreover, it is also preferable to use two or more types together.

It is preferable that content of Co (cobalt), Al (aluminum), or Zr (zirconium) with respect to Ti (titanium) is 0.05-30 mass% with respect to Ti, respectively, More preferably, it is 0.1-10 mass%, More preferably Preferably it is 0.2-7 mass%, Especially preferably, it is 0.3-5 mass%, Most preferably, it is 0.5-3 mass%.

Co (cobalt), Al (aluminum) and Zr (zirconium) may be present in at least one of the inside and the surface of the inorganic fine particles mainly composed of titanium dioxide, but are present in the interior of the inorganic fine particles mainly composed of titanium dioxide. It is preferable to make it, and it is most preferable to exist in both an inside and a surface.

In order to make Co (cobalt), Al (aluminum), and Zr (zirconium) exist inside inorganic fine particles containing titanium dioxide as a main component (for example, doping), there are various methods. For example, ion implantation method (vol. 18, N0.5, pp. 262-268, 1998; Yasushi Aoki), Japanese Patent Laid-Open No. 11-263620, Japanese Patent Laid-Open No. 11-512336 And the method described in European Patent Publication No. 0335773 and Japanese Patent Application Laid-open No. Hei 5-330825.

A method of introducing Co (cobalt), Al (aluminum), Zr (zirconium) in the particle formation process of the inorganic fine particles mainly composed of titanium dioxide (for example, Japanese Patent Laid-Open No. 11-512336, European Patent Publication No. 0335773, described in JP-A-5-330825).

Co (cobalt), Al (aluminum) and Zr (zirconium) are also preferably present as oxides.

The inorganic fine particles containing titanium dioxide as a main component may further contain other elements depending on the purpose. Other elements may be contained as impurities. Examples of other elements include Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Mg, Si, P, and S.

[Surface Treatment of Inorganic Particles]

You may surface-treat the inorganic fine particle which has a titanium dioxide used for this invention as a main component. Surface treatment is performed using an inorganic compound or an organic compound. Examples of the inorganic compound used for the surface treatment include inorganic compounds containing cobalt (CoO ₂ , Co ₂ O ₃ , Co ₃ O _4, etc.), inorganic compounds containing aluminum (Al ₂ O ₃ , Al (OH) ₃ Etc.), zirconium-containing inorganic compounds (ZrO ₂ , ZR (OH) _4, etc.), silicon-containing inorganic compounds (SiO _2, etc.), iron-containing inorganic compounds (Fe ₂ O _3, etc.), and the like. .

Particularly preferred are inorganic compounds containing cobalt, inorganic compounds containing aluminum, and inorganic compounds containing zirconium, and inorganic compounds containing cobalt and organic compounds used for Al (OH) ₃ surface treatment include polyols, Alkanolamines, stearic acid, silane coupling agents and titanate coupling agents. A silane coupling agent is the most preferable, For example, the compound represented by the said General formula (3) or General formula (4) is mentioned.

As for content of a silane coupling agent, 1-90 mass% of the total solid of a high refractive index layer is preferable, More preferably, it is 2-80 mass%, Especially preferably, it is 5-50 mass%.

As the titanate coupling agent, for example, metal alkoxides such as tetramethoxytitanium, tetraethoxytitanium and tetraisopropoxytitanium, and prenacuto (KR-TTS, KR-46B, KR-55, KR- 41B etc .; Ajinomoto Co., Ltd.) etc. are mentioned.

As an example of the organic compound used for surface treatment, a polyol, an alkanolamine, the organic compound which has another anionic group, etc. are preferable, and an organic compound which has a carboxyl group, a sulfonic acid group, or a phosphoric acid group is especially preferable.

Stearic acid, lauric acid, oleic acid, linoleic acid, linoleic acid and the like can be preferably used.

It is preferable that the organic compound used for surface treatment further has a crosslinking or a polymerizable functional group. Examples of the crosslinking or polymerizable functional group include ethylenically unsaturated groups (eg, (meth) acrylic groups, allyl groups, styryl groups, vinyloxy groups, etc.) capable of addition reaction and polymerization reaction by radical species, and cationic polymerizable groups. (Epoxy group, oxatanyl group, vinyloxy group, etc.), polycondensation-reactive group (N-methylol group, such as a hydrolyzable silyl group), etc. are mentioned, Preferably it is group which has an ethylenically unsaturated group.

These surface treatment can also use two or more types together. It is especially preferable to use the inorganic compound containing aluminum and the inorganic compound containing zirconium together.

The inorganic fine particle containing the titanium dioxide of this invention as a main component may have a core / shell structure by surface treatment, as described in Unexamined-Japanese-Patent No. 2001-166104.

The shape of the inorganic fine particles mainly composed of titanium dioxide contained in the high refractive index layer is preferably rice grains, spherical shapes, cubes, fusiforms, or indefinite shapes, particularly preferably indefinite or fusiform forms.

[Dispersant of Inorganic Particles]

A dispersant can be used for dispersion of the inorganic fine particles which contain the titanium dioxide used for the high refractive index layer of this invention as a main component.

It is particularly preferable to use a dispersant having an anionic group for the dispersion of the inorganic fine particles containing titanium dioxide of the present invention as a main component.

As the anionic group, a group having an acidic proton such as a carboxyl group, a sulfonic acid group (and a sulfo group), a phosphoric acid group (and a phosphono group), a sulfonamide group, or a salt thereof is effective, and in particular, a carboxyl group, a sulfonic acid group, a phosphoric acid group and Salts are preferred, and carboxyl groups and phosphoric acid groups are particularly preferred. The number of the anionic groups contained in the dispersing agent per molecule should just contain 1 or more.

In order to further improve the dispersibility of the inorganic fine particles, a plurality of anionic groups may be contained. It is preferable that it is two or more on average, More preferably, it is five or more, Especially preferably, it is ten or more. In addition, the anionic group contained in a dispersing agent may contain two or more types in 1 molecule.

It is preferable that a dispersing agent contains a crosslinking or a polymerizable photofunctional group further. Examples of the crosslinking or polymerizable functional group include ethylenically unsaturated groups (eg, (meth) acryloyl groups, allyl groups, styryl groups, vinyloxy groups, etc.) capable of addition and polymerization reactions by radical species, and cationic polymerizable groups ( Epoxy groups, oxatanyl groups, vinyloxy groups, and the like), polycondensation reactive groups (N-methylol groups such as hydrolyzable silyl groups), and the like, and the like, and preferably functional groups having ethylenically unsaturated groups.

Preferred dispersants for use in the dispersion of the inorganic fine particles mainly composed of titanium dioxide used in the high refractive index layer of the present invention have anionic groups and crosslinking or polymerizable functional groups, and also have a crosslinking or polymerizable functional group in the side chain. to be.

Although the mass mean molecular weight (Mw) of the dispersing agent which has an anionic group and crosslinking or a polymerizable functional group, and has this crosslinking or a polymerizable functional group in a side chain is not specifically limited, It is preferable that it is 1000 or more. The more preferable mass average molecular weight (Mw) of a dispersing agent is 2000-1 million, More preferably, it is 5000-200000, Especially preferably, it is 10000-100000.

As the anionic group, a group having an acidic proton, such as a carboxyl group, a sulfonic acid group (sulfo), a phosphoric acid group (phosphono), a sulfonamide group, or a salt thereof is effective, and a carboxyl group, a sulfonic acid group, a phosphoric acid group or a salt thereof is particularly preferable. , Carboxyl group and phosphoric acid group are particularly preferred. It is preferable that the number of the anionic groups contained in the dispersing agent per molecule is 2 or more on average, More preferably, it is 5 or more, Especially preferably, it is 10 or more. In addition, the anionic group contained in a dispersing agent may contain two or more types in 1 molecule.

The dispersing agent which has an anionic group and crosslinking or a polymerizable functional group, and has the crosslinking or a polymerizable functional group in a side chain has the said anionic group in a side chain or a terminal. As a method of introducing an anionic group into the side chain, for example, an anionic group-containing monomer (for example, (meth) acrylic acid, maleic acid, partially esterified maleic acid, itaconic acid, crotonic acid, 2-carboxyethyl (meth) acryl Polymers such as a method of polymerizing a rate, 2-sulfoethyl (meth) acrylate, mono-2- (meth) acryloyloxyethyl ester, etc., a method of reacting an acid anhydride to a polymer having a hydroxyl group, an amino group, or the like It can be synthesized using the reaction.

In the dispersing agent having an anionic group in the side chain, the composition of the anionic group-containing repeating unit is in the range of 10 ^{-4 to} 100 mol%, preferably 1 to 50 mol%, particularly preferably 5 to 20 mol% in the total repeating units. .

On the other hand, as a method of introducing an anionic group to the terminal, a method of performing a polymerization reaction in the presence of an anionic group-containing chain transfer agent (for example, thioglycolic acid), an anionic group-containing polymerization initiator (for example Wako Pure Chemical Industries, Ltd.) It can synthesize | combine by the method etc. which perform a polymerization reaction using manufacture V-501).

Particularly preferred dispersants are dispersants having anionic groups in the side chain.

Examples of the crosslinking or polymerizable functional group include ethylenically unsaturated groups (eg, (meth) acrylic groups, allyl groups, styryl groups, vinyloxy groups, etc.) and cationic polymerizable groups (epoxy groups) capable of addition and polymerization reactions by radical species. , An oxanyl group, a vinyloxy group, etc.), a polycondensation-reactive group (N-methylol group, such as a hydrolyzable silyl group), etc. are mentioned, Preferably it is group which has an ethylenically unsaturated group.

The number of crosslinking or polymerizable functional groups contained in the dispersant per molecule is preferably 2 or more on average, more preferably 5 or more, particularly preferably 10 or more. In addition, the crosslinking or polymerizable functional group contained in a dispersing agent may contain two or more types in 1 molecule.

In the preferred dispersant used in the present invention, examples of repeating units having an ethylenically unsaturated group in the side chain include poly-1,2-butadiene and poly-1,2-isoprene structures or esters or amides of (meth) acrylic acid. As the repeating unit, those having a specific residue (R group of -COOR or -CONHR) bound thereto can be used. Examples of the specific residue (R group) include-(CH ₂ ) _n -CR ₁ = CR ₂ R ₃ ,-(CH ₂ 0) _n -CH ₂ CR ₁ = CR ₂ R ₃ ,-(CH ₂ CH ₂ 0) _n -CH ₂ CR ₁ = CR ₂ R ₃ ,-(CH ₂ ) _n -NH-CO-O-CH ₂ CR ₁ = CR ₂ R ₃ ,-(CH ₂ ) _n -O-CO-CR ₁ = CR ₂ R ₃ And-(CH ₂ CH ₂ 0) ₂ -X (R ₁ to R ₃ are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkoxy group, an aryloxy group, and R ₁ and Or R ₂ or R ₁ and R ₃ may be bonded to each other to form a ring, n is an integer of 1 to 10, and X is a dicyclopentadienyl residue. Specific examples of the ester residues include -CH ₂ CH = CH ₂ , -CH ₂ CH ₂ 0-CH ₂ CH = CH ₂ , -CH ₂ CH ₂ OCOCH = CH ₂ , -CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ , -CH ₂ C (CH ₃ ) = CH ₂ , -CH ₂ CH = CH-C ₆ H ₅ , -CH ₂ CH ₂ OCOCH = CH-C ₆ H ₅ , -CH ₂ CH ₂ -NHCOO-CH ₂ CH = CH ₂ and -CH ₂ CH ₂ OX (X is a dicyclopentadienyl residue). Specific examples of the amide moiety include -CH ₂ CH = CH ₂ , -CH ₂ CH ₂ -Y (Y is a 1-cyclohexenyl moiety) and -CH ₂ CH ₂ -OCO-CH = CH ₂ , -CH ₂ CH ₂ -OCO-C (CH ₃ ) = CH ₂ is included.

In the dispersant having an ethylenically unsaturated group, free radicals (growth radicals in the polymerization process of a polymerization initiator radical or a polymerizable compound) are added to the unsaturated bond group, so as to directly or in between the molecules, or a polymerization chain of the polymerizable compound. It is then polymerized to form crosslinks between the molecules and to cure. Alternatively, atoms in the molecule (e.g., hydrogen atoms on carbon atoms adjacent to unsaturated bond groups) are evicted by free radicals to produce polymer radicals, which bond with each other to form crosslinks and cure between the molecules.

As a method of introducing a crosslinking or polymerizable functional group into the side chain, for example, as described in Japanese Patent Application Laid-Open No. 3-249653, the crosslinking or polymerizable functional group-containing monomer (for example, allyl (meth) acrylate and glycy Copolymerization of di (meth) acrylate, trialkoxysilylpropylmethacrylate, etc.), butadiene or isoprene, copolymerization of a vinyl monomer having a 3-chloropropionic acid ester moiety, followed by dehydrochlorination, polymer reaction Can be synthesized by crosslinking or introduction of a polymerizable functional group (for example, a polymer reaction of an epoxy group-containing vinyl monomer to a carboxyl group-containing polymer).

Although the containing unit of a crosslinking or a polymerizable functional group may comprise all the repeating units other than the anionic group containing repeating unit, Preferably it is 5-50 mol% in all crosslinking or a repeating unit, Especially preferably, it is 5-30 mol%. .

The preferable dispersing agent of this invention may be a copolymer with a suitable monomer other than the monomer which has a crosslinking or a polymerizable functional group, and an anionic group. Although it does not specifically limit about a copolymerization component, It selects from various viewpoints, such as dispersion stability, compatibility with other monomer components, and the strength of a forming film. Preferred examples include methyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene and the like.

Although the form of the preferred dispersant of the present invention is not particularly limited, it is preferable that it is a block copolymer or a random copolymer, and it is particularly preferable that it is a random copolymer in terms of cost and synthetic ease.

Although the specific example of the dispersing agent used preferably for this invention below is shown, the dispersing agent for this invention is not limited to these. In addition, the random copolymer is shown unless otherwise stated.

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

It is preferable that the usage-amount with respect to the inorganic fine particle which has a titanium dioxide of a dispersing agent as a main component is in the range of 1-50 mass%, It is more preferable that it is the range of 5-30 mass%, It is most preferable that it is 5-20 mass%. . In addition, you may use two or more types of dispersing agents together.

[Formation method of high refractive index layer, etc.]

Inorganic fine particles containing titanium dioxide as a main component used for the high refractive index layer are used for formation of the high refractive index layer in the state of dispersion. In the dispersion of the inorganic fine particles, it is dispersed in the dispersion medium in the presence of the dispersant.

As the dispersion medium, it is preferable to use a liquid having a boiling point of 60 to 170 캜. Examples of dispersion media include water, alcohols (e.g. methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), esters (e.g. methyl acetate , Ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (e.g. hexane, cyclohexane), halogenated hydrocarbons (e.g. methylene chloride, chloroform, carbon tetrachloride), aromatic Hydrocarbons (eg benzene, toluene, xylene), amides (eg dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ethers (eg diethyl ether, dioxane, tetrahydrofuran), ether alcohol (Eg, 1-methoxy-2-propanol). Toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are preferred.

Particularly preferred dispersion media are methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone.

Inorganic fine particles disperse using a disperser. Examples of dispersers include sand grinder mills (eg pinned bead mills), high speed impeller mills, pebble mills, roller mills, attritors and colloid mills. Sand grinder mills and high speed impeller mills are particularly preferred. Moreover, you may preliminarily disperse | distribute. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three roll mill, a kneader and an extruder.

Inorganic fine particles are preferably finely dispersed in the dispersion medium, and have a mass average diameter of 1 to 200 nm. Preferably it is 5-150 nm, More preferably, it is 10-100 nm, Especially preferably, it is 10-80 nm.

By refining the inorganic fine particles to 200 nm or less, it is possible to form a high refractive index layer in which transparency is not impaired.

The high refractive index layer used in the present invention may be a binder (for example, an ionizing radiation curable polyfunctional monomer as exemplified in the description of the hard coat layer) in a dispersion liquid in which inorganic fine particles are dispersed in a dispersion medium in the manner described above. Functional oligomer, etc.), a photoinitiator, a sensitizer, a coating solvent, etc., are added to form a coating composition for forming a high refractive index layer, and a coating composition for forming a high refractive index layer is applied on a hard coat layer, and an ionizing radiation curable compound (for example, , Polyfunctional monomers, polyfunctional oligomers, and the like) is preferably cured and formed by a crosslinking reaction or a polymerization reaction. As a specific example of a binder, a photoinitiator, a sensitizer, and a coating solvent, the compound illustrated by the hard coat layer can be used.

It is also preferable to crosslink or polymerize the binder of the high refractive index layer with the dispersant at the same time or after the application of the layer.

The binder of the high refractive index layer thus produced is crosslinked or polymerized with the preferred dispersant and the ionizing radiation curable polyfunctional monomer or polyfunctional oligomer to form a binder containing an anionic group of the dispersant. The binder of the high refractive index layer has the function of maintaining the dispersed state of the inorganic fine particles in the anionic group, and the crosslinking or polymerization structure imparts the film forming ability to the binder, and the physical strength and chemical resistance of the high refractive index layer containing the inorganic fine particles. Improves weather resistance.

Inorganic fine particles have a function of controlling the refractive index of the high refractive index layer, and also have a function of suppressing curing shrinkage.

In the high refractive index layer, the inorganic fine particles are preferably dispersed as finely as possible, and the mass average diameter is 1 to 200 nm. The mass average diameter of the inorganic fine particles in the high refractive index layer is preferably 5 to 150 nm, more preferably 10 to 100 nm, and most preferably 10 to 80 nm.

By refining the inorganic fine particles to 200 nm or less, it is possible to form a high refractive index layer in which transparency is not impaired.

It is preferable that content of the inorganic fine particle in a high refractive index layer is 10-90 mass% with respect to the mass of a high refractive index layer, More preferably, it is 15-80 mass%, Especially preferably, it is 15-75 mass%. Inorganic fine particles may use two or more types together in a high refractive index layer.

Since the low refractive index layer is provided on the high refractive index layer, the refractive index of the high refractive index layer is preferably higher than that of the transparent support.

A high refractive index layer contains an ionizing radiation curable compound containing an aromatic ring, an ionizing radiation curable compound containing halogenated elements other than fluorine (for example, Br, I, Cl, etc.), and atoms such as S, N, and P The binder obtained by crosslinking or polymerization reaction, such as an ionizing radiation curable compound, can also be used preferably.

The refractive index of the high refractive index layer is preferably 1.55 to 2.40, more preferably 1.60 to 2.20, still more preferably 1.65 to 2.10, and most preferably 1.80 to 2.00.

For example, when three layers are formed in the order of the medium refractive index layer, the high refractive index layer, and the low refractive index layer on the hard coat layer, the refractive index of the medium refractive index layer is 1.55 to 1.80, and the refractive index of the high refractive index layer is 1.80 to 2.40, low. It is preferable that the refractive index of a refractive index layer is 1.20-1.46.

In the high refractive index layer, in addition to the above components (inorganic fine particles, polymerization initiators, photosensitizers, etc.), resins, surfactants, antistatic agents, coupling agents, thickeners, anti-colorants, colorants (pigments, dyes), antifoaming agents, leveling agents , Flame retardants, ultraviolet absorbers, infrared absorbers, adhesives, polymerization inhibitors, antioxidants, surface modifiers, conductive metal fine particles, and the like may be added.

The film thickness of a high refractive index layer can be designed suitably according to a use. When using a high refractive index layer as an optical interference layer mentioned later, 30-200 nm is preferable, More preferably, it is 50-170 nm, Especially preferably, it is 60-150 nm.

[Other layers of antireflection film]

In order to produce an antireflection film having more excellent antireflection performance, it is preferable to form a medium refractive index layer having a refractive index between the refractive index of the high refractive index layer and the refractive index of the transparent support.

It is preferable to produce a medium refractive index layer as described in the high refractive index layer of this invention, and a refractive index can be adjusted by controlling the content rate of the inorganic fine particle in a film.

In the antireflection film, you may form layers other than what was mentioned above. For example, you may form an adhesive layer, a shield layer, an antifouling layer, a sliding layer, or an antistatic layer. The shield layer is formed to shield electromagnetic waves or infrared rays.

[Formation method of antireflection film]

Each layer of the antireflection film of the present invention can be formed by the following coating method, but is not limited to this method.

Known methods such as dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, extrusion coating method (see US Patent No. 2681294 specification), microgravure coating method Among them, the microgravure coating method is preferable.

The microgravure coating method used in the present invention is a gravure roll having a diameter of about 10 to 100 mm, preferably about 20 to 50 mm and a gravure pattern imprinted on the entire circumference of the gravure roll with respect to the conveying direction of the support under the support. While rotating the back, the excess coating liquid was scraped off by the doctor blade on the surface of the gravure roll, and the coating liquid was transferred to the lower surface of the support at the position where the upper surface of the support was free. Coating is a coating method characterized by the above-mentioned. The transparent support in the form of a roll is continuously wound, and at least one layer of the low refractive index layer containing at least the hard coat layer or the fluorine-containing polymer can be coated on one side of the wound support by the microgravure coating method.

As the coating conditions by the microgravure coating method, the number of lines of the gravure pattern carved into the gravure roll is preferably 50-800 / inch, more preferably 100-300 / inch, and the depth of the gravure pattern is 1-. 600 micrometers is preferable, 5-200 micrometers is more preferable, It is preferable that the rotation speed of a gravure roll is 3-800 rpm, It is more preferable that it is 5-200 rpm, It is preferable that the conveyance speed of a support body is 0.5-100 m / min. 1-50 m / min is more preferable.

It is preferable that each layer of the antireflection film is heat-dried after coating, and then irradiated with ionizing radiation such as ultraviolet rays or electron beams and cured.

The ionizing radiation used in the present invention can be used without limitation as long as the compound can be activated and crosslinked with ultraviolet rays, electron beams, γ rays, or the like, but ultraviolet rays and electron beams are preferable. Ultraviolet is preferable in that it is obtained. As a light source of the ultraviolet-ray which photopolymerizes an ultraviolet-ray reactive compound, any light source which generate | occur | produces an ultraviolet-ray can be used. 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, a metal halide lamp, a xenon lamp, etc. can be used. Moreover, ArF excimer laser, KrF excimer laser, an excimer lamp, a synchrotron radiation, etc. can also be used. Although irradiation conditions differ with each lamp, 20 mJ / cm <2> or more of irradiation light quantity is preferable, More preferably, it is 50mJ / cm <2> -10000mJ / cm <2>, Especially preferably, it is 50mJ / cm <2> -2000mJ / cm <2>.

Ultraviolet irradiation may be irradiated every time one layer is formed with respect to each of the several layer (medium refractive index layer, high refractive index layer, low refractive index layer) which comprises an antireflection layer, and may be irradiated after lamination | stacking. Or you may investigate combining them. From the viewpoint of productivity, it is preferable to irradiate ultraviolet rays after laminating the multilayers.

Moreover, an electron beam can also be used similarly. Examples of the electron beam include 50 to 1000 keV, preferably 100 to 300 keV, emitted from various electron beam accelerators such as cockloft walton type, van degraf type, resonant transformer type, insulation core transformer type, linear type, dynamtron type and high frequency type. The electron beam which has energy is mentioned.

When each layer is formed by crosslinking reaction or polymerization reaction by the ionizing radiation, the crosslinking reaction or polymerization reaction is preferably carried out in an atmosphere having an oxygen concentration of 10% by volume or less. By forming it in the atmosphere whose oxygen concentration is 10 volume% or less, the layer excellent in physical strength and chemical-resistance can be formed.

* Preferably, it is formed by the crosslinking reaction or polymerization reaction of an ionizing radiation curable compound in the atmosphere whose oxygen concentration is 6 volume% or less, More preferably, the oxygen concentration is 4 volume% or less, Especially preferably, the oxygen concentration is 2 volume%. It is volume% or less, Most preferably, it is 1 volume% or less.

As a method of reducing the oxygen concentration to 10 vol% or less, it is preferable to replace the atmosphere (nitrogen concentration about 79 vol%, oxygen concentration about 21 vol%) with a separate gas, particularly preferably with nitrogen (nitrogen purge). )

(Polarizer)

The polarizing plate of this invention consists of a polarizing film and two protective films arrange | positioned at both sides. The antireflection film of the present invention is used as one protective film, and the retardation film of the present invention is used as the other protective film.

The polarizing film includes an iodine polarizing film and a dye polarizing film or a polyene polarizing film using a dichroic dye. Iodine type polarizing film and dye type polarizing film are generally manufactured using polyvinyl alcohol-type film.

The transparent support of the antireflection film or the slow axis of the retardation film and the transmission axis of the polarizing film are arranged to be substantially parallel.

The moisture permeability of a protective film is important for productivity of a polarizing plate. The polarizing film and the protective film are attached with an aqueous adhesive, and the adhesive solvent is dried by being diffused in the protective film. The higher the moisture permeability of the protective film, the faster the drying and the higher the productivity. The higher the moisture permeability of the protective film, the higher the moisture permeability in the polarizing film due to the use environment (under high humidity) of the liquid crystal display device.

The moisture permeability of the protective film is determined by the thickness, free volume, hydrophilicity and the like of the transparent support and the polymer film (and the polymerizable liquid crystal compound).

When using the light-diffusion film and antireflection film of this invention as a protective film of a polarizing plate, it is preferable that it is 100-1000 g / m <2> * 24hrs, and, as for a water vapor transmission rate, it is more preferable that it is 300-700g / m <2> * 24hrs.

In the case of film forming, the thickness of the transparent support can be adjusted by a lip flow rate and a line speed, or by stretching and compression. Since moisture permeability differs according to the main material to be used, it is possible to make it a preferable range by adjusting thickness.

In the case of film forming, the free volume of the transparent support can be adjusted by drying temperature and time. Also in this case, since moisture permeability differs according to the main material to be used, it can be set as a preferable range by adjusting a free volume.

Hydrophilicity of the transparent support can be adjusted by an additive. Moisture permeability becomes high by adding a hydrophilic additive in the said free volume, On the contrary, moisture permeability can be made low by adding a hydrophobic additive.

By controlling the moisture permeability independently, it becomes possible to manufacture a polarizing plate having optical compensation ability at low cost and high productivity.

(LCD)

The polarizing plate of this invention can be advantageously used for image display apparatuses, such as a liquid crystal display device, and it is preferable to use for the outermost layer of a display.

