KR20140110999A - Hard coating film, polarizing plate, glass scattering prevention film for image display device, touch panel, and liquid crystal display device - Google Patents

Abstract

Disclosure of the Invention Problems to be Solved by the Invention A problem to be solved by the present invention is to provide a hard coating film which suppresses slippage between films and can prevent the winding deviation, and suppresses buckling deformation and distortion of the film when the film is wound into a roll shape to suppress occurrence of flatness and unevenness And to provide a hard coating film. Another object of the present invention is to provide a glass shatterproof film, a touch panel, a polarizing plate and a liquid crystal display device for an image display device having good visibility using the hard coating film. The hard coat film of the present invention is a hard coat film having a hard coat layer on at least one side of a cellulose ester film having a film thickness in the range of 5 to 34 占 퐉 and before and after the alkali treatment when the hard coat layer is alkali- the logarithm of the difference between the contact angle (θ _Δ) characterized in that in the range of 5 to 55 °.
(Alkali treatment condition)
Alkaline solution: 2.5 mol / L potassium hydroxide solution
Processing temperature: 50 ° C
Processing time: 120 seconds

Description

Technical Field [0001] The present invention relates to a hard coating film, a polarizing plate, a glass shatterproof film for an image display, a touch panel, and a liquid crystal display device.

The present invention relates to a hard coating film, a polarizing plate using the same, a glass scattering prevention film for an image display device, a touch panel, and a liquid crystal display device. More particularly, the present invention relates to a hard coating film which suppresses the deterioration of planarity and unevenness when wound in a roll form, a polarizing plate having excellent visibility using the hard coating film, a glass scattering prevention film for an image display device, ≪ / RTI >

2. Description of the Related Art In recent years, liquid crystal display devices have attracted attention as image display devices. BACKGROUND ART Liquid crystal display devices are widely used for monitors and televisions in personal computers and portable apparatuses in various advantages such as miniaturization and thinning with low voltage and low power consumption. On the surface of the liquid crystal display device, a film having a hard coat layer (hereinafter referred to as a hard coat film) is used on a cellulose ester film such as a treacetate film in order to prevent physical damage.

Generally, a panel of a liquid crystal display device is structured by sandwiching liquid crystal cells between two polarizing plates. The polarizing plate used on the surface side is a polarizing plate that is formed by orienting a film of polyvinyl alcohol (hereinafter abbreviated as PVA), in which iodine or a dichroic dye is adsorbed and absorbed, between a hard coating film and a cellulose ester film in a predetermined direction Layer structure in which an element (polarizing film) is interposed. When a hard coating film or a cellulose ester film is laminated on a polarizing film, these films are subjected to alkali treatment and then laminated in order to improve the adhesion between the PVA and the hard coating film or the PVA and the cellulose ester film.

In recent years, the emergence of smart phones and the like has led to the demand for miniaturization and thinning of monolithic LCDs, and it is also desired to reduce the thickness of polarizing plates and other members used in liquid crystal display devices. Therefore, there is a strong demand for a thin film of a hard coating film or a cellulose ester film used for a polarizing plate.

Further, the thin film hard coat film needs to have some degree of slippery property in order to prevent the occurrence of scratches and wrinkles in the roll transportation during its production. Therefore, it is considered desirable to make the logarithmic contact angle of the surface relatively high.

On the other hand, from the viewpoint of production, the polarizing plate is manufactured in a roll-to-roll manner and is produced in a roll state. The manufacture of a liquid crystal display device by a roll-to-panel method in which a protective film of a polarizing plate is thinned, and the polarizing plate itself is rolled up in a roll state or is wound by a polarizing plate in a roll- Is also under review.

However, the reason why the polarizing plate is wound in the roll state is that because of the three-layer structure, the stress due to the self weight of the wound product is large and the polarizing plates overlap each other more easily in the roll form. It is necessary to form an air layer between the polarizing plate and the polarizing plate wound in a roll form in order to suppress adhesion between the polarizing plates. When the thin film hard coating film imparted with the slidability as described above is used as it is, The air layer is compressed, and the problem of winding deviation when the compressed air layer escapes to the outside of the wound product increases, resulting in a decrease in productivity.

Particularly, in the polarizing plate in which the hard coating film or the cellulose ester film is composed of a thin film, the compressed air layer tends to escape to the outside of the wound product, and thus the problem of winding displacement is liable to occur.

In addition, the polarizing plate composed of a thin film film is liable to buckle and deform due to stress when wound in a roll shape, and unevenness due to deterioration of planarity and deformation is liable to occur. Particularly, after the durability test on the assumption of long-term transportation, unevenness due to deterioration or deformation of planarity was remarkable.

In the roll state of the polarizing plate, the hard coat layer of the hard coating film and the cellulose ester film are wrapped with each other facing each other. The technique of preventing winding displacement of such a film is disclosed in, for example, Patent Document 1.

The technique disclosed in Patent Document 1 is characterized in that one or two or more strip-shaped end hard coating layers are provided at both ends in the width direction of the hard coating layer, and the thickness of the end hard coating layer is made thicker than the hard coating layer thickness, To prevent the winding displacement by reducing the slidability of the film.

In the above technique, although some effect is obtained in the prevention of winding displacement in a single film, the effect is insufficient particularly in the prevention of the winding displacement in the polarizing plate in which the hard coating film or the cellulose ester film is thinned. In addition, it is difficult to control only the thickness of the end film to be a thick film, which has a problem in productivity.

Japanese Patent Application Laid-Open No. 2011-218618

SUMMARY OF THE INVENTION The present invention has been made in consideration of the above-described problems, and it is an object of the present invention to provide a film forming apparatus capable of preventing slippage between films and preventing winding deviation when wound in a roll form, And suppressing distortion to suppress the occurrence of planarity deterioration and unevenness. Another object of the present invention is to provide a polarizing plate having excellent visibility using the hard coating film, a glass shatterproofing film for use in an image display device, a touch panel, and a liquid crystal display device.

The present inventors, in order to solve the above problems, in the process of review for such causes of the problem, is a thin film and the hard coat film having a hard coating layer on a substrate film, a difference in logarithmic contact angle before and after the alkali treatment of the hard coating layer (θ _Δ ) Is adjusted within a specific range, slippage between the films is suppressed when the hard coating film or the polarizing plate using the hard coating film is wound in a roll form, so that the air layer between the roll- The hard coat film and the polarizer can be obtained without causing the air layer to escape to the outside, so that the polarizing plate can be obtained. Further, since the air layer is held between the roll-shaped layers, the stress load on the film is suppressed, so that buckling deformation and distortion are less likely to occur even in a thin film, and deterioration in planarity and unevenness can be suppressed. That is, by making the constitution that the surface state of the hard coating layer of the hard coating film changes before and after the alkali saponification treatment performed when the hard coating film to be a protective film is attached to the polarizer at the time of manufacturing the polarizing plate, It is possible to solve both the problem and the problem as a polarizing plate in a roll shape.

In addition, the hard coating film of the present invention is excellent in blocking property (adherence between films) and excellent in planarity and unevenness because air layers are held between roll-shaped layers in addition to winding displacement, And provides excellent visibility when used in a protective film, a touch panel, and a liquid crystal display device.

That is, the above object of the present invention is solved by the following means.

1. A hard coat film having a hard coat layer on at least one side of a cellulose ester film having a film thickness in the range of 5 to 34 mu m and a difference in logarithmic contact angles before and after the alkali treatment when the hard coat layer is alkali- &thetas; _DELTA ) is in the range of 5 to 55 DEG.

(Alkali treatment condition)

Alkaline solution: 2.5 mol / L potassium hydroxide solution

Processing temperature: 50 ° C

Processing time: 120 seconds

2. The hard coat film according to claim 1, wherein the logarithmic contact angle (?) Of the hard coat layer before the alkali treatment is in the range of 50 to 120 °.

3. The hard coating film according to claim 1 or 2, wherein the logarithmic contact angle of the hard coat layer is lowered after the alkali treatment before the alkali treatment under the alkali treatment condition.

4. The hard coating film according to any one of claims 1 to 3, wherein the hard coating layer has an arithmetic mean roughness (Ra) (JIS B0601: 2001) of 2 to 100 nm.

5. The hard coat film according to any one of claims 1 to 4, wherein the hard coat layer contains an isocyanurate derivative of active energy ray curable type.

6. The cellulose ester film according to any one of the items 1 to 5, wherein the in-plane retardation value (Ro) is in the range of 0 to 10 nm when the retardation value is measured at an optical wavelength of 590 nm in an environment of a temperature of 23 캜 and a relative humidity of 55% Is in the range of -10 to 10 nm. The hard coating film according to any one of claims 1 to 5, wherein the retardation value (Rth) of the hard coating film is in the range of -10 to 10 nm.

7. A polarizing plate comprising a polarizing element sandwiched between a hard coating film according to any one of claims 1 to 6 and a cellulose ester film having a film thickness within a range of 5 to 34 占 퐉.

8. A glass shatterproof film for use in an image display device, characterized by using the hard coating film according to any one of claims 1 to 6.

9. A touch panel comprising the hard coating film according to any one of claims 1 to 6.

10. The liquid crystal display device according to claim 7, wherein the polarizing plate is provided on at least one surface of the liquid crystal cell.

By the above-mentioned means of the present invention, it is possible to provide a hard coating film having a high slipping property between the films and an effect of preventing winding dislocation when the film is wound into a roll shape in a thin film. Further, since the hard coating film is excellent in planarity and unevenness, it is possible to provide a polarizing plate having excellent visibility, a glass shatterproofing film for an image display device, a touch panel, and a liquid crystal display device by using the hard coating film.

The mechanism and mechanism for manifesting the effects of the present invention are not clarified, but are estimated as follows.

The wettability (logarithmic contact angle) of the hard coat layer of the hard coat film and the wettability of the cellulose ester film used as the substrate are made close to each other to be hydrophilic so that the slip when the films are in contact with the hard coat layer It is presumed that the effect of preventing the winding displacement is obtained. Further, it is presumed that the air layer between the roll-shaped layers is also maintained so that the stress load on the film is suppressed, so that buckling deformation and distortion are less likely to occur, and a hard coating film excellent in planarity and unevenness is obtained.

1 is an example of a touch panel display device using a hard coating film according to the present invention.
2 is an example of an image display apparatus with a touch panel.
3 is an example of a schematic cross-sectional view of a glass scattering prevention film for an image display device used in an image display apparatus.
4 is a sectional view of the polarizing plate 101. Fig.

The hard coat film of the present invention is a hard coat film having a hard coat layer on at least one side of a cellulose ester film having a film thickness in the range of 5 to 34 占 퐉 and before and after the alkali treatment when the hard coat layer is alkali- the logarithm of the difference between the contact angle (θ _Δ) characterized in that in the range of 5 to 55 °.

(Alkali treatment condition)

Alkaline solution: 2.5 mol / L potassium hydroxide solution

Processing temperature: 50 ° C

Processing time: 120 seconds

This feature is a technical feature that is common to the claims of the claims 1 to 10.

As the embodiment of the present invention, it is preferable that the logarithmic contact angle (?) Of the hard coat layer before the alkali treatment is within a range of 50 to 120 °, and the logarithmic contact angle of the hard coat layer is an alkali treatment It is preferable to decrease after the alkali treatment.

As an embodiment of the present invention, it is preferable that the arithmetic average roughness (Ra) (JIS B0601: 2001) of the hard coat layer is in the range of 2 to 100 nm from the viewpoint of the effect of the present invention, , And the effect of preventing the winding displacement is improved.

Further, it is preferable that the hard coat layer contains an active energy ray-curable isocyanurate derivative because the effect of suppressing the slidability between the films increases.

In the present invention, the retardation value (Ro) of the cellulose ester film is in the range of 0 to 10 nm when the retardation value is measured at an optical wavelength of 590 nm in an environment of a temperature of 23 캜 and a relative humidity of 55% , And the retardation value (Rth) in the thickness direction is in the range of -10 to 10 nm. This has the effect of obtaining a hard coat film having good visibility.

Further, even if a polarizing plate having a polarizing element sandwiched and supported by using the hard coating film according to the present invention and a cellulose ester film having a film thickness in the range of 5 to 34 占 퐉 is used, it is possible to prevent winding displacement.

The hard coating film of the present invention is suitable for a glass shatterproof film, a touch panel, and a liquid crystal display for an image display device because of its good visibility.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention and its constituent elements, and specific details and modes for carrying out the present invention will be described in detail. In the present application, " to " is used to mean that the numerical values described before and after the lower limit and the upper limit are included.

<Difference between the number of the contact angle before and after the alkali treatment (θ _Δ)>

First, the difference (?) _Between the logarithmic contact angles before and after the alkali treatment according to the present invention will be described.

A hard coating film of the present invention, a is in the range of 5 to 55 ° difference in the number of the contact angle before and after the alkali treatment of the hard coating layer (θ _Δ). More preferably, it is within the range of 15 to 50 ° contact angle difference between the number _(Δ θ).

Here, the difference (?) _Between the logarithmic contact angles before and after the alkali treatment is a value obtained by multiplying the logarithmic contact angle (?) Of the hard coat layer before the alkali treatment of the hard coat film by the logarithmic contact angle ), And is a value obtained by subtracting the difference (?) _Between the logarithmic contact angles before and after the alkali treatment.

The conditions for the alkali treatment are conditions for immersing the hard coating film for 120 seconds in a 2.5 mol / L potassium hydroxide solution at a temperature of 50 占 폚.

The logarithmic contact angle was measured by measuring the contact angle (manufactured by Kyowa Chemical Industry Co., Ltd.) under an atmosphere of a temperature of 23 DEG C and a relative humidity of 55% after allowing the sample to stand for 24 hours under an atmosphere of a temperature of 23 DEG C and a relative humidity of 55% , Product name: DropMaster DM100), the contact angle of pure water after 1 minute of 1 L drop of pure water is measured. Also, it is a value obtained by performing the measurement seven times and averaging the five measured values excluding the maximum value and the minimum value of the measured value.

In the present invention, when the difference (?) _Between the logarithmic contact angles before and after the alkali treatment of the hard coat layer satisfies the above-described range, the hard coat layer exhibits hydrophilicity and can suppress the slidability between the hard coat films, The effect of preventing winding displacement can be obtained.

The logarithmic contact angle [theta] of the hard coat layer before alkali treatment is preferably in the range of 50 to 120 [deg.], More preferably in the range of 60 to 110 [deg.]. The logarithmic contact angle? A of the hard coat layer after the alkali treatment is not particularly limited as long as the difference between the hard coat layer and the hard coat layer before alkali treatment is in the range of 5 to 55 占 In the range of suppressing the winding deviation in the roll polarizing plate It is suitably selectable, specifically in the range of 40 to 110 DEG, and particularly preferably in the range of 40 to 80 DEG.

Further, the contact angle of the logarithmic deterioration after alkali treatment, it is a preferable embodiment in the present invention that the difference between the logarithmic contact angle (θ _Δ) satisfies the above range.

The alkali treatment of the present invention includes a step of dipping at least the hard coating film in an alkali solution (hereinafter also referred to as a saponification process), washing with water and drying, and the conditions of the alkali treatment are the above-mentioned conditions.

After the alkali treatment, neutralization may be performed in the acidic water process, followed by washing with water and drying.

Kinds of additive such as a surfactant or a fluorine-containing compound which will be described later, or both, is by adjusting the curing conditions of the hard coating layer forming method (adjustment of oxygen concentration, etc.), tea logarithmic contact angle before and after the alkali treatment (θ _Δ) so as to satisfy the above range Can be adjusted.

