KR20130113484A - Hard coating film and image display device - Google Patents

Abstract

An object of the present invention is to provide a hard coat film and an image display device aimed at improving blocking and flexibility after an endurance test. It has an easily bonding layer on both surfaces of at least 1 type of base film selected from an acrylic resin film, a polypropylene resin film, a cycloolefin resin film, and a polyester resin film, and a hard-coat layer is laminated | stacked on at least one surface of the said easily bonding layer. WHEREIN: The said easily bonding layer contains at least 1 sort (s) chosen from polyester-based resin, acrylic resin, and urethane-type resin, and the said hard-coat layer contains an active energy ray hardening type isocyanurate derivative. Hard coat film, characterized in that.

Description

Hard coat film and image display device {HARD COATING FILM AND IMAGE DISPLAY DEVICE}

The present invention relates to a hard coat film and an image display apparatus, and to a hard coat film and an image display apparatus aimed at improving blocking and flexibility after an endurance test.

Background Art In recent years, hard coat films have been used for display devices such as displays, mobile phones, portable games, touch panels, and the like to prevent scratches and to prevent scattering of glass display surfaces such as CRTs and PDPs. Polycarbonate films, polypropylene films, cycloolefin films, polyester films are generally used for the base film of the hard coat film, and the biaxially stretched film of the polyester film has excellent mechanical properties, flame resistance or Since it has chemical resistance etc., it is used suitably.

However, when using a polyester film for the base film mentioned above, there existed a problem in the interlayer adhesion of an interference color nonuniformity and a hard-coat layer and a base film.

The interference color nonuniformity is generally about 1.66 in the in-plane refractive index of the polyester film, and the refractive index of the ultraviolet curable acrylic resin layer suitably used for the hard coat layer of the hard coat film is generally about 1.5. Interference occurs at the interface between the polyester film and the ultraviolet curable acrylic resin layer, and color unevenness occurs due to the interference. This interference color unevenness is transparent, and since the hard coat film is detected under a special fluorescent lamp called a three-wavelength fluorescent lamp rather than sunlight or an incandescent lamp, there existed a request for improvement. In addition, the interlayer adhesion between the hard coat layer and the base film was remarkably deteriorated in the humidity conditions assuming a bathroom or a high temperature and high humidity region where a mobile telephone or the like is used.

About the technique of improving these problems, the technique of forming an easily bonding layer on a polyester film is disclosed by patent document 1, for example. Although the above-mentioned problems are improved in the above technology, a problem arises in that blocking occurs when the sheet is wound and stored in a roll shape after manufacture of the hard coat film, or cut and stacked in a sheet shape for bonding to a display device. It was. Since the blocking pattern generate | occur | produced in a hard coat film by blocking, the problem that aesthetics was remarkably damaged when using a hard coat film for a display apparatus occurred.

The blocking was remarkable after the endurance test assuming the transport and long-term storage of the hard coat film. In addition, when used as a film for processing titration when the hard coat film is used for the display device or as a film for the surface of the touch panel, the hard coat film is required to have flexibility since it is used by press-fitting with a pen or a finger at the time of information input. In particular, there has been a problem that flexibility deteriorates after endurance tests assuming various usage environments.

Japanese Patent Publication No. 2007-253512

Accordingly, an object of the present invention is to provide a hard coat film and an image display device aimed at improving blocking and flexibility after an endurance test.

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

1. It has an easily bonding layer on both surfaces of at least 1 sort (s) of base film chosen from an acrylic resin film, a polypropylene resin film, a cycloolefin resin film, and a polyester resin film, and has a hard-coat layer in at least one surface of the said easily bonding layer. In this laminated hard coat film, the easily bonding layer contains at least one selected from polyester resins, acrylic resins and urethane resins, and the hard coat layer further comprises an active energy ray-curable isocyanurate derivative. It contains, The hard coat film characterized by the above-mentioned.

2. Said base film is polyester resin film, The said hard coat film of 1 characterized by the above-mentioned.

3. Said easily bonding layer consists of polyester resin, The said hard coat film of 1 or 2 characterized by the above-mentioned.

4. The polyester resin of the said easily bonding layer contains two components of polyester resin (X) and (Y), and the said polyester resin (X) and (Y) contain the following acid as an acid component, respectively. The hard coat film in any one of said 1-3 characterized by the above-mentioned.

Polyester resin (X): Sodium sulfonate isophthalic acid is contained in an acid component.

Polyester resin (Y): Trimellitic acid is contained in an acid component.