The liquid crystal display device has a liquid crystal cell and two polarizing plates arranged on both sides thereof, and the liquid crystal cell carries a liquid crystal between two electrode substrates.

It is preferable that a liquid crystal cell is VA mode.

In the VA mode liquid crystal cell, the rod-like liquid crystal molecules are oriented substantially vertically when no voltage is applied.

The liquid crystal cell of VA mode WHEREIN: (1) The liquid crystal cell of narrow VA mode which aligns rod-shaped liquid crystalline molecules substantially vertically when voltage is not applied, and substantially horizontally when voltage is applied. In addition to 2-176625, (2) a liquid crystal cell (of MVA mode) (SID97, Digest of Tech. Papers (Preliminary Publication) 28 (1997) 845, which multi-domains the VA mode for viewing angle enlargement. ), (3) Liquid crystal cell of mode (n-ASM mode) in which rod-shaped liquid crystalline molecules are substantially vertically aligned when no voltage is applied and twisted multidomain is aligned when voltage is applied (Preliminary Papers of the Japanese Liquid Crystal Discussion Forum, 58-59). (1998)) and (4) a liquid crystal cell of SURVAIVAL mode (presented by LCD International 98).

Next, as a result of earnestly examining in order to achieve the said 3rd objective, this inventor obtained the following knowledge about retardation value.

In other words, the Re retardation value and Rth retardation value are defined by the refractive index in the three-axis direction, and the Re / Rth ratio can be controlled by an additive having a large contribution to the retardation. It was found that the Rth ratio became large and the Re / Rth ratio also increased due to the addition amount. In addition, it was found that the slope of the Re / Rth ratio with respect to the draw ratio was determined by the additive, and the slope was small in the disk-like compound described in European Patent 0911656A2.

In addition, when the optimum Re and Rth values are realized by the tenter stretching method, it is necessary to increase the amount of Re / Rth increase with respect to the draw ratio. Specifically, it is preferable to use an additive having a structure in which the difference between nx and ny tends to be large. As a result of the study, it has been found that it can be achieved by using an aromatic compound having at least two aromatic rings. Among them, it was found that a rod-like compound having at least two aromatic rings and having a linear molecular structure is more preferable.

Moreover, when the functional film which has the optical compensation function mentioned above is applied to a polarizing plate, it turns out that a normal cellulose acylate film in which the outermost layer on the opposite side does not have an antireflective function is easy to be scratched, and this outermost layer is a countermeasure. It turned out that the extent of a wound | wound is reduced by making a protective film into a specific antireflection film.

The said 3rd objective of this invention is achieved by the polarizing plates of following (20)-(36), and the liquid crystal display device of following (37), (38).

<Third aspect>

(20) A polarizing plate in which at least one functional film is disposed on both sides of a polarizing film, wherein at least one of the functional films on one side is composed of only one cellulose acylate film, and the cellulose acylate film is 100 mass of cellulose acylate. Rth Rita which contains 0.01-20 mass parts of aromatic compounds which have an at least 2 aromatic ring with respect to a part, Re Retardation value defined by following formula (I) is 20-70 nm, and is defined by following formula (II) Dation value is 70-400 nm,

At least one sheet of the functional film on the other side is made of an antireflection film having at least one of an anti-glare hard coat layer and a high refractive index layer on a transparent support, and a low refractive index layer.

(I) Re = (nx-ny) × d

(II) Rth = {(nx + ny) / 2-nz} × d

[Wherein, nx is a refractive index in the slow axis direction in the film plane; ny is a refractive index in the fast axis direction in the film plane; nz is a refractive index in the thickness direction of the film; And d is the thickness of the film.]

The film thickness of the said cellulose acylate film is 40 micrometers or more and 70 micrometers or less, The polarizing plate as described in (20) characterized by the above-mentioned.

(22) The polarizing plate according to (20) or (21), wherein the aromatic compound is a rod-like compound having a linear molecular structure.

(23) The polarizing plates according to (20) to (22), wherein the cellulose acylate is cellulose acetate having an acetylation degree of 59.0 to 61.5%.

(24) The said cellulose acylate film was extended | stretched by 3 to 100% of draw ratio, The polarizing plates as described in (20)-(23) characterized by the above-mentioned.

(25) The polarizing plates according to (20) to (24), wherein the Re retardation value of the cellulose acylate film is 40 to 70 nm and the Rth retardation value is 90 to 250 nm.

The polarizing plates as described in (23)-(25) whose Re / Rth change amount per 1% of draw ratios is 0.01 or more and 0.04 or less.

(27) Stretching in the direction orthogonal to the longitudinal direction while conveying in the longitudinal direction in a state where the residual solvent amount of the cellulose acylate film is 2% or more and 30% or less, and the slow axis of the film is orthogonal to the longitudinal direction of the film. The polarizing plate as described in (20)-(26) characterized by having made the direction to say.

(28) The organosilane compound represented by following General formula (1), and / or its hydrolyzate, in the composition for formation of at least any one of an anti-glare hard-coat layer and a low refractive index layer of the said antireflection film, and / Or the partial condensate is contained, The polarizing plate in any one of (20)-(27) characterized by the above-mentioned.

General formula (1): (R ¹⁰ ) _m -Si (X) _4-m

[In General Formula (1), R <^10> represents a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group. X represents a hydroxyl group, an alkoxy group, a halogen atom, a R ² COO group, R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and m represents an integer of 1-3.]

(29) The low refractive index layer of the antireflection film contains at least one kind of silica fine particles, at least one species of the silica fine particles is hollow silica fine particles, and the refractive index of the fine particles is 1.17 to 1.40. The polarizing plate as described in (28).

(30) The polarizing plate according to (20) to (29), wherein the anti-glare hard coat layer of the antireflection film contains particles of a mat and a binder, and a difference in refractive index between the particles of a mat and a binder is 0.03 or more and 0.2 or less. .

(31) The polarizing plates according to (20) to (30), wherein the anti-glare hard coat layer of the antireflection film contains particles of a matt agent having an average particle diameter of 0.5 to 7 µm.

(32) The transparency image transparency of the said antireflection film is 15%-60%, The polarizing plates as described in (20)-(31) characterized by the above-mentioned.

The surface modifier contained in the functional film of the said antireflection film contains a fluoro aliphatic group, The polarizing plates as described in (20)-(32) characterized by the above-mentioned.

(34) The polarizing plates according to (29) to (33), wherein the average particle diameter of at least one species of silica fine particles contained in the low refractive index layer of the antireflection film is 30% or more and 100% or less of the thickness of the low refractive index layer. .

The low refractive index layer of the said antireflection film contains a fluorine-containing polymer, and this fluorine-containing polymer is represented by following General formula (2), The polarizing plates as described in (20)-(34) characterized by the above-mentioned.

[Formula 1]

In general formula (2)

x

60, 5

y

70, 0

z

65 를 만족하는 값을 나타낸다.In General formula (2), L represents a C1-C10 coupling group, m represents 0 or 1. X represents a hydrogen atom or a methyl group. A represents the polymerization unit of arbitrary vinyl monomers, and may be comprised from single component or multiple components. x, y, z represent mole% of each component, 30

x

60, 5

y

70, 0

z

The value satisfying 65 is shown.

(36) The antireflection film is an antireflection film having an antistatic layer, wherein the surface resistivity of the antistatic layer is 10 ¹¹ Ω / □ or less (25 ° C., 60% RH), and the haze is 20% or less. The polarizing plate as described in (20)-(35).

(37) The polarizing plate of any one of (20)-(36) is used for the outermost surface of a liquid crystal display device, The liquid crystal display device characterized by the above-mentioned.

(38) The liquid crystal display device according to (37), wherein the liquid crystal cell of the liquid crystal display device is a liquid crystal cell in VA mode or TN mode.

The polarizing plate of the third aspect of the present invention is excellent in both the optical compensation function and the antireflection function without increasing the number of constituents of the polarizing plate, and can exhibit an effect that the surface scars are not particularly noticeable when thinned. have. And the liquid crystal display device provided with the polarizing plate of this invention has a wide viewing angle of a favorable screen, few reflections of an external light source and a background, and is highly visible.

Hereinafter, the polarizing plate of the 3rd aspect of this invention is demonstrated in detail.

The polarizing plate of this invention is a polarizing plate formed by arrange | positioning the polarizing film and at least 1 functional film in the both sides, respectively, At least one functional film of the functional film of one side consists only of a specific cellulose acylate film, and the function of the other side The film is characterized by consisting of a specific antireflection film.

Hereinafter, after first explaining the functional film on one side, the functional film and the polarizing plate on the other side will be described in order.

<About functional film of one side>

The functional film of one side consists only of the cellulose acylate film with which at least 1 functional film was specified.

[Retardation of Film]

In this specification, Re retardation value and Rth retardation value of each film are defined by following formula (I) and (II), respectively.

(I) Re = (nx-ny) × d

(II) Rth = {(nx + ny) / 2-nz} × d

In Formula (I) and (II), nx is the refractive index of the slow axis direction (direction in which a refractive index becomes largest) in a film plane. In formula (I) and (II), ny is the refractive index of the fast-axis axis direction (the direction which refractive index becomes minimum) in a film plane. In Formula (II), nz is the refractive index of the thickness direction of a film. In formula (I) and (II), d is the thickness of the film which makes a unit nm.

And Re Retardation value of the said specific cellulose acylate film is 20 nm or more and 70 nm or less, Preferably it is 40-70 nm, And Rth retardation value is 70 nm or more and 400 nm or less, Preferably 90-250 nm. If the Re retardation value is less than 20 nm or exceeds 70 nm, the optical compensation performance is lowered. If the Rth retardation value is also less than 70 nm or more than 400 nm, the optical compensation performance is lowered. These can be adjusted by the kind, addition amount, and draw ratio of the aromatic compound contained in a cellulose acylate. In this way, the cellulose acylate film with optical anisotropy can be obtained.

Specifically, it is preferable to stretch the cellulose acylate film at a draw ratio of 3 to 100% in order to obtain each retardation value described above.

Although the stretching method is not particularly limited, it can be carried out by tenter stretching or the like.

As for Re / Rth change amount per 1% of draw ratios, 0.01 or more and 0.04 or less are preferable.

In addition, the residual solvent amount of the cellulose acetate film at the time of extending | stretching is 2% or more and 30% or less, extending | stretching in the direction orthogonal to a longitudinal direction, conveying in the longitudinal direction in that state, and the slow axis of the film is a longitudinal direction of the film. Stretching in the direction orthogonal to is preferable to obtain a retardation value.

When using two optically anisotropic cellulose acylate films for a liquid crystal display device, it is preferable that the Rth retardation value of a film is 70-200 nm. When using one optically anisotropic cellulose acylate film for a liquid crystal display device, it is preferable that the Rth retardation value of a film is 150-400 nm.

Moreover, it is preferable that birefringence ((DELTA) n: nx-ny) of a cellulose acylate film exists in the range of 0.00025-0.00088. Moreover, it is preferable that birefringence {(nx + ny) / 2-nz} of the thickness direction of a cellulose acylate film is 0.00088-0.005.

The raw material component of the said cellulose acylate film is demonstrated.

[Cellulose Acylate Film]

The raw material surface of the cellulose acylate used for this invention can use a well-known raw material, and can also synthesize | combine synthesis by a well-known method. For example, the raw material described in p.180-190 of the "Wood chemistry" (Kyoritsu Publication, 1968) p.180-190, etc. are mentioned. As for the viscosity average polymerization degree of a cellulose acylate, 200-700 are preferable, 250-500 are more preferable, 250-350 are the most preferable. Moreover, it is preferable that the cellulose ester used for this invention has a narrow molecular weight distribution of Mw / Mn (Mw is a weight average molecular weight, Mn is a number average molecular weight) by gel permeation chromatography. As a specific value of Mw / Mn, it is preferable that it is 1.5-5.0, It is more preferable that it is 2.0-4.5, It is most preferable that it is 3.0-4.0.

It is preferable to use an acetyl group, a propionyl group, butyryl group, and the acyl group of a cellulose acylate film may have a plurality of acyl groups selected from these, and an acetyl group is especially preferable. As for the substitution degree of all the acyl groups, 2.7-3.0 are preferable and 2.8-2.95 are more preferable. Substitution degree of the acyl group in this invention measures the binding degree of the fatty acid couple | bonded with the hydroxyl group in cellulose, and is obtained by calculation. As a measuring method, it can measure based on ASTM-D-817-91 and ASTM-D-817-96.

In addition, the substitution state of the acyl group with respect to a hydroxyl group is measured by ¹³ C NMR method.

It is most preferable that an acyl group is an acetyl group, When using the cellulose acetate whose acyl group is an acetyl group, 59.0-62.5% of an acetylation degree is preferable, and 59.0-61.5% are more preferable. When the acetylation degree is in this range, Re does not become larger than a desired value by the conveyance tension at the time of casting | flow_spread, and there are few in-plane deviations, and a retardation value changes little by greenhouse degree.

As for the substitution degree of the acyl group of a 6-position, 0.9 or more are preferable from a viewpoint of suppressing the dispersion | variation of Re and Rth.

[Aromatic Compounds Having at least Two Aromatic Rings]

In this invention, in order to adjust the retardation of a cellulose acylate film, the aromatic compound which has at least 2 aromatic ring is used as a retardation increasing agent. An aromatic compound is used in 0.01-20 mass parts with respect to 100 mass parts of cellulose acylates. It is preferable to use an aromatic compound in the range of 0.05-15 mass parts with respect to 100 mass parts of cellulose acylate, and it is more preferable to use in the range which is 0.1-10 mass parts.

Even when the usage-amount of an aromatic compound is less than 0.01 mass part or exceeds 20 mass parts, optical compensation performance is inferior.

You may use together 2 or more types of aromatic compounds. The aromatic ring of the aromatic compound includes an aromatic heterocyclic ring in addition to the aromatic hydrocarbon ring.

The aromatic hydrocarbon ring is particularly preferably 6 membered rings (ie, benzene rings). It is preferable that an aromatic heterocyclic ring is 5-membered ring, 6-membered ring, or 7-membered ring, and it is more preferable that it is 5-membered ring or 6-membered ring. As a hetero atom, a nitrogen atom, an oxygen atom, and a sulfur atom are preferable, and a nitrogen atom is especially preferable.

Examples of aromatic heterocycles include furango, thiophene, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazol ring, imidazole ring, pyrazole ring, furazan ring and triazole. Ring, pyran ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring and 1,3,5-triazine ring.

As the aromatic ring, a benzene ring, a furango ring, a thiophene ring, a pyrrole ring, an oxazole ring, a thiazole ring, an imidazole ring, a triazole ring, a pyridine ring, a pyrimidine ring, a pyrazine ring, and 1,3, 5-triazine ring is preferred, and benzene ring and 1,3,5-triazine ring are more preferred. It is particularly preferable that the aromatic compound has at least one 1,3,5-triazine ring.

It is preferable that the number of the aromatic rings which an aromatic compound has is 2-20, It is more preferable that it is 2-12, It is further more preferable that it is 2-8, It is most preferable that it is 2-6.

The bonding relationship of each aromatic ring can be classified into (a) forming a condensed ring, (b) directly connecting to a single bond, and (c) bonding through a linking group (because of aromatic rings, spiro bonding Cannot form). The coupling relationship may be any of (a) to (c). That is, as said aromatic compound used in this invention, the compound which each said aromatic ring condensed and formed the condensed ring, the compound in which each said aromatic ring was directly connected by the single bond, and the coupling group which each said aromatic ring mentions later The compound which is couple | bonded through is mentioned.

Examples of the condensed ring of (a) (condensed ring of two or more aromatic rings), that is, the aromatic compound formed by forming the condensed ring include indene ring, naphthalene ring, azulene ring, fluorene ring, phenanthrene ring, anthracene Ring, acenaphthylene ring, naphthacene ring, pyrene ring, indole ring, isoindole ring, benzofuran ring, benzothiophene ring, indoligin ring, benzoxazole ring, benzothiazol ring, benzoimidazol ring, benzo Triazole ring, purine ring, indazole ring, chromen ring, quinoline ring, isoquinolin ring, quinodine ring, quinazoline ring, cinnoline ring, quinoxaline ring, phthalazine ring, pteridine ring, carbazole Ring, acridine ring, phenanthridine ring, xanthene ring, phenazine ring, phenothiazine ring, phenoxatin ring, phenoxazine ring and thianthrene ring. Among these, naphthalene ring, azulene ring, indole ring, benzoxazole ring, benzothiazole ring, benzoimidazole ring, benzotriazole ring and quinoline ring are preferable.

It is preferable that the single bond of (b) is a bond between carbon atoms of two or more aromatic rings. Two aromatic rings may be bonded to two or more single bonds, and an aliphatic ring or a non-aromatic heterocycle may be formed between the two aromatic rings.

It is preferable that the linking group of (c) couple | bonds with the carbon atom of two aromatic rings. The linking group is preferably an alkylene group, an alkenylene group, an alkynylene group, -CO-, -O-, -NH-, -S-, or a combination thereof. The alkylene group may have a cyclic structure. As the cyclic alkylene group, cyclohexylene is preferable and 1,4-cyclohexylene is particularly preferable. It is preferable that it is a linear structure which is not branched by a linear alkylene group. 1-20 are preferable and, as for the carbon atom number of an alkylene group, 1-8 are more preferable. The alkenylene group and the alkynylene group preferably have a chain structure rather than a cyclic structure, and preferably have a non-branched linear structure. It is preferable that it is 2-10, and, as for carbon number of an alkenylene group and an alkynylene group, it is more preferable that it is 2-4.

An example of a connector made of a combination is shown below. In addition, the left-right relationship of the example of the following coupler may be reversed.

c1: -CO-O-

c2: -CO-NH-

c3: -alkylene-O-

c4: -NH-CO-NH-

c5: -NH-CO-O-

c6: -O-CO-O-

c7: -O-alkylene-O-

c8: -CO-alkenylene-

c9: -CO-alkenylene-NH-

c10: -CO-alkenylene-0-

c11: -alkylene-CO-O-alkylene-0-CO-alkylene-

c12: -O-alkylene-CO-O-alkylene-O-CO-alkylene-O-

c13: -O-CO-alkylene-CO-O-

c14: -NH-CO-alkenylene-

c15: -O-CO-alkenylene

The aromatic ring and the linking group may have a substituent. Examples of the substituent include halogen atom (F, Cl, Br, I), hydroxyl, carboxyl, cyano, amino, nitro, sulfo, carbamoyl, sulfamoyl, ureido, alkyl group, alkenyl group, alkynyl group, Aliphatic acyl group, aliphatic acyloxy group, alkoxy group, alkoxycarbonyl group, alkoxycarbonylamino group, alkylthio group, alkylsulfonyl group, aliphatic amide group, aliphatic sulfonamide group, aliphatic substituted amino group, aliphatic substituted carbamoyl group, aliphatic substituted alcohol Pamoyl groups, aliphatic substituted ureido groups and non-aromatic heterocyclic groups are included.

It is preferable that carbon number of an alkyl group is 1-8. A chain alkyl group is more preferable than a cyclic alkyl group, and a linear alkyl group is especially preferable. The alkyl group may further have a substituent (for example, hydroxyl, carboxyl, alkoxy group, alkyl substituted amino group). Examples of the alkyl group (including substituted alkyl groups) include methyl, ethyl, n-butyl, n-hexyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxyethyl and 2-diethylaminoethyl .

* It is preferable that carbon number of an alkenyl group is 2-8. The chain alkenyl group is more preferable than the cyclic alkenyl group, and a linear alkenyl group is particularly preferable. The alkenyl group may further have a substituent. Examples of alkenyl groups include vinyl, allyl and 1-hexenyl.

It is preferable that the carbon atom number of an alkynyl group is 2-8. A chain alkynyl group is more preferable than a cyclic alkynyl group, and a linear alkynyl group is especially preferable. The alkynyl group may further have a substituent. Examples of the alkynyl group include ethynyl, 1-butynyl and 1-hexynyl.

The number of carbon atoms of the aliphatic acyl group is preferably 1 to 10. Examples of aliphatic acyl groups include acetyl, propanoyl and butanoyl.

The aliphatic acyloxy group preferably has 1 to 10 carbon atoms. Examples of aliphatic acyloxy groups include acetoxy.

It is preferable that the number of carbon atoms of an alkoxy group is 1-8. The alkoxy group may further have a substituent (for example, an alkoxy group). Examples of the alkoxy group (including a substituted alkoxy group) include methoxy, ethoxy, butoxy and methoxyethoxy.

The number of carbon atoms of the alkoxycarbonyl group is preferably 2 to 10. Examples of the alkoxycarbonyl group include methoxycarbonyl and ethoxycarbonyl.

The number of carbon atoms of the alkoxycarbonylamino group is preferably 2 to 10. Examples of the alkoxycarbonylamino group include methoxycarbonylamino and ethoxycarbonylamino.

The number of carbon atoms of the alkylthio group is preferably 1 to 12. Examples of the alkylthio group include methylthio, ethylthio and octylthio. It is preferable that the carbon atom number of an alkylsulfonyl group is 1-8.

Examples of alkylsulfonyl groups include methanesulfonyl and ethanesulfonyl.

The number of carbon atoms of the aliphatic amide group is preferably 1 to 10. Examples of aliphatic amide groups include acetamide.

The aliphatic sulfonamide group preferably has 1 to 8 carbon atoms. Examples of aliphatic sulfonamide groups include methanesulfonamide, butanesulfonamide and n-octanesulfonamide.

It is preferable that carbon number of an aliphatic substituted amino group is 1-10. Examples of the aliphatic substituted amino group include dimethylamino, diethylamino and 2-carboxyethylamino.

It is preferable that the carbon atom number of an aliphatic substituted carbamoyl group is 2-10. Examples of the aliphatic substituted carbamoyl group include methylcarbamoyl and diethylcarbamoyl.

It is preferable that carbon number of the aliphatic substituted sulfamoyl group is 1-8. Examples of aliphatic substituted sulfamoyl groups include methylsulfamoyl and diethylsulfamoyl. It is preferable that the carbon atom number of an aliphatic substituted ureido group is 2-10.

Examples of aliphatic substituted ureido groups include methylureido.

Examples of nonaromatic heterocyclic groups include piperidino and morpholino.

As said aromatic compound, the rod-shaped compound which has a molecular structure in which a molecular structure is linear among the above-mentioned examples is preferable. Linear molecular structure means linear in the thermodynamic most stable structure. The most thermodynamically stable structure can be obtained by crystal structure analysis or molecular orbital calculation. For example, the molecular orbital calculation software (for example, WinMOPAC 2000, manufactured by Fujitsu Co., Ltd.) can be used to calculate the molecular orbital to obtain the structure of the molecule in which the heat of production of the compound is the smallest. The linear molecular structure means that the angle of the molecular structure is 140 degrees or more in the thermodynamic most stable structure obtained by calculation as described above.

Specific examples of the aromatic compound having at least two aromatic rings include, but are not limited to, the following compounds.

[Formula 2]

(3)

[Formula 4]

[Chemical Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Chemical Formula 9]

[Formula 10]

[Formula 11]

[Chemical Formula 12]

[Chemical Formula 13]

It is preferable that the molecular weight of a retardation increasing agent is 300-800.

[Production of Cellulose Acylate Film]

It is preferable to use the method of patent document 4 about manufacture of a cellulose acylate film. For example, the solution preparation, the casting method, the plasticizer, the deterioration inhibitor, etc. are also described in patent document 4, and it is preferable to use this method and a raw material. The draw ratio is 3 to 100%, preferably 5 to 80%.

As for the stretching method, tenter stretching is preferably used from the viewpoint of in-plane uniformity. An extending | stretching process may be performed in the middle of a film forming process, and you may extend | stretch the disk wound up by film forming. In the former case, you may extend | stretch in the state containing a residual solvent, and a residual solvent is extended | stretched to 2 to 35%, Preferably it is 2 to 30%.

30-140 micrometers is preferable, as for the film thickness of the said cellulose acylate film, 40-90 micrometers is more preferable, 40-70 micrometers is still more preferable.

About the surface treatment of a cellulose acylate film, the alkali saponification process mentioned later in <the functional film of the other side> is mentioned. Moreover, the method described in patent document 4 [surface treatment of a cellulose acetate film] can also be used.

In the present invention, the above-described functional film on one side may be formed only by a functional film made of only the cellulose acylate film, or may be formed by overlapping the film with another functional film. As said other functional film, the retardation change film of the said cellulose acylate film, the cellulose acylate film of a normal blank, etc. are mentioned, for example.

<About the functional film of the other side>

Next, the functional film on the other side will be described.

The said other side functional film | membrane consists of the antireflection film in which the at least 1 functional film was specified. The specific antireflection film is a film having at least one of an antiglare hard coat layer, a hard coat layer having no antiglare property, a medium refractive index layer or a high refractive index layer and a low refractive index layer. The hard-coat layer which does not have anti-glare property may be a light-diffusion layer. It is also preferable to form an antistatic layer between the transparent support and the hard coat layer. One layer may be sufficient as a hard-coat layer, and two or four layers may be sufficient as it. The low refractive index layer is coated and formed as the outermost layer.

It demonstrates with reference to the basic structure of the antireflection film preferable as one Embodiment of this invention.

5 and 6 are cross-sectional views schematically showing the structure of the antireflection film.

The antireflection film 31 schematically shown in FIG. 5 includes the antiglare hard coat layer 34 formed on the transparent support 32, the hard coat layer 33 formed on the transparent support, and the hard coat layer 33. And the low refractive index layer 35 formed as the outermost layer. Matte particles 36 are dispersed in the anti-glare hard coat layer 34. The hard coat layer of reference 33 is not necessarily required, and the anti-glare hard coat layer 34 may be provided directly on the transparent support 32. The medium refractive index layer 37 and the high refractive index layer 38 may be formed on the anti-glare hard coat layer 34 in the same manner as in FIG. 6.

The antireflective film typically shown in FIG. 6 includes a hard support layer 33 formed on the transparent support 32, a hard support layer 36, and a medium refractive index layer 37 formed on the hard coat layer 33. It consists of the high refractive index layer 38 formed on the refractive index layer 37, and the low refractive index layer 35 formed as outermost layer.

It is also preferable to form an antistatic layer under the hard coat layer. The transparent support 32, the medium refractive index layer 37, the high refractive index layer 38, and the low refractive index layer 35 have a refractive index which satisfies the following relationship.