<Hard Coating Film>

(Hard coat layer)

The hard coating layer according to the present invention is preferable because it contains an active ray hardening resin because it has excellent mechanical strength (scratch resistance, pencil hardness). In other words, it is a layer mainly composed of a resin which is cured by cross-linking reaction by irradiation of active rays (also referred to as active energy rays) such as ultraviolet rays or electron rays. As the active ray hardening resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and the active ray hardening resin layer is formed by irradiating an active ray such as ultraviolet rays or electron rays. As the active ray curable resin, ultraviolet curable resin, electron beam curable resin and the like can be mentioned as typical ones, and a resin which is cured by irradiation with ultraviolet rays is particularly preferable in view of excellent mechanical film strength (scratch resistance, pencil hardness). Examples of the ultraviolet curable resin include ultraviolet curable acrylate resin, ultraviolet curable urethane acrylate resin, ultraviolet curable polyester acrylate resin, ultraviolet curable epoxyacrylate resin, ultraviolet curable polyol acrylate resin, Ultraviolet curing type epoxy resin and the like are preferably used, and among them, ultraviolet curing type acrylate type resin or ultraviolet ray curing type urethane acrylate type resin is preferable.

As the ultraviolet curable acrylate resin, polyfunctional acrylate is preferable. Examples of the polyfunctional acrylate include those selected from the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate desirable. Here, the polyfunctional acrylate is a compound having two or more acryloyloxy groups or methacryloyl groups in the molecule. Examples of the monomer of polyfunctional acrylate include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexane diol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylol Pentaerythritol triacrylate, pentaerythritol triacrylate, pentaerythritol triacrylate, pentaerythritol triacrylate, pentaerythritol triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, Ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, glycerin triacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol penta Acrylate, dipentaerythritol (Acryloyloxyethyl) isocyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, Acrylate, trimethylolethane trimethacrylate, tetramethylol methane trimethacrylate, tetramethylolmethane tetramethacrylate, pentaglycerol trimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane trimethacrylate, Acrylate, trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerin trimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol penta methacrylate , Dipentaerythritol hexamethacrylate, active energy ray-curable isocyanurate It may be preferably mentioned the derivatives. From the object and effects of the present invention, it is preferable that the hard coat layer according to the present invention contains an isocyanurate derivative of active energy ray-curable type.

The active energy ray-curable isocyanurate derivative may be any compound having a structure in which at least one ethylenic unsaturated group is bonded to the skeleton of isocyanuric acid, and is not particularly limited. However, the isocyanurate derivative represented by the formula (1) A compound having at least one ethylenic unsaturated group and at least one isocyanurate ring is preferable in view of the object effect of the present invention. The ethylenic unsaturated group is preferably an acryloyl group, a methacryloyl group, a styryl group or a vinyl ether group, more preferably a methacryloyl group or an acryloyl group, and particularly preferably an acryloyl group.

&Lt; Formula 1 >

In the formula, L ² is a divalent linking group, and is preferably a substituted or unsubstituted alkyleneoxy group or polyalkyleneoxy group having 4 or less carbon atoms in which a carbon atom is bonded to an isocyanurate ring, Are each an alkyleneoxy group, and may be the same or different. R ² represents a hydrogen atom or a methyl group, and may be the same or different. Specific compounds represented by the formula (1) are shown below, but are not limited thereto.

(2)

(3)

&Lt; Formula 4 >

As other compounds, isocyanuric acid diacrylate compounds and isocyanuric acid ethoxy-modified diacrylates represented by the following formula (2) are preferable.

&Lt; Formula 5 >

As other examples, an isocyanurate derivative of active energy ray-curable type of? -Caprolactone denaturation may be used, specifically, a compound represented by the following formula (3).

(6)

At the positions of R ₁ to R ₃ in the chemical structural formulas, functional groups represented by the following a, b, and c are attached. At least one of R ₁ to R ₃ is a functional group of b.

a: -H, or - (CH ₂ ) _n -OH (n = 1 to 10, preferably n = 2 to 6)

b = - (CH ₂ ) _n -O- (COC ₅ H ₁₀ ) _m -COCH = CH ₂ (n = 1 to 10, preferably n = 2 to 6, m =

n: 1 to 10, preferably n = 2 to 6), and c: - (CH ₂ ) _n -OR (R represents a (meth) acryloyl group,

Specific compounds represented by the formula (3) are shown below, but are not limited thereto.

&Lt; Formula 7 >

Commercially available products of the isocyanuric acid triacrylate compound include, for example, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., and the like. Commercially available products of isocyanuric acid diacrylate compounds include Aronix M-215 manufactured by Toagosei Co., Ltd., and the like. Examples of the mixture of isocyanuric acid triacrylate compound and isocyanuric acid diacrylate compound include Aronix M-315 and Aronix M-313 manufactured by Toagosei Co., Ltd. Active energy of? -caprolactone denaturation As the isocyanurate derivative of the ray-curable type, A-9300-1CL manufactured by Shin Nakamura Kagaku Kogyo K.K., which is? -caprolactone modified tris- (acryloxyethyl) isocyanurate, Aronix M-327 manufactured by Toagosei Co., Ltd., and the like, but the present invention is not limited thereto.

These commercially available products include Adeka Optomer N series, Sunrad H-601, RC-750, RC-700, RC-600, RC-500, RC-611 and RC- 612 (manufactured by Sanyo Chemical Industries, ARONIX M-3100, ARONIX M-327 (manufactured by Doagosei Co., Ltd.), NK-ester A (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-6100, M-8030, M-8060, Aronix M-215, Aronix M- -MM-3L, NK-ester AD-TMP, NK-ester ATM-35E, NK ester A-DOG, NK ester A-IBD-2E, A-9300, A-9300-1CL )), PE-3A (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

Examples of the ultraviolet curable urethane acrylate resin include a resin obtained by reacting an isocyanate with a hydroxyl group-containing compound such as an alcohol, a polyol, and / or a hydroxy group-containing acrylate, or by reacting a polyurethane Is obtained by esterifying the compound with (meth) acrylic acid. More specifically, it is an addition reaction product of a polyisocyanate and an acrylate having at least one hydroxyl group in one molecule and at least one (meth) acryloyl group. Examples of the polyisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, An isocyanate group bonded to an alicyclic hydrocarbon such as dicyclohexylmethane diisocyanate, isophorone diisocyanate, norbornane diisocyanate, and 1,4-cyclohexane diisocyanate, isocyanate groups such as 2, (Hereinafter abbreviated as alicyclic diisocyanate), a compound having two isocyanate groups bonded to aliphatic hydrocarbons such as trimethylene diisocyanate and hexamethylene diisocyanate (hereinafter abbreviated as aliphatic diisocyanate), phenylene diisocyanate , Aromatic diisocyanates such as toluene diisocyanate And aromatic aliphatic diisocyanates such as xylylene diisocyanate. These polyisocyanates may be used alone or in combination of two or more, and preferably aliphatic diisocyanates and alicyclic diisocyanates. Among them, isophorone diisocyanate, norbornadiisocyanate, toluene diisocyanate and hexamethylene diisocyanate are preferable. Examples of the acrylate having one hydroxyl group and one or more (meth) acryloyl groups in one molecule include trimethylol propane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol And penta (meth) acrylate. Examples of the polyacrylates include adducts of the polyacrylates and? -Caprolactone, adducts of the polyacrylates and the alkylene oxide, and epoxies Acrylates and the like. The acrylate having one hydroxy group and one or more (meth) acryloyl groups in one molecule may be used alone or in combination of two or more.

Among the acrylates having one hydroxy group and at least one (meth) acryloyl group in one molecule, acrylate having one hydroxy group in one molecule and 3 to 5 (meth) acryloyl groups is preferable. Examples of such acrylates include pentaerythritol triacrylate and dipentaerythritol pentaacrylate.

Specific examples of the ultraviolet curing type urethane acrylate resin include commercially available products such as Shiko UV-1700B, Dong UV-6300B, Dong UV-7600B, Dong UV-7630B, Dong UV-7640B, NK oligo UA-53H, NK oligo UA-33H, NK oligo UA-33H, UA-306H, UA- NK oligo UA-15HA, and the like.

The viscosity of the active ray curable resin can be measured by using a B-type viscometer under the condition of stirring at 25 ° C by mixing the resin with a disperser. A monofunctional acrylate may also be used.

Examples of monofunctional acrylates include isobornyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, isostearyl acrylate, benzyl acrylate, ethyl carbitol acrylate, phenoxy ethyl acrylate, Acrylate, isooctyl acrylate, tetrahydrofurfuryl acrylate, behenyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, cyclohexyl acrylate, . Such a monofunctional acrylate is available from Nippon Kasei Kogyo Co., Shin-Nakamura Kagaku Kogyo Co., Ltd., Osaka Yuki Kagaku Kogyo Co., Ltd.

In the case of using a monofunctional acrylate, it is preferable that the monofunctional acrylate is contained in a ratio of polyfunctional acrylate: monofunctional acrylate = 80: 20 to 98: 2 in terms of the mass ratio of the polyfunctional acrylate to the monofunctional acrylate.

(Photopolymerization initiator)

The hard coat layer preferably contains a photopolymerization initiator for accelerating curing of the active ray curable resin. The amount of the photopolymerization initiator is preferably in the range of from 20: 100 to 0.01: 100 as the photopolymerization initiator: active ray curable resin in a mass ratio. Specific examples of the photopolymerization initiator include alkylphenone, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone,? -Amyloxime ester, thioxanthone, etc., and derivatives thereof. It is not.

Such a photopolymerization initiator may be a commercially available product, and examples thereof include IRGACURE 184, IRGACURE 907, IRGACURE 651 manufactured by BASF Japan Ltd., and the like.

(Conductive agent)

The hard coat layer may contain a conductive agent for imparting antistatic properties. Preferable examples of the conductive agent include metal oxide particles or a π conjugated conductive polymer. An ionic liquid is also preferably used as the conductive compound.

(additive)

From the viewpoint of controlling the difference (?) _Between the logarithmic contact angles before and after the alkali treatment within the above-described range, the hard coat layer is preferably coated with a silicone surfactant, a fluorine surfactant, an anionic surfactant, and a fluorine-siloxane graft compound, Or the like may be added. In addition, a compound having an HLB value in the range of 3 to 18 may be contained. The water repellency can be controlled by adjusting the kind and amount of these additives, and it is easy to control the angle? _{Within the} above range.

The HLB value is Hydrophile-Lipophile-Balance, hydrophilic-lipophilic-balance, and is a value indicating the hydrophilicity or lipophilicity of the compound. The smaller the HLB value is, the higher the lipophilicity is, and the larger the value, the higher the hydrophilicity. The HLB value in the present invention can be obtained by the following calculation formula.

HLB = 7 + 11.7 Log (Mw / Mo)

In the formula, Mw represents the molecular weight of the hydrophilic group, Mo represents the molecular weight of the lipophilic group, and Mw + Mo = M (molecular weight of the compound). Specific compounds of the compounds having an HLB value in the range of 3 to 18 are exemplified below, but the present invention is not limited thereto. () Represents the HLB value.

Emulsion 102 (6.3), Emergene 103 (8.1), Emergene 104P (9.6), Emergen 105 (9.7), Emergene 106 (10.5), Emergene 108 Emergen 120 (15.3), Emergen 123P (16.9), Emergen 147 (16.3), Emergen 210P (10.7), Emergen 220 (14.2), Emergene 306P (9.4), Emergene 320P (13.9), Emergen 404 (8.8), Emergen 408 (10.0), Emergen 409PV (12.0), Emergen 420 (13.6), Emergen 430 (16.2), Emergene 705 (10.5), Emergene 707 Emergen 2020G-HA (13.0), Emergen 2025G (15.7), Emergene 1118S-70 (16.4) EMULGEN LS-114 (14.0) manufactured by Nisshin Chemical Industry Co., Ltd., Surfynol 104E (4), Surfynol 104H (4) manufactured by Nisshin Chemical Industry Co., , Surfynol 104A (4), Surfynol 104BC (4), Surfynol 104DPM (4), Surfynol 104PA (4), Surfynol 104PG-50 ), Surinol 440 (8), Surinol 465 (13), Surinol 485 (17), Surinol SE (6) ), X-22-4272 (7), X-22-6266 (8), KF-351 (12), KF-352 (7), KF-353 (10) manufactured by Shinetsu Chemical Industry Co., ), KF-354L (16), KF-355A (12), KF-615A (10), KF-945 (4), KF- , And KF-6004 (5). Examples of the silicone surfactants include polyether-modified silicones, and KF series manufactured by Shin-Etsu Chemical Co., Ltd. and the like. Examples of acrylic copolymers include commercially available compounds such as BYK-350 and BYK-352 manufactured by Big Chem Japan Co., Examples of the fluorochemical surfactant include Megafax RS series, Megafax F-444 and Megafax F-556 manufactured by DIC Corporation. The fluorine-siloxane graft compound refers to a copolymer compound obtained by grafting at least a polysiloxane and / or an organopolysiloxane containing a siloxane and / or an organosiloxane group to a fluorine resin. Such a fluorine-siloxane grafted compound can be produced by a method as described in the following Examples. Examples of commercially available products include ZX-022H, ZX-007C, ZX-049 and ZX-047-D manufactured by Fuji Kasei Kogyo Co., Examples of the fluorine-based compound include OptuT DSX and Optol DAC manufactured by Daikin Industries, Ltd. These components are preferably added in an amount of 0.005 parts by mass or more and 5 parts by mass or less based on the solid component in the hard coating composition.

(Ultraviolet absorber)

The hard coating layer may further contain an ultraviolet absorber described in a cellulose ester film to be described later. As the constitution of the film containing the ultraviolet absorber, when it is composed of two or more layers, it is preferable that the ultraviolet absorber is contained in the hard coat layer in contact with the cellulose ester film.

The content of the ultraviolet absorber is preferably in the range of 0.01: 100 to 10: 100 in terms of the mass ratio of the ultraviolet absorber: hard coat layer constituent resin. When two or more layers are provided, the film thickness of the hard coat layer in contact with the cellulose ester film is preferably in the range of 0.05 to 2 mu m. The lamination of two or more layers may be formed as a simultaneous middle layer. In the simultaneous intermediate layer, two or more hard coating layers are applied on a substrate by wet on wet without a drying step to form a hard coating layer. In order to laminate the second hard coating layer wet on wet without the drying process being performed on the first hard coat layer, it is possible to carry out the simultaneous double layering in the slot die having the plurality of slits or in order by the extrusion coater.

(solvent)

The hard coat layer is prepared by coating the above-mentioned hard coat layer on the cellulose film by applying the following method to the hard coat layer composition by diluting the cellulose ester film with a solvent capable of swelling or partially dissolving the cellulose ester film, drying and curing the hard coat layer .

Examples of the solvent include ketones (methyl ethyl ketone, acetone, etc.) and / or acetic acid esters (such as methyl acetate, ethyl acetate and butyl acetate), alcohols (ethanol, methanol), propylene glycol monomethyl ether, cyclohexanone, methyl isobutyl ketone . The coating amount of the hard coat layer is suitably in the range of 0.1 to 40 mu m, preferably in the range of 0.5 to 30 mu m, as the wet film thickness. The dry film thickness is in the range of 0.01 to 20 占 퐉 in average film thickness, preferably in the range of 0.5 to 10 占 퐉. More preferably in the range of 0.5 to 5 占 퐉.

As a method of applying the hard coat layer, a known method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, and an ink jet method may be used.

(Hard Coating Layer Forming Method)

The hard coat layer composition may be applied, dried, irradiated with active rays to be cured (also referred to as UV curing treatment), and if necessary, subjected to UV curing treatment followed by heat treatment. The heat treatment temperature after UV curing treatment is preferably 80 DEG C or higher, more preferably 100 DEG C or higher, and particularly preferably 120 DEG C or higher. By performing the heat treatment after the UV curing treatment at such a high temperature, a hard coat layer having excellent film strength can be obtained.