5. The hard coat layer contains an active energy ray-curable isocyanurate derivative (A) and an active energy ray-curable resin (B) other than an isocyanurate derivative, and the active energy ray-curable isocyanurate derivative. The mass ratio of active energy ray hardening resin (B) other than (A) and the isocyanurate derivative is 10: 90-50: 50, The hard coat film in any one of said 1-4 characterized by the above-mentioned.

6. Said hard-coat layer contains ultraviolet absorber, The hard coat film in any one of said 1-5 characterized by the above-mentioned.

7. The image display apparatus containing the hard coat film in any one of said 1-6.

8. The liquid crystal display device in which the image display apparatus of said 7 contains a touch panel, The hard-coat film in any one of said 1-6 is used for the structural member of the said touch panel, The image display characterized by the above-mentioned. Device.

According to this invention, the hard-coat film and image display apparatus which aimed at the improvement of the blocking and flexibility after an endurance test can be provided.

1 is an example when the hard coat film of the present invention is used for a touch panel.
It is a schematic diagram of a liquid crystal display device with a touch panel.
It is a schematic diagram of a conductive hard coat film.
4 is a schematic view of a resistive touch panel.

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

MEANS TO SOLVE THE PROBLEM In order to prevent the interlayer adhesion of a hard-coat layer and a base film, and an interference color nonuniformity, this inventor repeated earnest examination about the said subject, and comprises the easily bonding layer formed between a hard-coat layer and a base film with a specific resin composition. In addition, by using an active energy ray-curable isocyanurate derivative for the hard coat layer, the surface energy of the easy bonding layer and the hard coat layer is controlled, and the easy bonding layer and the hard coat layer form a low affinity state. By finding the favorable performance for the blocking property after an endurance test, and making a hard coat film into the said structure, the elasticity of a hard coat film does not deteriorate even after an endurance test, and it finds out that favorable flexibility is obtained, and has reached this invention.

Hereinafter, the detail of the hard coat film which comprises this invention is demonstrated.

<Hard coat layer>

First, the active energy ray hardening type isocyanurate derivative which is a characteristic of this invention contained in a hard-coat layer is demonstrated.

In addition, when describing active energy ray hardening type resin other than an active energy ray hardening type isocyanurate derivative and an isocyanurate derivative, it describes simply as active energy ray hardening type resin.

(Active energy ray curable isocyanurate derivative)

An active energy ray hardening type means resin which hardens | cures through a crosslinking reaction etc. by irradiation of active rays, such as an ultraviolet-ray or an electron beam, and is a resin which has an ethylenically unsaturated group specifically ,.

The active energy ray-curable isocyanurate derivative may be a compound having a structure in which one or more ethylenically unsaturated groups are bonded to the isocyanuric acid skeleton, and there is no particular limitation, but three or more ethylene in the same molecule represented by the following general formula (1) Compounds having a unsaturated unsaturated group and at least one isocyanurate ring are preferred in view of the desired effects of the present invention. The kind of ethylenically unsaturated group is acryloyl group, methacryloyl group, styryl group, and vinyl ether group, More preferably, it is a methacryloyl group or acryloyl group, Especially preferably, it is acryloyl group.

In formula, L <^2> is a bivalent coupling group, Preferably it is a substituted or unsubstituted C4 or less alkyleneoxy group or polyalkyleneoxy group which a carbon atom couple | bonds with the isocyanurate ring, Especially preferably, alkyl It is a lenoxy group and may be same or different, respectively. R <^2> represents a hydrogen atom or a methyl group, and may be same or different, respectively. Although the specific compound represented by General formula (1) is shown below, it is not limited to these.

An isocyanuric-acid diacrylate compound is mentioned as another compound, The isocyanuric acid ethoxy modified diacrylate represented by following General formula (2) is preferable.

Moreover, the active energy ray hardening type isocyanurate derivative of (epsilon) -caprolactone modification can also be mentioned, A compound represented by following formula (3) specifically, is mentioned.

_One of R ₁ to R ₃ of the chemical structural formula is attached to a functional group represented by a, b, and c, and 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 ) nO- (COC ₅ H ₁₀ ) m-COCH = CH ₂ (n = 1 to 10, preferably n = 2 to 6, m = 2 to 8)

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

Although the specific compound represented by General formula (3) is shown below, it is not limited to these.