Refractive Index of High Refractive Index Layer> Refractive Index of Middle Refractive Index Layer> Refractive Index of Transparent Support> Refractive Index of Low Refractive Index Layer

In the layer structure like FIG. 6, it is preferable that it is an antireflection film which satisfy | fills the conditions described in Unexamined-Japanese-Patent No. 59-50401, and it is more preferable to satisfy the following conditions.

In each condition, the medium refractive index layer is represented by the following formula (III), the high refractive index layer by the following formula (IV), and the low refractive index layer by the following formula (V).

Is 500 nm, h is 1, i is 2, j is 1.

Equation (Ⅲ)

(hλ / 4) × 0.80 <n _l d _l <(hλ / 4) × 1.00

Equation (Ⅳ)

* (iλ / 4) × 0.75 <n ₂ d ₂ <(iλ / 4) × 0.95

Equation (Ⅴ)

(jλ / 4) × 0.95 <n ₃ d ₃ <(jλ / 4) × 1.05

The high refractive index, the medium refractive index, and the low refractive index described herein refer to the height of the relative refractive index between the layers. In addition, in FIG. 6, the high refractive index layer is used as an optical interference layer, and the antireflection film which has the very outstanding antireflection performance can be manufactured.

In addition, the hard coat layer in the antireflection film shown in FIG. 6 may be a hard coat layer having no anti-glare property, or may be an anti-glare hard coat layer.

[Organosilane compound and / or its hydrolyzate and / or its subcondensate]

The anti-glare hard coat layer and the low refractive index layer which comprise the antireflection film of this invention are the organosilane compound and / or its hydrolyzate, and / or its in the coating liquid which forms this layer in at least one layer. It is preferable from the viewpoint of abrasion resistance to contain a partial condensate and what is called a sol component (it calls it hereafter). In particular, it is preferable to contain an organosilane compound, its hydrolyzate and / or its partial condensate in the liquid for the low refractive index layer in order to achieve both antireflection performance and scratch resistance. It is preferable to contain a silane compound, its hydrolyzate, and / or its subcondensate, or a mixture thereof. This sol component condenses in a drying and heating process after apply | coating a coating liquid, forms a hardened | cured material, and becomes the binder of the said layer. In addition, when the hardened | cured material has a polymerizable unsaturated bond, the binder which has a three-dimensional structure is formed by irradiation of actinic light.

It is preferable that an organosilane compound is represented by following General formula (1).

Formula (1) (R ¹⁰ ) _m -Si (X) _4-m

In the said General formula (1), R <^10> represents a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, hexyl, decyl, hexadecyl and the like. The alkyl group is preferably 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples of the aryl group include phenyl and naphthyl, and are preferably phenyl groups.

X represents a hydroxyl group or a hydrolyzable group, and as the hydrolyzable group, for example, an alkoxy group (an alkoxy group having 1 to 5 carbon atoms is preferable. For example, a methoxy group, an ethoxy group, and the like), a halogen atom (Eg, Cl, Br, I, etc.), and R ² COO (R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. For example, CH ₃ COO, C ₂ H ₅ COO, etc. may be mentioned.) The group represented by is mentioned, Preferably it is an alkoxy group, Especially preferably, it is a methoxy group or an ethoxy group.

m represents the integer of 1-3, Preferably it is 1 or 2, Especially preferably, it is 1.

Or R ¹⁰ X in the presence of the plurality, a plurality of R ¹⁰ or X may be the same or different, respectively.

The substituent contained in R ¹⁰ is not particularly limited, but may be a halogen atom (fluorine, chlorine, bromine, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (methyl, ethyl, i-propyl, propyl, t-butyl, etc.). ), Aryl groups (phenyl, naphthyl, etc.), aromatic heterocyclic groups (furyl, pyrazolyl, pyridyl, etc.), alkoxy groups (methoxy, ethoxy, i-propoxy, hexyloxy, etc.), aryloxy ( Phenoxy, etc.), alkylthio groups (methylthio, ethylthio, etc.), arylthio groups (phenylthio, etc.), alkenyl groups (vinyl, 1-propenyl, etc.), acyloxy groups (acetoxy, acryloyloxy, Methacryloyloxy, etc.), alkoxycarbonyl groups (methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl groups (phenoxycarbonyl, etc.), carbamoyl groups (carbamoyl, N-methylcarbamoyl, N , N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl, etc., acylamino groups (acetylamino, benzoylamino, acrylami , There may be mentioned methacrylic amino, etc.), these substituents may be further substituted.

The compound of General formula (1) may use two or more types together. Although the specific example of a compound represented by General formula (1) below is shown, it is not limited.

[Formula 14]

[Formula 15]

Among these, (M-1), (M-2), and (M-5) are especially preferable.

The hydrolyzate and / or partial condensate of the organosilane compound used in the present invention will be described in detail.

The hydrolysis reaction and / or condensation reaction of the organosilane are generally carried out in the presence of a catalyst. As a catalyst, Inorganic acids, such as hydrochloric acid, a sulfuric acid, nitric acid; Organic acids such as oxalic acid, acetic acid, formic acid, methanesulfonic acid and toluenesulfonic acid; Inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia; Organic bases such as triethylamine and pyridine; Metal alkoxides such as triisopropoxy aluminum and tetrabutoxy zirconium; And metal chelate compounds having a metal such as Zr, Ti, or Al as the center metal.

Although the hydrolysis and condensation reaction of the organosilane can be carried out in a solvent or without a solvent, it is preferable to use an organic solvent in order to uniformly mix the components. For example, alcohols, aromatic hydrocarbons, ethers , Ketones, esters and the like are preferred.

0.3 to 2 moles, preferably 0.5 to 1 mole of water, is added to 1 mole of the hydrolyzable group of the organosilane, at 25 to 100 ° C. in the presence or absence of the solvent and in the presence of a catalyst. It is performed by stirring.

In the present invention, the general formula of R ³ OH (wherein, R ³ is an alkyl group of 1 to 10 carbon atoms) and an alcohol represented by formula R ⁴ COCH ₂ COR ⁵ (formula, R ⁴ is a group of 1 to 10 carbon atoms At least one metal chelate compound having as its core metal a metal selected from Zr, Ti or Al as a ligand, an alkyl group and R ⁵ representing an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms It is preferable to hydrolyze by stirring at 25-100 degreeC in presence of.

The metal chelate compound is an alcohol represented by general formula R ³ OH (wherein R ³ represents an alkyl group having 1 to 10 carbon atoms) and general formula R ⁴ COCH ₂ COR ⁵ (wherein R ⁴ represents 1 to 10 carbon atoms). The alkyl group, R ⁵ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms) is preferably a central metal having a metal selected from Zr, Ti or Al as a ligand, without particular limitation. Can be used. If it is this category, you may use together 2 or more types of metal chelate compounds. Specific examples of the metal chelate compound used in the present invention include tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium and n-butoxytris (ethylacetoacetate) zirconium Zirconium chelate compounds such as tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium and tetrakis (ethylacetoacetate) zirconium; Titanium chelate compounds such as diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium and diisopropoxy bis (acetylacetone) titanium; Diisopropoxyethylacetoacetate aluminum, diisopropoxyacetylacetate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetyl Aluminum chelate compounds such as acetonate) aluminum and monoacetylacetonate bis (ethylacetoacetate) aluminum.

Among these metal chelate compounds, tri-n-butoxyethylacetoacetate zirconium, diisopropoxy bis (acetylacetonate) titanium, diisopropoxyethylacetoacetate aluminum, and tris (ethylacetoacetate) aluminum are preferred. These metal chelate compounds can be used individually by 1 type or in mixture of 2 or more types. Moreover, the partial hydrolyzate of these metal chelate compounds can also be used.

The metal chelate compound of the present invention is preferably 0.01 to 50% by mass, more preferably 0.1 to 50% by mass, and more preferably to organosilane, from the viewpoint of the rate of condensation reaction and the film strength when the coating film is used. Preferably it is used in the ratio of 0.5-10 mass%.

In addition to the composition containing the hydrolyzate and / or partial condensate and the metal chelate compound of the organosilane compound, the coating liquid of the anti-glare hard coat layer to the low refractive index layer used in the present invention, It is preferable that the / -ketoester compound is added.

It is used in the present invention represented by the general formula R ⁴ COCH ₂ COR ^5, and β- diketone compound and / or β- keto ester compound represented by, for formation of the room overt hard coat layer or low refractive index layer used in the present invention It acts as a stability enhancer of the composition. Here, R <^4> represents a C1-C10 alkyl group, R <^5> represents a C1-C10 alkyl group or a C1-C10 alkoxy group. R ⁴ and R ⁵ constituting the β-diketone compound and / or β-ketoester compound are the same as R ⁴ and R ⁵ constituting the metal chelate compound.

Specific examples of the β-diketone compound and / or β-ketoester compound include acetylacetone, methyl acetoacetate, acetoacetic acid, acetoacetic acid-n-propyl, acetoacetic acid-i-propyl, acetoacetic acid-n- Butyl, acetoacetic acid-sec-butyl, acetoacetic acid-t-butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2, 4-nonane-dione, 5-methyl- hexane-dione, etc. are mentioned. Among these, ethyl acetoacetate and acetylacetone are preferable, and acetylacetone is particularly preferable. These β-diketone compounds and / or β-ketoester compounds may be used alone or in combination of two or more thereof. In the present invention, the β-diketone compound and / or the β-ketoester compound are preferably 2 moles or more, more preferably 3 to 20 moles, per 1 mole of the metal chelate compound. If it is less than 2 mol, the storage stability of the composition obtained may fall, and it is not preferable.

The hydrolyzate and / or partial condensate of the organosilane compound is preferably less in the case of the surface layer which is a relatively thin film, and more preferably in the case of the lower layer which is a thick film. In the case of the surface layer like a low refractive index layer, 0.1-50 mass% of the total solid of a containing layer (addition layer) is preferable, 0.5-20 mass% is more preferable, and 1-10 mass% is the most preferable.

0.001-50 mass% of the total solid of a containing layer (addition layer) is preferable, as for the addition amount with respect to layers other than a low refractive index layer, 0.01-20 mass% is more preferable, 0.05-10 mass% is still more preferable, 0 1-5 mass% is especially preferable.

In the present invention, first, a composition containing a hydrolyzate and / or partial condensate and a metal chelate compound of the organosilane compound is prepared, and a liquid to which a β-diketone compound and / or a β-ketoester compound is added thereto. Is preferably contained in the coating liquid of at least one of the hard coat layer and the low refractive index layer to form the coating.

5-100 mass% is preferable, as for the usage-amount of the sol component of the organosilane with respect to a fluorine-containing polymer in a low refractive index layer, 5-40 mass% is more preferable, 8-35 mass% is more preferable, 10 30 mass% is especially preferable. If the amount is small, the effect of the present invention is hardly obtained. If the amount is too large, the refractive index increases or the shape and surface shape of the film deteriorate.

[Inorganic fine particles which can be contained in low refractive index layer]

Next, the inorganic fine particles which can be contained in the low refractive index layer of this invention are described.

The coating formation amount of the inorganic fine particles is preferably 1 mg / m 2 to 100 mg / m 2, more preferably 5 mg / m 2 to 80 mg / m 2, still more preferably 10 mg / m 2 to 60 mg / m 2. When too small, the effect of improving scratch resistance decreases, and when too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance and integral reflectance such as black reproducibility may deteriorate. .

The inorganic fine particles are preferably low refractive index in that they are contained in the low refractive index layer. For example, the fine particle of magnesium fluoride and a silica is mentioned. In particular, silica fine particles are preferable in view of refractive index, dispersion stability, and cost. The average particle diameter of the silica fine particles is preferably 20% or more and 150% or less of the thickness of the low refractive index layer, more preferably 30% or more and 100% or less, still more preferably 40% or more and 60% or less. That is, when the thickness of the low refractive index layer is 100 nm, the particle diameter of the silica fine particles is preferably 20 nm or more and 150 nm or less, more preferably 30 nm or more and 100 nm or less, still more preferably 40 nm or more and 60 nm or less. .

When the particle diameter of the silica fine particles is too small, the effect of improving the scratch resistance is small. When the particle size of the silica fine particles is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance and integration reflectance of black reproducibility may deteriorate. It is desirable to. The silica fine particles may be crystalline or amorphous, may be monodisperse particles, or agglomerated particles may be used as long as the particle size is satisfied. Although spherical shape is most preferable, even if it is an indefinite shape, there is no problem.

Herein, the average particle diameter of the inorganic fine particles is measured by a Coulter counter.

In order to reduce the refractive index increase of the low refractive index layer, it is preferable to use hollow silica fine particles, and the hollow silica fine particles preferably have a refractive index of 1.17 to 1.40, more preferably 1.17 to 1.35, and more preferably 1.17. It is -1.30. The refractive index here shows the refractive index as the whole particle | grain, and does not show the refractive index only of the outer silica which forms hollow silica particle. At this time, if the radius of the voids in the particle is a and the radius of the particle outer shell is b, the porosity x is expressed by the following formula (i).

(Formula Ⅷ)

^{x = (4πa 3/3)} / (4πb 3/3) × 100

The porosity x is preferably 10 to 60%, more preferably 20 to 60%, most preferably 30 to 60%.

When the hollow silica particles are made to have a lower refractive index and a larger porosity, the outer shell becomes thinner and weaker as the particle strength. Therefore, particles having a low refractive index of less than 1.17 are not established from the viewpoint of scratch resistance.

In addition, the refractive index of these hollow silica particles was measured with the Abbe refractometer (made by Atago Co., Ltd.).

Moreover, at least 1 sort (s) of silica microparticles | fine-particles (referred to as "microparticles of a small size particle size") whose average particle diameter is less than 25% of the thickness of a low refractive index layer are called silica microparticles | fine-particles of the said particle size ("silica microparticles | fine-particles of a large size particle size") It is also preferable to use together.

Since the silica fine particles having a small size particle size may exist in the gaps between the silica fine particles having a large size particle size, the silica fine particles can contribute as a retainer for the silica fine particles having a large size particle size.

When the low refractive index layer is 100 nm, 1 nm or more and 20 nm or less are preferable, as for the average particle diameter of the silica fine particle of small size particle size, 5 nm or more and 15 nm or less are more preferable, 10 nm or more and 15 nm or less are especially preferable. . The use of such silica fine particles is preferable in view of raw material cost and fat and oil effect.

When using together the silica particle of large size particle size and the silica particle of small size particle size, it is preferable to use within 100 mass parts with respect to 100 mass parts of silica particle of large size particle diameter.

Silica fine particles are used in physical surface treatments such as plasma discharge treatment, corona discharge treatment, surfactants, coupling agents, etc., in order to stabilize dispersion or enhance affinity and binding properties with binder components in dispersion liquids or coating liquids. Chemical surface treatment may be performed. The use of a coupling agent is particularly preferred. As a coupling agent, an alkoxy metal compound (for example, a titanium coupling agent and a silane coupling agent) is used preferably. Especially, a silane coupling process is especially effective.

The coupling agent is a surface treatment agent of the inorganic filler of the low refractive index layer, and is used for surface treatment in advance before preparation of the layer coating liquid, but is preferably added as an additive during preparation of the layer coating liquid and contained in the layer. Do.

It is preferable for the silica fine particles to be previously dispersed in the medium before surface treatment in order to reduce the load on the surface treatment.

The above description about the silica fine particles also applies to other inorganic fine particles.

[Surface Modifier]

In this invention, a fluoro aliphatic group containing polymer (henceforth simply a "fluorine-type polymer") can be used as a surface modifier for the functional layer in the functional film of an antireflection film. Hereinafter, the fluoro aliphatic group containing monomer which is a formation material of the fluoro aliphatic group containing polymer used for this invention is demonstrated.

The functional layer in the present invention may be either an optical functional layer or a physical functional layer, and examples of the optical functional layer include a high refractive index layer and a light diffusing layer, and examples of the physical functional layer include a hard coat layer and the like. The layer which also serves as both functional layers may be used, for example, an anti-glare hard coat layer and the like.

The amount of the fluoroaliphatic group-containing monomer used in the present invention is 50 mol% or more, preferably 70-100 mol%, more preferably 80-100 mol% based on each monomer of the fluorine-based polymer. .

As for the preferable mass mean molecular weight of the fluoro aliphatic group containing polymer used by this invention, 3,000-100,000 are preferable, 6,000-80,000 are more preferable, 8,000-60,000 are further more preferable.

In addition, the preferable addition amount of the fluoro aliphatic group containing polymer used by this invention is the range of 0.001-5 mass% with respect to a coating liquid, Preferably it is the range of 0.005-3 mass%, More preferably, it is 0.01-1 mass Range of%. If the amount of the fluorine-based polymer added is less than 0.001% by mass, the effect is insufficient. If the amount of the fluorine-based polymer is more than 5% by mass, drying of the coating film may be insufficient, or surface failure may occur.

The example of the specific structure of the fluoro aliphatic group containing polymer contained in the functional layer of this invention is shown. In addition, the number in a formula shows the molar ratio of each monomer component. Mw represents the mass average molecular weight.

[Chemical Formula 16]

[Chemical Formula 17]

Next, each layer which comprises the antireflection film of this invention is demonstrated.

[Hard Coat Layer]

The hard coat layer is a so-called smooth hard coat layer that is not anti-glare and used for imparting physical strength to the antireflection film, and as shown in FIGS. 1 and 2, the surface of the transparent support, in particular the transparent support and the It is preferable to form between an anti-glare hard coat layer, a transparent support and a light-diffusion layer, and a transparent support and a high refractive index layer.

The hard coat layer is preferably formed by a crosslinking reaction or an polymerization reaction of the ionizing radiation curable compound. For example, it can form by apply | coating the coating composition containing an ionizing radiation curable polyfunctional monomer and a polyfunctional oligomer on a transparent support body, and carrying out a crosslinking reaction or a polymerization reaction of a polyfunctional monomer and a polyfunctional oligomer.

As a functional group of an ionizing radiation curable polyfunctional monomer or a polyfunctional oligomer, a thing of light, an electron beam, and a radiation polymerizable thing is preferable, and a photopolymerizable functional group is especially preferable. As a photopolymerizable functional group, unsaturated polymerizable functional groups, such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group, etc. are mentioned, Especially, a (meth) acryloyl group is preferable. As a specific example of a polyfunctional monomer, the polyfunctional monomers of Unexamined-Japanese-Patent No. 2003-4903 are mentioned.

In addition, the hard coat layer preferably contains inorganic fine particles having an average particle diameter of 200 nm or less. The average particle diameter here is a mass average diameter. By making the average particle diameter of a primary particle 200 nm or less, the hard-coat layer which does not impair transparency can be formed.

As inorganic fine particles, fine particles such as silicon dioxide, aluminum oxide, calcium carbonate, barium sulfate, talc, kaolin, calcium sulfate, titanium dioxide, zirconium oxide, tin oxide, ITO, and zinc oxide are added to the inorganic fine particles exemplified in the high refractive index layer. Can be mentioned. Preferably, silicon dioxide, titanium dioxide, zirconium oxide, aluminum oxide, tin oxide, ITO, zinc oxide.

The preferred average particle diameter of the primary particles of the inorganic fine particles and the average particle diameter of the actual dispersed particles in the hard coat layer are the same as those of the later high refractive index layer. The content of the inorganic fine particles in the hard coat layer is preferably 10 to 90 mass%, more preferably 15 to 80 mass%, particularly preferably 15 to 75 mass%, based on the total mass of the hard coat layer.

The film thickness of a hard coat layer can be designed suitably according to a use. It is preferable that the film thickness of a hard-coat layer is 0.2-10 micrometers, More preferably, it is 0.5-7 micrometers, Especially preferably, it is 0.7-5 micrometers.

In the pencil hardness test according to JIS K 5400, the strength of the hard coat layer is preferably at least H, more preferably at least 2H, and most preferably at least 3H.

In the taper test according to JIS K 5400, the smaller the amount of abrasion of the test piece before and after the test, the better.

In the formation of the hard coat layer, the oxygen concentration when formed by the crosslinking reaction or the polymerization reaction of the ionizing radiation curable compound is the same as the high refractive index layer described later.

[Anti-glare Hard Coat Layer]

Next, the anti-glare hard coat layer will be described below.

The anti-glare hard coat layer is a layer which is necessarily used either of this and a high refractive index layer, and contains a binder for imparting hard coat properties and mat particles for imparting anti-glare properties, and further has high refractive index and crosslinking shrinkage. It contains inorganic fine particles as necessary for prevention and high strength.

As a binder, the binder polymer which has a saturated hydrocarbon chain or a polyether chain as a main chain is preferable, and the binder polymer which has a saturated hydrocarbon chain as a main chain is more preferable. In addition, the binder polymer preferably has a crosslinked structure.

As a binder polymer which has a saturated hydrocarbon chain as a main chain, the polymer of ethylenically unsaturated monomer is preferable. As a binder polymer which has a saturated hydrocarbon chain as a main chain and has a crosslinked structure, the (co) polymer of the monomer which has two or more ethylenically unsaturated groups is preferable.

In order to achieve a high refractive index, it is preferable to contain at least one atom selected from an aromatic ring, a halogen atom other than fluorine, a sulfur atom, a phosphorus atom, and a nitrogen atom in the structure of this monomer.

As a monomer which has two or more ethylenically unsaturated groups, it is preferable to use the polyfunctional monomer of Unexamined-Japanese-Patent No. 2003-4903.

Specific examples of the high refractive index monomers include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinylphenyl sulfide, 4-methacryloxyphenyl-4'-methoxyphenylthio ether, and the like. You may use together 2 or more types of these monomers.

In the present invention, the binder and the coating film refer to the layered structure except for the particles of the mat agent, and have the same meaning.

The anti-glare hard coat layer prepares a coating liquid containing a monomer having an ethylenically unsaturated group as a material for forming a binder polymer, an optical radical initiator or a thermal radical initiator, matte particles, and inorganic fine particles, and applying the coating liquid onto a transparent support. After curing, it can be formed by curing by ionizing radiation or polymerization by heat.

It is preferable to use the compound of Unexamined-Japanese-Patent No. 2003-4903 as an optical radical initiator. Commercially available photo cleavage type optical radical polymerization initiators include Irgacure (651, 184, 907) manufactured by Nippon Chabigai Co., Ltd. and the like as preferable examples.

It is preferable to use an optical radical initiator in 0.1-15 mass parts with respect to 100 mass parts of polyfunctional monomers, More preferably, it is 1-10 mass parts.

In addition to an optical radical initiator, you may use a photosensitizer. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.

As the thermal radical initiator, organic or inorganic peroxides, organic azo and diazo compounds and the like can be used.

Specific examples of the organic peroxide include benzoyl peroxide, halogen perbenzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide, inorganic peroxide, hydrogen peroxide, ammonium persulfate and potassium persulfate. As azo compounds, diazoaminobenzene, p-nitrobenzenedia, such as 2-azo-bis-isobutyronitrile, 2-azo-bis-propionitrile, 2-azo-bis-cyclohexanedinitrile, etc. Zonium etc. can be mentioned.

A coating solution containing a polyfunctional epoxy compound, a photoacid generator or a thermal acid generator, mat particles, and an inorganic filler is prepared, and the coating solution is coated on a transparent support, and then cured by an ionizing radiation or a polymerization reaction by heat. It is also possible to form a hard coat layer.

Instead of or in addition to a monomer having two or more ethylenically unsaturated groups, a crosslinkable functional group may be introduced into the polymer using a monomer having a crosslinkable functional group, and a crosslinked structure may be introduced into the binder polymer by reaction of the crosslinkable functional group. do.

Examples of crosslinkable functional groups include isocyanate groups, epoxy groups, aziridine groups, oxazoline groups, aldehyde groups, carbonyl groups, hydrazine groups, carboxyl groups, methylol groups and active methylene groups. Metal alkoxides such as vinylsulfonic acid, acid anhydrides, cyanoacrylate derivatives, melamines, etherified methylols, esters and urethanes, and tetramethoxysilanes can also be used as monomers for introducing a crosslinked structure. Like a block isocyanate group, you may use the functional group which shows crosslinkability as a result of a decomposition reaction. That is, in this invention, even if it does not show a reaction immediately, what is necessary is just to show reactivity as a result of decomposition | disassembly.

The binder polymer which has these crosslinkable functional groups can form a crosslinked structure by heating after apply | coating.

The mat particles are used for the purpose of imparting anti-glare properties, and the average particle diameter is preferably 0.5 to 10 µm, more preferably 0.5 to 7.0 µm.

It is preferable to set the compounding quantity of mat agent particle | grains into the quantity used as 10-1000 mg / m <2>, More preferably, it is 100-700 mg / m <2>. Since particle diameter and content influence anti-glare property, they are adjusted to the extent of layer film thickness and target anti-glare property.

Specific examples of the mat material particles, for example of the inorganic compound particles such as silica particles, TiO ₂ particles; Resin particle | grains, such as an acryl particle, a crosslinked acrylic particle, a methacryl particle, a crosslinked methacryl particle, a polystyrene particle, a crosslinked styrene particle, melamine resin particle, benzoguanamine resin particle, are mentioned preferably. Among them, crosslinked styrene particles, crosslinked acrylic particles, and silica particles are preferable.

Although the shape of the particle | grains made from a mat | matte can be used either spherical or indefinite, it is preferable that it is monodisperse. Moreover, you may use together 2 or more types of mat agent particle | grains from which a particle diameter differs.

The particle size distribution of the particles of mat is converted into the particle number distribution by the distribution measured by the Coulter counter method.

Although anti-glare property is judged by the sensory evaluation of the film sample which blackened the back surface side normally, in order to make objectivity, the correlation with an optical measurement value is also performed. Correlation depends on application prescription and layer composition, and often has some constant relationship with haze, transmission image clarity, scattering angle distribution, and the like. In the antireflection film of the present invention, there was a correlation with transmission image clarity. In order to reduce the influence of scratches and to avoid image opacity, the transmission image clarity is preferably 10% to 99%. When the hard coat layer in the present invention is anti-glare, the transmissive image clarity is preferably 10% to less than 65%, more preferably 10% to 55%, and most preferably 10% to 50%. In addition, when the hard coat layer in the present invention is not anti-glare, the transmissive image clarity is preferably 65% to 99%, more preferably 70% to 99%, and most preferably 80% to 99%.