The drying is preferably carried out by a high-temperature treatment at 90 deg. More preferably, the temperature of the rate drying section is 90 ° C or more and 125 ° C or less. Condensation occurs in the coating film resin at the time of formation of the hard coat layer by the high temperature treatment in the rate-decreasing drying section. As a result, irregular surface roughness easily appears on the surface of the hard coat layer, easy to do.

In general, the drying process is known to change gradually from a constant drying rate to a gradually decreasing state when drying starts, and it is known that a constant drying rate is divided into a constant rate drying rate and a decreasing drying rate, Quot; In the constant rate drying period, all the heat input is consumed for evaporation of the solvent on the surface of the coating film, and when the solvent on the surface of the coating film is decreased, the evaporation surface moves from the surface to the inside of the rate reducing drying section. Since then, the temperature of the coating film surface rises and becomes close to the hot air temperature, so that the temperature of the active ray-curable resin composition is elevated and the resin viscosity is lowered and the fluidity is thought to increase.

As the light source for the UV curing treatment, any light source that generates ultraviolet rays can be used without limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp and the like can be used.

Irradiation conditions vary depending on the respective lamps, but the irradiation amount of the active rays is usually in the range of 50 to 1000 mJ / cm ² , preferably in the range of 50 to 300 mJ / cm ² . In addition, in the UV curing treatment, oxygen removal (for example, substitution with an inert gas such as nitrogen purge) may be performed in order to prevent reaction inhibition by oxygen. By adjusting the removal amount of the oxygen concentration, the cured state of the surface can be controlled. This makes it possible to control the presence state of the additive on the surface of the hard coat layer as described above, and as a result, it is easy to control _? When irradiating the active line, it is preferable to perform the tension while applying a tensile force in the film transport direction, and more preferably, the tension is applied in the width direction. The tensile force to be imparted is preferably 30 to 300 N / m. The method of applying the tension is not particularly limited, and the tension may be given in the carrying direction on the back roller, or in the width direction or the biaxial direction by the tenter. As a result, a film excellent in planarity can be obtained.

(Surface shape)

The arithmetic mean roughness (Ra) (JIS B0601: 2001) of the hard coat layer is preferably in the range of 2 to 100 nm, particularly preferably in the range of 5 to 80 nm. By setting the arithmetic mean roughness (Ra) in the above range, the effect of the present invention can be appropriately obtained even after a more severe vibration test.

It is preferable that the height of the projection shape to be the arithmetic average roughness Ra is in the range of 2 nm to 4 탆. Also, the width of the protrusion shape is within the range of 50 nm to 300 mu m, preferably within the range of 50 nm to 100 mu m.

The 10-point average roughness Rz of the hard coat layer is preferably 10 times or less the center line average roughness Ra and the average peak-to-valley distance Sm is preferably 5 to 150 mu m, more preferably 20 to 100 mu m, It is preferable that the standard deviation of the height of the convex portion from the deepest concave and convex portion is 0.5 占 퐉 or less, the standard deviation of the average range of curling distance Sm with respect to the center line is 20 占 퐉 or less and the inclined angle is 0 to 5 占 퐉 is 10% or more. The arithmetic mean roughnesses Ra, Sm and Rz are values measured with an optical interference type surface roughness meter (NewView, manufactured by ZYGO) according to JIS B0601: 2001.

(Hayes)

It is preferable that the haze of the hard coating film is in the range of 0.2 to 10% in terms of visibility when used in an image display apparatus. The haze can be measured in accordance with JIS-K7105 and JIS K7136.

(Hardness)

In the hard coat film of the present invention, pencil hardness, which is an index of hardness, is not less than HB, more preferably not less than H. HB or more, it is difficult to cause scratches in the polarizing plate forming step. The pencil hardness was measured by using a pencil for test specified in JIS S6006 under the condition of a weight of 500 g and a hard coat layer and / or a functional layer at a temperature of 23 캜 and a relative humidity of 55% Measured according to the pencil hardness evaluation method prescribed by JIS K5400.

Next, the cellulose ester film according to the present invention will be described.

<Cellulose Ester Film>

A cellulose ester film as a base material of the hard coating film according to the present invention and a cellulose ester film bonded to the back side of the polarizing plate will be described.

Examples of the cellulose ester film (hereinafter also referred to as a cellulose acetate film) include triacetyl cellulose film, cellulose acetate propionate film, cellulose diacetate film, and cellulose acetate butyrate film. Further, the cellulose ester film can be produced by using a combination of a polyester resin such as polyethylene terephthalate and polyethylene naphthalate, a polycarbonate resin, a polyethylene resin, a polypropylene resin, a norbornene resin, a fluororesin and a cycloolefin polymer You can. Examples of commercially available products of the cellulose ester film include Konica Minolta Tact KC8UX, KC4UX, KC8UY, KC4UY, KC6UA, KC4UA, KC4UE and KC4UZ (manufactured by Konica Minolta Advantest Co., Ltd.). The refractive index of the cellulose ester film is preferably 1.45 to 1.55. The refractive index can be measured in accordance with JIS K7142-2008.

(Cellulose ester resin)

The cellulose ester resin (hereinafter also referred to as a cellulose ester) is preferably a low-fat fatty acid ester of cellulose. The lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms and includes, for example, cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate and the like, A mixed fatty acid ester such as phthalate, phonate, cellulose acetate butyrate and the like can be used.

Among these, cellulose esters of cellulose which are particularly preferably used are cellulose diacetate, cellulose triacetate, and cellulose acetate propionate. These cellulose esters can be used alone or in combination.

The cellulose diacetate preferably has an average degree of acetalization (amount of bound acetic acid) of 51.0 to 56.0%. Commercially available products include L20, L30, L40 and L50 manufactured by Daicel Co., and Ca398-3, Ca398-6, Ca398-10, Ca398-30 and Ca394-60S manufactured by Eastman Chemical Co.,

The cellulose triacetate preferably has an average degree of acetalization (amount of bonded acetic acid) of 54.0 to 62.5%, more preferably a cellulose triacetate having an average degree of acetatization of 58.0 to 62.5%.

As cellulose triacetate, cellulose triacetate A having a number average molecular weight (Mn) of 125000 or more and less than 155000, a weight average molecular weight (Mw) of 265000 or more and less than 310000, a Mw / Mn of 1.9 to 2.1, It is preferable to contain cellulose triacetate B having a number average molecular weight (Mn) of 155,000 or more and less than 180,000, Mw of 290000 or more and less than 360000, and Mw / Mn of 1.8 to 2.0.

The cellulose acetate propionate is represented by the following formulas (I) and (II) when the substitution degree of the acetyl group is X and the degree of substitution of the propionyl group is Y, the acyl group having 2 to 4 carbon atoms as a substituent, ) At the same time.

(I) 2.6? X + Y? 3.0

(II) 0? X? 2.5

Among them, it is preferable that 1.9? X? 2.5 and 0.1? Y? 0.9.

The degree of substitution degree of the acyl group can be measured according to ASTM-D817-96.

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

Solvent: methylene chloride

Column: Shodex K806, K805, K803G

(Using three connected products manufactured by Showa Denko K.K.)

Column temperature: 25 ° C

Sample concentration: 0.1 mass%

Detector: RI Model 504 (manufactured by GL Science)

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

Flow rate: 1.0 ml / min

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

(Thermoplastic acrylic resin)

As the cellulose ester film, a thermoplastic acrylic resin may be used in combination. When used in combination, the mass ratio of the thermoplastic acrylic resin to the cellulose ester resin is preferably in the range of from 95: 5 to 50:50 in the thermoplastic acrylic resin: cellulose ester resin.

The acrylic resin also includes a methacrylic resin. The acrylic resin is not particularly limited, but it preferably contains a range of 50 to 99 mass% of methyl methacrylate units and 1 to 50 mass% of other monomer units copolymerizable therewith. Examples of other copolymerizable monomers include alkyl methacrylates having 2 to 18 carbon atoms in the alkyl number, alkyl acrylates having 1 to 18 carbon atoms in the alkyl number, alpha, beta -unsaturated acids such as acrylic acid and methacrylic acid, Aromatic vinyl compounds such as styrene,? -Methylstyrene,?,? - unsaturated nitriles such as acrylonitrile and methacrylonitrile, maleic anhydride, maleimide , N-substituted maleimide, and glutaric anhydride. These may be used singly or in combination of two or more.

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

The weight average molecular weight of the acrylic resin can be measured by gel permeation chromatography. As commercially available products of acrylic resin, for example, Delpet 60N and 80N (manufactured by Asahi Kasei Chemicals Co., Ltd.), Dianal BR52, BR80, BR83, BR85 and BR88 (manufactured by Mitsubishi Rayon Co., Ltd.), KT75 (Manufactured by Nippon Polyurethane Industry Co., Ltd.). Two or more acrylic resins may be used in combination.

(Fine particles)

In the cellulose ester film according to the present invention, in order to improve the handling property, it is preferable to use an acrylic resin such as acrylic particles, silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, kaolin, talc, calcined calcium silicate, It is preferable to contain a matting agent such as inorganic fine particles or crosslinked polymers such as aluminum, magnesium silicate and calcium phosphate. The acrylic particle is not particularly limited, but is preferably a multi-layered acrylic granular composite. Of these, silicon dioxide is preferable in that the haze of the cellulose ester film can be reduced. The primary average particle diameter of the fine particles is preferably 20 nm or less, more preferably in the range of 5 to 16 nm, and particularly preferably in the range of 5 to 12 nm.

The cellulose acetate film according to the present invention preferably contains an ester or sugar ester represented by the following formula (X) from the viewpoint of improving dimensional stability in environmental changes. First, the ester represented by the formula (X) will be described.

(X) B- (GA) _n- GB

(Wherein B is a hydroxy group or a carboxylic acid residue, G is an alkylene glycol residue having 2 to 12 carbon atoms or an aryl glycol residue having 6 to 12 carbon atoms or an oxyalkylene glycol residue having 4 to 12 carbon atoms, An alkylene dicarboxylic acid residue of 12 to 12 carbon atoms or an aryl dicarboxylic acid residue of 6 to 12 carbon atoms, and n represents an integer of 1 or more)

Examples of the alkylene glycol component having 2 to 12 carbon atoms in the formula (X) include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, Propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2- Ethyl-1,3-propanediol (3,3-dimethylol pentane), 2-n-butyl- Pentanediol 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2- -Nonanediol, 1,10-decanediol, 1,12-octadecanediol, and the like, and these glycols are used as one kind or a mixture of two or more kinds. Particularly, alkylene glycol having 2 to 12 carbon atoms is particularly preferable because of its excellent compatibility with cellulose acetate. Examples of the aryl glycol component having 6 to 12 carbon atoms include hydroquinone, resorcin, bisphenol A, bisphenol F, and bisphenol. These glycols can be used singly or as a mixture of two or more kinds.

Examples of the oxyalkylene glycol component having 4 to 12 carbon atoms include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol and the like, and the glycol may be one or two Can be used as the above mixture. Examples of the alkylene dicarboxylic acid component having 4 to 12 carbon atoms include succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid and dodecanedicarboxylic acid, Or a mixture of two or more thereof. Examples of the arylene dicarboxylic acid component having 6 to 12 carbon atoms include phthalic acid, terephthalic acid, isophthalic acid, 1,5-naphthalene dicarboxylic acid, and 1,4-naphthalene dicarboxylic acid. Specific examples of the compound represented by the formula (X) (compounds X-1 to X-17) are shown below, but the present invention is not limited thereto.

(8)

&Lt; Formula 9 >

&Lt; Formula 10 >

Next, the sugar ester will be described. The sugar ester is an ester other than a cellulose ester, and is a compound obtained by esterifying all or a part of the sugar OH groups such as the following monosaccharides, 2 sugars, 3 sugars or oligosaccharides. Examples of sugar include glucose, galactose, mannose, fructose, xylose, arabinose, lactose, sucrose, nisthos, 1F-fructosylnitose, stachyose, maltitol, lactitol, Oz, cellobiose, maltose, cellotriose, maltotriose, raffinose and kestose. In addition to these, gentiobiose, gentiootriose, gentiotetraose, xylotriose, galactosyl sucrose and the like can be mentioned. Of these compounds, compounds having a furanose structure and / or a pyranose structure are particularly preferable. Among these, sucrose, cestose, nisthose, 1F-fructosylnitose, stachyose and the like are preferable, and sucrose is more preferable. As the oligosaccharide, maltooligosaccharide, isomaltooligosaccharide, fructooligosaccharide, galactooligosaccharide, and xylooligosaccharide are also preferably used.

The monocarboxylic acid used to esterify the sugar is not particularly limited and known aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, and aromatic monocarboxylic acids can be used. The carboxylic acid used may be a single kind or a mixture of two or more kinds. Preferred aliphatic monocarboxylic acids are acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethylhexanecarboxylic acid, But are not limited to, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachic acid, behenic acid, lignoceric acid, Unsaturated fatty acids such as montanic acid, melissic acid and lactic acid, and unsaturated fatty acids such as undecylenic acid, oleic acid, sorbic acid, linolic acid, linolenic acid, arachidonic acid and octetic acid. Examples of preferred alicyclic monocarboxylic acids include cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, and derivatives thereof. Examples of preferred aromatic monocarboxylic acids include benzoic acid, aromatic monocarboxylic acids having an alkyl group and an alkoxy group introduced into the benzene ring of benzoic acid, cinnamic acid, benzilic acid, biphenylcarboxylic acid, naphthalenecarboxylic acid, tetralincarboxyl An aromatic monocarboxylic acid having two or more benzene rings such as an acid, and derivatives thereof, and more specifically, xylyl acid, hemelitic acid, mesitylene acid, phentylic acid,? -Isoduryl acid, O-, m, p-anisic acid, creosoteic acid, o-toluic acid, hydroxycarboxylic acid, isostearic acid, , m, p-homosalicylic acid, o-pyrocatechic acid,? -resoric acid, vanillic acid, isobanilic acid, veratric acid, o-veratric acid, gallic acid, aspartic acid, mandelic acid, Vanillic acid, homo veratric acid, o-homo veratric acid, phthalic acid, and p-cumaric acid. Benzoic acid is particularly preferable. Among the esters, an acetyl compound having an acetyl group introduced by esterification is preferable. Specific examples of sugar esters that can be used in the present invention are shown below, but the present invention is not limited thereto.

&Lt; Formula 11 >

&Lt; Formula 12 >

&Lt; Formula 13 >

&Lt; Formula 14 >

&Lt; Formula 15 >

The sugar ester is preferably a compound represented by the formula (Y). Hereinafter, the compound represented by the formula (Y) will be described.

&Lt; Formula 16 >

(R ₁ to R ₈ in the formula are, a hydrogen atom, a substituted or unsubstituted alkylcarbonyl group having 2 to 22, or a substituted or unsubstituted aryl group having a carbon number of 2 to 22, R ₁ to R ₈ is, They may be the same or different.)

Hereinafter, the compound represented by the formula (Y) is represented more specifically (compounds Y-1 to Y-23), but is not limited thereto. In the following table, when the average degree of substitution is less than 8.0, any one of R ₁ to R ₈ represents a hydrogen atom.

&Lt; Formula 17 >

&Lt; Formula 18 >

(19)

The substitution degree distribution can be adjusted to an intended substitution by controlling the esterification reaction time or by mixing a compound having a difference in substitution degree.

The ester or sugar ester represented by the formula (X) is preferably contained in the cellulose acetate film in an amount of 1 to 30 mass%, more preferably 5 to 25 mass%, more preferably 5 to 20 mass% By mass or less, particularly preferably within a range of 0.1 to 5% by mass.

(Other additives)

[Plasticizer]

The cellulose acetate film according to the present invention may contain a plasticizer, if necessary.