As a commercial item of an isocyanuric-acid triacrylate compound, A-9300 by Shin-Nakamura Chemical Industries Co., Ltd. etc. are mentioned, for example. As a commercial item of the isocyanuric-acid diacrylate compound, Toagosei Co., Ltd. Aronix M-215 etc. are mentioned, for example. As a mixture of an isocyanuric-acid triacrylate compound and an isocyanuric-acid diacrylate compound, Toagosei Co., Ltd. Aronix M-315, Aronix M-313, etc. are mentioned, for example.

As active energy ray hardening type isocyanurate derivative of (epsilon) -caprolactone modification, A-9300-1CL by Shin-Nakamura Chemical Co., Ltd. which is (epsilon) -caprolactone modified tris- (acryloxyethyl) isocyanurate, Aronix M-327 by Toagosei Co., Ltd., etc. are mentioned, It is not limited to these.

(Active energy ray curable resins other than isocyanurate derivatives)

Examples of the active energy ray-curable resins other than the isocyanurate derivatives include ultraviolet-curable urethane acrylate resins, ultraviolet-curable polyester acrylate-based resins, ultraviolet-curable epoxy acrylate-based resins, ultraviolet-curable polyol acrylate-based resins or ultraviolet-curable epoxys. Resin etc. are used preferably. Especially, ultraviolet curable acrylate resin is preferable.

As ultraviolet curable acrylate resin, polyfunctional acrylate is preferable. The polyfunctional acrylate is selected from the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate and dipentaerythritol polyfunctional methacrylate. desirable. Here, polyfunctional acrylate is a compound which has 2 or more acryloyloxy group or a methacroyloxy group in a molecule | numerator.

As a monomer of a polyfunctional acrylate, for example, ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylol propane triacrylate, trimethylol ethane Triacrylate, tetramethylol methane triacrylate, tetramethylol methane tetraacrylate, pentaglycerol triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, glycerin triacrylic The rate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, etc. are mentioned preferably.

Monofunctional acrylate can also be used as active energy ray hardening type resin other than an isocyanurate derivative. As monofunctional acrylate, isoboroyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, isostearyl acrylate, benzyl acrylate, ethyl carbitol acrylate, phenoxy ethyl acrylate, lauryl acryl Elate, isooctyl acrylate, tetrahydrofurfuryl acrylate, behenyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, cyclohexyl acrylate, etc. are mentioned. Can be. As monofunctional acrylate, it can obtain from Shin-Nakamura Chemical Industries, Ltd., and Osaka Yuki Chemical Industries. These compounds are used individually or in mixture of 2 or more types, respectively.

When using an active energy ray hardening type isocyanurate derivative and active energy ray hardening type resin other than an isocyanurate derivative in combination with a hard-coat layer, active energy ray hardening type isocyanurate derivative (A) and isocyanurate By using the content mass ratio of active energy ray-curable resin (B) other than a derivative in the range of (A) :( B) = 10: 90-50: 50, the objective effect of this invention can be exhibited more after a severe weathering test further. It is preferable at the point.

(Photoinitiator)

It is preferable that a hard-coat layer contains a photoinitiator in order to accelerate | stimulate hardening of active energy ray hardening-type resin. As a photoinitiator amount, it is preferable to contain in a mass ratio as photoinitiator: active-energy-ray-curable resin = 20: 100-0.01: 100.

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

(Manufacturing method)

Further, the hard coat layer according to the present invention is formed by diluting the above-described active energy ray-curable resin with a solvent or the like to form a hard coat layer coating composition and applying, drying and curing the film on the easy-adhesive layer of the film base material by the following method. It is preferable from a viewpoint of productivity. Examples of the solvent include alcohols (methanol, isopropyl alcohol, 1-methoxy-2-propanol, etc.), ketones (methyl ethyl ketone, acetone, methyl isobutyl ketone, etc.) or acetate esters (methyl acetate, ethyl acetate, butyl acetate, and the like). A solvent containing is preferable.

Moreover, 0.1-40 micrometers is suitable as a coating film thickness, Preferably it is 0.5-30 micrometers. Moreover, as dry film thickness, average film thickness is 0.1-30 micrometers, Preferably it is 1-20 micrometers, Especially preferably, it is 6-15 micrometers.

As the coating, a known coating method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die (extrusion) coater, or an inkjet method can be used. The drying is preferably performed at a temperature of 40 ° C. or higher in the rate-sensitive drying section in that the dilution solvent does not remain in the hard coat layer. More preferably, the temperature in the rate-sensitive drying section is 80 ° C. or higher and 130 ° C. or lower.

In general, it is known that the drying process changes from a constant state to a slowly decreasing state when drying starts, and a constant drying rate is referred to as a constant rate drying section, and a drying rate decreases as a reduced rate drying section. It is called.