The anti-glare hard coat layer is composed of an oxide of at least one metal in addition to the particles of the mat in order to increase the refractive index and the elastic modulus of the layer, and in an dispersed state, the average particle diameter is 200 nm or less, preferably 100 nm or less, More preferably, inorganic fine particles of 60 nm or less are contained. As the inorganic fine particles, it is preferable to use those specifically exemplified as the inorganic fine particles contained in the antiglare layer in JP-A-2003-4903. 1-200 nm is preferable, as for the average particle diameter of a primary particle, 2-100 nm is more preferable, and its 3-50 nm is further more preferable.

Inorganic fine particles are also preferably treated with a silane coupling treatment or a titanium coupling agent, and a surface treatment agent having a functional group capable of reacting with one binder on the surface of the fine particles is preferably used.

It is preferable that the addition amount of these inorganic fine particles is 10 to 90% of the total mass of an anti-glare hard-coat layer, More preferably, it is 20 to 80%, Especially preferably, it is 30 to 75%.

In addition, since such inorganic fine particles have a particle size sufficiently smaller than the wavelength of light, scattering does not occur, and the dispersion in which the filler is dispersed in the binder polymer acts as an optically uniform material.

The bulk refractive index of the mixture of the binder of the anti-glare hard coat layer of the present invention and the inorganic fine particles is preferably 1.48 to 2.00, more preferably 1.50 to 1.80.

The difference between the refractive index of the matte particles and the binder (the refractive index of the refractive index binder of the matte particles) is preferably 0.03 to 0.2, more preferably 0.05 to 0.15. When this difference is made 0.03 or more, anti-glare property is expressed efficiently, and when it is 0.2 or less, white does not increase too much and cost increase can also be suppressed.

It is preferable that the refractive index of the said binder is 1.48-1.8. Moreover, it is preferable that the refractive index of the said mat agent particle is 1.3-1.8.

The refractive index of the binder can be measured with an Abbe refractometer (manufactured by ATAGO), an ellipsometer (Nippon Bunco Co., Ltd.), or the like.

What is necessary is just to select suitably the kind and quantity ratio of a binder and an inorganic fine particle in order to make refractive index into the said range, and a selection content can easily know experimentally beforehand.

1-10 micrometers is preferable and, as for the film thickness of an anti-glare hard-coat layer, 2-6 micrometers is more preferable.

[Light Diffusion Layer]

Moreover, it is also preferable to form a light-diffusion layer as one of the layers which comprise a functional layer. The present inventors confirmed that the intensity distribution of the scattered light measured by the goniophotometer correlated with the viewing angle improvement effect. That is, the more the light emitted from the backlight diffuses into the light diffusion film provided on the surface of the polarizing plate on the viewer's side, the better the viewing angle characteristic. However, if too diffused, backscatter may increase, leading to a decrease in front luminance or excessive scattering, resulting in deterioration of image clarity. Therefore, it is necessary to control the scattered light intensity distribution in a predetermined range. Therefore, as a result of earnest examination, in order to achieve the desired viewing characteristics, the scattered light intensity of 30 ° correlated with the visual angle improvement effect is particularly 0.01% to 0.2% for the light intensity of 0 ° of the scattered light profile. Preferably, 0.02%-0.15% are more preferable, 0.03%-0.1% are especially preferable.

Scattered light profile can be measured about the created light-scattering film using the automatic variable angle photometer GP-5 type by Murakami Color Research Institute.

The light diffusing layer may correspond to at least one of an anti-glare hard coat layer and a high refractive index layer according to the transmission image clarity or the refractive index value in the layer classification of the antireflective film of the present invention.

[High refractive index layer, medium refractive index layer]

In the antireflection film, a high refractive index layer is also optionally used with the antiglare hard coat layer in order to provide better antireflection performance.

The refractive index of the said high refractive index layer is 1.55-2.40, and if there exists a layer in this range, it can be said that the high refractive index layer in this invention exists. Although the range of this refractive index is what is called a high refractive index layer or a medium refractive index layer, in this specification below, these layers may be named generically and high refractive index layer.

In addition, when a high refractive index layer and a medium refractive index layer are mixed like the structure shown in FIG. 2 mentioned above, the layer of refractive index 1.8-2.4 will be called the high refractive index layer, and the layer of refractive index 1.8-1.55 will be called a medium refractive index layer. However, the relationship between the high and the medium refractive index is relative, and the boundary refractive index value may fluctuate by about 0.2. Refractive index can be suitably adjusted with the kind and ratio of the inorganic fine particle and binder to add.

* [Inorganic fine particles which can be contained in high refractive index layer]

The high refractive index layer contains inorganic fine particles mainly composed of titanium dioxide containing at least one element selected from cobalt, aluminum and zirconium. A main component means the component with most content (mass%) among the components which comprise particle | grains.

Inorganic fine particles mainly containing titanium dioxide in the present invention preferably have a refractive index of 1.90 to 2.80, and most preferably 2.20 to 2.80. It is preferable that the mass mean diameter of a primary particle is 1-200 nm, More preferably, it is 2-100 nm, Especially preferably, it is 2-80 nm.

By containing at least one element selected from Co, Al, and Zr in the inorganic fine particles containing titanium dioxide as a main component, the photocatalytic activity of titanium dioxide can be suppressed, and the weather resistance of the high refractive index layer can be improved.

You may surface-treat the inorganic fine particle which has a titanium dioxide used for this invention as a main component. Surface treatment is carried out using an inorganic compound containing cobalt, an inorganic compound such as Al (OH) ₃ , Zr (OH) ₄ , or an organic compound such as a silane coupling agent. The inorganic fine particles containing titanium dioxide of the present invention as a main component may have a core / shell structure as described in JP 2001-166104 A by surface treatment.

The shape of the inorganic fine particles mainly composed of titanium dioxide contained in the high refractive index layer is preferably rice grains, spherical shapes, cubes, fusiforms, or indefinite shapes, and particularly preferably indefinite or fusiform forms.

[Dispersant]

A dispersant may be used to disperse the inorganic fine particles. It is particularly preferable to use a dispersant having an anionic group for the dispersion.

As the anionic group, a group having an acidic proton, such as a carboxyl group, a sulfonic acid group (and a sulfo group), a phosphoric acid group (and a phosphono group), a sulfonamide group, or a salt thereof is effective, and particularly, a carboxyl group, a sulfonic acid group, a phosphoric acid group and salts thereof Preferably, a carboxyl group and a phosphoric acid group are especially preferable. Although the number of the anionic groups contained in a dispersing agent per molecule should just contain 1 or more, it is preferable that it is 2 or more on average, More preferably, it is 5 or more, Especially preferably, it is 10 or more. The anionic group may contain more than one kind in one molecule. In addition, the dispersant preferably contains a crosslinking or polymerizable functional group.

It is preferable that a dispersing agent is 0.5-40 mass% with respect to an inorganic fine particle, More preferably, it is 1-30 mass%, Especially preferably, it is 3-25 mass%.

[High refractive index layer and its formation method]

Inorganic fine particles mainly composed of titanium dioxide used in the high refractive index layer are used in the formation of the high refractive index layer in the state of dispersion.

In the dispersion of the inorganic fine particles, it is dispersed in the dispersion medium in the presence of the dispersant.

As the dispersion medium, it is preferable to use a liquid having a boiling point of 60 to 170 캜. Examples of the dispersion medium include water, alcohols, ketones, esters, aliphatic hydrocarbons, halogenated hydrocarbons, aromatic hydrocarbons, amides, ethers, ether alcohols. Toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are preferred.

Particularly preferred dispersion media are methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone.

It is preferable that it is 3000-100 mass% with respect to an inorganic fine particle, and, as for a dispersion medium, 2000-125 mass% is more preferable.

Inorganic fine particles are dispersed using a disperser. Examples of dispersers include sand grinder mills (eg pinned bead mills), high speed impeller mills, pebble mills, roller mills, attritors and colloid mills. Particular preference is given to sand grinder mills and high speed impeller mills. In addition, preliminary dispersion treatment may be performed. Examples of dispersers used in predispersion treatment include ball mills, three roll mills, kneaders and extruders.

It is preferable that the inorganic fine particle dispersion is refined as much as possible in the dispersion medium, and the mass average diameter is 1 to 200 nm. Preferably it is 5-150 nm, More preferably, it is 10-100 nm, Especially preferably, it is 10-80 nm.

By refining the inorganic fine particles to 200 nm or less, a high refractive index layer which does not impair transparency can be formed.

The high refractive index layer used in the present invention is a binder precursor (such as the anti-glare hard coat layer described above) and photopolymerization, which is required for matrix formation, in a dispersion liquid in which inorganic fine particles are dispersed in a dispersion medium as described above. Add an initiator or the like to form a coating composition for forming a high refractive index layer, and apply a coating composition for forming a high refractive index layer on a transparent support to form an ionizing radiation curable compound (for example, a polyfunctional monomer or a polyfunctional oligomer). It is preferable to form by hardening | curing by a crosslinking reaction or a polymerization reaction.

It is preferable to use a photoinitiator for the polymerization reaction of a photopolymerizable polyfunctional monomer. As a photoinitiator, an optical radical polymerization initiator and a photocationic polymerization initiator are preferable, and an optical radical polymerization initiator is especially preferable. As an optical radical polymerization initiator, the same thing as the above-mentioned anti-glare hard coat layer is used.

In the high refractive index layer, the binder further preferably has a silanol group. As the binder further has silanol groups, the physical strength, chemical resistance and weather resistance of the high refractive index layer are further improved.

The silanol group is, for example, by adding a compound represented by the general formula (1) having a crosslinking or polymerizable functional group to the coating composition for forming the high refractive index layer, and applying the coating composition onto a transparent support to give the dispersant, A functional monomer, a polyfunctional oligomer, and the compound represented by the said General formula (1) can be introduce | transduced into a binder by crosslinking or polymerizing.

In the high refractive index layer, the binder preferably has an amino group or a quaternary ammonium group. In the monomer having an amino group or a quaternary ammonium group, the inorganic fine particles in the high refractive index layer maintain good dispersibility, and thus a high refractive index layer excellent in physical strength, chemical resistance and weather resistance can be produced.

The binder crosslinked or polymerized has a structure in which the main chain of the polymer is crosslinked or polymerized. Examples of the main chain of the polymer include polyolefins (saturated hydrocarbons), polyethers, polyureas, polyurethanes, polyesters, polyamines, polyamides and melamine resins. Polyolefin backbones, polyether backbones and polyurea backbones are preferred, polyolefin backbones and polyether backbones are more preferred, and polyolefin backbones are most preferred.

The binder is preferably a copolymer having a repeating unit having an anionic group and a repeating unit having a crosslinking or polymerizing structure. It is preferable that the ratio of the repeating unit which has an anionic group in a copolymer is 2-96 mol%, It is more preferable that it is 4-94 mol%, It is most preferable that it is 6-92 mol%. The repeating unit may have two or more anionic groups. The proportion of the repeating unit having a crosslinked or polymerized structure in the copolymer is preferably 4 to 98 mol%, more preferably 6 to 96 mol%, and most preferably 8 to 94 mol%.

The high refractive index layer may contain fine inorganic fine particles in addition to the inorganic fine particles mainly containing titanium dioxide. The other inorganic fine particles may use the inorganic fine particles contained in the anti-glare hard coat layer, and are preferably finely dispersed. The preferred post-dispersion particle size and primary particle size are as described in the column of the anti-glare hard coat layer. same.

It is preferable that content of the inorganic fine particle in a high refractive index layer is 10-90 mass% with respect to the mass of a high refractive index layer, More preferably, it is 15-80 mass%, Especially preferably, it is 15-75 mass%. Inorganic fine particles may use two or more types together in a high refractive index layer.

When the low refractive index layer is provided on the high refractive index layer, the refractive index of the high refractive index layer is preferably higher than that of the transparent support.

A high refractive index layer contains an ionizing radiation curable compound containing an aromatic ring, an ionizing radiation curable compound containing halogenated elements other than fluorine (for example, Br, I, Cl, etc.), and atoms such as S, N, and P The binder obtained by crosslinking or polymerization reactions, such as an ionizing radiation curable compound, can also be used preferably.

In order to form a low refractive index layer on the high refractive index layer and produce an antireflection film, the refractive index of the high refractive index layer is preferably 1.55 to 2.40, more preferably 1.60 to 2.20, still more preferably 1.65 to 2.10, most preferably Preferably 1.80 to 2.00.

In addition to the above components (inorganic fine particles, polymerization initiators, photosensitizers, etc.), the high refractive index layer includes resins, surfactants, antistatic agents, coupling agents, thickeners, colorants, colorants (pigments, dyes), anti-glare particles, antifoaming agents. , Leveling agents, flame retardants, ultraviolet absorbers, infrared absorbers, tackifiers, polymerization inhibitors, antioxidants, surface modifiers, conductive metal fine particles, and the like.

The film thickness of a high refractive index layer can be designed suitably according to a use. When using a high refractive index layer as said light-diffusion layer, 30-200 nm is preferable, More preferably, it is 50-170 nm, Especially preferably, it is 60-150 nm.

In the formation of the high refractive index layer, the crosslinking reaction or polymerization reaction of the ionizing radiation curable compound has an oxygen concentration of 10 vol% or less, preferably an oxygen concentration of 6 vol% or less, particularly preferably an oxygen concentration of 2 vol% or less Most preferably, it is preferable to carry out in atmosphere of 1 volume% or less.

[Low refractive index layer]

The low refractive index layer is an essential layer of the antireflection film, and the refractive index of the low refractive index layer is preferably 1.20 to 1.49, more preferably in the range of 1.30 to 1.44.

In addition, it is preferable that the low refractive index layer satisfy the following formula (i) from the viewpoint of low reflectivity.

Formula (Ⅶ)

(m / 4) x 0.7 <n ₁ d ₁ <(m / 4) x 1.3

In the formula, m is a positive odd number, n ₁ is the refractive index of the low refractive index layer, and d ₁ is the film thickness (nm) of the low refractive index layer. In addition, (lambda) is a wavelength and is a value of the range of 500-550 nm.

In addition, satisfying the above formula (i) means that m (positive odd number, usually 1) exists that satisfies the formula (i) in the wavelength range.

The raw material which forms the said low refractive index layer is demonstrated below.

The low refractive index layer preferably contains a fluorine-containing polymer as the low refractive index binder. As the fluorine-containing polymer, a fluorine-containing polymer that crosslinks by heat or ionizing radiation having a coefficient of friction of 0.03 to 0.15 and a contact angle to water of 90 to 120 ° is preferable. As described above, an inorganic filler for improving the film strength may be used.

As a fluorine-containing polymer used for a low refractive index layer, hydrolysis and dehydration condensation of a perfluoroalkyl group containing silane compound [for example, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane] In addition to water, the fluorine-containing copolymer which consists of a fluorine-containing monomeric unit and the structural unit for providing crosslinking reactivity can be mentioned.

Specific examples of the fluorine-containing monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, perfluorooctylethylene, hexafluoropropylene, perfluoro-2,2 -Dimethyl-1,3-dioxol, etc.), partial or fully fluorinated alkylester derivatives of (meth) acrylic acid (e.g., biscot 6FM (manufactured by Osaka Organic Chemicals), M-2020 (manufactured by Daikin), etc.), Although fully or partially fluorinated vinyl ether etc. are mentioned, Preferably it is perfluoro olefins, Especially preferably, it is hexafluoropropylene from a viewpoint of refractive index, solubility, transparency, availability, etc.

As the structural unit for imparting crosslinking reactivity, a structural unit obtained by polymerization of a monomer having a self-crosslinking functional group in a molecule, such as glycidyl (meth) acrylate and glycidyl vinyl ether, a carboxyl group or a hydroxyl group, an amino group, and a sulfo group Monomers having, for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, maleic acid, croton Structural unit obtained by superposition | polymerization of an acid etc., Structural unit which introduce | transduced the crosslinking reactive groups, such as (meth) acryloyl group, by polymer reaction into these structural units (for example, a method of making a chloroacrylate react with respect to a hydroxyl group, etc.). Can be introduced).

-메틸스티렌 등), 비닐에테르류 (메틸비닐에테르, 에틸비닐에테르, 시클로헥실비닐에테르 등), 비닐에스테르류 (아세트산비닐, 프로피온산비닐, 계피산비닐 등), 아크릴아미드류 (N-tert부틸아크릴아미드, N-시클로헥실아크릴아미드 등), 메타크릴아미드류, 아크릴로니트릴 유도체 등을 들 수 있다.In addition to the fluorine-containing monomer unit and the structural unit for imparting crosslinking reactivity, a monomer containing no fluorine atom may be copolymerized appropriately in view of solubility in a solvent and transparency of a coating film. The monomer unit which can be used in combination is not particularly limited, and for example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylate esters (methyl acrylate, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate) Methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyltoluene,

-Methyl styrene, etc.), vinyl ethers (methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamic acid, etc.), acrylamides (N-tertbutyl acrylamide , N-cyclohexyl acrylamide, etc.), methacrylamide, an acrylonitrile derivative, etc. are mentioned.

About the said polymer, you may use together a hardening | curing agent suitably as described in Unexamined-Japanese-Patent No. 10-25388 and Unexamined-Japanese-Patent No. 10-147739, respectively.

Particularly useful fluorine-containing polymers in the present invention are random copolymers of perfluoroolefins and vinyl ethers or vinyl esters. In particular, it is preferable to have a crosslinkable reaction group (a radical reactive group, such as a (meth) acryloyl group, an ring-opening polymerizable group, such as an epoxy group, an oxetanyl group, etc.) which can be independently reacted. These crosslinking reactive group-containing polymerized units preferably occupy 5 to 70 mol% of the total polymerized units of the polymer, and particularly preferably 30 to 60 mol%.

The following general formula (2) is mentioned as a preferable aspect of a fluorine-containing polymer used for this invention.

[Chemical Formula 18]

In general formula (2)

In General formula (2), L represents a C1-C10 coupling group, More preferably, it is a C1-C6 coupling group, Especially preferably, it is a C2-C4 coupling group, It may be linear or may have a branched structure, It may have a ring structure and may have a hetero atom selected from O, N, and S.

Preferred examples include *-(CH ₂ ) ₂ -O-**, *-(CH ₂ ) ₂ -NH-**, *-(CH ₂ ) ₄ -O-**, *-(CH ₂ ) ₆ -O -**, *-(CH ₂ ) ₂ -O- (CH ₂ ) ₂ -O-**, * -CONH- (CH ₂ ) ₃ -O-**, * -CH ₂ CH (OH) CH ₂ -O-**, * -CH ₂ CH ₂ OCONH (CH ₂ ) ₃ -O-** (* indicates the linking site on the polymer main chain side, ** indicates the linking site on the (meth) acryloyl group side. .) And the like. m represents 0 or 1;

In General Formula (2), X represents a hydrogen atom or a methyl group. From the viewpoint of curing reactivity, more preferably, it is a hydrogen atom.

In Formula (2), A represents a repeating unit derived from an arbitrary vinyl monomer, and is not particularly limited as long as it is a constituent of a monomer copolymerizable with hexafluoropropylene, and the adhesion to the substrate and the Tg of the polymer (film hardness) Contribution), solubility in solvents, transparency, slipperiness, dustproof and antifouling properties can be appropriately selected, and may be composed of a single or a plurality of vinyl monomers depending on the purpose.

Preferred examples include vinyl such as methyl vinyl ether, ethyl vinyl ether, t-butyl vinyl ether, cyclohexyl vinyl ether, isopropyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, glycidyl vinyl ether and allyl vinyl ether. Vinyl esters such as ethers, vinyl acetate, vinyl propionate and vinyl butyrate, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl methacrylate and allyl (meth) (Meth) acrylates such as acrylate and (meth) acryloyloxypropyltrimethoxysilane, styrene derivatives such as styrene and p-hydroxymethylstyrene, and unsaturated carboxylic acids such as crotonic acid, maleic acid and itaconic acid And derivatives thereof, and the like, and more preferably vinyl ether derivatives and vinyl ester derivatives, and particularly preferably vinyl ether. A conductor.

x

60, 5

y

70, 0

z

65 를 만족하는 값을 나타낸다. 바람직하게는 35

X

55, 30

y

60, 0

z

20 의 경우이고, 특히 바람직하게는 40

x

55, 40

y

55, 0

Z

10 의 경우이다. 다만, x+y+z=100 이다.x, y, z represent mol% of each component, and 30

x

60, 5

y

70, 0

z

The value satisfying 65 is shown. Preferably 35

X

55, 30

y

60, 0

z

In the case of 20, particularly preferably 40

x

55, 40

y

55, 0

Z

In case of 10. However, x + y + z = 100.

The following general formula (3) is mentioned as a more preferable form of general formula (2) of the said fluorine-containing polymer used for this invention.

[Formula 19]

In general formula (3)

In General formula (3), X represents the same meaning as General formula (2), and its preferable range is also the same.

n

10 의 정수를 나타내고, 2

n

6 인 것이 바람직하고, 2

n

4 인 것이 특히 바람직하다.n is 2

n

Represents an integer of 10 and 2

n

It is preferable that it is 6, 2

n

It is especially preferable that it is four.

B represents the repeating unit derived from arbitrary vinyl monomers, and may be comprised by a single composition, or may be comprised by several composition. As an example, what was described as the example of A in the said General formula (2) is suitable.

X

60, 5

y

70 을 만족하는 것이 바람직하고, 더욱 바람직하게는 35

x

55, 30

y

60 인 경우이고, 특히 바람직하게는 40

x

55, 40

y

55 인 경우이다. z1 및 z2 에 관해서는 0

z1

65, 0

z2

65 을 만족하는 것이 바람직하고, 더욱 바람직하게는 0

z1

30, 0

z2

10 인 것이 바람직하고, 0

z1

10, 0

z2

5 인 것이 특히 바람직하다. 단, x+y+z1+z2=100 이다.x, y, z1 and z2 represent mol% of each repeating unit, and x and y are each 30

X

60, 5

y

It is preferable to satisfy 70, more preferably 35

x

55, 30

y

60, particularly preferably 40

x

55, 40

y

55. 0 for z1 and z2

z1

65, 0

z2

It is preferable to satisfy 65, more preferably 0

z1

30, 0

z2

Preferably 10, 0

z1

10, 0

z2

It is especially preferable that it is five. However, x + y + z1 + z2 = 100.

The polymer represented by General formula (2) or (3) introduce | transduces a (meth) acryloyl group by the above-mentioned method into the polymer which contains the hexafluoropropylene component and the hydroxyalkyl vinyl ether component, for example. It can synthesize | combine by making it.

The low refractive index layer-forming composition of the present invention preferably contains a fluorine-containing copolymer containing the above-mentioned fluorine-containing monomer unit as a component in the form of a liquid, and suitable various additives and radical polymerization initiators as necessary. It is prepared by dissolving in a solvent. At this time, the concentration of the solid content is appropriately selected depending on the application, but is generally about 0.01 to 60% by mass, preferably 0.5 to 50% by mass, particularly preferably about 1% to 20% by mass.

Although it is not always advantageous to add an additive such as a curing agent in view of the film hardness of the low refractive index layer, from the viewpoint of interfacial adhesion with the high refractive index layer and the like, a polyfunctional (meth) acrylate compound, a polyfunctional epoxy compound, and a polyisocyanate A small amount of hardening | curing agents, such as a compound, an aminoplast, a polybasic acid, or its anhydride, can also be added. When adding these, it is preferable that it is the range of 0-30 mass% with respect to the total solid of the low refractive index layer film, It is more preferable that it is the range of 0-20 mass%, It is especially preferable that it is the range of 0-10 mass%.

In order to impart properties such as antifouling properties, water resistance, chemical resistance and slipperiness, a known silicone or fluorine antifouling agent, lubricant and the like may be appropriately added. When adding these additives, it is preferable to add in the range of 0.01-20 mass% of the total solid content of the low refractive index layer, More preferably, it is the case which is added in the range of 0.05-10 mass%, Especially preferably, it is 0.1- 5 mass%.

As a preferable example of a silicone type compound, what has a substituent in the terminal and / or side chain of the compound chain which contains two or more dimethylsilyloxy units as a repeating unit is mentioned. In the compound chain containing dimethylsilyloxy as a repeating unit, structural units other than dimethylsilyloxy may be contained. The substituents may be the same or different and preferably have a plurality of substituents. Examples of preferred substituents include groups including acryloyl group, methacryloyl group, vinyl group, aryl group, sannamoyl group, epoxy group, oxetanyl group, hydroxyl group, fluoroalkyl group, polyoxyalkylene group, carboxyl group, amino group and the like. have. Although there is no restriction | limiting in particular in molecular weight, It is preferable that it is 100,000 or less, It is especially preferable that it is 50,000 or less, It is most preferable that it is 3000-30000. Although there is no restriction | limiting in particular in the silicon atom content of a silicone type compound, It is preferable that it is 18.0 mass% or more, It is especially preferable that it is 25.0-337 mass%, It is most preferable that it is 30.0-37.0 mass%. Examples of preferred silicone compounds include Shin-Etsu Chemical Co., Ltd., X-22-174DX, X-22-2426, X-22-164B, X-22-164C, X-22-170DX, X-22-176D, X -22-1821 (above brand name) and Jitso Co., Ltd., FM-0725, FM-7725, DMS-U22, RMS-033, RMS-083, UMS-182 (above brand name), etc. are mentioned, but are limited to these It doesn't happen.

As a fluorine-type compound, the fluoro aliphatic group containing polymer as a surface modifier mentioned above, and the fluorine-type polymer used as a binder in a low refractive index layer are also preferable, and the compound which has other fluoroalkyl groups is also preferable. The fluoroalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and is linear (for example, -CF ₂ CF ₃ , -CH ₂ (CF ₂ ) ₄ H, or -CH ₂ (CF _2). ) ₈ CF ₃ , -CH ₂ CH ₂ (CF ₂ ) ₄ H etc.), but also branched structure (for example -CH (CF ₃ ) ₂ , -CH ₂ CF (CF ₃ ) ₂ , -C (CH ₃ ) CF ₂ CF ₃ , -CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H and the like, even if the alicyclic structure (preferably 5 or 6 rings, for example perfluorocyclohexyl group, perfluoro Or a cyclocyclopentyl group or an alkyl group substituted therewith) or may have an ether bond (for example, -CH ₂ OCH ₂ CF ₂ CF ₃ , -CH ₂ CH ₂ OCH ₂ C ₄ F ₈ H, -CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F ₁₇ , -CH ₂ CH ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ H, etc.). Plural fluoroalkyl groups may be contained in the same molecule.