Examples of the plasticizer include, but are not limited to, polyvalent carboxylic acid ester plasticizers, glycolate plasticizers, phthalate ester plasticizers, phosphate ester plasticizers, polyhydric alcohol ester plasticizers, and acrylic plasticizers. Of these, an acrylic plasticizer is preferable in that it is easy to control the cellulose ester film by a retardation value described later.

The polyhydric alcohol ester plasticizer is preferably a plasticizer containing an ester of a divalent or higher aliphatic polyhydric alcohol and a monocarboxylic acid and having an aromatic ring or a cycloalkyl ring in the molecule. Preferably 2 to 20, aliphatic polyhydric alcohol esters. Preferable specific examples of the polyhydric alcohol ester plasticizers include the compounds described in paragraphs [0058] to [0061] of JP-A No. 2006-113239.

The glycolate-based plasticizer is not particularly limited, but alkyl phthalyl alkyl glycolates can be preferably used. The alkyl phthalyl alkyl glycolates include, for example, methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octylphthalyl octyl glycolate, Ethyl phthalyl methyl glycolate, ethyl phthalyl propyl glycolate, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl phthalyl methyl glycolate, butyl phthalyl ethyl glycolate, propyl phthalyl butyl Glycolate, butyl phthalyl propyl glycolate, methyl phthalyl octyl glycolate, ethyl phthalyl octyl glycolate, octylphthalyl methyl glycolate, and octylphthalyl ethyl glycolate.

Examples of the phthalate ester plasticizers include diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, dicyclohexylterephthalate, .

Examples of the phosphate ester plasticizer include triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate, octyldiphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate and the like.

The polycarboxylic acid ester plasticizer is a compound containing an ester of a polyvalent carboxylic acid and an alcohol having a valence of 2 or more, preferably 2 to 20, Specific examples include triethyl citrate, tributyl citrate, acetyl triethyl citrate (ATEC), acetyl tributyl citrate (ATBC), benzoyl tributyl citrate, acetyltriphenyl citrate, acetyl tribenzyl citrate, Dibutyl, diacetyl dibutyl tartrate, tributyl trimellitate, tetrabutyl pyromellitate, and the like, but are not limited thereto.

The acrylic plasticizer is preferably an acrylic polymer, and the acrylic polymer is preferably a homopolymer or copolymer of acrylic acid or methacrylic acid alkyl ester. Examples of the monomer of the acrylic acid ester include methyl acrylate, ethyl acrylate, propyl acrylate (i-, n-), butyl acrylate (n-, i-, s-, t-) , s-), hexyl acrylate (n- and i-), heptyl acrylate (n- and i-), octyl acrylate (n- and i-), nonyl acrylate (n- and i-) and myristyl acrylate -, i-), acrylic acid (2-ethylhexyl), acrylic acid (? -caprolactone), acrylic acid (2-hydroxyethyl), acrylic acid (2- hydroxypropyl) (2-methoxyethyl), acrylic acid (2-ethoxyethyl), and the like, or those obtained by replacing the acrylic acid ester with a methacrylic acid ester have. The acrylic polymer is a homopolymer or a copolymer of the above monomers, and preferably has 30 mass% or more of acrylic acid methyl ester monomer units and more preferably 40 mass% or more of methacrylic acid methyl ester monomer units. In particular, a homopolymer of methyl acrylate or methyl methacrylate is preferred.

When the above-mentioned plasticizer is contained in the cellulose acetate film according to the present invention, the amount of the plasticizer is preferably in the range of 1 to 50 mass%, more preferably 5 to 35 mass%, based on the cellulose acetate. , More preferably from 5 to 25% by mass.

(Ultraviolet absorber)

The cellulose acetate film according to the present invention may contain an ultraviolet absorber. Since the ultraviolet absorber absorbs ultraviolet rays of 400 nm or less, the durability can be improved. The ultraviolet absorber preferably has a transmittance at a wavelength of 370 nm of preferably 10% or less, more preferably 5% or less, further preferably 2% or less. Specific examples of ultraviolet absorbers include, but are not limited to, oxybenzophenone compounds, benzotriazole compounds, salicylic ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, , And inorganic powders.

More specifically, for example, there can be mentioned 5-chloro-2- (3,5-di-sec-butyl-2-hydoxylphenyl) -2H-benzotriazole, (2-2H-benzotriazol- Yl) -6- (straight chain and branched dodecyl) -4-methylphenol, 2-hydroxy-4-benzyloxybenzophenone and 2,4-benzyloxybenzophenone. For example, a commercially available product may be used. For example, a tinuvin such as Tinuvin 109, Tinuvin 171, Tinuvin 234, Tinuvin 326, Tinuvin 327 and Tinuvin 328 manufactured by BASF Japan Co., Can be used.

The ultraviolet absorber preferably used is benzotriazole ultraviolet absorber, benzophenone ultraviolet absorber, triazine ultraviolet absorber, and particularly preferably benzotriazole ultraviolet absorber, benzophenone ultraviolet absorber and the like.

In addition, a discotic compound such as a compound having 1,3,5-triazine ring is also preferably used as an ultraviolet absorber. As the ultraviolet absorber, a polymer ultraviolet absorber can be preferably used, and a polymer-type ultraviolet absorber is preferably used.

As the benzotriazole ultraviolet absorber, TINUVIN 109 (octyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol- Yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl- , A mixture of TINUVIN 928 (2- (2H-benzotriazol-2-yl) -6- (1 -methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) ) Can be used. As the triazine type ultraviolet absorbent, TINUVIN 400 (2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) (Reaction product of 5-hydroxyphenyl and oxirane), TINUVIN 460 (2,4-bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) Triazine), TINUVIN 405 (2- (2,4-dihydroxyphenyl) -4,6-bis- (2,4-dimethylphenyl) ) -Glycidic acid ester) and the like can be used.

The ultraviolet absorber may be added by dissolving the ultraviolet absorber in an alcohol such as methanol, ethanol or butanol, or an organic solvent such as methylene chloride, methyl acetate, acetone, or dioxolane, or a mixed solvent thereof, Dope), or may be added directly to the dope composition. Inorganic powders, which are not dissolved in an organic solvent, are dispersed in an organic solvent and cellulose acetate using a dissolver or a sand mill, and then added to the dope.

The amount of the ultraviolet absorber to be used is preferably in the range of 0.5 to 10 mass%, more preferably in the range of 0.6 to 4 mass% with respect to the cellulose acetate film.

(Antioxidant)

The cellulose acetate film according to the present invention may also contain an antioxidant (deterioration inhibitor). The antioxidant has a role of slowing down or preventing the decomposition of the cellulose acetate film due to halogen in the residual solvent amount in the cellulose acetate film or phosphoric acid in the phosphoric acid plasticizer. As the antioxidant, a hindered phenol-based compound is preferably used, and examples thereof include 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol Bis (n-octylthio) -6- (4-hydroxy-3-hydroxyphenyl) propionate, Di-t-butyl anilino) -1,3,5-triazine, 2,2-thio-diethylenebis [3- (3,5- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis -Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris- (3,5- Di-t-butyl-4-hydroxybenzyl) -isocyanurate and the like. The amount of these compounds to be added is preferably in the range of 1 to 10000 ppm, more preferably in the range of 10 to 1000 ppm, in mass ratio with respect to the cellulose acetate film.

(fault)

It is preferable that the cellulose ester film has a defect size of not less than 5 占 퐉 and not more than 10 cm / square. More preferably not more than 0.5 / 10 cm square, more preferably not more than 0.1 / 10 cm square. Here, the diameter of the defect refers to the diameter when the defect has a circular shape, and when the defect is not circular, the range of the defect is determined by observing with a microscope by the following method, and the maximum diameter is defined as the diameter of the circumscribed circle.

The range of the defect is the size of the shadow when the defect is observed as the transmitted light of the differential interference microscope when the defect is bubble or foreign matter. If the defect is a change in surface shape such as a transfer of a roller scratch or a scratch, the size can be confirmed by observing the defect as reflected light of a differential interference microscope.

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

Further, even when it can not be visually confirmed, a coating film can not be uniformly formed when a hard coat layer is formed, which may cause defects (coating defects). Here, the defect means defects in the film (defective foams) in the film due to rapid evaporation of the solvent in the step of drying the solution film, and foreign matter (foreign matter defect) in the film due to foreign matter contained in the film forming solution It says. Further, the base film preferably has a breaking elongation at least in one direction of 10% or more, more preferably 20% or more, in the measurement according to JIS-K7127-1999. The upper limit of the elongation at break is not particularly limited, but is about 250% in practice. In order to increase the elongation at break, it is effective to suppress defects in a film caused by foreign matter or foaming.

(Optical characteristics)

The cellulose ester film preferably has a total light transmittance of 90% or more, and more preferably 93% or more. The practical upper limit is about 99%. The haze value is preferably 2% or less, and more preferably 1.5% or less. The total light transmittance and the haze value can be measured in accordance with JIS K7361 and JIS K7136.

Further, it is preferable that the in-plane retardation value (Ro) of the cellulose ester film is in the range of 0 to 5 nm and the retardation value (Rth) in the thickness direction is in the range of -10 to 10 nm. It is more preferable that Rth is in the range of -5 to 5 nm.

Ro and Rth are values defined by the following formulas (i) and (ii).

Formula _{(i) Ro = (n x} -n y) × d

Formula (ii) Rth = {(n x + n y) / 2-n z} × d

(Where n _x is refractive index in the slow axis direction in the plane of the cellulose ester film, n _y is refractive index in the direction orthogonal to the slow axis in the plane of the cellulose ester film, n _z is refractive index in the thickness direction of the cellulose ester film, d is the cellulose ester (Nm) of the film)

The retardation can be obtained at a wavelength of 590 nm under an environment of 23 deg. C and a relative humidity of 55% using, for example, KOBRA-21ADH (manufactured by Oji Chemical Industry Co., Ltd.). Use of a cellulose ester film controlled to the above retardation value is preferable because of its excellent visibility when used in an image display device such as a touch panel or a liquid crystal display device. The retardation can be adjusted by the kind and amount of the above plasticizer, the film thickness of the cellulose ester film, the stretching condition, and the like.

(Formation of Cellulose Ester Film)

Next, an example of a film-forming method of a cellulose ester film is described, but the present invention is not limited thereto. As the film forming method of the cellulose ester film, a manufacturing method such as an inflation method, a T-die method, a calendering method, a cutting method, a soft method, an emulsion method, and a hot press method can be used.

(Organic solvent)

The organic solvent useful for forming the resin solution (dope composition) when the cellulose ester film is prepared by the solution casting method is not limited as long as it can dissolve the cellulose ester resin and other additives at the same time. Examples of the chlorinated organic solvent include methylene chloride and examples of the non-chlorinated organic solvent include methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, , Ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3 , 3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro Propanol, iso-propanol, n-butanol, sec-butanol and tert-butanol, and methylene chloride, methyl acetate, ethyl acetate and acetone are preferably used Can be used. The solvent is preferably a dope composition obtained by dissolving a cellulose ester resin and other additives in a total amount of 15 to 45 mass%.

[Solution flexible film-forming method]

In the solution casting film forming method, there are a step of preparing a dope by dissolving a resin and an additive in a solvent, a step of dipping the dope on a belt-shaped or drum-shaped metal support, a step of drying the dope as a web, , A step of stretching or maintaining the width, a step of drying, and a step of winding the finished cellulose ester film.

As the metal support, a stainless steel belt or a drum finishing the surface of the cast iron is preferably used.

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

The preferred support temperature is appropriately determined in the range of 0 to 100 캜, more preferably in the range of 5 to 30 캜. Alternatively, it is preferable that the web be gelled by cooling to peel off the drum in a state containing a large amount of residual solvent. A method of controlling the temperature of the metal support is not particularly limited, but there is a method of spraying warm air or cold air with extreme pressure, or a method of bringing warm water into contact with the metal support. Use of hot water is preferable because heat is efficiently transferred and the time until the temperature of the metal support becomes constant is short.

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

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

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

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

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

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

In the film drying process, generally, a method of drying by conveying the web by a roller drying method (a method of alternately passing and drying webs through a plurality of rollers arranged up and down) or a tenter method is employed.

In the stretching step, stretching can be performed sequentially or simultaneously in the longitudinal direction (MD direction) and the width direction (TD direction) of the film. The stretching magnifications in the biaxial directions orthogonal to each other are preferably set in the range of 1.0 to 2.0 times in the MD direction and 1.05 to 2.0 times in the TD direction, respectively, and in the range of 1.0 to 1.5 times in the MD direction, And in the TD direction in the range of 1.05 to 2.0 times. For example, there is a method in which a plurality of rollers are provided with a main speed difference, and the rollers are driven in the MD direction using a roller speed difference therebetween; a method in which both ends of the web are fixed with clips or pins, A method of stretching in the MD direction, a method of stretching in the transverse direction and stretching in the TD direction, or a method of simultaneously stretching the MD direction and the TD direction and stretching in both directions.

This width maintenance or stretching in the width direction of the film forming step is preferably performed by a tenter, and may be a pin tenter or a clip tenter.

The film transporting tension in the film forming process of the tenter or the like varies depending on the temperature, but is preferably in the range of 120 to 200 N / m, more preferably in the range of 140 to 200 N / m. And most preferably in the range of 140 to 160 N / m.

The stretching temperature is preferably in the range of (Tg-30) to (Tg + 100) C, more preferably in the range of (Tg-20) to (Tg + 80) , More preferably in the range of (Tg-5) to (Tg + 20) 占 폚.

The Tg of the cellulose ester film can be controlled depending on the material species constituting the film and the ratio of the constituent materials. The Tg of the cellulose ester film at the time of drying is preferably 110 DEG C or more, more preferably 120 DEG C or more. Particularly preferably 150 ° C or higher. The glass transition temperature is preferably 190 占 폚 or lower, more preferably 170 占 폚 or lower. The Tg of the cellulose ester film can be determined by the method described in JIS K7121. The temperature at the time of stretching is preferably 150 占 폚 or more, and the stretching magnification is preferably 1.15 times or more, because the surface is appropriately roughened. Roughening the surface of the cellulose ester film is preferable because slipperiness is improved and surface formability is improved.

[Melting flexible film forming method]

The cellulose ester film may be formed by a melt soft-film forming method. The melt-blown film-forming method refers to a method in which a composition including a cellulose ester resin, a plasticizer and other additives is heated and melted to a temperature at which fluidity is exhibited, and then a melt containing a fluid cellulose ester is softened.

In the melt soft-film-forming method, a melt-extrusion method is preferable in terms of mechanical strength and surface precision. It is preferable that a plurality of raw materials used for melt extrusion are usually previously kneaded and pelletized.

The pelletization may be carried out by any known method. For example, dry cellulose esters, plasticizers and other additives are fed to an extruder by a feeder, kneaded using a single- or twin-screw extruder, extruded from a die into a strand shape, Or by air cooling and cutting.

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

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

It is preferable that the extruder is processed at a low temperature as low as possible so as to suppress pelletization so as to suppress the shear force and deteriorate the resin (decrease in molecular weight, coloration, gel formation, etc.). For example, in the case of a twin-screw extruder, it is preferable to use a deep groove-type screw to rotate in the same direction. In terms of kneading uniformity, occlusal type is preferable.

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

The above pellets are extruded by using a uniaxial or biaxial type extruder and the extruded product is filtered at a temperature of about 200 to 300 DEG C by using a filter such as a leaf disc type to remove foreign matter. Then, the film is nipped with a cooling roller and an elastic touch roller, and solidified on a cooling roller to form a cellulose ester film.

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

The extrusion flow rate is preferably adjusted stably by introducing a gear pump. In addition, a stainless steel fiber sintered filter is preferably used as the filter used for removing the foreign matter. The stainless steel fiber sintering filter is formed by integrally forming a stainless steel fiber body in a state of being entangled with each other and then pressing and sintering the contact portion. The filtration accuracy can be adjusted by changing the density by the thickness of the fiber and the amount of compression.