It is preferable that the fluorine-based compound further has a substituent (for example, acryloyl group, methacryloyl group, epoxy group, etc.) that contributes to bond formation or compatibility with the low refractive index layer film.

The film thickness of the low refractive index layer is preferably 20 to 300 nm, more preferably 40 to 200 nm, particularly preferably 60 to 150 nm.

0.01 to 20% by mass of the total solid content of the low refractive index layer when a polyoxyalkylene compound, a cationic surfactant, and a compound contained in the silicon compound, the fluorine compound, and the like are added to the low refractive index layer as an additive. It is preferable to add in the range of, More preferably, it is the case of adding in 0.05-10 mass%, Especially preferably, it is 0.1-5 mass%. Examples of preferred compounds include, but are not limited to, Dainippon Ink, Co., Ltd., Megapak F-150 (trade name), Tole Dow Corning Corporation, SH-3748 (trade name), and the like.

[Antistatic layer]

* It is preferable to form the transparent antistatic layer which has an electroconductive material in the said antireflection film for antistatic. Although the transparent antistatic layer may be newly formed independently, you may provide an antistatic function by containing an electrically-conductive material in an anti-glare hard-coat layer, a light-diffusion layer, a high refractive index layer, a medium refractive index layer, and a low refractive index layer. In particular, it is preferable to form an antistatic layer between the hard coat layer and the transparent support.

The conductive material is preferably formed of fine particles of an oxide or a nitride of a metal. Examples of oxides or nitrides of metals include tin oxide, indium oxide, zinc oxide and titanium nitride. Among them, tin oxide and indium oxide are particularly preferred, and other elements may be further contained, mainly containing oxides or nitrides of these metals. A main component means the component with most content (mass%) among the components which comprise particle | grains. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, S, B, Nb, In, V and halogen Atoms are included. In order to increase the conductivity of tin oxide and indium oxide, it is preferable to add Sb, P, B, Nb, In, V and halogen atoms. Antimony-tin oxide, indium-tin oxide, and zinc antimonate are preferable.

Other than these, metal particulates, ionic high molecular compounds, polyoxyalkylene compounds, cationic surfactants, and the like are also preferably used. The degree of antistatic capability is more preferably 10 ¹¹ Ω / □ or less (25 ° C., 60% RH) of the antistatic layer and less than 10 ¹⁰ Ω / □, and the haze of the antistatic layer is 20% or less. desirable.

[Transparent support]

It is preferable to use a plastic film as a transparent support body of the said antireflection film. Examples of the polymer forming the plastic film include cellulose esters (e.g., triacetyl cellulose, diacetyl cellulose, typically TAC-TD80U, TD80UF, etc., manufactured by Fujishashin Film Co., Ltd.), polyamides, polycarbonates, polyesters (e.g., polyethylene terephthalate). And polyethylene naphthalate), polystyrene, polyolefin, norbornene-based resin (Aton: trade name, manufactured by JSR Corporation), amorphous polyolefin (Xeonex: trade name, manufactured by Nippon Zeon), and the like. Among these, triacetyl cellulose, polyethylene terephthalate and polyethylene naphthalate are preferable, and triacetyl cellulose is particularly preferable.

Triacetyl cellulose consists of a single layer or a plurality of layers. Triacetyl cellulose of a single layer is made by drum casting or band casting disclosed in Japanese Patent Application Laid-open No. Hei 7-11055 or the like, and triacetyl cellulose composed of the latter plural layers is disclosed in Japanese Patent Laid-Open No. 61-94725, It is produced by the so-called shared federal law disclosed in Japanese Patent Application Laid-Open No. 62-43846 and the like.

The said antireflection film forms an adhesion layer on one side, and is used as a protective film for polarizing plates. In this case, in order to make it fully adhere | attach, it is preferable to form a saponification process after forming the outermost layer which preferably contains a fluorine-containing polymer on a transparent support body. The saponification treatment is carried out by a known method, for example, by immersing the film in an alkaline liquid for an appropriate time. After immersion in an alkaline liquid, it is preferable to wash with water sufficiently, or to immerse in dilute acid to neutralize an alkali component so that an alkali component may not remain in the film.

By the saponification treatment, the transparent support surface on the side opposite to the side having the outermost layer is hydrophilized.

The hydrophilized surface is particularly effective for improving the adhesion with a polarizing film containing polyvinyl alcohol as a main component. In addition, since the surface of the hydrophilized surface is less likely to adhere to dust in the air, it is difficult for dust to enter between the polarizing film and the antireflection film when bonding with the polarizing film, and is effective in preventing point defects caused by dust. Do.

It is preferable to perform saponification process so that the contact angle with respect to the water of the transparent support surface on the opposite side to the side which has outermost layer may be 40 degrees or less. More preferably, it is 30 degrees or less, Especially preferably, it is 20 degrees or less.

As a specific means of an alkali saponification process, two means of the following (1) and (2) are mentioned. (1) is excellent in that it can be processed in the same process as the widely used triacetyl cellulose film, but since the saponification process is carried out to the antireflection film surface, the surface is alkali hydrolyzed and the film is deteriorated. Soiling can be a problem. In that case, although it is a special process, (2) is excellent.

(1) After forming the antireflection layer on the transparent support, the back surface of the film is saponified by dipping at least once in an alkaline liquid.

(2) Before or after the antireflection layer is formed on the transparent support, the alkali liquid is applied to the side opposite to the side on which the antireflection film of the antireflection film is formed, heated, washed with water and / or neutralized to form the film. Only saponification process of the back side of.

Although the said antireflection film can be formed with the following method, it is not limited to this method.

First, the coating liquid containing the component for forming each layer is prepared.

Next, in the case of forming the hard coat layer, the coating liquid for forming the hard coat layer may be a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method or an extrudate. The microgravure coating method is particularly preferable for coating and heating and drying the transparent support by the precoat method (see US Patent 2681294 specification). Thereafter, light irradiation or heating polymerizes and hardens a monomer for forming a hard coat layer. This forms a hard coat layer.

Here, if necessary, the hard coat layer may be provided in plural layers, and the smooth hard coat layer may be applied and cured in the same manner before the antiglare hard coat layer is applied. An anti-glare hard coat layer can also be formed similarly to a hard coat layer.

Next, the coating liquid for forming a low refractive index layer similarly is apply | coated on an anti-glare hard-coat layer, and a low refractive index layer is formed by light irradiation or heating. In this way, one aspect of the antireflection film is obtained.

In the microgravure coating method used in the present invention, a gravure roll having a diameter of about 10 to 100 mm, preferably about 20 to 50 mm and having a gravure pattern imprinted on its entire circumference under the support and in the conveying direction of the support While rotating the gravure roll with respect to the gravure roll, the excess coating liquid was scraped off from the surface of the gravure roll by a doctor blade, and the coating liquid of the lower surface of the support in the position where the upper surface of the support was in a free state. It transfers a coating liquid to and coats it. It is a coating method characterized by the above-mentioned. The transparent support in roll form is continuously removed, and at least one layer of the low refractive index layer containing at least the hard coat layer or the fluorine-containing polymer can be coated on one side of the unsupported support by the microgravure coating method. .

As the coating conditions by the microgravure coating method, the number of gravure patterns imprinted on the gravure roll is preferably 50 to 800 / inch, more preferably 100 to 300 / inch, and the depth of the gravure pattern is 1 to 600 µm. It is preferable, 5-200 micrometers is more preferable, It is preferable that the rotation speed of the gravure roll is 3-800 rpm, It is more preferable that it is 5-200 rpm, It is preferable that the conveyance speed of a support body is 0.5-100 m / min, 1-50 m / min is more preferable.

The antireflection film thus formed preferably has a haze value in the range of 3 to 70%, more preferably 4 to 60%, and an average reflectance of 450 nm to 650 nm is preferably 3.0% or less, more preferably. Preferably 2.5% or less.

By having an antireflection film in the range of the said haze value and average reflectance, favorable anti-glare property and anti-reflection property are obtained without accompanying deterioration of a transmission image.

Moreover, it is preferable that the transmissive image clarity of an antireflection film is 15%-60% in the point which anti-glare property and black brightness exist in the preferable range.

Here, transmission image sharpness can be measured by the method as described in an Example.

In this invention, the said functional film of the other side may be formed only by the functional film which consists only of the said antireflection film, and may overlap and form the other functional film with this film.

As another functional film, a hard coat film, a color filter film, etc. are mentioned, for example.

&Lt; Configuration of Polarizer &

A polarizing plate is usually comprised by two functional films which attach a polarizing film on both surfaces. Usually, each functional film is mainly comprised by one protective film, respectively. As for the polarizing plate of this invention, the said cellulose acylate film is made into at least 1 sheet of one side of two protective films which affix a polarizing film from both surfaces, and this cellulose acylate film is at least 1 sheet of the opposite side through the polarizing film between the said cellulose acylate films, Use an antireflection film.

When a cellulose acylate film and an antireflection film serve as a protective film, the manufacturing cost of a polarizing plate can be reduced. Moreover, by using the said antireflection film for the outermost surface of a polarizing plate, projection of external light etc. can be prevented, and it can be set as the polarizing plate excellent also in flaw resistance, antifouling property, etc. That is, the preferable structure of the polarizing plate of this invention is a functional film which consists of a polarizing film, the functional film which consists of a cellulose acylate film laminated | stacked on one side of this polarizing film, and the antireflection film laminated | stacked on the other side of this polarizing film. The surface of one side of a polarizing plate is formed of the cellulose acylate film, and the surface of the other side is formed of the antireflection film.

As a polarizing film, you may use a well-known polarizing film and the polarizing film cut | disconnected from the long polarizing film whose absorption axis of a polarizing film is neither parallel nor perpendicular to a longitudinal direction.

The stretching method of a polymer film is described in detail in Paragraph 0020-0030 of Unexamined-Japanese-Patent No. 2002-86554.

The polarizing plate of the present invention can be applied to an image display device such as a liquid crystal display (LCD), a plasma display panel (PDP), an electroluminescence display (ELD) or a cathode ray tube display (CRT). Since the polarizing plate of this invention has a transparent support body, it is used by adhering the transparent support side to the image display surface of an image display apparatus. The polarizing plate of the present invention is preferably used for the outermost surface of the liquid crystal display device.

The polarizing plate of the present invention is a transmissive, reflective mode of modes such as twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), optically-complied bend cell (OCB), and the like. It can use suitably for a type | mold or a semi-transmissive liquid crystal display device. In particular, the liquid crystal display device of the present invention is preferably in the TN mode or the VA mode.

In the liquid crystal cell of VA mode, (1) the liquid crystal cell of VA mode of narrow meaning which aligns rod-shaped liquid crystalline molecules substantially vertically when no voltage is applied and is substantially horizontally aligned when voltage is applied. In addition to 2-176625, (2) a liquid crystal cell (in MVA mode) of multi-domain VA mode (see SID97, Digest of tech.Papers (preliminary) 28 (1997) 845) for expanding the viewing angle) (3) Liquid crystal cell of a mode (n-ASM mode) in which rod-shaped liquid crystalline molecules are substantially vertically aligned when no voltage is applied and torsional multidomain alignment is applied when voltage is applied (Preliminaries 58-59 (Japan Liquid Crystal Debate) 1998) and (4) a liquid crystal cell of SURVAIVAL mode (presented by LCD International 98).

The OCB mode liquid crystal cell is a liquid crystal display device using a bend alignment mode liquid crystal cell that aligns rod-shaped liquid crystalline molecules in a substantially opposite direction (symmetrically) at the top and bottom of the liquid crystal cell. 5410422 is disclosed in each specification. Since the rod-like liquid crystal molecules are symmetrically aligned at the top and bottom of the liquid crystal cell, the liquid crystal cell in the bend alignment mode has a magneto-optic compensation function. Therefore, this liquid crystal mode is also called OCB (Optically Compensatory Bend) liquid crystal mode. The liquid crystal display of the bend alignment mode has an advantage that the response speed is high.

In the liquid crystal cell of the ECB mode, the rod-like liquid crystal molecules are substantially horizontally aligned when voltage is not applied, and is most often used as a color TFT liquid crystal display device, and has been described in many documents. For example, "EL, PDP, LCD Display" is published in the Tore Research Center (2001).

In particular, the liquid crystal display device in the TN mode or the IPS mode is particularly preferable in that the polarizing plate of the present invention has the antireflection effect and the viewing angle enlargement effect at the thickness of one polarizing plate.

Example

Although this invention is demonstrated by the following Example, this invention is not limited to these. In addition, "part" and "%" are mass references | standards unless there is particular notice.

<Example of 1st aspect>

The pair of polarizing plates and the pair of optical compensation sheets formed on the liquid crystal display device (manufactured by Fujitsu Co., Ltd.) using the vertical alignment liquid crystal cell were removed, and the liquid crystal cell was taken out. Between the cells taken out and the polarizer, several transparent samples having various Re retardation values and Rth retardation values are piled up so that their axes overlap, and an optimal retardation with good viewing angle characteristics and black display becomes neutral. As a result, it was found that the Re value was 52 nm and the Rth value was 132 nm, and the target optical performance was obtained.

(Production of Retardation Film R-1)

Each component of the following cellulose acetate solution composition was thrown into the mixing tank, it stirred while heating, each component was melt | dissolved, and the cellulose acetate solution A was prepared.

(Composition of Cellulose Acetate Solution A)

100 parts by mass of cellulose acetate having an acetylation degree of 60.9%

Triphenyl phosphate (plasticizer) 7.8 parts by mass

Biphenyl diphenyl phosphate (plasticizer) 3.9 parts by mass

318 parts by mass of methylene chloride (first solvent)

47 parts by mass of methanol (second solvent)

16 mass parts of following retardation control agents (1), 87 mass parts of methylene chlorides, and 13 mass parts of methanol were thrown into another mixing tank, and it stirred while heating, and prepared the solution of retardation control agents (1).

36 mass parts of said retardation control agent (1) solutions were mixed with 474 mass parts of cellulose acetate solutions A, and it fully stirred, and dope was prepared. The addition amount of the retardation control agent (1) was 5.0 mass parts with respect to 100 mass parts of cellulose acetates.

Retardation Control (1)

[Formula 22]

The obtained dope was cast using a band softener. The film with 15 mass% of residual solvents was transversely stretched by the tenter using the tenter on 130 degreeC conditions, and the cellulose acetate film (thickness: 80 micrometers) was produced. About the produced cellulose acetate film (retardation film R-1), Re-retardation value and Rth retardation value in wavelength 633nm were measured using the ellipsometer (M-150, Nippon Bunco Co., Ltd. product). . The results are shown in Table 1.

(Production of Retardation Film R-2)

16 mass parts of following retardation control agents (2), 87 mass parts of methylene chlorides, and 13 mass parts of methanol were thrown into the mixing tank, and it stirred while heating, and prepared the solution of retardation control agents (2).

36 mass parts of said retardation control agent (2) solutions were mixed with 474 mass parts of cellulose acetate solutions A, and it fully stirred, and dope was prepared. The addition amount of the retardation control agent (2) was 5.0 mass parts with respect to 100 mass parts of cellulose acetates.

Retardation Control (2)

(23)

The cellulose acetate film which was transversely stretched was produced like retardation film R-1 except having set draw ratio to 28% and film thickness to 82 micrometers. About the produced cellulose acetate film (retardation film R-2), Re retardation value and Rth retardation value were evaluated like retardation film R-1. The results are shown in Table 1.

(Production of Retardation Film R-3)

Each component of the following addition solution composition was put into the mixing tank, stirred while heating to dissolve each component, and the addition liquid which added the new additive to the retardation regulator was adjusted.

(Addition solution composition)

16 parts by mass of the retardation control agent

1 part by mass of trimethyl trimellitate

Methylene chloride (first solvent) 87 parts by mass

13 parts by mass of methanol (second solvent)

44 mass parts of said addition solutions were mixed with 474 mass parts of cellulose acetate solutions A, and it fully stirred, and dope was prepared. The addition amount of the retardation control agent (1) was 6.0 mass parts with respect to 100 mass parts of cellulose acetates.

In the same manner as in the retardation film R-1, a cellulose acetate film transversely stretched was produced. About the produced cellulose acetate film (retardation film R-3), Re retardation value and Rth retardation value were evaluated like retardation film R-1. The results are shown in Table 1.

(Production of Retardation Film R-4)

16 mass parts of following retardation control agents (3), 87 mass parts of methylene chlorides, and 13 mass parts of methanol were thrown into the mixing tank, and it stirred while heating, and prepared the solution of retardation control agents (3).

30 mass parts of said retardation control agent (3) solutions were mixed with 474 mass parts of cellulose acetate solutions A, and it fully stirred, and dope was prepared. The addition amount of the retardation regulator was 4.2 mass parts with respect to 100 mass parts of cellulose acetates.

Retardation Control (3)

&Lt; EMI ID =

After being flexible on a band, it separated by 32% of the residual solvent, and then transversely stretched with the tenter stretching machine. The draw ratio was 15%, and the draw temperature was 110 ° C. Then, it dried by the warm air of 130 degreeC, and produced the cellulose acetate film. The film thickness of the film after drying was 96 micrometers. About the obtained cellulose acetate film (retardation film R-4), Re retardation value and Rth retardation value were evaluated like retardation film R-1. The results are shown in Table 1.

(Production of Retardation Film R-5)

The cellulose acetate film A (retardation film R-5) was produced and evaluated similarly to retardation film R-1 except having used cellulose acetate solution A as a dope as it is, and not extending | stretching with a film thickness of 80 micrometers. . The results are shown in Table 1.

(Preparation of Coating Liquid A for Hard Coat Layer)

The following composition was thrown into the mixing tank, it stirred, and it was set as the hard-coat layer coating liquid A.

(Coating Liquid A Composition for Hard Coat Layer)

Desolite Z 7404 100 parts by mass

(Zirconia fine particle-containing hard coat composition liquid: JSR Corporation)

DPHA 31 parts by mass

(UV curable resin: produced by Nippon Kayaku Co., Ltd.)

KBM-5103 10 parts by mass

(Silane coupling agent: manufactured by Shin-Etsu Chemical Co., Ltd.)

KE-P150 8.9 parts by mass

(1.5 μm silica particles: manufactured by Nippon Shokubai Co., Ltd.)

MXS-300 3.4 parts by mass

(3.0 μm crosslinked PMMA particles: manufactured by Soken Chemical Co., Ltd.)

Methyl ethyl ketone (MEK) 29 parts by mass

13 parts by mass of methyl isobutyl ketone (MIBK)

(Preparation of Coating Liquid B for Hard Coat Layer)

The following composition was thrown into the mixing tank, it stirred, and it was set as the hard-coat layer coating liquid B.

(Coating Liquid B Composition for Hard Coat Layer)

Desolite Z 7404 100 parts by mass

(Zirconia fine particle-containing hard coat composition liquid: JSR Corporation)

DPHA 31 parts by mass

(UV curable resin: produced by Nippon Kayaku Co., Ltd.)

KBM-5103 10 parts by mass

(Silane coupling agent: manufactured by Shin-Etsu Chemical Co., Ltd.)

KE-P150 4.3 parts by mass

(1.5 μm silica particles: manufactured by Nippon Shokubai Co., Ltd.)

Methyl ethyl ketone (MEK) 29 parts by mass

13 parts by mass of methyl isobutyl ketone (MIBK)

(Preparation of titanium dioxide fine particle dispersion)

Titanium dioxide fine particles (MPT-129C, manufactured by Ishihara Industries Co., Ltd.) containing cobalt and surface-treated with aluminum hydroxide and zirconium hydroxide were used as the titanium dioxide fine particles.

38.6 g of the following dispersing agents and 704.3 g of cyclohexanone were added to this particle 257.1 g, and it disperse | distributed with dynomil, and prepared the titanium dioxide dispersion liquid of the mass mean diameter 70nm.

Dispersant

(25)

(Preparation of coating liquid for medium refractive index layer)

The following composition was put into a mixing tank and stirred, and it filtered with the polypropylene filter of 0.4 micrometers of pore diameters, and prepared the coating liquid for medium refractive index layers.

(Coating Liquid Composition for Medium Refractive Index Layer)

100 parts by mass of the titanium dioxide fine particle dispersion

DPHA 66 parts by mass

(UV curable resin: produced by Nippon Kayaku Co., Ltd.)

Irgacure 907 3.5 parts by mass

(Photoinitiator: Chiba Co., Ltd. product)

Gay cure DETX 1.2 parts by mass

(Sensitizer: Nippon Kayaku Co., Ltd.)

Methyl ethyl ketone (MEK) 543 parts by mass

2,103 parts by mass of cyclohexanone

(Preparation of coating liquid for high refractive index layer)

The following composition was thrown into the mixing tank, stirred, and filtered by the polypropylene filter of 0.4 micrometer of pore diameters after that, and the coating liquid for high refractive index layers was prepared.

(Coating liquid composition for high refractive index layer)

100 parts by mass of titanium dioxide fine particle dispersion

DPHA 8.2 parts by mass

(UV curable resin: produced by Nippon Kayaku Co., Ltd.)

Irgacure 907 0.68 parts by mass

(Photoinitiator: Chiba Co., Ltd. product)

Kayacure DETX 0.22 parts by mass

(Sensitizer: Nippon Kayaku Co., Ltd.)

Methyl ethyl ketone (MEK) 78 parts by mass

243 parts by mass of cyclohexanone

(Preparation of sol liquid a)

A reactor with a stirrer, a reflux cooler, 120 parts by mass of methyl ethyl ketone, 100 parts by mass of acryloyloxypropyltrimethoxysilane (KBM-5103 (trade name); manufactured by Shin-Etsu Chemical Co., Ltd.), diisopropoxy aluminum ethyl aceto After adding 3 parts by mass of acetate and mixing, 30 parts by mass of ion-exchanged water were added and reacted at 60 ° C for 4 hours, and then cooled to room temperature to obtain a sol liquid a. The mass average molecular weight was 1800, and the component whose molecular weight is 1000-20000 was 100% among the components more than an oligomer component. In addition, from gas chromatography analysis, acryloyloxypropyltrimethoxysilane as a raw material did not remain at all.

(Synthesis of Perfluoroolefin Copolymer (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 equipped with a 100 ml stainless steel stirrer, and the system was degassed and replaced with nitrogen gas. In addition, 25 g of hexafluoropropylene (HFP) was introduced into an autoclave and heated up to 65 ° C. The pressure at the time the temperature in the autoclave reached 65 ° C was 5.4 kg / cm 2. The reaction was continued for 8 hours while maintaining the temperature, and the heating was stopped and left to cool when the pressure reached 3.2 kg / cm 2. When the internal temperature dropped to room temperature, the unreacted monomer was removed, and the autoclave was opened to extract the reaction solution. The obtained reaction liquid was thrown into a large excess of hexane, and the precipitated polymer was extracted 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. After drying, 28 g of a polymer was obtained. 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, and 19 g of a perfluoroolefin copolymer (1) was obtained by reprecipitating the obtained polymer with hexane. The refractive index of the obtained polymer was 1.421.

(26)

(Preparation of coating liquid A for low refractive index layers)

The following composition was thrown into the mixing tank, and after stirring, it filtered with the polypropylene filter of 1 micrometer of pore diameters, and prepared coating liquid A for low refractive index layers.

(Coating Liquid A Composition for Low Refractive Index Layer)

Opstar JN7228A 100 parts by mass

Thermal crosslinkable fluorine-containing polymer composition: manufactured by JSR Co., Ltd.)

MEK-ST 4.3 parts by mass

(Silica dispersion average particle diameter: 15 nm: manufactured by Nissan Chemical Co., Ltd.)

MEK-ST particle size difference 5.1 parts by mass

(Silica dispersion average particle diameter: 45 nm: manufactured by Nissan Chemical Co., Ltd.)

Sol solution a 2.2 parts by mass

15 parts by mass of methyl ethyl ketone (MEK)

3.6 parts by mass of cyclohexanone

(Preparation of coating liquid B for low refractive index layers)

The following composition was put into the mixing tank, and after stirring, it filtered with the polypropylene filter of 1 micrometer of pore diameters, and prepared the coating liquid B for low refractive index layers.

(Preparation of coating liquid B for low refractive index layers)

DPHA 1.4 g

(UV curable resin: produced by Nippon Kayaku Co., Ltd.)

5.6 g perfluoroolefin copolymer (1)

20.0 g hollow silica fine particle dispersion

(Silver silica fine particle dispersion having surface modification of hollow silica CS-60 IPA (manufactured by Shokubai Chemical Co., Ltd.) with KBM-5103 (surface modulus vs. silica 30wt%, refractive index 1.31, average particle diameter 60nm, Shell thickness 10nm, solid content concentration 18.2%)

RMS-033 0.7 g

(Reactive Silicone: Gelest Co., Ltd.)

Irgacure 907 0.2 g

(Photoinitiator: Chiba Co., Ltd. product)

Sol solution a 6.2g

Methyl ethyl ketone (MEK) 306.9 g

9.0 g of cyclohexanone

(Production of Antireflection Film A-01)

A 80-micrometer-thick cellulose triacetate film (TD80U, manufactured by Fujishashin Film Co., Ltd.) as a support was unrolled from a roll, and on the support, the coating liquid A for the hard coat layer was selected at 135 pieces / inch and a depth of 60 μm. A microgravure roll having a diameter of 50 mm having a gravure pattern and a doctor blade were applied under conditions of a conveying speed of 10 m / min, dried at 60 ° C. for 150 seconds, and then again cooled to 160 W / cm under a nitrogen purge with a metal-cooled metal halide lamp. (Igraphics Co., Ltd. product) was used, the ultraviolet-ray of illumination intensity 400mW / cm <2> and irradiation amount 250mJ / cm <2> was irradiated, hardened an application layer, and the hard-coat layer 1 was formed and wound. After hardening, the gravure roll rotation speed was adjusted so that the thickness of a hard-coat layer might be 3.5 micrometers.

The refractive index of the binder containing the zirconia microparticles | fine-particles which comprise the hard-coat layer 1, 1.5 micrometers of silica particles, and 3.0 micrometers of PMMA particles was 1.62, 1.44, and 1.49, respectively.

The support on which the hard coat layer 1 was applied was uncoiled again, and the coating liquid A for the low refractive index layer was selected as 200 micrograms per inch and a gravure pattern having a gravure pattern of 30 μm in depth and a doctor blade. Using a carrier speed of 10 m / min, dried at 120 ℃ for 150 seconds, and then dried again at 140 ℃ 8 minutes, and then air cooled metal halide lamp of 240 W / cm under nitrogen purge (manufactured by Eye Graphics Co., Ltd.) ) Was used to irradiate ultraviolet rays with an illuminance of 400 mW / cm 2 and an irradiation amount of 900 mJ / cm 2 to form and wind the low refractive index layer 1. After hardening, the gravure roll rotation speed was adjusted so that the thickness of the low refractive index layer might be 100 nm.

(Production of Antireflection Films A-02 to 05)

The amount of the KE-P150 (silica 1.5 µm particles) added to the coating liquid A for the hard coat layer was changed to 7.0 parts by mass, 4.6 parts by mass, 2.1 parts by mass, and 0 parts by mass (not added) to form a hard coat layer (2, 3). , 4, 5) except that antireflection films A-02, A-03, A-04, and A-05 were produced in the same manner as in the antireflection film A-01.

(Production of Antireflection Films A-06 to 08)

The amount of the KE-P150 (silica 1.5 μm particles) added to the coating liquid A for the hard coat layer was changed to 4.6 parts by mass, and the hard coat layers 6, 7, 8 were made to have a thickness of 3.2 μm, 3.0 μm, or 2.7 μm. ) Was formed in the same manner as the antireflection film A-01, except that the antireflection films A-06, A-07, and A-08 were produced, respectively.

(Production of antireflection film A-09)

Except having formed the hard-coat layer 9 using the coating liquid B for hard-coat layers, it carried out similarly to anti-reflective film A-01, and produced anti-reflective film A-09.

The refractive index of the binder containing the zirconia microparticles | fine-particles which comprise the hard-coat layer 9, and 1.5 micrometers of silica particles was 1.62 and 1.44, respectively.

(Production of antireflection film A-10, 11)

Antireflection film except that the hard coat layers 10 and 11 were formed by changing the addition amount of KE-P150 (silica 1.5 μm particles) of the coating liquid B for hard coat layer to 2.0 parts by mass and 0 parts by mass (not added). In the same manner as in A-01, antireflection films A-10 and A-11 were produced, respectively.

(Production of antireflection films A-12, 13)

The antireflection film A- was formed in the same manner as the antireflection films A-03 and A-09 except that the low refractive index layer 2 was formed on the hard coat layers 3 and 9 using the coating liquid B for low refractive index layer. 12 and A-13 were produced, respectively.

(Production of Antireflection Film A-14)

In the same manner as in the antireflection film A-09, only the hard coat layer 9 was formed, and the film without the low refractive index layer was used as the antireflection film A-14.

(Production of Antireflection Film A-15)

As a support, the cellulose triacetate film (TD80U, manufactured by Fujishashin Film Co., Ltd.) having a thickness of 80 µm was released in a roll form, and the coating liquid B for a hard coat layer was applied onto the support using a gravure coater. After drying at 100 ° C, an air-cooled metal halide lamp of 160 W / cm (manufactured by Igraphics) was used while purging with nitrogen so that the oxygen concentration was 1.0 vol% or less, and the illuminance was 400 mW / cm 2, and the irradiation amount was 300 mJ / cm 2. UV light was irradiated to cure the coating layer to form a hard coat layer 12 having a thickness of 3.5 mu m.

On the hard coat layer 12, the coating liquid for medium refractive index layers was apply | coated using the gravure coater. After drying at 100 ° C., an air-cooled metal halide lamp of 240 W / cm (manufactured by Igraphics) was used while purging with nitrogen so that the oxygen concentration was 1.0 vol% or less, and the illuminance was 550 mW / cm 2, and the irradiation amount was 600 mJ / cm 2. Was irradiated with ultraviolet light to cure the coating layer to form a medium refractive index layer (refractive index 1.65, film thickness 67 nm).

On the medium refractive index layer, the coating liquid for high refractive index layer was apply | coated using the gravure coater. After drying at 100 ° C., an air-cooled metal halide lamp of 240 W / cm (manufactured by Igraphics) was used while purging with nitrogen so that the oxygen concentration was 1.0 vol% or less, and the illuminance was 550 mW / cm 2 and the irradiation dose was 600 mJ / cm 2. Ultraviolet rays were irradiated to cure the coating layer to form a high refractive index layer (refractive index 1.93, film thickness 107 nm).

On the high refractive index layer, the coating liquid A for low refractive index layers was apply | coated using the gravure coater. After drying at 80 ° C., an air-cooled metal halide lamp of 160 W / cm (manufactured by Eye Graphics Co., Ltd.) was used while purging with nitrogen so that the oxygen concentration was 1.0 vol% or less, and the illuminance was 550 mW / cm 2 and the irradiation dose was 600 mJ / cm 2. Ultraviolet light was irradiated to form a low refractive index layer 3 (refractive index 1.43, film thickness 86 nm). In this way, the antireflection layer 3 was formed on the hard-coat layer, and the antireflection film A-15 was produced.

(Saponification treatment of antireflection film and retardation film)

An aqueous 1.5 mol / 1 sodium hydroxide solution was prepared and kept at 55 ° C. A diluted sulfuric acid aqueous solution of 0.005 mol / 1 was prepared and kept at 35 ° C. The produced antireflection film and the retardation film were immersed in the sodium hydroxide aqueous solution for 2 minutes, and then immersed in water to sufficiently wash the sodium hydroxide aqueous solution. Subsequently, it was immersed in the said diluted sulfuric acid aqueous solution for 1 minute, and then immersed in water, and the diluted sulfuric acid aqueous solution was wash | cleaned sufficiently. Finally, the sample was sufficiently dried at 120 ° C.

In this way, the antireflection film and the retardation film in which the saponification process was completed were produced.

(Production of polarizing plate)

Iodine was adsorbed on the stretched polyvinyl alcohol film to prepare a polarizing film. The antireflection films A-01 to A-15 having been saponified were attached to one side of the polarizing film using a polyvinyl alcohol-based adhesive so that the support side (triacetyl cellulose) of the antireflection film was at the polarizing film side. In addition, the saponification-treated retardation films R-1 to R-5 were attached to the other side of the polarizing film so that the slow axis of the retardation film and the transmission axis of the polarizing film were substantially parallel using a polyvinyl alcohol-based adhesive. In this way, a polarizing plate is produced and a list of the produced polarizing plates is shown in Table 1.

(Evaluation of Antireflection Film, Retardation Film, and Polarizing Plate)

The following items were evaluated about the obtained antireflection film, retardation film, and polarizing plate. The results are shown in Table 1.

(1) Re, Rth retardation

Re-retardation value and Rth retardation value in wavelength 633nm were measured using the ellipsometer (M-150, Nippon Bunco Co., Ltd. product). The results are shown in Table 1.

(2) Center line average roughness (Ra)

The surface roughness of the antireflection film was measured by an atomic force microscope (AFM: Atomic Force Mi croscope, SPI3800N, manufactured by Seiko Instruments Co., Ltd.).

(3) Hayes

The haze of the antireflection film was measured using a haze meter MODEL 1001 DP (manufactured by Nippon Denshoku Industries Co., Ltd.).

(4) transmission image sharpness

The transmission image sharpness of the antireflection film was measured with an optical comb of 0.5 mm using a mapping tester (ICM-2D type) manufactured by Suga Test Machine Co., Ltd.

(5) Integral reflectance

The antireflection film was mounted on the integrating sphere of the spectrophotometer V-550 (manufactured by Nippon Bunco Co., Ltd.), and the integral reflectance was measured in the wavelength region of 380 to 780 nm to calculate an average reflectance of 450 to 650 nm to reflect the film. The protection was evaluated.

(6) black reproducibility

The polarizing plate on the viewing side formed in the liquid crystal display device (VL-1530S, manufactured by Fujitsu Co., Ltd.) using the VA type liquid crystal cell was removed, and instead of the polarizing plate produced above, It adhere | attached through the adhesive so that the transmission axis of a polarizing plate might correspond with the polarizing plate which was affixed on the product. In a bright room of 1000 lux, the liquid crystal display device was made black display, and the following criteria evaluated by visual observation from various viewpoints.

A: black enough

B: There is very little white

C: There is a weak white period

0: There is a strong white period

(7) Goniophotometer Scattering Strength Ratio

Using an automatic variable photometer GP-5 type (manufactured by Murakami Color Research Institute), the antireflection film was placed vertically with respect to the incident light, and the scattered light profile was measured over the entire orientation. Scattered light intensity of emission angle 30 ° for light intensity of emission angle 0 ° was determined.

(8) left and right color taste change

With respect to the liquid crystal display device prepared by evaluating the black reproducibility, the degree of yellow coloring of the white display when the time was tilted left and right was evaluated by visual observation based on the following criteria.

(Judgement standard of left and right color taste change)

A: Does not feel the coloring of yellow

B: Slightly colored yellow

C: weakly colored yellow

D: Strongly colored yellow

(9) viewing angle

About the liquid crystal display device created by evaluation of the said black reproducibility, the viewing angle of contrast 10 was computed from the measurement of a black display and a white display using the measuring device (EZ-Contrast 160D, ELDIM make).

[Table 1]

The following are clear from the result shown in Table 1. A retardation film having a Re retardation value of 20 to 70 nm, a Rth retardation value of 70 to 400 nm, and a Re / Rth ratio of 0.2 to 0.4, a hard coat layer having internal scattering resistance, and Ra having an antireflection of 0.10 μm or less The polarizing plate which combined the film improves the visibility in the darkroom displayed by contrast, the viewing angle characteristic with respect to a hue change, antireflective property, and black reproducibility to a very high level when used for a VA mode liquid crystal display device. . In addition, hollow silica fine particles are used for the low refractive index layer, and the medium / high / low refractive index layer and the multilayer optical interference layer are laminated, thereby exhibiting excellent antireflection.

<Example of 2nd aspect>

(Preparation of Coating Liquid A for Hard Coat Layer)

The following composition was thrown into the mixing tank, it stirred, and it was set as the hard-coat layer coating liquid A.

(Composition of Coating Liquid A for Hard Coat Layer)

Desolite Z7404 100 parts by mass

(Zirconia fine particle-containing hard coat composition liquid: manufactured by JSR Co., Ltd.)

DPHA 31 parts by mass

(UV curable resin: manufactured by Nippon Kayaku Co., Ltd.)

KBM-5103 10 parts by mass

(Silane coupling agent: manufactured by Shin-Etsu Chemical Co., Ltd.)

KE-P150 8.5 parts by mass

(1.5 μm silica particles: manufactured by Nippon Shokubai Co., Ltd.)

Methyl ethyl ketone (MEK) 29 parts by mass

13 parts by mass of methyl isobutyl ketone (MIBK)

(Preparation of Coating Liquid B for Hard Coat Layer)

The following composition was put into the mixing tank, it stirred, and it was set as the hard-coat layer coating liquid B.

(Coating Liquid B Composition for Hard Coat Layer)

Desolite Z7404 100 parts by mass

(Zirconia fine particle-containing hard coat composition liquid: manufactured by JSR Co., Ltd.)

DPHA 31 parts by mass

(UV curable resin: manufactured by Nippon Chemical Co., Ltd.)

KBM-5103 10 parts by mass

(Silane coupling agent: manufactured by Shin-Etsu Chemical Co., Ltd.)

KE-P150 8.9 parts by mass

(1.5 μm silica particles: manufactured by Nippon Shokubai Co., Ltd.)

MXS-300 3.4 parts by mass

(3.0㎛ crosslinked PMMA particle: manufactured by Soken Chemical Co., Ltd.)

Methyl ethyl ketone (MEK) 29 parts by mass

13 parts by mass of methyl isobutyl ketone (MIBK)

(Preparation of coating liquid C for hard coat layer)

Except for changing KE-P150 (1.5 μm silica particles: Nippon Shokubai Co., Ltd.) to 12 parts by mass of MX-150 (1.5 μm crosslinked PMMA particles: Soken Chemical Co., Ltd.) In the same manner, a coating liquid C for a hard coat layer was produced.

(Preparation of coating liquid D for hard coat layer)

The following composition was put into the mixing tank, it stirred, and it was set as the hard-coat layer coating liquid D.

(Coating Liquid D Composition for Hard Coat Layer)

Desolite Z7404 100 parts by mass

(Zirconia fine particle-containing hard coat composition liquid: manufactured by JSR Co., Ltd.)

DPHA 31 parts by mass

(UV curable resin: manufactured by Nippon Chemical Co., Ltd.)

KBM-5103 10 parts by mass

(Silane coupling agent: manufactured by Shin-Etsu Chemical Co., Ltd.)

Methyl ethyl ketone (MEK) 29 parts by mass

13 parts by mass of methyl isobutyl ketone (MIBK)

(Preparation of titanium dioxide fine particle dispersion)

Titanium dioxide fine particles (MPT-129C, manufactured by Ishihara Industrial Co., Ltd.) containing cobalt and surface-treated with aluminum hydroxide and zirconium hydroxide were used as the titanium dioxide fine particles.

The following dispersing agent 38.6g and 704.3g of cyclohexanone were added to this particle 257.1g, and it disperse | distributed by dynomil, and prepared the titanium dioxide dispersion liquid of the mass mean diameter 70nm.

Dispersant

[Formula 15]

(Preparation of coating liquid for medium refractive index layer)

The following composition was thrown into the mixing tank, stirred, and filtered with a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating liquid for medium refractive index layer.

(Coating Liquid Composition for Medium Refractive Index Layer)

100 parts by mass of the titanium dioxide fine particle dispersion

DPHA 66 parts by mass

(UV curable resin: manufactured by Nippon Chemical Co., Ltd.)

Irgacure 907 3.5 parts by mass

(Photoinitiator: manufactured by Chiba Chemical Co., Ltd.)

Gay cure DETX 1.2 parts by mass

(Sensitizer: Nippon Kayaku Co., Ltd.)

Methyl ethyl ketone (MEK) 543 parts by mass

2,103 parts by mass of cyclohexanone

(Preparation of coating liquid for high refractive index layer)

The following composition was thrown into the mixing tank and stirred, and it filtered with the polypropylene filter of 0.4 micrometers of pore diameters, and prepared the coating liquid for high refractive index layers.

(Coating liquid composition for high refractive index layer)

100 parts by mass of the titanium dioxide fine particle dispersion

DPHA 8.2 parts by mass

(UV curable resin: manufactured by Nippon Kayaku Co., Ltd.)

Irgacure 907 0.68 parts by mass

(Photoinitiator: manufactured by Chiba Chemical Co., Ltd.)

Kayacure DETX 0.22 parts by mass

(Sensitizer: Nippon Kayaku Co., Ltd.)

Methyl ethyl ketone (MEK) 78 parts by mass

243 parts by mass of cyclohexanone

(Preparation of sol liquid a)

A reactor with a stirrer, a reflux cooler, 120 parts by mass of methyl ethyl ketone, 100 parts by mass of acryloyloxypropyltrimethoxysilane (KBM-5103 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.), diisopropoxy aluminum ethyl acetate After adding 3 parts by mass of acetate and mixing, 30 parts by mass of ion-exchanged water were added and reacted at 60 ° C for 4 hours, and then cooled to room temperature to obtain a sol solution a. The mass average molecular weight was 1800, and the component whose molecular weight is 1000-20000 was 100% among the components more than an oligomer component. In addition, no acryloyloxypropyltrimethoxysilane of the raw material remained at all from gas chromatography analysis.

(Preparation of coating liquid A for low refractive index layers)

The following composition was put into a mixing tank, stirred, and filtered with a polypropylene filter having a pore diameter of 1 μm to prepare a coating solution A for low refractive index layer.

(Coating Liquid A Composition for Low Refractive Index Layer)

Opstar JN7228A 100 parts by mass

(Thermocrosslinkable fluorine-containing polymer composition: manufactured by JSR Co., Ltd.)

MEK-ST 4.3 parts by mass

(Silica dispersion product average particle diameter: 15nm: manufactured by Nissan Chemical Co., Ltd.)

5.1 parts by mass of difference in particle size of MEK-ST

(Silica dispersion product average particle diameter 45nm: manufactured by Nissan Chemical Co., Ltd.)

Sol solution a 2.2 parts by mass

15 parts by mass of methyl ethyl ketone (MEK)

3.6 parts by mass of cyclohexanone

(Synthesis of Perfluoroolefin Copolymer (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 equipped with a 100 ml stainless steel stirrer, and the system was degassed and replaced with nitrogen gas. Furthermore, 25 g of hexafluoropropylene (HFP) was introduced into an autoclave and heated up to 65 degreeC. The pressure at the time the temperature in the autoclave reached 65 ° C was 5.4 kg / cm 2. The reaction was continued for 8 hours while maintaining the temperature, and the heating was stopped and left to cool when the pressure reached 3.2 kg / cm 2. Unreacted monomer was removed at the time when the internal temperature fell to room temperature, the autoclave was opened, and the reaction liquid was taken out. The obtained reaction liquid was thrown into excess hexane, and the precipitated polymer was taken out by removing a solvent by decantation. The polymer was again dissolved in a small amount of ethyl acetate and reprecipitated twice from hexane to completely remove the remaining monomers. After drying, 28 g of a polymer was obtained. Next, 20 g of this 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, and the organic layer was extracted and concentrated. Then, 19 g of a perfluoroolefin copolymer (1) was obtained by reprecipitating the obtained polymer with hexane. The refractive index of the obtained polymer was 1.421.

[Chemical Formula 16]

(Preparation of coating liquid B for low refractive index layers)

The following composition was thrown into the mixing tank and stirred, and it filtered with the polypropylene filter of 1 micrometer of pore diameters, and prepared the coating liquid B for low refractive index layers.

(Composition of Coating Liquid B for Low Refractive Index Layer)

100 parts by mass of perfluoroolefin copolymer (1)

X-22-164B (manufactured by Shin-Etsu Chemical Co., Ltd.) 2.0 parts by mass

9.2 parts by mass of particle size difference of MEK-ST

(Silica dispersion average particle diameter 45nm: manufactured by Nissan Chemical Co., Ltd.)

Sol solution a 2.6 parts by mass

Irgacure 907 5.0 parts by mass

(Photoinitiator: manufactured by Chiba Chemical Co., Ltd.)

Methyl ethyl ketone (MEK) 1990 parts by mass

60 parts by mass of cyclohexanone

(Production of Antireflection Film A-01)

As a support, a 80-micrometer-thick cellulose triacetate film (TD80U, manufactured by Fujishashin Film Co., Ltd.) was unrolled into rolls, and the gravure pattern having a depth of 135 microns / inch and a depth of 60 micrometers was applied to the coating liquid A for the hard coat layer. Using a microgravure roll having a diameter of 50 mm and a doctor blade, they were applied under conditions of a conveying speed of 10 m / min, dried at 60 ° C. for 150 seconds, and then again cooled to 160 W / cm under a nitrogen purge with an air-cooled metal halide lamp (iGraphics) (Manufactured by Co., Ltd.), ultraviolet rays having an illuminance of 400 mW / cm 2 and an illuminance of 250 mJ / cm 2 were irradiated to cure the coating layer to form and wind the hard coat layer 1. After hardening, the gravure roll rotation speed was adjusted so that the thickness of a hard-coat layer might be 3.5 micrometers.

The refractive index of the binder containing the zirconia microparticles | fine-particles which comprise the hard-coat layer 1, and 1.5 micrometers of silica particles was 1.62 and 1.44, respectively.

The support on which the hard coat layer 1 was applied was again released, and the coating solution A for the low refractive index layer was obtained with a microgravure roll and a doctorblate having a diameter of 200 mm / inch and a gravure pattern having a depth of 30 μm. Using a carrier speed of 10 m / min, and dried for 150 seconds at 120 ℃, then 8 minutes at 140 ℃ and then air cooled metal halide lamp of 240 W / cm under nitrogen purge (iGraphics Co., Ltd.) UV light having an illuminance of 400 mW / cm 2 and an irradiation amount of 900 mJ / cm 2, was produced to form a low refractive index layer 1. After hardening, the gravure roll rotation speed was adjusted so that the thickness of the low refractive index layer might be 100 nm.

(Production of Antireflection Films A-02 to 05)

The anti-reflection film A- was applied to the hard coat layer except that the hard coat layers 2, 3, 4, and 5 were formed so that the thickness of the hard coat layer was 3.5 µm, 3.2 µm, 3.0 µm, and 2.7 µm, respectively. In the same manner as in 01, antireflection films A-02, A-03, A-04, and A-05 were produced, respectively.

The refractive index of the binder containing the zirconia microparticles | fine-particles which comprise hard-coat layers 2-5, 1.5 micrometers particle | grains of silica, and 3.0 micrometers of PMMA particles was 1.62, 1.44, and 1.49, respectively.

(Production of Antireflection Films A-06 to 09)

By the coating liquid A for the hard coat layer, the number and rotation of the microgravure roll are adjusted so that the thickness of the hard coat layer is 1.7 µm, 2.2 µm, 6.2 µm, and 9.8 µm, and the hard coat layer 6, 7, 8 , 9), and the antireflection films A-06 and A- in the same manner as in the antireflection film A-01 except that the low refractive index layer 2 was formed again using the coating liquid B for the low refractive index layer. 07, A-08, and A-09 were produced, respectively.

(Production of Antireflection Film A-10)

Except having provided the hard-coat layer 10 by the coating liquid C for hard-coat layers so that the thickness of a hard-coat layer might be set to 3.5 micrometers, it carried out similarly to anti-reflective film A-06, and produced the anti-reflective film A-10.

The refractive index of the binder containing the zirconia microparticles | fine-particles which comprise the hard-coat layer 10, PMMA 1.5 micrometer particle, and PMMA particle 3.0 micrometer is 1.62 and 1.49, respectively. 1.49.

(Production of Antireflection Film A-11)

Except having provided the hard-coat layer 11 by the coating liquid D for hard-coat layers so that the thickness of a hard-coat layer might be set to 3.5 micrometers, it carried out similarly to anti-reflective film A-06, and produced the anti-reflective film A-11.

The refractive index of the binder containing the zirconia fine particles which comprise the hard-coat layer 11 was 1.62.

(Production of Antireflection Film A-12)

The coating liquid A for hard-coat layer was apply | coated on the support body 4 using the gravure coater. After drying at 100 ° C., a nitrogen-fueled 160 W / cm air halide lamp (manufactured by Eye Graphics Co., Ltd.) was purged with nitrogen so that the oxygen concentration was 1.0 vol% or less, and the illuminance was 400 mW / cm 2 and the irradiation dose was 300 mJ / cm 2. Ultraviolet rays were irradiated to cure the coating layer to form a hard coat layer 12 having a thickness of 3.5 mu m.

The coating liquid for medium refractive index layers was apply | coated on the hard-coat layer 12 using the gravure coater. After drying at 100 ° C., an illuminance of 550 mW / cm 2 and irradiation amount of 600 mJ / cm 2 were obtained by using an air-cooled metal halide lamp of 240 W / cm (manufactured by Igraphics) while purging nitrogen so that the oxygen concentration was 1.0 vol% or less. Was irradiated with ultraviolet light to cure the coating layer to form a medium refractive index layer (refractive index 1.65, film thickness 67 nm).

The coating liquid for high refractive index layers was apply | coated on the medium refractive index layer using the gravure coater. After drying at 100 ° C, using an air-cooled metal halide lamp of 240 W / cm (manufactured by Ipix Co., Ltd.) while purging nitrogen so that the oxygen concentration is 1.0 vol% or less, illuminance of 550 mW / cm 2, irradiation amount 600 mJ / cm 2 Was irradiated with ultraviolet light to cure the coating layer, thereby forming a high refractive index layer (refractive index 1.93, film thickness 107 nm).

The coating liquid B for low refractive index layers was apply | coated on the high refractive index layer using the gravure coat roll. After drying at 80 ° C, using an air-cooled metal halide lamp of 160 W / cm (manufactured by Ipix Co., Ltd.) while purging nitrogen so that the oxygen concentration is 1.0 vol% or less, illuminance of 550 mW / cm 2, irradiation amount 600 mJ / cm 2 Ultraviolet light was irradiated to form a low refractive index layer (refractive index 1.43, film thickness 86 nm). Thus, the antireflection layer 3 was formed on the hard-coat layer, and the antireflection film A-12 was produced.

(Production of Antireflection Film A-13)

In the same manner as in the antireflection film A-02, only the hard coat layer 2 was formed, and the film not forming the low refractive index layer was used as the antireflection film A-13.

(Saponification of antireflection film)

A 1.5 mol / L aqueous sodium hydroxide solution was prepared and kept at 55 ° C. A 0.005 mol / L diluted aqueous sulfuric acid solution was prepared and kept at 35 ° C. The produced antireflection film was immersed in the aqueous sodium hydroxide solution for 2 minutes, and then immersed in water to thoroughly wash the aqueous sodium hydroxide solution. Subsequently, the solution was immersed in the diluted sulfuric acid aqueous solution for 1 minute, and then immersed in water to sufficiently wash the diluted sulfuric acid aqueous solution. Finally, the sample was sufficiently dried at 120 ° C.

In this way, the antireflection film in which the saponification process was completed was produced.

(Production of polarizing plates PA-01 to 13 with antireflection film)

Iodine was adsorbed on the stretched polyvinyl alcohol film to prepare a polarizing plate. The polyvinyl alcohol-type adhesive agent was used for the antireflection films A-01-A-13 which completed the saponification process, and it adhere | attached on one side of a polarizing film so that the support body side (triacetyl cellulose) of an antireflection film might be a polarizing film side. Moreover, the viewing angle which has an optical compensation layer in which the disc surface of a discotic structural unit inclines with respect to a film surface, and the angle which the disc surface of this discotic structural unit and a film surface make changes in the depth direction of an optically anisotropic layer. The enlarged film (Wide View Film Super Ace, manufactured by Fujishashin Film Co., Ltd.) was saponified and adhered to the other side of the polarizing film using a polyvinyl alcohol-based adhesive. In this way, polarizing plates PA-01 to 13 were produced.

(Evaluation of Antireflection Film and Polarizing Plate)

The following items were evaluated about the obtained antireflection film and polarizing plate. The results are shown in Table 1.

(1) Center line average roughness Ra

The surface roughness of the antireflection film was measured by an atomic force microscope (AFM: Atomic Force Microscope, SPI3800N, manufactured by Seiko Instruments Co., Ltd.).