Additives such as plasticizers and particles may be mixed with the resin in advance, or may be put in the middle of the extruder. In order to uniformly add it, it is preferable to use a mixing device such as a static mixer.

It is preferable that the temperature of the cellulose ester film on the touch roller side when nipping the cellulose ester film with the cooling roller and the elastic touch roller is equal to or higher than Tg (Tg + 110 deg. C) of the film. For the roller having the surface of the elastic body used for such a purpose, known rollers can be used.

The elastic touch roller is also referred to as a nip pressure roller. As the elastic touch roller, a commercially available one may be used.

When the cellulose ester film is peeled from the cooling roller, it is preferable to control the tensile force to prevent deformation of the film.

The cellulose ester film obtained as described above is preferably stretched by the stretching operation after passing through a process in contact with a cooling roller.

As the stretching method, a known roller stretching machine, a tenter or the like can be preferably used. The stretching temperature is preferably in the range of Tg to (Tg + 60) 占 폚 of the resin constituting the film.

Before winding, the end portion may be slit and cut with a width to become a product, and knurling (embossing) may be carried out at both ends to prevent sticking or scratching during winding. The knurling process can be performed by heating or pressurizing using a metal ring having a concavo-convex pattern on its side surface. The clip holding portions at both ends of the film are usually cut and reused because the cellulose ester film is deformed and can not be used as a product.

(Physical Properties of Cellulose Ester Film)

The film thickness of the cellulose ester film in the present invention is characterized by being in the range of 5 to 34 mu m. The effect of the present invention can be obtained in a cellulose ester film having a film thickness within the range. Preferably in the range of 10 to 30 mu m. The width of the cellulose ester film is preferably in the range of 1 to 4 m. If it exceeds 4 m, it becomes difficult to transport.

The length of the cellulose ester film is preferably in the range of 500 to 10,000 m, and more preferably in the range of 1000 to 8000 m. By setting the length to the above range, the processability in coating of the hard coat layer and the like and the handling property of the cellulose ester film itself are excellent.

The arithmetic mean roughness (Ra) of the cellulose ester film is preferably in the range of 2 to 10 nm, more preferably in the range of 2 to 5 nm. The arithmetic mean roughness (Ra) can be measured according to JIS B0601: 1994.

The logarithmic contact angle of the cellulose ester film before alkali treatment is generally in the range of 40 to 80 °, preferably in the range of 50 to 70 °. The logarithmic contact angle after the alkali treatment varies depending on the alkali treatment conditions, but is generally in the range of 10 to 60 °, preferably in the range of 20 to 60 °. The logarithmic contact angle is a value measured in accordance with the method described in the method for measuring the logarithmic contact angle of the hard coat layer.

It is presumed that the hard coating layer is in a laminated state between the hydrophilic layers due to the lowering of the logarithmic contact angle by the alkali treatment and the close contact angle with the cellulose ester film.

As a method of alkali treatment, a cellulose ester film is immersed in an alkali solution, followed by washing with water. After the alkali treatment, neutralization may be performed in the acidic water process, followed by washing with water and drying.

Examples of the alkali solution include a potassium hydroxide solution and a sodium hydroxide solution. The concentration of the hydroxide ion is preferably in the range of 0.1 to 5 mol / L, and more preferably in the range of 0.5 to 3 mol / L. Further, the temperature of the alkali solution is preferably in the range of 25 to 90 占 폚, more preferably in the range of 40 to 70 占 폚. The alkali treatment time is in the range of 5 seconds to 5 minutes, preferably 30 seconds to 3 minutes.

&Lt; Other layer >

In the hard coat film of the present invention, other layers such as an antireflection layer and a conductive layer can be formed.

<Antireflection layer>

The hard coating film according to the present invention can be used as an antireflection film having a function of preventing reflection of external light by providing an antireflection layer on the hard coat layer.

It is preferable that the antireflection layer is laminated in consideration of the refractive index, the film thickness, the number of layers, the layer order, and the like so that the reflectance is reduced by optical interference. It is preferable that the antireflection layer is formed by combining a low refractive index layer having a refractive index lower than that of the protective film as a support or a high refractive index layer and a low refractive index layer having a refractive index higher than that of the protective film as a supporting chain. Particularly preferably, three antireflection layers composed of three or more refractive index layers and having different refractive indexes from the support side are used as the medium refractive index layer (a layer having a refractive index higher than that of the support and having a refractive index lower than that of the high refractive index layer) / high refractive index layer / Low refractive index layer are preferably laminated in this order. Alternatively, an antireflection layer having a layer structure of four or more layers in which two or more high refractive index layers and two or more low refractive index layers are alternately laminated is also preferably used. As the layer structure, the following structure is conceivable, but the present invention is not limited thereto.

Cellulose ester film / hard coat layer / low refractive index layer

Cellulose ester film / hard coat layer / high refractive index layer / low refractive index layer

Cellulose ester film / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer

Hard coat layer / cellulose ester film / hard coat layer / low refractive index layer

Hard coat layer / cellulose ester film / hard coat layer / high refractive index layer / low refractive index layer

Hard coating layer / cellulose ester film / hard coating layer / medium refractive index layer / high refractive index layer / low refractive index layer

Low Refractive Index Layer / Hard Coating Layer / Cellulose Ester Film / Hard Coating Layer / Low Refractive Index Layer

(Low refractive index layer)

The low refractive index layer preferably contains silica-based fine particles, and the refractive index thereof is preferably in the range of 1.30 to 1.45 at a temperature of 23 캜 and a wavelength of 550 nm.

The film thickness of the low refractive index layer is preferably in the range of 5 nm to 0.5 탆, more preferably in the range of 10 nm to 0.3 탆, and most preferably in the range of 30 nm to 0.2 탆.

As for the composition for forming a low refractive index layer, it is preferable that the silica-based fine particles have at least one outer layer and at least one particle of porous or hollow particles therein. Particularly, it is preferable that the particles having the respective outer layers and the inside of which are porous or hollow are hollow silica-based fine particles.

The composition for forming a low refractive index layer may contain an organosilicon compound represented by the following formula (OSi-1), a hydrolyzate thereof, or a polycondensate thereof.

(OSi-1): Si (OR) ₄

The organosilicon compound represented by the formula: wherein R represents an alkyl group having 1 to 4 carbon atoms. Specifically, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane and the like are preferably used.

In addition, a solvent, a silane coupling agent, a curing agent, a surfactant, and the like may be added as needed. And may contain a compound having a thermosetting property and / or a photo-curability mainly comprising a fluorine-containing compound containing a fluorine atom in a range of 35 to 80 mass% and containing a crosslinkable or polymerizable functional group. Specific examples thereof include a fluorine-containing polymer, a fluorine-containing sol-gel compound, and the like. As the fluorine-containing polymer, for example, a hydrolyzate or a dehydration condensation product of a perfluoroalkyl group-containing silane compound [for example, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane] , A fluorine-containing copolymer having a fluorine-containing monomer unit and a crosslinkable reactive unit as a constituent unit. Other additives such as a solvent, a silane coupling agent, a curing agent, a surfactant and the like may be added as required.

(High refractive index layer)

The refractive index of the high refractive index layer is preferably adjusted in the range of 1.4 to 2.2 in the measurement of the wavelength of 550 nm at 23 캜. The thickness of the high refractive index layer is preferably from 5 nm to 1 탆, more preferably from 10 nm to 0.2 탆, and most preferably from 30 nm to 0.1 탆. Means for adjusting the refractive index can be achieved by adding metal oxide fine particles or the like. The refractive index of the metal oxide fine particles to be used is preferably 1.80 to 2.60, and more preferably 1.85 to 2.50.

The kind of the metal oxide fine particles is not particularly limited and is selected from among Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P and S A metal oxide having at least one kind of element may be used.

(Conductive layer)

In the hard coat film, a conductive layer may be formed on the hard coat layer. As the conductive layer to be installed, generally known conductive materials can be used. For example, metal oxides such as indium oxide, tin oxide, indium tin oxide, gold, silver and palladium can be used. These can be formed as a thin film on a hard coating film by a vacuum deposition method, a sputtering method, an ion plating method, a solution coating method or the like. It is also possible to form the conductive layer by using the above-mentioned organic conductive material as the? -Conjugated conductive polymer.

In particular, a conductive material containing any one of indium oxide, tin oxide, and indium tin oxide, which is excellent in transparency and conductivity and can be obtained at a relatively low cost, can be suitably used. Since the thickness of the conductive layer varies depending on the material to which it is applied and can not be said to be uniform, it is not more than 1000 Ω or less, preferably not more than 500 Ω in terms of surface resistivity, Or more and 80 nm or less, preferably 70 nm or less. In such a thin film, interference fringes of visible light due to thickness irregularity of the conductive layer are hard to occur.

<Polarizer>

The polarizing plate using the hard coating film of the present invention will be described. The polarizing plate can be manufactured by a general method.

For example, a fully saponified polyvinyl alcohol aqueous solution is applied to at least one surface of a polarizing film prepared by subjecting the hard coating film of the present invention to alkali saponification treatment and then treating the hard coating film by immersion stretching in a iodine solution, .

On the other side, the hard coat film may be used, or the cellulose ester film described above may be used. The film thickness of the cellulose ester film used on the other side is preferably in the range of 5 to 34 mu m from the viewpoint of improving the smoothness and the curl balance and further enhancing the effect of preventing the winding deviation.

Also, commercially available products such as KC8UX, KC4UX, KC4UY, KC8UY, KC6UA, KC4UA, KC4UE, KC4CZ, KC8UCR, KC4FR (manufactured by Konica Minolta Advantest Co., Ltd.), Attonfilm (manufactured by JSR Corporation) (Manufactured by Nippon Zeon Co., Ltd.) and the like can be used.

The polarizing film which is a main component of the polarizing plate is a device that allows only light of a polarization plane in a certain direction to pass therethrough. A typical polarizing film currently known is a polyvinyl alcohol polarizing film, which is obtained by dyeing a polyvinyl alcohol film with iodine And a dichroic dye is dyed. However, the present invention is not limited thereto.

The polarizing film may be a film obtained by forming a polyvinyl alcohol aqueous solution, uniaxially stretching it, dyeing it, dyeing it, uniaxially stretching it, and preferably durability treatment with a boron compound. The film thickness of the polarizing film is in the range of 5 to 30 탆, preferably in the range of 8 to 15 탆.

And one side of the hard coating film according to the present invention is bonded to the surface of the polarizing film to form a polarizing plate. Preferably, it is bonded by an aqueous adhesive mainly composed of fully saponified polyvinyl alcohol or the like.

(Adhesive layer)

The pressure-sensitive adhesive layer used for one side of the film for bonding with the substrate of the liquid crystal cell is preferably not only optically transparent but also exhibits appropriate viscoelasticity and adhesive properties.

Specific examples of the adhesive layer include a polymer such as an adhesive such as an acrylic copolymer, an epoxy resin, a polyurethane, a silicone polymer, a polyether, a butyral resin, a polyamide resin, a polyvinyl alcohol resin, A film can be formed by a drying method, a chemical hardening method, a thermal hardening method, a thermal melting method, a photo-curing method, or the like and cured. Among them, the acrylic copolymer is preferable because it is easy to control the adhesive property and has excellent transparency, weather resistance, durability and the like.

<Winding>

The thickness of the air layer held between the layers when the hard coating film of the present invention, the cellulose ester film of the present invention or the polarizing plate using the hard coating film of the present invention is rolled is preferably in the range of 0.5 to 10 탆 And more preferably in the range of 1 to 5 mu m. The thickness t 'of the air layer is a value obtained from an equation of t' = [{(D ² -d ² ) / 4L} -t].

D is the winding diameter, d is the winding core diameter, L is the winding length, and t is the thickness of the film.

In addition, a method of winding a hard coating film or the like is a method of winding a film by providing a roller touching the film in front of the winding shaft or a method of winding the film by a roller A film take-up portion for winding the film on the take-up core by rotating the take-up core in such a manner that the film is wound around the take-up core while gradually moving away from the take- An osylate reeling method and the like can be used.

The thickness of the air layer can be controlled by adjusting the above winding conditions such as tension conditions at the time of winding.

<Image Display Device>

The hard coat film of the present invention is preferable in that it is used in an image display device and exhibits excellent visibility (clearability). Examples of the image display device include reflective, transmissive, and semi-transmissive liquid crystal display devices, liquid crystal display devices of various driving systems such as TN type, STN type, OCB type, VA type, IPS type and ECB type, An EL display device, a plasma display, and the like. Of these image display devices, the hard coating film of the present invention is preferably used for a liquid crystal display device or a touch panel display device because it is excellent in high visibility.

<Touch panel>

An example of the case where the hard coating film of the present invention is used for a touch panel display device is shown in Fig.

A conductive film 12 is formed on a hard coating film 11 (hereinafter referred to as a both-side hard coating film) 11 on both sides of which a hard coating layer according to the present invention is provided and is laminated on the glass substrate 13 on which the conductive film 15 is formed. And the conductive layers are opposed to each other with a predetermined gap facing each other, whereby the resistive touch panel 10 can be constructed. On the ends of the both-side hard coating film 11 and the glass substrate 13 according to the present invention, electrodes (not shown) are disposed. The conductive film 12 is brought into contact with the conductive film 15 on the glass substrate 13 by pressing the double-sided hard coating film 11 with a finger or a pen. And this contact is electrically detected through the electrode at the end, whereby the pressed position is detected. On the conductive film 15 of the glass substrate 13, a dot-shaped spacer 14 is disposed as necessary. 2, the inner-touch-panel-equipped image display device 20 can be constructed by mounting the touch panel 10 of Fig. 1 in the liquid crystal display panel.

The hard coating film of the present invention can be applied to an inner touch panel as shown in Fig. 2 using, for example, a touch panel member under the upper surface side polarizing plate of a liquid crystal display device (upper surface side polarizing plate / liquid crystal cell / lower surface side polarizing plate configuration) It can also be used for capacitive touch panels. In the electrostatic capacity type touch panel, it is preferable that the conductive film 12 has an electrode pattern of a lattice shape or the like arranged at a predetermined pitch. The electrode pattern of the conductive film can be formed by forming an electrode pattern by masking the conductive film with an electrode pattern after forming the conductive film, or by conducting laser irradiation and patterning the conductive film continuously.

<Glass Shatterproofing Film for Image Display Device>

Next, the glass shatterproof film for an image display apparatus using the hard coating film of the present invention will be described. Fig. 3 shows an example of a schematic cross-sectional view of a glass scattering prevention film for an image display apparatus using the hard coating film of the present invention in an image display apparatus.

The image display device 30 includes an image display panel 31 and a conductive glass substrate 33 disposed on the display portion (display surface) of the image display panel 31 via a pressure sensitive adhesive layer 32, And a glass scattering prevention film 41 for an image display apparatus bonded on the substrate 33.

The conductive glass substrate 33 is composed of a glass substrate 34 and a conductive film 35. The glass shatterproof film 41 for an image display device is adhered to the glass substrate 34 by a pressure sensitive adhesive layer 43. [

The glass shatterproof film 41 for an image display device including the hard coating film 42 of the present invention has high adhesion with a pressure sensitive adhesive and the like, and it is not necessary to perform the adhesion facilitating treatment. In addition, it is possible to obtain sufficient shatterproofing properties in the glass shatterproof film. Further, after the durability test, deformation and the like are less likely to occur and the flatness (visibility) is excellent.

The hard coating film 42 preferably has a refractive index in a range of 1.45 to 1.55 at a wavelength of 589 nm measured in accordance with JIS K7142-2008. The refractive index of the pressure-sensitive adhesive layer 43 at a wavelength of 589 nm measured in accordance with JIS K7142-2008 is preferably in the range of 1.40 to 1.55, more preferably in the range of 1.45 to 1.52.

The refractive index of the pressure-sensitive adhesive layer 43 can be controlled by, for example, increasing the refractive index by including an aromatic ring, or by lowering the refractive index by containing fluorine atoms.

By setting the refractive indexes of the pressure-sensitive adhesive layer 43 and the glass scattering-prevention film 41 for an image display device within the above ranges, the refractive index when bonded to a glass substrate or the like is small and excellent in interference fringes.

The thickness of the pressure-sensitive adhesive layer is preferably in the range of 5 to 30 mu m, more preferably in the range of 10 to 25 mu m. Examples of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer include acrylic pressure-sensitive adhesives, silicone pressure-sensitive adhesives, urethane pressure-sensitive adhesives, rubber pressure-sensitive adhesives, and polyester pressure-sensitive adhesives. The pressure-sensitive adhesive may be any of an emulsion type, a solvent type, and a solventless type. Among these pressure-sensitive adhesives, an acrylic pressure-sensitive adhesive is preferable from the viewpoints of ease of adhesion control and weather resistance. The acrylic pressure-sensitive adhesive preferably has a crosslinked acrylic resin having a weight average molecular weight in the range of 50 to 2,000,000, preferably 70 to 170,000. When the weight average molecular weight is in the above range, a film for preventing scattering in which the adhesive force and the holding force are balanced can be obtained. The above-mentioned weight average molecular weight is a value in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

As the acrylic resin contained in the acrylic pressure-sensitive adhesive, a (meth) acrylate-based copolymer is used. Examples of the (meth) acrylic ester-based copolymer include a copolymer of a (meth) acrylic acid ester having an alkyl group of an alkyl group of 1 to 20 carbon atoms, a monomer having a functional group having an active hydrogen, . Examples of the (meth) acrylic esters having 1 to 20 carbon atoms in the alkyl moiety of the ester moiety include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, Butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and isooctyl have. These may be used alone or in combination of two or more. Examples of the monomer having a functional group having active hydrogen include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (Meth) acrylic acid hydroxyalkyl esters such as methyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate, acrylamide, methacrylamide, N-methylacrylamide Acrylamides such as N-methylmethacrylamide, N-methylolacrylamide and N-methylolmethacrylamide, and acrylamides such as methylaminoethyl (meth) acrylate and monoethylaminoethyl (meth) Methacrylic acid monoalkylaminoalkyl, ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid and citraconic acid. These may be used alone or in combination of two or more.

In the acrylic pressure-sensitive adhesive, the (meth) acrylic ester-based copolymer used as the resin component may be any of random, block, and graft copolymers in terms of the copolymerization type. As the crosslinking agent used in the crosslinking treatment, a polyisocyanate compound or an epoxy compound is preferably used. The crosslinking agent may be used singly or in combination of two or more kinds. The amount to be used varies depending on the kind of the crosslinking agent, but is usually in the range of 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass based on 100 parts by mass of the solid content of the (meth) acrylic acid ester copolymer. To the acrylic pressure-sensitive adhesive, a tackifier, an antioxidant, an ultraviolet absorber, a light stabilizer, a softener, a silane coupling agent, a filler and the like may be added. Further, a protective film and a release sheet may be adhered to the pressure-sensitive adhesive layer (43). Examples of the base material of the release sheet include polyethylene terephthalate, polyethylene, polypropylene film, and the like. In order to have releasability on the surface of the base material for a release sheet, a releasing agent such as a fluorine resin, a silicone resin, or a long chain alkyl group-containing carbamate is adhered to the surface thereof by coating. The thickness of the release sheet base is preferably in the range of 5 to 300 mu m, more preferably in the range of 10 to 200 mu m.

Example

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto. In the examples, &quot; part &quot; or &quot;% &quot; is used, and &quot; mass part &quot; or &quot; mass% &quot;

Example 1

(Production of Cellulose Ester Film 1)

· Preparation of silicon dioxide dispersion

Aerosil R812

(Average particle diameter of primary particles: 7 nm, manufactured by Nippon Aerosil Co., Ltd.) 10 parts by mass

90 parts by mass of ethanol

The resulting mixture was stirred with a dissolver for 30 minutes and dispersed with Manton-Gaulin. 88 parts by mass of methylene chloride was added to the silicon dioxide dispersion while stirring, and the mixture was stirred with a dissolver for 30 minutes to prepare a silicon dioxide dispersion diluted solution. And filtrated with a fine particle dispersion diluent filter (Adventic Orient Co., Ltd .: polypropylene wind cartridge filter TCW-PPS-1N).

&Lt; Preparation of Dope Composition 1 &

(Cellulose ester resin)

Cellulose triacetate A (cellulose triacetate synthesized from a linter surface, acetyl group degree of substitution 2.88, Mn = 140,000) 90 parts by mass

(additive)

5 parts by mass of the ester (Exemplified Compound X-1) represented by the formula (X)

4 parts by mass of the ester (Exemplary Compound X-12) represented by the formula (X)

(Ultraviolet absorber)

3 parts by mass of TINUVIN 928 (BASF Japan Ltd.)

(Fine particles)

Silicon dioxide dispersion diluted solution 4 parts by mass

(menstruum)

Methylene chloride 432 parts by mass

Ethanol 38 parts by mass

(DOPE COMPOSITION 1) was prepared by heating the mixture in a sealed container and completely dissolving it with stirring, and filtering it with use of Azumi Rossi No.24 manufactured by Azumi Co., Ltd.

Subsequently, using a belt casting machine, the stainless steel band support was uniformly flexible. In the stainless steel band support, the solvent was evaporated until the amount of the residual solvent became 100%, and peeled off from the stainless band support. The web of the cellulose ester film was evaporated at 35 DEG C to form a slit of 1.15 m in width and dried at a drying temperature of 140 DEG C while being stretched by a tenter in the TD direction (width direction of the film) to 1.15 times. Thereafter, the inside of the drying apparatus at 120 캜 was dried for 15 minutes while being conveyed by a plurality of rollers, slit into 1.3 m wide, knurled to 10 mm in width and 5 탆 in height at both ends of the film, To obtain a cellulose ester film 1. The film thickness of the cellulose ester film 1 was 25 占 퐉 and the winding length was 5000 m.

Further, the drawing magnification in the MD direction calculated from the rotating speed of the stainless steel band support and the operating speed of the tenter was 1.01 times.

(Production of Cellulose Ester Film 2 to 5)

Cellulose ester films 2 to 5 were prepared in the same manner as in the preparation of cellulose ester film 1 except that the film thickness was changed as shown in Table 1.

[Production of Hard Coating Film 1]

The following hard coat layer composition 1 was filtered on a surface A of a cellulose ester film 1 prepared above (a surface not in contact with a flexible belt) with a polypropylene filter having a pore diameter of 0.4 탆 and then coated with an extrusion coater, Dried at a drying section temperature of 50 캜 and a reduced drying section temperature of 50 캜 and then irradiated with ultraviolet light with an illuminance of 100 mW / cm ² using an ultraviolet lamp while nitrogen was purged so that the oxygen concentration was 1.0 vol% / cm &lt; ² &gt; to form a hard coat layer 1 having a dry film thickness of 2.5 [micro] m and winding up the air layer to a thickness of 4 [micro] m.

&Quot; Hard Coat Layer Composition 1 &quot;

&Lt; Preparation of fluorine-siloxane graft compound >

The name of the commercial product used for the production of the fluorine-siloxane graft compound.

Radical Polymerizable Fluoropolymer (A): Cefral Coat CF-803 (having a hydroxyl number of 60 and a number average molecular weight of 15000, manufactured by Central Glass Co., Ltd.)

One end radical polymerizable polysiloxane (B): SILLA PLAIN FM-0721 (number average molecular weight 5000, manufactured by Chisso Corporation)

Radical polymerization initiator: Perbutyl O (t-butylperoxy-2-ethylhexanoate, manufactured by Nippon Yushi Co., Ltd.)

Curing agent: Sumidule N3200 (buret-type prepolymer of hexamethylene diisocyanate; manufactured by Sumitomo Bayer Urethane Co., Ltd.)

(Synthesis of radically polymerizable fluororesin)

(1554 parts by mass), xylene (233 parts by mass), and 2-isocyanatoethyl methacrylate (2-isocyanatoethyl methacrylate) were added to a glass reactor equipped with a mechanical stirrer, a thermometer, a condenser and a dry nitrogen gas inlet. (6.3 parts by mass), and the mixture was heated to 80 DEG C under a dry nitrogen atmosphere. After reacting at 80 DEG C for 2 hours and confirming disappearance of absorption of isocyanate by the infrared absorption spectrum of the sample, the reaction mixture was taken out to obtain a radically polymerizable fluororesin of 50 mass% through urethane bonding.

(Preparation of fluorine-siloxane graft compound)

(26.1 parts by mass), xylene (19.5 parts by mass) and n-butyl acetate (16.3 parts by mass) were added to a glass reactor equipped with a mechanical stirrer, a thermometer, a condenser and a dry nitrogen gas inlet, (1.8 parts by mass), methyl methacrylate (2.4 parts by mass), n-butyl methacrylate (1.8 parts by mass), lauryl methacrylate (1.8 parts by mass), 2-hydroxyethyl methacrylate (5.2 parts by mass), and perbutyl O (0.1 parts by mass) were charged and heated to 90 占 폚 in a nitrogen atmosphere, and then maintained at 90 占 폚 for 2 hours. Perfluoro-siloxane grafted compound having a weight average molecular weight of 171,000 was obtained by adding perbutyl O (0.1 part) and further holding at 90 占 폚 for 5 hours. The weight average molecular weight was determined by GPC. The mass% of the fluorine-siloxane graft compound was determined by HPLC (liquid chromatography).

(Active ray curable resin)

Pentaerythritol tri / tetraacrylate

(NK Ester A-TMM-3L, Shin-Nakamura Chemical Industry Co., Ltd.), 70 parts by mass

Trimethylolpropane triacrylate

(A-TMPT, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 30 parts by mass

(Photopolymerization initiator)

6 parts by mass of Irgacure 184 (BASF Japan Ltd.)

(additive)

Fluorine-siloxane graft compound (35 mass%) 2 mass parts

(solvent)

20 parts by mass of propylene glycol monomethyl ether

30 parts by mass of methyl acetate

70 parts by mass of methyl ethyl ketone

[Production of Hard Coating Film 2]

The hard coating film 2 was prepared in the same manner as in the preparation of the hard coating film 1 except that the following hard coating layer composition 2 was used.

&Quot; Hard Coat Layer Composition 2 &quot;

(Active ray curable resin)

Pentaerythritol tri / tetraacrylate

(NK Ester A-TMM-3L, Shin-Nakamura Chemical Industry Co., Ltd.), 70 parts by mass

Trimethylolpropane triacrylate

(A-TMPT, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 30 parts by mass

(Photopolymerization initiator)

6 parts by mass of Irgacure 184 (BASF Japan Ltd.)

(additive)

2 parts by mass of an optool DAC (fluorine-based compound, manufactured by Daikin Industries, Ltd.)

(solvent)

20 parts by mass of propylene glycol monomethyl ether

30 parts by mass of methyl acetate

70 parts by mass of methyl ethyl ketone

[Production of Hard Coating Film 3]

A hard coat film 3 was prepared in the same manner as in the preparation of the hard coat film 1 except that the following hard coat layer composition 3 was used.

&Quot; Hard Coat Layer Composition 3 &quot;

(Active ray curable resin)

Pentaerythritol tri / tetraacrylate

(NK Ester A-TMM-3L, Shin-Nakamura Chemical Industry Co., Ltd.), 70 parts by mass

Trimethylolpropane triacrylate

(A-TMPT, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 30 parts by mass

6 parts by mass of Irgacure 184 (BASF Japan Ltd.)

(additive)

KF-354L

(Polyether-modified silicone oil, Shinetsu Chemical Industry Co., Ltd.) 2 parts by mass

(solvent)

20 parts by mass of propylene glycol monomethyl ether

30 parts by mass of methyl acetate

70 parts by mass of methyl ethyl ketone

[Production of Hard Coating Film 4]

A hard coating film 4 was prepared in the same manner as in the preparation of the hard coating film 1 except that the following hard coating layer composition 4 was used.

&Quot; Hard Coat Layer Composition 4 &quot;

(Active ray curable resin)

Pentaerythritol tri / tetraacrylate

(NK Ester A-TMM-3L, Shin-Nakamura Chemical Industry Co., Ltd.), 70 parts by mass

Trimethylolpropane triacrylate

(A-TMPT, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 30 parts by mass

(Photopolymerization initiator)

6 parts by mass of Irgacure 184 (BASF Japan Ltd.)

(additive)

2 parts by mass of BYK-UV3510 (polyether-modified polydimethylsiloxane, manufactured by Big Chemical Japan K.K.)

(solvent)

20 parts by mass of propylene glycol monomethyl ether

30 parts by mass of methyl acetate

70 parts by mass of methyl ethyl ketone

[Production of Hard Coating Film 5]

A hard coat film 5 was prepared in the same manner as in the preparation of the hard coat film 1 except that the following hard coat layer composition 5 was used.

&Quot; Hard Coat Layer Composition 5 &quot;

(Active ray curable resin)

Pentaerythritol tri / tetraacrylate

(NK Ester A-TMM-3L, Shin-Nakamura Chemical Industry Co., Ltd.), 70 parts by mass

Trimethylolpropane triacrylate

(A-TMPT, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 30 parts by mass

(Photopolymerization initiator)

6 parts by mass of Irgacure 184 (BASF Japan Ltd.)

(solvent)

20 parts by mass of propylene glycol monomethyl ether

30 parts by mass of methyl acetate

70 parts by mass of methyl ethyl ketone

[Production of hard coat film 6]

A hard coat film 6 was prepared in the same manner as in the preparation of the hard coat film 1 except that the following hard coat layer composition 6 was used.

&Quot; Hard Coat Layer Composition 6 &quot;

(Active ray curable resin)

Pentaerythritol tri / tetraacrylate

(NK Ester A-TMM-3L, Shin-Nakamura Chemical Industry Co., Ltd.), 70 parts by mass

Trimethylolpropane triacrylate

(A-TMPT, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 30 parts by mass

(Photopolymerization initiator)

6 parts by mass of Irgacure 184 (BASF Japan Ltd.)

(additive)

KF-354L

(Polyether-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by mass

(Ultraviolet absorber)

2 parts by mass of TINUVIN 928 (BASF Japan)

(solvent)

20 parts by mass of propylene glycol monomethyl ether

30 parts by mass of methyl acetate

70 parts by mass of methyl ethyl ketone

[Production of Hard Coating Film 7]

A hard-coating film 7 in the form of a roll was prepared in the same manner as in the preparation of the hard coating film 1 except that the film was irradiated with an ultraviolet lamp without nitrogen purge.

[Production of Hard Coating Film 8]

A hard-coating film 8 in the form of a roll was prepared in the same manner as in the preparation of the hard coat film 2 except that the film was irradiated with an ultraviolet lamp without nitrogen purging.

[Production of hard coating films 9 to 12]

Hard coat films 9 to 12 in the form of rolls were prepared in the same manner as in the preparation of the hard coat film 7 except that the cellulose ester film 1 was changed to the cellulose ester films 2 to 5 shown in Table 1, respectively.

[Production of hard coating film 13]

A hard coating film 13 was prepared in the same manner as in the preparation of the hard coating film 1 except that the following hard coating layer composition 7 was used.

&Quot; Hard Coat Layer Composition 7 &quot;

(Active ray curable resin)

Pentaerythritol tri / tetraacrylate

(NK Ester A-TMM-3L, Shin-Nakamura Chemical Industry Co., Ltd.) 35 parts by mass

Urethane acrylate

(NK Oligo UA-1100H, Shin-Nakamura Chemical Industry Co., Ltd.), 65 parts by mass

(Photopolymerization initiator)

6 parts by mass of Irgacure 184 (BASF Japan Ltd.)