(2) haze

The haze of the antireflection film was measured using a haze meter MODEL 1001DP (manufactured by Nippon Denshoku Industries Co., Ltd.).

(3) transmission image sharpness

The transmission image clarity of the antireflection film was measured with an optical comb of 0.5 mm using a mapping tester manufactured by Suga Test Co., Ltd. (ICM-2D type).

(4) mirror reflectance

An antireflection film was attached to the adapter ARV-474 of the spectrophotometer V-550 (manufactured by Nippon Bunco Co., Ltd.), and a specular reflectance of -5 ° with an exit angle of 5 ° at an incident angle of 5 ° in a wavelength region of 380 to 780 nm was obtained. It measured, and calculated the average reflectance of 450-650 nm, and evaluated antireflection property.

(5) Integral reflectance

The antireflection film was mounted on the integrating sphere of the spectrophotometer V-550 (manufactured by Nippon Bunco Co., Ltd.), and the integral reflectance was measured in the wavelength region of 380 to 780 nm, and the average reflectance of 450 to 650 nm was calculated to calculate the antireflection film. Was evaluated.

(6) black reproducibility

Remove the polarizing plate on the viewing side installed in the liquid crystal display device (TH-15TA2, manufactured by Matsushita Electric Industry Co., Ltd.) using a TN type liquid crystal cell, and instead, the antireflection film side recognizes the polarizing plates PA-01 to 13. On the side, it adhere | attached through the adhesive so that the transmission axis of a polarizing plate might correspond with the polarizing plate stuck to the product. The liquid crystal display device was made black display in the bright room of 1000 lux, and it evaluated by the following criteria visually from various viewpoints.

A: black enough

B: There is very little white

C: There is a weak white period

0: There is a strong white period

(7) Goniophotometer Scattering Strength Ratio

Using an automatic variable photometer GP-5 type (manufactured by Murakami Color Research Institute), the antireflection film was placed vertically with respect to the incident light, and the scattered light profile was measured over the entire orientation. The scattered light intensity of the exit angle of 30 ° was calculated for the light intensity of the exit angle of 0 °.

(8) viewing angle

* The viewing angle of contrast 10 was calculated from the measurement of black display and white display using a measuring instrument (EZ-Contrast 160D, manufactured by ELDIM) for the liquid crystal display device produced by the evaluation of the black reproducibility.

[Table 1]

<Example of 3rd aspect>

(Synthesis of the following perfluoroolefin copolymer (1))

[Chemical Formula 20]

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 100 ml sterilized stirrer, and the inside of the system was degassed and replaced with nitrogen gas. 25 g of hexafluoropropylene (HFP) was again introduced into an autoclave and heated up to 65 degreeC. The pressure at the time the temperature in the autoclave reached 65 ° C was 5.4 kg / cm 2. The reaction was continued for 8 hours while maintaining the temperature, and the heating was stopped and left to cool when the pressure reached 3.2 kg / cm 2. Unreacted monomer was removed at the time when the internal temperature fell to room temperature, the autoclave was opened, and the reaction liquid was taken out. The obtained reaction liquid was thrown into excess hexane, and the precipitated polymer was taken out by removing a solvent by decantation. The polymer was again dissolved in a small amount of ethyl acetate and reprecipitated twice from hexane to completely remove the remaining monomers. After drying, 28 g of a polymer was obtained.

Next, 20 g of this 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, and the organic layer was extracted and concentrated. Then, 19 g of a perfluoroolefin copolymer (1) was obtained by reprecipitating the obtained polymer with hexane. The refractive index of the obtained polymer was 1.421.

(Synthesis of bloso type surface modifier P-8)

In a reactor equipped with a stirrer and a reflux condenser, 1H, 1H, 7H-dodecafluoroheptyl acrylate 39.93g, dimethyl 2,2'-azobisisobutyrate 1.1g, 2-butanone 30g under a nitrogen atmosphere for 6 hours The reaction was completed by heating to 78 ° C. The mass average molecular weight was 2.9 × 10 ⁴ .

(Preparation of sol liquid a)

Stirrer, reactor with reflux condenser, 120 parts of methyl ethyl ketone, 100 parts of acryloyloxypropyl trimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), diisopropoxy aluminum ethyl acetaldehyde 3 30 parts of ion-exchange water was added after making a part add and mix, and after making it react for 4 hours at 60 degreeC, it cooled to room temperature and obtained the sol liquid a. The mass average molecular weight was 1600, and the component whose molecular weight is 1000-20000 was 100% among the components more than an oligomer component. In addition, no acryloyloxypropyltrimethoxysilane of the raw material remained at all by gas chromatography analysis.

(Preparation of coating liquid-1 for antistatic layer for hard coat layer formation having antistatic property)

To the mixture of 190 g of ethanol and 82 g of methyl ethyl ketone, 176 g of tin oxide dispersion liquid doped with antimony described later was added. 2.4 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) was added thereto, followed by polymerization initiator (irgacure 184, Chivas Specialty Chemicals Co., Ltd.). 0.3 g of (Preparation) were added and mixed and stirred. Ultrasonic dispersion of an oscillation tip immersion type was prepared in this liquid over 10 minutes for coating liquid-1 for antistatic layer.

The obtained antistatic layer coating liquid-1 was applied to a triacetyl cellulose film (0.2% haze of only film) having a thickness of 80 µm by the method described in the application of the internal constituent layer described later. The haze of this sample was 2.8%. The surface resistivity of this sample was measured by the original electrode method and found to be 1.8 × 10 ¹⁰ Ω / □ (25 ° C., 60% RH).

(Preparation of antimony dope tin oxide dispersion)

의 유리비드를 150g 첨가하여 내압 핀에 넣고, 페인트 쉐이커로 50시간 분산하였다. 평균입경은 85㎚ 이었다.1 mm to a mixed liquid in which 132 g of ethanol and 3 g of carboxylic acid group-containing acrylic polymer were added to 15 g of tin oxide fine particle powder (SN-100P manufactured by Ishihara Techno Co., Ltd.) doped with antimony.

150 g of glass beads were added, placed in a pressure resistant pin, and dispersed in a paint shaker for 50 hours. The average particle diameter was 85 nm.

(Preparation of coating liquid A for anti-glare hard coat layer)

50 g of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (PETA, manufactured by Nippon Kayaku Co., Ltd.) was diluted with 38.5 g of toluene. In addition, 2 g of a polymerization initiator (Irgacure 184, manufactured by Chivas Specialty Chemicals Co., Ltd.) was added, followed by mixing and stirring. The refractive index of the coating film obtained by apply | coating this solution and UV-curing was 1.51.

In this solution, 1.7 g of a 30% toluene dispersion of a crosslinked polystyrene particle having a mean particle size of 3.5 μm (refractive index of 1.61, SX-350, manufactured by Soken Chemical Co., Ltd.), which was dispersed at 10000 rpm for 20 minutes using a polytron disperser, and an average particle size of 3.5 13.3 g of a 30% toluene dispersion of μm-crosslinked acrylic-styrene particles (refractive index 1.55, manufactured by Soken Chemical Co., Ltd.) was added, and finally, 0.75 g of the fluorine-based surface modifier (P-8) and a silane coupling agent (KBM-5103). 10 g of Shin-Etsu Chemical Co., Ltd. product was added, and the liquid mixture was obtained.

The mixed solution was filtered through a polypropylene filter having a pore diameter of 30 μm to prepare a coating solution A of the anti-glare hard coat layer.

The surface tension before adding the fluorine-type surface modifier (P-8) to this coating liquid A was 35 mN / m, and the surface tension after addition was 32 mN / m.

(Preparation of coating liquid B for anti-glare hard coat layer)

Except having changed the fluorine-type surface modifier (P-8) of the said coating liquid A for anti-glare hard-coat layers into said (P-13), it carried out similarly to this coating liquid A, and prepared coating liquid B for anti-glare hard-coat layers. .

The surface tension before adding the fluorine-type surface modifier (P-13) to this coating liquid B was 35 mN / m, and the surface tension after addition was 30 mN / m.

* (Preparation of coating liquid C for anti-glare hard coat layer)

Except having changed all the particle diameters of the crosslinked polystyrene and crosslinked acryl-styrene particle | grains of the said coating liquid A for anti-glare hard-coat layers into 4.5 micrometers, it carried out similarly to coating liquid A, and prepared coating liquid C for anti-glare hard-coat layers.

The surface tension before adding the fluorine-type surface modifier (P-13) to this coating liquid C was 35 mN / m, and the surface tension after addition was 30 mN / m.

(Preparation of coating liquid D for anti-glare hard coat layer)

Except having changed all the particle diameters of the crosslinked polystyrene and crosslinked acryl-styrene particle | grains of the coating liquid A for anti-glare hard-coat layers into 2.5 micrometers, it carried out similarly to coating liquid A, and prepared coating liquid D for anti-glare hard-coat layers.

The surface tension before adding the fluorine-type surface modifier (P-13) to this coating liquid D was 35 mN / m, and the surface tension after addition was 30 mN / m.

(Preparation of Coating Liquid B for Light Diffusion Layer)

Commercially available zirconia-containing UV curable hard coat liquid (Desolite Z7404, manufactured by JSR Co., Ltd., concentration of about 61% solids, about 70% ZrO ₂ content in solids, polymerizable monomer, polymerization initiator) 285 g, dipentaerythritol pentaacrylic acid 85 g of a mixture of the rate and pentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) was mixed, and further diluted with 60 g of methyl isobutyl ketone and 17 g of methyl ethyl ketone. Again, 28 g of a silane coupling agent (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed and stirred. The refractive index of the coating film obtained by apply | coating this solution and UV-curing was 1.61, and the conditions of the high refractive index layer in this invention were satisfied.

In addition, 30% methyl isobutyl ketone dispersion of class-reinforced crosslinked PMMA particles (refractive index 1.49, MXS-300, manufactured by Soken Chemical Co., Ltd.) having an average particle diameter of 3.0 µm was dispersed in a solution using a polytron dispersion machine for 20 minutes at 10000 rpm. 35g was added, and the dispersion liquid which disperse | distributed 30% methyl ethyl ketone dispersion liquid of the silica particle (refractive index 1.46, Sea host KE-P150, Nippon Shokubai Co., Ltd.) of 1.5 micrometers of average particle diameters at 10000 rpm by 30 minutes by polytron disperser 90 g of was added, and finally 0.12 g of a fluorine-based surface modifier (P-8) was mixed and stirred to prepare a finished liquid.

The mixed solution was filtered through a polypropylene filter having a pore diameter of 30 μm to prepare a coating solution B of a photoacid layer.

(Preparation of Coating Liquid C for Light Diffusion Layer)

* In the coating liquid B for the light diffusion layer, instead of silica particles having an average particle size of 1.5 µm, classification-reinforced high-crosslinked PMMA particles having an average particle diameter of 1.5 µm (MXS-150H, crosslinking agent ethylene glycol dimethacrylate, crosslinking agent amount 30%, Soken Chemical A coating solution C for light-diffusion layer was prepared in the same manner as in the coating solution A, except that 130 g of a 30% methyl ethyl ketone dispersion having a manufacture and a refractive index of 1.49) was used.

The refractive index of the coating film obtained by apply | coating this solution and UV-curing was 1.61, and the conditions of the high refractive index layer in this invention were satisfied.

(Preparation of coating liquid A for low refractive index layers)

Thermal crosslinkable fluorine-containing polymer with a refractive index of 1.42 (JN7228A, solid content concentration 6%, manufactured by JSR Corporation) 15 g, silica gel (silica, MEK-ST, average particle diameter 15 nm, solid content concentration 30%, manufactured by Nissan Chemical Co., Ltd.) 0.6 g, silica Sol (silica, MEK-ST particle size difference, average particle diameter 45nm, solid concentration 30%, Nissan Chemical Co., Ltd.) 0.8g, sol solution a 0.4g, methyl ethyl ketone 3g and cyclohexane 0.6g are added, After stirring, it filtered with the polypropylene filter of 1 micrometer of pore diameters, and prepared coating liquid A for low refractive index layers.

(Preparation of coating liquid B for low refractive index layers)

15.2 g of perfluoroolefin copolymer (1), silica gel (silica, MEK-ST particle size difference product, average particle diameter 45nm, solid content concentration 30%, Nissan Chemical Co., Ltd.) 1.4g, reactive silicone X-22- 164B (brand name; Shin-Etsu Chemical Co., Ltd.) 0.3g, sol liquid a 7.3g, a photoinitiator (Irgacure 907 (brand name), Chiba Chemical Co., Ltd.) 0.76g, methyl ethyl ketone 301g, cyclohexanone 9.0g is added, After stirring, it filtered with the polypropylene filter of 5 micrometers of pore diameters, and prepared coating liquid B for low refractive index layers.

(Adjustment of Coating Liquid C for Low Refractive Index Layer)

In the coating liquid B for low refractive index layer, 19.5 g of hollow silica sol (refractive index: 1.31, average particle diameter: 60 nm, solid concentration: 20%) was used instead of silica sol, and 11.7 g of perfluoroolefin copolymer (1), Except having changed the methyl ethyl ketone amount into 280g, addition amount was also included and it carried out similarly to the said coating liquid B, and produced the coating liquid C for low refractive index layers.

Example 1

(1) Application of the inner layer

The 80-micrometer-thick triacetyl cellulose film (TAC-TD80U, manufactured by Fujishashin Film Co., Ltd., transparent support) was unrolled in roll form, and as shown in Table 1, the respective internal constituent layers (antistatic layer, anti-glare hard coat) Layer, light diffusion layer) using a microgravure roll and a doctor blade having a diameter of 180 mm / inch and a gravure pattern having a gravure pattern of 40 μm in depth and a doctor blade, the rotation speed of the gravure roll was 30 rpm and the conveyance speed was 30 m / min. After apply | coating on conditions, and drying for 150 second at 60 degreeC, the ultraviolet-ray of illuminance 400mW / cm <2> and irradiation amount 250mJ / cm <2> was irradiated using the air-cooled metal halide lamp of 160W / cm (made by IGraphics) under nitrogen purge again. It irradiated, hardened | coated the coating layer, and formed and wound the inner constituent layer of thickness 6micrometer.

Further, coating was formed such that the antistatic layer, the anti-glare hard coat layer, and the light diffusion layer were formed in order from the transparent support side.

(2) Application of Low Refractive Index Layer

Next, the triacetyl cellulose film obtained by coating the inner layer was unwound again, and as shown in Table 1, the coating solution for the low refractive index layer was 50 mm in diameter having a gravure pattern of 180 / inch and a depth of 40 µm. Using microgravure roll and doctor blade, applied at conditions of rotational speed of gravure roll 30rpm, conveyance speed 15m / min, dried at 120 ° C for 150 seconds, dried at 140 ° C for 8 minutes and then 240W under nitrogen purge Using a / cm air-cooled metal halide lamp (manufactured by Igraphics Co., Ltd.), ultraviolet light having a roughness of 400 mW / cm 2 and an irradiation amount of 900 mJ / cm 2 was irradiated to form a low refractive index layer having a thickness of 100 nm.

The combination of each coating layer was performed as Table 1.

(Saponification of antireflection film)

The following processes were performed with respect to the said samples 101-109 after application | coating.

A 1.5 mol / L aqueous sodium hydroxide solution was prepared and kept at 55 ° C. A 0.005 mol / L diluted aqueous sulfuric acid solution was prepared and kept at 35 ° C. The produced antireflection film was immersed in the aqueous sodium hydroxide solution for 2 minutes, and then immersed in water to thoroughly wash the aqueous sodium hydroxide solution. Subsequently, the solution was immersed in the diluted sulfuric acid aqueous solution for 1 minute, and then immersed in water to sufficiently wash the diluted sulfuric acid aqueous solution. Finally, the sample was sufficiently dried at 120 ° C.

Thus, the antireflection film samples 101-109 which completed the saponification process were obtained.

[Example 2]

(Preparation of Coating Liquid A for Hard Coat Layer)

To a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) 315.0 g, methyl ethyl ketone dispersion liquid of silica fine particles (MEK-ST, solid content concentration 30% by mass, Nissan Chemical 450.0g, the methyl ethyl ketone 15.0g, cyclohexanone 220.0g, and 16.0g of photoinitiators (Irgacure 907, Nippon Chiba-gai Co., Ltd. product) were added, and it stirred. It filtered with the polypropylene filter of pore diameter 0.4 micrometer, and prepared coating liquid A for hard-coat layers.

(Preparation of titanium dioxide fine particle dispersion)

As titanium dioxide fine particles, titanium dioxide fine particles (MPT-129, manufactured by Ishihara Industries Co., Ltd.) containing cobalt and surface-treated with aluminum hydroxide and zirconium hydroxide were used.

38.6 g of the following dispersing agents and 704.3 g of cyclohexane were added to this particle 257.1 g, and it disperse | distributed with dinomil, and prepared the titanium dioxide dispersion liquid with a mass mean diameter of 70 nm.

Dispersant

[Chemical Formula 21]

(Preparation of Coating Liquid A for Medium Refractive Index Layer)

* 88.9 g of the titanium dioxide dispersion, 58.4 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA), 3.1 g of a photopolymerization initiator (irgacure 907), a photosensitizer (gayacure DETX, Nippon 1.1 g of Kayaku Co., Ltd.), 482.4 g of methyl ethyl ketone, and 1869.8 g of cyclohexanone were added and stirred. Finally, 0.5 g of a fluorine-based surface modifier (P-8) was added and sufficiently stirred, and then filtered through a polypropylene filter having a pore diameter of 0.4 µm to prepare a coating solution A for a medium refractive index layer.

(Preparation of coating liquid A for high refractive index layers)

To 586.8 g of the titanium dioxide dispersion, 47.9 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), a photopolymerization initiator (irgacure 907, Nippon Chiba Vagina) 4.0g, the sensitizer (Kayacure DETX, Nippon Kayaku Co., Ltd. product) 1.3g, methyl ethyl ketone 455.8g, and cyclohexanone 1427.8g were added and stirred. Finally, 0.5 g of a fluorine-based surface modifier (P-8) was added and sufficiently stirred, and then filtered through a polypropylene filter having a pore diameter of 0.4 µm to prepare a coating solution A for high refractive index layer.

(Preparation of coating liquid D for low refractive index layers)

Thermal crosslinkable fluorine-containing polymer with refractive index of 1.42 (JN7228A, solid content concentration 6%, manufactured by JSR Co., Ltd.) 9 g, silica sol (silica, MEK-ST particle diameter difference product, average particle diameter 45nm, solid content concentration 30%, Nissan Chemical Industrial company) 1.4g, sol liquid a 0.4g, methyl isobutyl ketone 3g, and cyclohexanone 0.6g were added and stirred, and the mixture was filtered through a polypropylene filter having a pore diameter of 1 μm to prepare a coating liquid D for low refractive index layer. .

(Preparation of coating liquid E for low refractive index layers)

The coating liquid E for low refractive index layers was prepared like the prescription similar to the coating liquid B for low refractive index layers of Example 1.

(Adjustment of Coating Liquid F for Low Refractive Index Layer)

The coating liquid F for low refractive index layers was prepared like the prescription similar to the coating liquid C for low refractive index layers of Example 1.

(Production of antireflection film)

The coating liquid for antistatic layer was apply | coated using the gravure coater on the 80-micrometer-thick triacetyl cellulose film (TD-80UF, Fujishashin Film Co., Ltd. make, transparent support body). After drying at 100 DEG C, the illuminance was 400 mW / cm 2 and the irradiation dose 300 mJ / cm 2 using a 160 W / cm air-cooled metal halide lamp (manufactured by Igraphics) while purging nitrogen so that the oxygen concentration was 1.0 vol% or less. Was irradiated with ultraviolet light to cure the coating layer to form an antistatic layer having a thickness of 0.7 μm.

The coating liquid for hard coat layer was apply | coated on the antistatic layer using the gravure coater. Drying conditions and ultraviolet irradiation conditions were carried out in the same manner as the above antistatic layer to form a hard coat layer having a thickness of 3.5 占 퐉.

The coating liquid for the medium refractive index layer was apply | coated on the hard-coat layer using the gravure coater. After drying at 100 ° C, using an air-cooled metal halide lamp of 240 W / cm (manufactured by Eye Graphics Co., Ltd.) while purging nitrogen so that the oxygen concentration is 1.0 vol% or less, illuminance 550 mW / cm 2, irradiation amount 600 mJ / cm 2 Was irradiated with ultraviolet light to cure the coating layer to form a medium refractive index layer (refractive index 1.65, film thickness 67 nm).

The coating liquid for high refractive index layers was apply | coated on the medium refractive index layer using the gravure coater. Dry conditions and ultraviolet irradiation conditions were performed similarly to the said high refractive index layer, and the high refractive index layer (refractive index 1.93, film thickness 107nm) was formed.

The coating solution for the low refractive index layer was applied on the high refractive index layer using a gravure coater, dried at 120 ° C. for 150 seconds, and then dried at 140 ° C. for 8 minutes, and then cooled with a 240 W / cm air-cooled metal halide lamp under a nitrogen purge. Ultraviolet light with a roughness of 400 mW / cm 2 and an irradiation dose of 900 mJ / cm 2 was irradiated with Graphics Co., Ltd. to form a low refractive index layer (refractive index of 1.43, film thickness of 86 nm).

The combination of each layer was performed as Table 2, and the antireflective film samples 201-204 were produced. As the coating liquid for antistatic layer, what was used in Example 1 was used.

(Saponification of antireflection film)

The saponification process similar to Example 1 was performed about the said sample 201-204 after application | coating, and the antireflection film samples 201-204 which completed the saponification process were produced.

[Example 3]

The following composition was put into a mixing tank, stirred while heating to dissolve each component to prepare a cellulose acetate solution.

16 mass parts of aromatic compounds 65, 80 mass parts of methylene chloride, and 20 mass parts of methanol were thrown into another mixing tank as a retardation increasing agent, and it stirred while heating, and prepared the retardation increasing agent solution. 25 mass parts of retardation increasing agent solutions were mixed with 474 mass parts of cellulose acetate solutions of Example 3, and it fully stirred, and dope was prepared. The addition amount of the retardation increasing agent was 3.5 mass parts with respect to 100 mass parts of cellulose acetates.

The obtained dope was cast using a band softener. A film having a residual solvent amount of 15% by mass was transversely stretched at a stretching ratio of 25% using a tenter at 130 ° C to prepare a cellulose acetate film (thickness: 80 µm). About the produced cellulose acetate film (optical compensation sheet), the Re-retardation value and Rth retardation value in wavelength 550nm were measured using the ellipsometer (M-150, Nippon Bunco Co., Ltd. product). The results are shown in Table 4.

Example 4

56 parts by mass of the same retardation synergist solution as in Example 3 was mixed with 474 parts by mass of the cellulose acetate solution to prepare a dope (using 7.8 parts by mass of the retardation enhancer based on 100 parts by mass of cellulose acetate), and the draw ratio was 14 Except having changed into%, the cellulose acetate film (optical compensation sheet) was produced and evaluated similarly to Example 3.

The results are shown in Table 4.

[Example 5]

16 mass parts, 87 mass parts of methylene chlorides, and 13 mass parts of methanol were thrown into the mixing tank as aromatic compounds (12) which are rod-shaped compounds as retardation increasing agent, and it stirred while heating, and prepared the retardation increasing agent solution. 36 mass parts of said retardation synergist solution was mixed with 474 mass parts of cellulose acetate solutions of Example 4, and it fully stirred, and dope was prepared. The addition amount of the retardation increasing agent was 5.0 mass parts with respect to 100 mass parts of cellulose acetates.

The obtained dope was cast using a band softener. A cellulose acetate film (thickness: 80 µm) was produced in the same manner as in Example 3 except that the draw ratio was 28%. Re-retardation value and Rth retardation value were measured like Example 3 about the produced cellulose acetate film (optical compensation sheet). The results are shown in Table 4.

Comparative Example 1

A cellulose acetate film (optical compensation sheet) was produced and evaluated in the same manner as in Example 3, except that the stretching treatment was not performed using the cellulose acetate solution as it is as a dope. The results are shown in Table 4.

From the result shown in the said table, it turns out that the Re value RtH value of the sample of Examples 3-5 of this invention is large from the comparative example 1 which is not extended | stretched with a retardation increasing agent.

[Example 6]

Each component of the following cellulose acetate solution composition was thrown into the mixing tank, it stirred while heating, and each component was dissolved and the cellulose acetate solution was prepared.

(Cellulose acetate solution composition)

100 parts by mass of cellulose acetate having acetonitrile degree of 60.9%

Triphenyl phosphate (plasticizer) 7.8 parts by mass

Biphenyl diphenyl phosphate (plasticizer) 3.9 parts by mass

318 parts by mass of methylene chloride (first solvent)

47 parts by mass of methanol (second solvent)

16 mass parts, 87 mass parts of methylene chlorides, and 13 mass parts of methanol were put into the other mixing tank as an aromatic compound (46) which is a rod-shaped compound as a retardation increasing agent, and it stirred while heating, and prepared the retardation increasing agent solution.

36 mass parts of retardation increasing agent solutions were mixed with 474 mass parts of cellulose acetate solutions, and it fully stirred, and dope was prepared. The addition amount of the retardation increasing agent was 5.0 mass parts with respect to 100 mass parts of cellulose acetates.

The obtained dope was cast using a band softener. A film having a residual solvent amount of 15% by mass was transversely stretched at a stretching ratio of 28% using a tenter at 130 ° C. to prepare a cellulose acetate film (thickness: 82 μm). About the produced cellulose acetate film (optical compensation sheet), the Re-retardation value and Rth retardation value in wavelength 590nm were measured using KOBRA 21ADH (manufactured by Ou Watch Co., Ltd.). The results are shown in Table 5.

[Example 7]

Each component of the following additive solution composition was put into a mixing tank, stirred while heating to dissolve each component, and the additive liquid in which the other additive was added to the retardation increasing agent was adjusted.

(Addition solution composition)

16 parts by mass of the retardation increasing agent used in Example 6

1 part by mass of trimethyl trimellitate

Methylene chloride (first solvent) 87 parts by mass

13 parts by mass of methanol (second solvent)

44 parts by mass of the retardation synergist solution was mixed with 474 parts by mass of the cellulose acetate solution of Example 6, and sufficiently stirred to prepare a dope. The addition amount of the retardation synergist was 6.0 mass parts with respect to 100 mass parts of cellulose acetates.