(additive)

KF-354L

(Polyether-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by mass

(solvent)

20 parts by mass of propylene glycol monomethyl ether

30 parts by mass of methyl acetate

70 parts by mass of methyl ethyl ketone

[Production of Hard Coating Film 14]

A hard coating film 14 was prepared in the same manner as in the preparation of the hard coating film 1 except that the following hard coating layer composition 8 was used.

&Quot; Hard Coat Layer Composition 8 &quot;

(Active ray curable resin)

Dipentaerythritol pentaacrylate

(NK Ester A-9550, Shin-Nakamura Chemical Industry Co., Ltd.) 35 parts by mass

Urethane acrylate

(NK Oligo UA-1100H, Shin-Nakamura Chemical Industry Co., Ltd.), 65 parts by mass

(Photopolymerization initiator)

6 parts by mass of Irgacure 184 (BASF Japan Ltd.)

(additive)

KF-354L

(Polyether-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by mass

(solvent)

20 parts by mass of propylene glycol monomethyl ether

30 parts by mass of methyl acetate

70 parts by mass of methyl ethyl ketone

[Production of hard coating film 15]

A hard coating film 15 was prepared in the same manner as in the preparation of the hard coating film 1 except that the following hard coating layer composition 9 was used.

&Quot; Hard Coat Layer Composition 9 &quot;

(Active ray curable resin)

Dipentaerythritol pentaacrylate

(NK Ester A-9550, Shin-Nakamura Chemical Industry Co., Ltd.) 35 parts by mass

Urethane acrylate

(NK Oligo UA-15HA, Shin-Nakamura Chemical Industry Co., Ltd.) (65 parts by mass)

(Photopolymerization initiator)

6 parts by mass of Irgacure 184 (BASF Japan Ltd.)

(additive)

KF-354L

(Polyether-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by mass

(solvent)

20 parts by mass of propylene glycol monomethyl ether

30 parts by mass of methyl acetate

70 parts by mass of methyl ethyl ketone

[Production of hard coating film 16]

A hard coat film 16 was prepared in the same manner as in the preparation of the hard coat film 1 except that the following hard coat layer composition 10 was used.

&Quot; Hard Coat Layer Composition 10 &quot;

(Active ray curable resin)

Dipentaerythritol pentaacrylate

(NK Ester A-9550, Shin-Nakamura Chemical Industry Co., Ltd.) 35 parts by mass

, 65 parts by mass of urethane acrylate (UA-306I, manufactured by Kyoeisha Chemical Co., Ltd.)

(Photopolymerization initiator)

6 parts by mass of Irgacure 184 (BASF Japan Ltd.)

(additive)

KF-354L

(Polyether-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by mass

(solvent)

20 parts by mass of propylene glycol monomethyl ether

30 parts by mass of methyl acetate

70 parts by mass of methyl ethyl ketone

[Production of Hard Coat Film 17]

A hard coat film 17 was prepared in the same manner as in the preparation of the hard coat film 1 except that the following hard coat layer composition 11 was used.

&Quot; Hard Coat Layer Composition 11 &quot;

(Active ray curable resin)

Dipentaerythritol pentaacrylate

(NK Ester A-9550, Shin-Nakamura Chemical Industry Co., Ltd.) 35 parts by mass

65 parts by mass of urethane acrylate (UA-306T, manufactured by Kyushu Chemical Co., Ltd.)

(Photopolymerization initiator)

6 parts by mass of Irgacure 184 (BASF Japan Ltd.)

(additive)

KF-354L

(Polyether-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by mass

(solvent)

20 parts by mass of propylene glycol monomethyl ether

30 parts by mass of methyl acetate

70 parts by mass of methyl ethyl ketone

[Production of Hard Coating Film 18]

A hard coat film 18 was prepared in the same manner as in the preparation of the hard coat film 1 except that the following hard coat layer composition 12 was used.

&Quot; Hard Coat Layer Composition 12 &quot;

(Active ray curable resin)

Dipentaerythritol pentaacrylate

(NK Ester A-9550, Shin-Nakamura Chemical Industry Co., Ltd.) 35 parts by mass

Urethane acrylate

(NK Oligo UA-1100H, Shin-Nakamura Chemical Industry Co., Ltd.), 65 parts by mass

(Photopolymerization initiator)

6 parts by mass of Irgacure 184 (BASF Japan Ltd.)

(additive)

KF-351A

(Polyether-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by mass

(solvent)

20 parts by mass of propylene glycol monomethyl ether

30 parts by mass of methyl acetate

70 parts by mass of methyl ethyl ketone

[Production of Hard Coating Film 19]

A hard coating film 19 was prepared in the same manner as in the preparation of the hard coating film 1 except that the following hard coating layer composition 13 was used.

&Quot; Hard coat layer composition 13 &quot;

(Active ray curable resin)

Dipentaerythritol pentaacrylate

(NK Ester A-9550, Shin-Nakamura Chemical Industry Co., Ltd.) 35 parts by mass

Urethane acrylate

(NK Oligo UA-1100H, Shin-Nakamura Chemical Industry Co., Ltd.), 65 parts by mass

(Photopolymerization initiator)

3 parts by mass of Irgacure 184 (BASF Japan Ltd.)

3 parts by mass of Irgacure 907 (manufactured by BASF Japan Ltd.)

(additive)

KF-351A

(Polyether-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by mass

(solvent)

20 parts by mass of propylene glycol monomethyl ether

30 parts by mass of methyl acetate

70 parts by mass of methyl ethyl ketone

[Production of Polarizer 101]

The polarizing plate 101 was produced using the hard coating film 1 (referred to as HF1 in Fig. 4) and the cellulose ester film 1 (referred to as CE1 in Fig. 4).

(a) Production of a polarizing film

10 parts by mass of glycerin and 170 parts by mass of water were impregnated with 100 parts by mass of polyvinyl alcohol (hereinafter abbreviated as PVA) having a saponification degree of 99.95 mol% and a degree of polymerization of 2400, melt-kneaded and defoamed, Extruded on a roller to form a film. Thereafter, it was dried and heat-treated to obtain a PVA film.

The obtained PVA film had an average thickness of 25 占 퐉, a moisture content of 4.4%, and a film width of 3 m. Then, the obtained PVA film was treated successively in the order of preliminary swelling, dyeing, uniaxial stretching by a wet method, fixing treatment, drying and heat treatment in order to produce a polarizing film. That is, the PVA film was preliminarily swollen by immersing in water at 30 ° C for 30 seconds and immersed in an aqueous solution having an iodine concentration of 0.4 g / liter and a potassium iodide concentration of 40 g / liter at 35 ° C for 3 minutes. Subsequently, uniaxial stretching was carried out six times in the aqueous solution at a boric acid concentration of 4% at a temperature of 50 DEG C under a tensile force of 700 N / m on the film, and the concentration of potassium iodide was 40 g / liter, the boric acid concentration was 40 g / And immersed in an aqueous solution of 10 g / liter at a temperature of 30 캜 for 5 minutes to carry out fixation treatment. Thereafter, the PVA film was taken out, subjected to hot air drying at a temperature of 40 占 폚, and then heat-treated at a temperature of 100 占 폚 for 5 minutes. The obtained polarizing film had an average thickness of 13 탆, a transmittance of 43.0%, a polarization degree of 99.5% and a dichroic ratio of 40.1 for the polarization performance.

(b) Production of polarizing plate

According to the following steps 1 to 4, the polarizing film and the cellulose ester film 1 were bonded to the hard coating film 1 to prepare a polarizing plate 101.

Step 1: The above-mentioned polarizing membrane was immersed in a storage tank of a polyvinyl alcohol adhesive solution having a solid content of 2% by mass for 1 to 2 seconds.

Step 2: Cellulose ester film 1 and hard coat film 1 were subjected to alkali treatment under the following conditions. Subsequently, a polarizing film (described as PV1 in Fig. 4) was immersed in the polyvinyl alcohol adhesive solution in Step 1. The excessive adhesive adhered to the immersed polarizing film was lightly removed, and the cellulose ester film 1 and the hard coating film 1 were sandwiched between the polarizing film and the hard coating film 1 as shown in Fig. And a roll-like polarizing plate 101 was produced.

(Alkali treatment)

Saponification process 2.5 mol / L-KOH 50 DEG C 120 sec

Washing process water 30 ℃ 60 seconds

Neutralization process 10 mass% aqueous solution of HCl 30 캜 45 sec

Washing process water 30 ℃ 60 seconds

After the saponification treatment, washing is carried out in the order of water washing, neutralization and washing, followed by drying at 100 ° C.

Step 3: The laminate was bonded to two rotating rollers at a pressure of 20 to 30 N / cm ² at a speed of about 2 m / min. At this time, care was taken to prevent air bubbles from entering.

Step 4: The sample prepared in Step 3 was dried for 5 minutes in a drier at a temperature of 100 占 폚 to prepare a roll-shaped polarizing plate.

&Lt; Production of polarizing plates 102 to 119 >

In the production of the polarizing plate 101, the polarizing plates 102 to 119 in the form of rolls were produced in the same manner except that the hard coating films 1 were changed to the hard coating films 2 to 19, respectively. No winding misalignment occurred in any of the roll polarizers.

<Fabrication of Liquid Crystal Display Device 201>

(Durability test evaluation)

The prepared roll-shaped polarizing plate 101 was surrounded by an aluminum moisture-proof sheet and stored for 25 days in a thermostatic chamber at 50 ° C and 80% relative humidity, assuming long-term transportation. After being stored for 25 days, an adhesive layer (referred to as NS1 in Fig. 4) was provided as follows, and then incorporated into a liquid crystal display device to produce a liquid crystal display device 201. [

(Adhesive layer)

A commercially available acrylic pressure-sensitive adhesive was applied to the cellulose ester film 1 of the polarizing plate so that the thickness after drying was 25 占 퐉 and dried in an oven at 110 占 폚 for 5 minutes to form a pressure-sensitive adhesive layer.

(Liquid crystal display device 201)

The polarizer on one side of the observer side was peeled off from the two polarizers provided with a liquid crystal layer sandwiched between a 21.5-inch liquid crystal display (IPS226V-PN, LG Electronics Japan Co., Ltd.) The pressure-sensitive adhesive layer was bonded to the liquid crystal cell glass so that the hard coating layer was on the viewer side. The liquid crystal display device 201 was fabricated by arranging the transmission axis of the polarizer on the observer side and the transmission axis of the polarizer on the backlight side to be orthogonal.

<Fabrication of Liquid Crystal Display Devices 202 to 219>

The liquid crystal display devices 202 to 219 were fabricated in the same manner as in the production of the liquid crystal display device 201 except that the polarizing plate 101 was changed to the polarizing plates 102 to 119, respectively.

"evaluation"

The following hard coating film, polarizing plate and liquid crystal display were evaluated for the following contents.

1. Hard Coating Film

, Difference between the number of the contact angle before and after the alkali treatment _(Δ θ)

The logarithmic contact angles? A of the respective hard coat layers after alkali treatment at the time of polarizing plate production were subtracted from the logarithmic contact angles? Of the respective hard coat layers before the alkali treatment of the hard coat films 1 to 19 to determine the difference θ _Δ ).

Here, the logarithmic contact angle was measured by using a contact angle meter (manufactured by Kyowa Chemical Industry Co., Ltd.) under an atmosphere of a temperature of 23 DEG C and a relative humidity of 55% after allowing the sample to stand for 24 hours under an atmosphere of a temperature of 23 DEG C and a relative humidity of 55% DropMaster DM100) was used to measure the contact angle of pure water after 1 minute of 1 L of pure water was dropped. Further, the measurement was performed seven times, and the average value of the five measured values excluding the maximum value and the minimum value of the measured value was defined as the contact angle of the sample.

2. Polarizer

· Winding deviation evaluation

The above-prepared roll-shaped polarizers 101 to 119 were placed on a stand and subjected to a vibration test for one hour in accordance with JIS Z0232 using a general-purpose vibration test apparatus J series (manufactured by IMV Japan), and the wind- The portions of the car without winding displacement were measured with a curved line and evaluated according to the following criteria.

?: 0 mm (no winding deviation)

○: less than 5 mm

?: 5 mm or more, 10 mm or less

×: more than 10 mm (practically problematic)

3. Liquid crystal display

The liquid crystal display devices 201 to 219 were evaluated for unevenness and planarity to evaluate visibility.

a. Uneven evaluation

Each of the liquid crystal display devices manufactured above was observed from the front with a black display, and the unevenness was evaluated based on the following criteria.

◎: No irregularity of strain was not observed at all

○: The variation of the origin due to slight deformation

Δ: Unevenness of small strain origin appears

X: Unevenness of the strain origin appears

b. Planarity evaluation

Each of the liquid crystal display devices manufactured above was placed on a desk having a height of 80 cm from the bottom and 40 W × 2 main color light straight tube fluorescent lamps (FLR40S · D / MX Panasonic Co., Ltd.) Ten sets were arranged at intervals of 1.5 m with one set. In this case, when the evaluator was located on the front of the display surface of the liquid crystal display panel, the evaluator was placed so that the fluorescent lamps came to the ceiling from the top of the evaluator's head backward, and the planarity was evaluated according to the following criteria.

◎: Fluorescent lamp looks straight

○: The fluorescent lamp seems to be slightly curved.

△: Fluorescent lamp is bent

X: Fluorescent light seems to be out of focus

The results of the above evaluation are shown in Table 1.

As can be seen from the results in Table 1, the number of the contact angle before and after the alkali treatment of the hard coating layer difference _(Δ θ) that is in the range of 5 to 55 °, also the range of the film is from 5 to 34㎛ thickness of the cellulose ester film It can be seen that the use of the inner hard coating film exerts an excellent effect on winding deviation. Further, it can be seen that the polarizing plate composed of the hard coating film of the present invention exhibits an excellent effect of unevenness and planarity after the durability test. Thus, it can be seen that the liquid crystal display device incorporating the polarizing plate constituted by the hard coating film of the present invention has excellent visibility.

For the hard coat films 1 to 19 before the alkali treatment, the hardness was confirmed by a pencil hardness test. Using the test pencil prescribed in JIS-S6006, the hard coat layer side of the hard coat films 1 to 19 was repeated five times with pencils of each hardness using a weight of 500 g according to the pencil hardness evaluation method prescribed by JIS-K5400 As a result of measuring the hardness of up to one scratch and scratch, the pencil hardness of the hard coat film of the present invention was all H or more.

Example 2

Hard coating films 20 to 24 were prepared in the same manner as in the preparation of hard coating film 3 of Example 1, except that the drying temperature of the hard coating layer was changed as shown in Table 2. Further, similarly to the polarizing plate 103 of Example 1, the hard-coating films 20 to 24 were respectively used to produce the roll-like polarizing plates 120 to 124. There was no occurrence of winding displacement.

Subsequently, the logarithmic contact angle of the hard coating films 20 to 24 before the alkali treatment and the logarithmic contact angle after the alkali treatment after the polarizing plate were measured to determine the difference (?) _Between the logarithmic contact angles before and after the alkali treatment.

The winding deviation of the polarizing plate 103 and the polarizing plates 120 to 124 was evaluated in the same manner, except that the vibration test time of the winding displacement evaluation in Example 1 was changed to 3 hours. Each of the hard coat layers of the hard coat films 3 and 20 to 24 was measured ten times using an optical interference type surface roughness meter (NewView 5030, manufactured by ZYGO), and the arithmetic mean of each hard coat layer And the roughness (Ra) was obtained.