In the same manner as in Example 6, a transversely stretched cellulose acetate film was prepared. About the produced cellulose acetate film (optical compensation sheet), Re retardation value and Rth retardation value were evaluated like Example 6. The results are shown in Table 5.

[Example 8]

16 mass parts, 87 mass parts of methylene chlorides, and 13 mass parts of methanol were thrown into the mixing tank as an aromatic compound (67) which is a rod-shaped compound as a retardation increasing agent, and it stirred while heating, and prepared the retardation increasing agent solution.

36 mass parts of said retardation synergist solutions were mixed with 474 mass parts of cellulose acetate solutions of Example 6, and it fully stirred, and dope was prepared. The addition amount of the retardation increasing agent was 5.0 mass parts with respect to 100 mass parts of cellulose acetates.

After removing from the band with 33% of the residual solvent and introducing into the tenter stretching machine, the stretching ratio was stretched to 28%. The film thickness after extending | stretching was 95 micrometers. After extending | stretching, the film detach | desorbed from the tenter was dried by the warm air of 140 degreeC, and the cellulose acetate film which made the residual solvent amount 1% or less was produced. About the produced cellulose acetate film (optical compensation sheet), Re retardation value and Rth retardation value were evaluated like Example 6. The results are shown in Table 5.

[Example 9]

16 parts by mass of the same retardation increasing agent as in Example 6, 3 parts by mass of Sumisorb 165F (manufactured by Sumitomo Chemical Co., Ltd.), 87 parts by mass of methylene chloride and 13 parts by mass of methanol were added to the mixing tank, followed by stirring while heating. A retardation synergist solution was prepared.

36 mass parts of said retardation synergist solutions were mixed with 474 mass parts of cellulose acetate solutions of Example 6, and it fully stirred, and dope was prepared. The addition amount of the retardation increasing agent was 5.0 mass parts with respect to 100 mass parts of cellulose acetates.

After removing from the band with 33% of the residual solvent and introducing into the tenter stretching machine, the stretching ratio was stretched to 28%. The film thickness after extending | stretching was 95 micrometers. After extending | stretching, the film detach | desorbed from the tenter was dried by the warm air of 140 degreeC, and the cellulose acetate film which made the residual solvent amount 1% or less was produced. About the produced cellulose acetate film (optical compensation sheet), Re retardation value and Rth retardation value were evaluated like Example 6. The results are shown in Table 5.

[Example 10]

16 parts by mass of the same retardation increasing agent as in Example 8, 1.2 parts by mass of ultraviolet absorber B (TINUVIN327, manufactured by Chivas Specialty Chemicals), 2.4 parts by mass of ultraviolet absorbent C (TINUVIN328, manufactured by Chivas Specialty Chemicals), methylene 87 parts by mass of chloride and 13 parts by mass of methanol were added, followed by stirring while heating to prepare a retardation synergist solution.

36 mass parts of said retardation synergist solutions were mixed with 474 mass parts of cellulose acetate solutions of Example 6, and it fully stirred, and dope was prepared. The addition amount of the retardation increasing agent was 5.0 mass parts with respect to 100 mass parts of cellulose acetates.

In the same manner as in Example 9, a cellulose acetate film was prepared. About the produced cellulose acetate film (optical compensation sheet), Re retardation value and Rth retardation value were evaluated like Example 6. The results are shown in Table 5.

[Example 11]

Each component of the following cellulose acylate solution composition was thrown into the mixing tank, it stirred while heating, and each component was dissolved and the cellulose acylate solution was prepared.

(Cellulose acylate solution composition)

* 100 parts by mass of cellulose acetate propionate having a degree of substitution of acetyl group of 1.90 and a degree of substitution of propionyl group of 0.80

8.5 parts by mass of triphenylphosphate

Ethyl phthalyl ethyl glycolate 2.0 parts by mass

290 parts by mass of methylene chloride

60 parts by mass of ethanol

5 parts by mass of acetate propionate, 6 parts by mass of Tinuvin 326 (manufactured by Chivas Specialty Chemicals, Inc.), 4 parts by mass of Tinuvin 109 (manufactured by Chiba Specialty Chemicals, Inc.), Tinuvin 171 5 parts by mass of methylene chloride and 8 parts by mass of ethanol were added to 5 parts by mass of Chivas Specialty Chemicals Co., Ltd., and stirred while heating to prepare an additive solution.

10 mass parts of additive solutions were mixed with 474 mass parts of cellulose acetate solutions, and it fully stirred, and dope was prepared.

A cellulosic acetate propionate film was stretched in the same manner as in Example 6 except that the draw ratio was 30% and the film thickness was 80 µm. About the produced cellulose acetate propionate film (optical compensation sheet), Re retardation value and Rth retardation value were evaluated like Example 6. The results are shown in Table 5.

[Example 12]

16 mass parts of retardation increasing agent of Example 3, 87 mass parts of methylene chloride, and 13 mass parts of methanol were thrown into the mixing tank, and it stirred while heating, and prepared the retardation increasing agent solution.

36 mass parts of said retardation synergist solutions were mixed with 474 mass parts of cellulose acetate solutions of Example 6, and it fully stirred, and dope was prepared. The addition amount of the retardation increasing agent was 5.0 mass parts with respect to 100 mass parts of cellulose acetates.

A transversely stretched cellulose acetate film (thickness: 80 µm) was produced in the same manner as in Example 6 except that the draw ratio was 28%. About the produced cellulose acetate film (optical compensation sheet), Re retardation value and Rth retardation value were evaluated like Example 6. The results are shown in Table 5.

[Example 13]

16 mass parts of aromatic compounds (66), 87 mass parts of methylene chlorides, and 13 mass parts of methanol were added to the mixing tank as a retardation increasing agent, and it stirred while heating, and prepared the retardation increasing agent solution.

30 mass parts of said retardation synergist solution was mixed with 474 mass parts of cellulose acetate solutions of Example 6, and it fully stirred, and dope was prepared. The addition amount of the retardation increasing agent was 4.2 mass parts with respect to 100 mass parts of cellulose acetates.

After being flexible on the band, the residue was separated with 32% of the residual solvent, and then stretched laterally with a tenter stretching machine. The draw ratio was 30%, and the draw temperature was 110 ° C. Then, it dried by the warm air of 130 degreeC, and produced the cellulose acetate film. The film thickness of the film after drying was 96 micrometers. About the obtained cellulose acetate film (optical compensation sheet), Re retardation value and Rth retardation value were evaluated like Example 6. The results are shown in Table 5.

Example 14

After using the dope prepared in Example 6, it was pliable on a band and peeled off with 32% of the residual solvent, and it lateral stretched by the tenter stretching machine. The draw ratio was 26%, and the draw temperature was 130 ° C. Then, it dried by the warm air of 130 degreeC, and produced the cellulose acetate film. Moreover, dope flow volume was adjusted so that the film thickness of the film after drying might be set to 92 micrometers. About the obtained cellulose acetate film (optical compensation sheet), Re retardation value and Rth retardation value were evaluated like Example 6. The results are shown in Table 5.

Example 15

16 parts by mass of the retardation increasing agent of Example 13, 3 parts by mass of ultraviolet absorber A (Sumitomo Chemical Co., Ltd. Sumisorb 165F), 87 parts by mass of methylene chloride, and 13 parts by mass of methanol were added to the mixing tank, followed by stirring while heating. Dation synergist solution was prepared.

30 mass parts of said retardation synergist solution was mixed with 474 mass parts of cellulose acetate solutions of Example 6, and it fully stirred, and dope was prepared. The addition amount of the retardation increasing agent was 4.2 mass parts with respect to 100 mass parts of cellulose acetates.

After being flexible on the band, the residue was separated with 32% of the residual solvent, and then stretched laterally with a tenter stretching machine. The draw ratio was 30%, and the draw temperature was 110 ° C. Then, it dried by the warm air of 130 degreeC, and produced the cellulose acetate film. The film thickness of the film after drying was 96 micrometers. About the obtained cellulose acetate film (optical compensation sheet), Re retardation value and Rth retardation value were evaluated like Example 1. The results are shown in Table 5.

[Example 16]

Iodine was adsorbed on the stretched polyvinyl alcohol film to prepare a polarizing film. The saponification process was carried out to the cellulose acetate film produced in Example 3, and it adhere | attached on one side of a polarizing film using the polyvinyl alcohol-type adhesive agent. The antireflection film sample 101 of the present invention was saponified and adhered to the opposite side of the polarizing film using a polyvinyl alcohol-based adhesive. The transmission axis of a polarizing film and the slow axis of the cellulose acetate film produced in Example 3 were arrange | positioned so that it might become parallel. The transmission axis of a polarizing film and the slow axis of the cellulose acetate film of the antireflection film sample 101 were arrange | positioned so that it may cross. In this way, a polarizing plate was produced.

Comparative Example 2

A polarizing plate was produced in the same manner as in Example 16 except that the cellulose acetate film produced in Comparative Example 1 was used.

[Examples 17-28]

The polarizing plate was produced like Example 16 except having used the cellulose acetate film produced in Examples 4-15.

Table 6 shows the results of evaluating the pencil hardness and the specular reflectance of the produced polarizing plate samples 16 to 28 and Comparative Example 2 polarizing plate samples.

Pencil hardness evaluation

Based on the pencil hardness evaluation described in JIS K 5400, the surface opposite to the optical compensation sheet surface of the polarizing plate, that is, the antireflection film surface, was evaluated. After adjusting the polarizing plate for 2 hours at 25 ° C. and 60% RH, using the test pencil of H to B specified in JIS S 6006, the highest pencil hardness was evaluated by the following criterion at 500 g load to be OK. Was taken as an evaluation value. It is preferable that hardness is high.

No wound to one wound in evaluation of n = 5: OK

3 or more wounds in the evaluation of n = 5: NG

In addition, when the presence or absence of a flaw is subtle and a rank cannot be distinguished clearly, it displayed with "-", and showed in the range. (E.g. 3H ~ 2H)

Specular reflectance

The adapter ARV-47 was mounted on the spectrophotometer V-550 (manufactured by Nippon Bunko Co., Ltd.), and the specular reflectance of the emission angle of -5 ° at the incident angle of 5 ° was measured in the wavelength range of 380 to 780 nm, and 450 to 650 nm. The average reflectance of was calculated to be the specular reflectance. It is preferable that the value is low.

[Example 29]

The pair of polarizing plates and the pair of optical compensation sheets formed on the liquid crystal display device (VL-1530S, manufactured by Fujitsu Co., Ltd.) using the vertical alignment liquid crystal cell were removed, and the polarizing plates produced in Example 16 instead. The cellulose acetate film produced in Example 3 was adhered to the observer side and the backlight side one by one through the pressure-sensitive adhesive so as to be the liquid crystal cell side. Cross nicol arrangement was made such that the transmission axis of the polarizer on the observer side was in the vertical direction and the transmission axis of the polarizer on the backlight side was in the left and right directions. About the produced liquid crystal display device, the viewing angle was measured in 8 steps from a black display (L1) to a white display (L8) using a measuring instrument (EZ-Contrast 160D, manufactured by ELDIM). The results are shown in Table 7.

[Example 30]

The pair of polarizing plates and the pair of optical compensation sheets formed on the liquid crystal display device (VL-1530S, manufactured by Fujitsu Co., Ltd.) using the vertical alignment type axel were removed, and the polarizing plates produced in Example 17 were replaced instead. 1 was adhere | attached on the observer side through an adhesive so that the cellulose acetate film produced in Example 4 might become a liquid crystal cell side. In addition, one commercially available polarizing plate (HLC2-5618HCS, manufactured by Sanlitz Co., Ltd.) was adhered to the backlight side. The cross nicol arrangement was made such that the transmission axis of the polarizer on the observer side was in the vertical direction and the transmission axis of the polarizer on the backlight side was in the left and right directions. About the produced liquid crystal display device, the viewing angle was measured in 8 steps from a black display (L1) to a white display (L8) using a measuring instrument (EZ-Contrast 160D, manufactured by ELDIM). The results are shown in Table 7.

[Examples 31 to 41]

The pair of polarizing plates and the pair of optical compensation sheets formed on the liquid crystal display device (VL-1530S, manufactured by Fujitsu Co., Ltd.) using the vertical alignment type axel were removed and manufactured in Examples 18 to 28 instead. One polarizing plate was adhere | attached on the observer side 1 piece via an adhesive so that the cellulose acetate film produced in Examples 5-15 might become a liquid crystal cell side. In addition, it adhere | attached similarly to the backlight side. The cross nicol arrangement was made such that the transmission axis of the polarizer on the observer side was in the vertical direction and the transmission axis of the polarizer on the backlight side was in the left and right directions. About the produced liquid crystal display device, the viewing angle was measured in 8 steps from a black display (L1) to a white display (L8) using a measuring instrument (EZ-Contrast 160D, manufactured by ELDIM). The results are shown in Table 7.

[Comparative Example 3]

A liquid crystal display device of Comparative Example 3 was produced in the same manner as in Example 29 except that the polarizing plate of Comparative Example 2 was used instead of the polarizing plate of Example 16 used in Example 29.

[Comparative Example 4]

A liquid crystal display device of Comparative Example 4 was produced in the same manner as in Example 30 except that the polarizing plate of Comparative Example 2 was used instead of the polarizing plate of Example 17 used in Example 30.

[Comparative Example 5]

For a liquid crystal display device (VL-1530S manufactured by Fujitsu Co., Ltd.) using a vertical alignment type accelerator cell, a black display (L1) to white display (L8) using a measuring instrument (EZ-Contrast 160D, manufactured by ELDIM) The viewing angle was measured in step 8 until. The results are shown in Table 7.

Table 7 shows that the viewing angle range without gray scale inversion in the liquid crystal display devices of Examples 29 to 41 of the present invention is wider than that of Comparative Example 5.

Example 42

A pair of polarizing plates formed on a liquid crystal display device (6E-A3, manufactured by Sharp Co., Ltd.) using a TN type liquid crystal cell was removed, and the polarizing plates produced in Example 18 were manufactured in Example 5 instead. The cellulose acetate film was adhered to the observer side and the backlight side one by one so as to be the liquid crystal cell side. The transmission axis of the polarizer on the observer's side and the transmission axis of the polarizer on the backlight's side were arranged to be in O mode. About the produced liquid crystal display device, the viewing angle was measured in 8 steps from a black display (L1) to a white display (L8) using a measuring instrument (EZ-Contrast 160D, manufactured by ELDIM). The results are shown in Table 8.

[Comparative Example 6]

From the black display (L1) to the white display (L8) using a measuring instrument (EZ-Contrast 160D, manufactured by ELDIM) for a liquid crystal display device (6E-A3 manufactured by Sharp Co., Ltd.) using a TN type liquid crystal cell In step 8, the viewing angle was measured. The results are shown in Table 8.

Embodiment 42 of the present invention has a wide viewing angle range without gray level inversion.

The following rub tests were done with respect to the liquid crystal display sample produced in Examples 29-42.

(Pencil hand rub strength)

The jig which bonded the tube which puts a pencil in the lower side of the metal dish was produced, and the pencil which inserted the core of 3 cm in length was inserted in this tube. The tip of the shim was wedge shaped at an angle of 60 °. The liquid crystal display device was placed horizontally so that the antireflection film was upward, and the jig loaded with a load of 0.5 kg was placed thereon, and the jig was moved about two centimeters horizontally by hand. The pencil hardness was appropriately changed, and the place where it was rubbed was changed five places, the antireflection film surface after rubbing was visually observed, and the hardness of the pencil which shows only two or less wounds was made into the hardness of the sample, and this was calculated | required.

The results are shown in Table 9.

Table 9 shows that the pencil hardness of the surface of the liquid crystal display device of Examples 29-42 of this invention is hard from Comparative Examples 3-6.

Example 43

Using the completed dope which adjusted the liquid in Example 5, only the casting conditions (discharge amount of the finished dope) were changed, and the following samples with different film thickness were produced.

Sample 43-1 film thickness 80 μm

Sample 43-2 film thickness 67 μm

Sample 43-3 film thickness 54 μm

Sample 43-4 film thickness 40㎛

[Examples 44-62, Comparative Examples 7-11]

Iodine was adsorbed on the stretched polyvinyl alcohol film to prepare a polarizing film. The saponification process was performed to the cellulose acetate film samples 43-1 to 43-4 of the film thickness produced in Example 43, and it adhere | attached on one side of a polarizing film using the polyvinyl alcohol-type adhesive agent. The antireflection film samples 101 to 109 and 201 to 204 of the saponification treatment were adhered to opposite sides with a polarizing film interposed therebetween using a polyvinyl alcohol adhesive. The transmission axis of the polarizing membrane and the slow axis of the cellulose acetate film produced in Example 43 were arranged to be parallel. The transmission axis of the polarizing film and the slow axis of the cellulose triacetate film of the antireflection film sample were arranged so as to be perpendicular to each other. In this way, a polarizing plate was produced.

The combination of the polarizing plate sample and the antireflection film sample is shown in Table 10 below. As a comparison, a polarizing plate using a commercially available cellulose-acetate film (Fuji Shashin Film Co., Ltd. product TD80UF, film thickness of 80 micrometers) was also inserted. Moreover, the polarizing plates of the following comparative example 12 and 13 were produced.

[Comparative Example 12]

Instead of the cellulose acetate film produced in Example 3 using the polarizing plate produced in Example 16, a saponification treatment was carried out on a commercially available cellulose triacetate film (Fuji-Tack TD80UF, manufactured by Fujishashin Film Co., Ltd.), and a polyvinyl alcohol-based adhesive Was applied, and the antireflection film sample of Sample 103 was adhered to the surface opposite to the cellulose acetate film surface in the same manner as in Example 16 to prepare a polarizing plate.

[Comparative Example 13]

The conventional polarizing plate was produced. In other words, neither the optical compensation sheet nor the antireflection film is adhered to both sides of the polarizing film, and the film subjected to saponification treatment to a commercially available cellulose triacetate film (Fuji-Tak TD8OUF, manufactured by Fujishashin Film Co., Ltd.) is bonded with a polyvinyl alcohol adhesive. The polarizing plate was produced.

The polarizing plates of Examples 44 to 62 and Comparative Examples 7 to 13 were evaluated according to the following tables. Table 11 shows sample contents, evaluation contents and results.

Table 11 shows that the pencil hardness and the reflectance of the polarizing plate using the antireflection film of the present invention together with the cellulose acetate film with the optical compensation function of the present invention are preferable.

For example, in Examples 46 to 49 for Comparative Examples 7 to 10, and Examples 58 to 61 for Comparative Examples 8 to 11, by combining the antireflection film of the present invention, the cellulose acetate film with optical compensation function Even if the film thickness is changed, the pencil hardness is strong without any difference.

Moreover, even if Examples 48-50 and Examples 58, 60, 61 were relatively thin, the fall of the pencil hardness was not seen but it was a preferable polarizing plate.

[Example 63]

Except having changed the coating liquid of the anti-glare hard-coat layer of the said antireflection film sample 103 into C, it apply | coated similarly to the said sample 103, and produced the sample 301. The polarizing plate was produced like Example 16 using this antireflection film sample and the cellulose acetate film sample with an optical compensation function of Example 43-3.

Example 64

Except having changed the coating liquid of the anti-glare hard-coat layer of the said antireflection film sample 103 into D, it applied similarly to the said sample 103, and produced the sample 302. The polarizing plate was produced like Example 16 using this antireflection film sample and the optical compensation sheet sample of Example 43-3.

Evaluation of transmission image clarity

* Using the filament measuring device (ICM-2D type) by Suga Test Machine Co., Ltd., the value of transmission image sharpness was measured with the optical comb of 0.5 mm.

Table 12 shows the evaluation results of the transmission image sharpness and pencil hardness.

It can be seen from Table 12 that lowering the transmission image sharpness makes the pencil hardness evaluation harder.

The back sides of the samples of Examples 63 and 64 were painted black to evaluate anti-glare properties. The sample was placed on a tabletop, and the ceiling fluorescent lamp was observed by a reflection image. The data of Example 63 showed little or no contour of the fluorescent lamp, and on the contrary, the data of Example 64 had a slightly unclear outline of the fluorescent lamp, but both samples were at acceptable levels.

[Example 65]

The pair of polarizing plates and the pair of optical compensation sheets provided in the liquid crystal display device (VL-1530S, manufactured by Fujitsu Co., Ltd.) using the vertical alignment type axel were removed, and the polarizing plates produced in Example 18 were replaced instead. 1 was adhere | attached on the observer side through an adhesive so that the cellulose acetate film produced in Example 5 might become a liquid crystal cell side. In addition, one commercially available polarizing plate (HLC2-5618HCS, manufactured by Sanlitz Co., Ltd.) was adhered to the backlight side. The cross nicol arrangement was made such that the transmission axis of the polarizer on the observer side was in the vertical direction and the transmission axis of the polarizer on the backlight side was in the left and right directions. About the produced liquid crystal display device, the viewing angle was measured in 8 steps from black display L1 to white display L8 using the measuring device (EZ-Contrast 160D, ELDIM make). As a result, the viewing angles (range of contrast ratio of 10 or more and no gray scale inversion on the black side) in the 45 ° direction from the transmission axis direction and the transmission axis were all preferably 80 ° or more. At the same time the projection of the background onto the screen was very small, resulting in excellent display quality.

[Example 66]

The pair of polarizing plates and the pair of optical compensation sheets provided in the liquid crystal display device (VL-1530S, manufactured by Fujitsu Co., Ltd.) using the vertical alignment type axel were removed, and the polarizing plate produced in Example 45 was instead replaced. The obtained cellulose acetate film was adhere | attached on the observer side and the backlight side one by one via an adhesive so that the produced cellulose acetate film might become a liquid crystal cell side. The cross nicol arrangement was made such that the transmission axis of the polarizer on the observer side was in the vertical direction and the transmission axis of the polarizer on the backlight side was in the left and right directions. About the produced liquid crystal display device, the viewing angle was measured in 8 steps from black display L1 to white display L8 using the measuring device (EZ-Contrast 160D, ELDIM make). As a result, the viewing angles (range of contrast ratio of 10 or more and no gray scale inversion on the black side) in the 45 ° direction from the transmission axis direction and the transmission axis were all preferably 80 ° or more. At the same time the projection of the background onto the screen was very small, resulting in excellent display quality.

[Example 67]

A pair of polarizing plates provided in a liquid crystal display device (6E-A3, manufactured by Sharp Co., Ltd.) using a TN type liquid crystal cell was removed, and the polarizing plate produced in Example 45 was instead used in Example 43-3. The produced cellulose acetate film was adhered to the observer side and the backlight side one by one so as to be on the liquid crystal cell side. The transmission axis of the polarizer on the observer's side and the transmission axis of the polarizer on the backlight's side were arranged to be in O mode. About the produced liquid crystal display device, the viewing angle was measured in 8 steps from black display L1 to white display L8 using the measuring device (EZ-Contrast 160D, ELDIM make). As a result, the viewing angle (range of contrast ratio of 10 or more and no gray scale inversion on the black side) was 18 ° in the upward direction, 24 ° in the downward direction, and 77 ° in the left and right directions. At the same time the projection of the background onto the screen was very small, resulting in excellent display quality.

The said pencil rubbing strength test was done about the liquid crystal display sample produced in Examples 65-67. As a result, all of Examples 65-67 were 2H of pencil hardness. As a result, it can be seen from the comparison with the pencil rubbing strengths of Comparative Examples 3 to 6 that the pencil hardness of Examples 65 to 67 is hard.

The following are clear from the result shown in Table 1. A retardation film having a Re retardation value of 20 to 70 nm, a Rth retardation value of 70 to 400 nm, and a Re / Rth ratio of 0.2 to 0.4, a hard coat layer having internal scattering resistance, and Ra having an antireflection of 0.10 μm or less The polarizing plate which combined the film improves the visibility in the darkroom displayed by contrast, the viewing angle characteristic with respect to a hue change, antireflective property, and black reproducibility to a very high level when used for a VA mode liquid crystal display device. . Furthermore, the use of hollow silica fine particles in the low refractive index layer and the lamination of the medium / high / low refractive index layer and the multilayer optical interference layer show very excellent antireflection properties.

1: antireflection film
2A, 2B: Hard Coat Layer
3: low refractive index layer
4A, 4B: Translucent Particles
5: medium refractive index layer
6: high refractive index layer
10, 20, 30: antireflection film
40: polarizer

Claims (7)

As a polarizing plate which arrange | positioned at least 1 functional film in each of both sides of a polarizing film,
At least one of the functional membranes on one side is composed of only one cellulose acylate film, and the cellulose acylate film contains 0.01 to 20 masses of an aromatic compound having at least two aromatic rings with respect to 100 parts by mass of cellulose acylate. It is contained, Re Retardation value defined by following formula (I) is 20-70 nm, Rth retardation value defined by following formula (II) is 70-400 nm,
At least one of the functional films on the other side contains, on the transparent support, a binder polymer having a saturated hydrocarbon chain as the main chain, matte particles having an average particle diameter of 0.5 to 7.0 µm, and an anti-glare hard having a film thickness of 1 to 10 µm. It consists of an anti-glare film which has a coat layer at least 1 layer, The polarizing plate characterized by the above-mentioned.
(I) Re = (nx-ny) × d
(II) Rth = {(nx + ny) / 2-nz} × d
(Wherein nx is the refractive index in the slow axis direction in the film plane; ny is the refractive index in the fast axis direction in the film plane; nz is the refractive index in the thickness direction of the film; and d is the thickness of the film.) The method of claim 1,
The anti-glare hard coat layer contains at least any one of crosslinked polystyrene particles or crosslinked acrylic-styrene particles. 3. The method according to claim 1 or 2,
The film thickness of the said cellulose acylate film is 40 micrometers or more and 70 micrometers or less, The polarizing plate characterized by the above-mentioned. 3. The method according to claim 1 or 2,
The said aromatic compound is a rod-shaped compound which has a linear molecular structure, The polarizing plate characterized by the above-mentioned. 3. The method according to claim 1 or 2,
The refractive index difference of the said mat agent particle | grains and this binder polymer is 0.03 or more and 0.2 or less, The polarizing plate characterized by the above-mentioned. The polarizing plate of Claim 1 or 2 is used for the outermost surface of a liquid crystal display device, The liquid crystal display device characterized by the above-mentioned. The method according to claim 6,
The liquid crystal cell of a liquid crystal display device is a liquid crystal cell of VA mode or TN mode, The liquid crystal display device characterized by the above-mentioned.

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