The durability test of the polarizing plate 103 and the polarizing plates 120 to 124 after the durability test was carried out in the same manner as in Example 1 except that the durability test was performed at 65 캜 and a relative humidity of 80% 124 was formed as shown in Fig. 4, and the viscoelasticity was evaluated by being embedded in a liquid crystal display device. The obtained results are shown in Table 2.

As can be seen from the results of Table 2, by using the hard coating film of the present invention in which the arithmetic average roughness (Ra) of the hard coat layer is controlled to 2 to 100 nm, excellent winding tolerance is obtained in a more severe vibration test Which is preferable. Further, by using the polarizing plate composed of the hard coating film of the present invention in which Ra is controlled to 2 to 100 nm, it is found that the effect of the unevenness and the planarity after the more severe endurance test is exerted. More preferably, the arithmetic mean roughness (Ra) of the hard coat layer is in the range of 5 to 80 nm.

Example 3

Hard coating films 25 and 26 were prepared in the same manner as the hard coating film 3 of Example 1 except that the active ray hardening resin of the hard coating layer composition was changed as shown in Table 3. In the same manner as in the polarizing plate 103 of Example 1, the polarizing plates 125 and 126 were produced using the hard coating films 25 and 26. There was no occurrence of winding displacement.

The logarithmic contact angle of the hard coating films 25 and 26 before the alkali treatment and the logarithmic contact angle after the alkaline treatment of the polarizing plate were measured to determine the difference (?) _Between the logarithmic contact angles before and after the alkali treatment. The winding deviation of the polarizing plate 103 and the polarizing plates 125 and 126 was evaluated in the same manner, except that the vibration test time of the winding displacement evaluation in Example 1 was changed to 2 hours.

An adhesive layer was formed on the polarizing plate 103 and the polarizing plates 125 and 126 after the durability test in the same manner as in Example 1 except that the conditions of the durability test on the assumption of long-term transportation were changed to 65 deg. C and relative humidity 80% And visibility was evaluated. The obtained results are shown in Table 3.

In addition, when pentaerythritol triacrylate was changed to PETA, trimethylolpropane triacrylate was changed to TMPTA, tris (2-acryloyloxyethyl) isocyanurate (NK ester A-9300, Shinnakamura Kagaku Kogyo ) (ICON), isocyanuric acid ethoxy-modified diacrylate (Aronix M-215, manufactured by Toagosei Co., Ltd.) is shown in Table 3.

As can be seen from the results in Table 3, the hard coat film of the present invention using an active energy ray-curable isocyanurate derivative as the hard coat layer has excellent resistance to winding displacement in a more severe vibration test, . Further, by using a polarizing plate composed of the hard coating film of the present invention using an isocyanurate derivative of active energy ray-curable type, it is possible to obtain an effect of excellent unevenness and planarity after a more severe endurance test.

Example 4

A dope composition 2 was prepared in the same manner as in the preparation of the dope composition 1 of the cellulose ester film 1 of Example 1, except that 8 mass parts of the acrylic polymer synthesized below was used instead of 4 mass parts of the additive X-12 Respectively. Subsequently, in the production of the cellulose ester film 1, the cellulose ester films 6 to 9 were produced in the same manner as in the case of changing the stretching conditions in the TD direction by the tenter as shown in Table 4. There was no occurrence of winding displacement.

(Synthesis of acrylic polymer)

Methyl acrylate 10 parts by mass

1 part by mass of 2-hydroxyethyl acrylate

1 part by mass of azobisisobutyronitrile (AIBN)

30 parts by mass of toluene

The above composition was introduced into a four-necked flask (inlet port, thermometer, reflux condenser, nitrogen inlet, stirrer), and the temperature was gradually raised to 80 DEG C and polymerization was carried out with stirring for 5 hours. Methanol, precipitated, washed with methanol, purified and dried to obtain an acrylic polymer having a weight average molecular weight of 5,000 (measured by GPC).

Both-side hard coating films 26 to 29 were produced in the same manner as in the production of the hard coating film 3 except that the hard coat layer composition 3 of Example 1 was provided on both sides of the cellulose ester films 6 to 9 thus prepared. In addition, in the hard coating film 3, the hard coating layer composition 3 was provided on both sides to prepare a double-side hard coating film 30.

The produced double-coated hard coating films 26 to 30 were subjected to alkali treatment under the same conditions as the alkali treatment in the production of the polarizing plate of Example 1 to measure the difference (?) _Between the logarithmic contact angles before and after the alkali treatment.

Further, in the same manner as in the vibration test of the polarizing plate of Example 1, the vibration test of the double-side hard coating films 26 to 30 was carried out to evaluate the winding displacement.

Subsequently, the in-plane retardation value (Ro) and the thickness direction retardation value (Rth) of the cellulose ester films 1 and 6 to 9 were measured by the following methods.

Measurement A three-dimensional refractive index was measured at an optical wavelength of 590 nm under an environment of a temperature of 23 캜 and a relative humidity of 55% using an automatic birefringence system KOBRA-21ADH (manufactured by Oji Chemical Industry Co., Ltd.) (N _x , n _y , n _z ) in each direction of the cellulose ester film were determined, and Ro and Rth of the cellulose ester film were determined from the following formula.

_{Ro = (n x -n y)} × d

The Rth = _{((n x + n y)} / 2-n z) × d.

(Where n _x is the refractive index in the direction of the slow axis in the substrate film plane, n _y is the refractive index in the direction perpendicular to the slow axis in the plane of the base film, n _z is the refractive index in the thickness direction of the base film, nm)

The obtained results are shown in Table 4.

(Production of conductive hard coat films 1 to 5)

Subsequently, conductive hard coating films 1 to 5 were prepared for the double-sided hard coating films 26 to 30 by the following method.

Conductive hard coat films 1 to 5 were prepared by providing a conductive film of indium tin oxide (ITO) having a surface resistivity of about 400? On both sides of double-side hard coating films 26 to 30 by using a sputtering method.

Subsequently, each of the above-prepared conductive hard coating films 1 to 5 was used in duplicate to produce an inner touch panel (FIG. 2). After forming the dots and spacers in advance in the conductive film 21D of one of the two conductive hard coating films, the two conductive films were opposed to each other to manufacture the inner touch panel. The obtained touch panel was built under the upper surface side polarizing plate 21F1 of the liquid crystal display device having the configuration of the upper surface side polarizing plate 21F1 / liquid crystal cell / lower surface side polarizing plate 21F2 to manufacture an inner touch panel, The front direction or the viewing direction was changed and observed, and visibility (color change) was evaluated according to the following criteria. The obtained results are shown in Table 4.

"evaluation"

Visibility (color change) evaluation

○: There is no change in color of the touch panel

?: Some change in color of the touch panel is observed

X: The color change of the touch panel is large. Practically problematic level

As can be seen from the results in Table 4, it is preferable that the conductive hard coating film composed of the double-side hard coating film according to the present invention is used in a touch panel to obtain excellent visibility (suppression of color change). Among them, a conductive hard coating film composed of a double-side hard coating film according to the present invention using a cellulose ester film having an in-plane retardation (Ro) of 0 to 5 nm and a retardation in the thickness direction adjusted to a range of -10 to 10 nm It is possible to obtain particularly good visibility (suppression of color change) by using it in a touch panel. Further, the double-sided hard coating film of the present invention has excellent winding displacement resistance.

Example 5

A hard coat film 31 was prepared in the same manner as the hard coat film 3 of Example 1, except that the cellulose ester film 1 was changed to the cellulose ester film 6. The same procedure as in Example 1 was repeated except that the cellulose ester film 1 bonded to the opposite side of the hard coating film was replaced with the cellulose ester film 6 by using the hard coating film 31, 127. Further, using the hard coating film 25, a roll-shaped polarizing plate 128 was produced in the same manner as in Example 1. There was no occurrence of winding displacement.

The logarithmic contact angle of the prepared hard coat film 31 before the alkali treatment and the logarithmic contact angle after the alkali treatment after the preparation of the polarizing plate were measured to obtain the difference (?) _Between the logarithmic contact angles before and after the alkali treatment.

Further, in the same manner as in Example 1, evaluation of the winding displacement of the polarizing plate 103, the polarizing plate 127, and the polarizing plate 128 was carried out. 4, an adhesive layer was formed on the polarizing plate 103, the polarizing plate 127, and the polarizing plate 128 after the durability test in the same manner as in Example 1, and the liquid crystal display device 227 and the liquid crystal display device 228 And evaluated in the same manner as in Example 1. [ In addition, color change of the visibility evaluation was evaluated based on the following criteria. The results obtained are shown in Table 5.

"evaluation"

· Color change

The visibility of the liquid crystal display device was evaluated based on the following criteria by changing the front direction or the viewing direction on the black display screen.

?: No change in color of the liquid crystal display device

?: A change in color tone of the liquid crystal display device was observed to some extent

X: Large change in color of the liquid crystal display device

As can be seen from the results in Table 5, a cellulose ester film prepared by adding an acrylic polymer and adjusting the in-plane retardation (Ro) in the range of 0 to 5 nm and the retardation in the thickness direction in the range of -10 to 10 nm The hard coating film according to the present invention is preferable because it has excellent winding displacement resistance and particularly excellent visibility when used in a liquid crystal display device.

Example 6

(Production of inorganic pressure-sensitive adhesive sheet)

The pressure-sensitive adhesive composition 1 was coated on the release face of a release sheet (trade name: SP-PET381031, thickness 38 占 퐉, manufactured by Lin Tec Corporation) using a die coater so that the thickness after drying was 15 占 퐉 and dried at 120 占 폚 for 2 minutes Sensitive adhesive layer was formed to obtain an inorganic pressure-sensitive adhesive sheet including a release sheet and a pressure-sensitive adhesive layer formed on the release surface.

&Quot; Adhesive-containing composition 1 &

The following composition was stirred to prepare a pressure-sensitive adhesive composition-containing composition 1.

100 parts by mass of an acrylic acid ester copolymer (molecular weight 800,000, concentration 35% by mass) obtained by copolymerizing n-butyl acrylate (79% by mass, 20% by mass of methyl acrylate and 1% by mass of 2-hydroxyethyl acrylate)

0.1 part by mass of toluene and xylene diisocyanate-based trifunctional adduct body (trade name: TD-75, concentration 75% by mass, manufactured by Soken Chemical &

[Production of glass shatterproof film for image display apparatus and image display apparatus]

The hard-coating films 1 to 19 in the roll form produced in Example 1 were surrounded by an aluminum moisture-proof sheet and stored for 25 days in a thermostatic chamber at a temperature of 50 ° C and a relative humidity of 80% on the assumption of long-term transportation. After the durability test, the pressure-sensitive adhesive layer of an inorganic pressure-sensitive adhesive sheet was bonded to both surfaces of the hard coating films 1 to 19 to obtain glass shatterproof films 1 to 19 for image display devices.

Subsequently, a glass plate with a thickness of 1 mm and the opposite side to the side where the hard coating layer was provided were bonded to each other. Then, the pressure sensitive adhesive layer of the inorganic pressure-sensitive adhesive sheet of each hard coating layer was laminated on a touch panel liquid crystal display (product name: LCD-USB10XB-T, IO · Data Device Manufacture Co., Ltd.) to manufacture image display devices 1 to 19, and visibility was evaluated based on the following criteria.

"evaluation"

· Visibility evaluation

In a room where 10 sets of two 40W × 2 main light straight fluorescent lamps (FLR40S · D / MX Panasonic Co., Ltd.) were arranged on the ceiling at intervals of 1.5 m, the image display device was placed in the black display state, Observations were made at various angles and the state of the reflected light reflected on the image display device was evaluated based on the following criteria.

Evaluation standard

&Amp; cir &amp;: A level at which interference stripes of reflected light reflected by the image display device are not seen at all

X: Interference streaks of the reflected light reflected by the image display device were slightly visible,

占:: A level at which interference stripes of reflected light reflected on the image display device can be clearly confirmed

· Evaluation of shatterproof prevention of glass shatterproof film for image display

Scattering prevention films 1 to 19 for image display devices in which an adhesive layer of an inorganic pressure-sensitive adhesive sheet is bonded only to the non-coated surface (the surface opposite to the surface on which the hard coating layer is provided) of the hard coating films 1 to 19 after the durability test Was bonded to a glass plate having a thickness of 1 mm.

Subsequently, a laminate including a glass plate and a shatterproof film was placed on the pedestal having a height of 10 mm such that the shatterproof film was directed upward.

Then, the steel ball was dropped on the shatterproof film of the laminate at a height of 30 cm, and the scattering state of the glass was visually observed and evaluated according to the following criteria.

"evaluation"

· Glass scattering prevention property

Evaluation standard

○: Shatterproof film was not torn

DELTA: Anti-scattering film slightly torn

X: Shatterproof film torn

As can be seen from the results of Table 6, the glass shatterproof film for an image display apparatus comprising the hard coating film of the present invention is excellent in visibility when used in an image display apparatus, .

[Industrial applicability]

The hard coating film of the present invention suppresses slippage between the films and prevents the winding deviation, and suppresses film buckling deformation and distortion when the film is wound into a roll shape, and is excellent in flatness and unevenness. to be. The hard coating film is suitable for a glass scattering prevention film, a touch panel, a polarizing plate and a liquid crystal display device for an image display device having good visibility.

10: Touch panel 11: Double-sided hard coating film
12: conductive film 13: glass substrate
14: Spacer 15: Conductive film
20: Image display device with inner touch panel
21A: hard coat layer 21B: hard coat layer
21C: cellulose ester film 21D: conductive film (ITO layer)
21E: liquid crystal cell 21F1: upper surface side polarizing plate
21F2: a lower surface side polarizing plate 21G:
DS: dot spacer 30: image display device
31: image display panel 32: pressure-sensitive adhesive layer
33: conductive glass substrate 34: glass substrate
35: conductive film
41: Glass shatterproof film for image display apparatus
42: hard coating film 43: pressure-sensitive adhesive layer
CE1: cellulose ester film HC1: hard coat layer
KF1: Hard Coating Film PV1: Polarizing Film
NS1: Adhesive layer

Claims (10)

The film thickness of the hard coat film having a hard coat layer on at least one side of a cellulose ester film in the range of 5 to 34㎛, the hard coating layer of the algebraic difference of the contact angle before and after the alkali treatment at the time when the alkali treatment under the following conditions (θ _Δ ) Is in the range of 5 to 55 [deg.].
(Alkali treatment condition)
Alkaline solution: 2.5 mol / L potassium hydroxide solution
Processing temperature: 50 ° C
Processing time: 120 seconds The method according to claim 1,
Wherein the logarithmic contact angle (?) Of the hard coat layer before the alkali treatment is in the range of 50 to 120 °. 3. The method according to claim 1 or 2,
Wherein the logarithmic contact angle of the hard coat layer is lowered after the alkali treatment before the alkali treatment under the alkali treatment condition. 4. The method according to any one of claims 1 to 3,
Wherein the hard coating layer has an arithmetic mean roughness (Ra) (JIS B0601: 2001) of 2 to 100 nm. 5. The method according to any one of claims 1 to 4,
Wherein the hard coating layer contains an isocyanurate derivative of active energy ray-curable type. 6. The method according to any one of claims 1 to 5,
When the retardation value (Ro) in the cellulose ester film is within a range of 0 to 10 nm when the retardation value is measured at an optical wavelength of 590 nm in an environment of a temperature of 23 캜 and a relative humidity of 55% (Rth) is in the range of -10 to 10 nm. A polarizing plate characterized in that a polarizing element is sandwiched and supported by using the hard coating film according to any one of claims 1 to 6 and a cellulose ester film having a film thickness within a range of 5 to 34 μm. A glass shatterproof film for an image display device, characterized by using the hard coating film according to any one of claims 1 to 6. A touch panel comprising the hard coating film according to any one of claims 1 to 6. A liquid crystal display device comprising the liquid crystal cell according to any one of claims 1 to 7.

Images