UV hardening treatment is generally used from a viewpoint of productivity, and hardening heat-processes after UV hardening treatment as needed. The heat treatment temperature after the 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 carrying out the heat treatment after the UV curing treatment at such a high temperature, the mechanical film strength (abrasion resistance, pencil hardness) of the hard coat layer is excellent.

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

Irradiation conditions are different for each lamp, and the irradiation amount of an active line is 50-1000mJ / cm <^2> normally, Preferably it is 50-300mJ / cm <^2> .

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

The hard coat layer may be one layer or a plurality of layers. In order to make it easy to control the hard-coat property, haze, and arithmetic surface roughness Ra of a hard-coat layer, you may divide and form in two or more layers. In addition, a hard-coat layer may be formed in the single side | surface of an easily bonding layer, and may be formed in both surfaces.

It is preferable that the film thickness of the uppermost layer in the case of forming two or more layers is 0.05-2 micrometers. Lamination | stacking of two or more layers can also be formed by simultaneous middle layer. Simultaneous intermediate | middle layer is a hard coat layer formed by apply | coating two or more hard-coat layers by wet on wet (wet coating method) on a base material, without passing through a drying process. In order to laminate | stack a 2nd hard-coat layer by wet on wet, without going through a drying process on a 1st hard-coat layer, you may carry out simultaneous intermediate | middle layering by the extrusion coater or the slot die which has several slits simultaneously.

(Other additives)

Moreover, it is preferable to contain a ultraviolet absorber in a hard coat layer from the point of the objective effect of this invention, and adhesiveness. An ultraviolet absorber is a compound which is excellent in the absorption ability of the ultraviolet-ray below wavelength 370nm, and has little absorption of the visible light of wavelength 400nm or more. Specific examples thereof include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex salt compounds, and the like. It is not limited. Although the following specific examples are mentioned as a benzotriazole type ultraviolet absorber, this invention is not limited to these.

UV-1: 2- (2'-hydroxy-5'-methylphenyl) benzotriazole

UV-2: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole

UV-3: 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole

UV-4: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole

UV-5: 2- (2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole

UV-6: 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol)

UV-7: 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole

UV-8: 2- (2H-benzotriazol-2-yl) -6- (linear and branched dodecyl) -4-methylphenol (TINUVIN 171, manufactured by BASF Japan)

UV-9: octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3 A mixture of -tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate (TINUVIN 109, manufactured by BASF Japan)

Although the following specific examples are shown as a benzophenone type ultraviolet absorber, this invention is not limited to these.

UV-10: 2,4-dihydroxybenzophenone

UV-11: 2,2'-dihydroxy-4-methoxybenzophenone

UV-12: 2-hydroxy-4-methoxy-5-sulfobenzophenone

UV-13: bis (2-methoxy-4-hydroxy-5-benzoylphenylmethane)

Since the said ultraviolet absorber is excellent in transparency of a hard-coat layer, a benzotriazole type ultraviolet absorber and a benzophenone type ultraviolet absorber are preferable. Moreover, commercial items, such as PUVA-30M (made by Otsuka Chemical Co., Ltd.), can also be used as a polymeric ultraviolet absorber. As a structure containing a ultraviolet absorber, although it can also be made to contain in a single-layer hard-coat layer, the structure which contains this ultraviolet-ray absorber in the hard-coat layer which consists of two or more layers, and contact | connects an easily bonding layer, etc. are mentioned. . It is preferable at the point which the objective effect of this invention is exhibited favorably because a hard-coat layer contains a ultraviolet absorber. As content, it is preferable to contain in a mass ratio as ultraviolet absorber: hard coat layer constituent resin = 0.01: 100-10: 100. When forming two or more layers, it is preferable that the film thickness of the hard-coat layer which contact | connects a base film is the range of 0.05-2 micrometers. Lamination | stacking of two or more layers can also be formed by simultaneous middle layer. Simultaneous middle layer is a hard coat layer formed by apply | coating two or more hard-coat layers by wet on wet on a base material, without going through a drying process. In order to laminate | stack a 2nd hard-coat layer by wet on wet, without going through a drying process on a 1st hard-coat layer, it is good to carry out simultaneous intermediate | middle layering by the extrusion coater or simultaneously by the slot die which has a some slit.

Moreover, in order to provide antistatic property, a hard coat layer may also contain a electrically conductive agent, As a preferable electrically conductive agent, a metal oxide particle or (pi) conjugated type conductive polymer is mentioned. In addition, an ionic liquid is also preferably used as the conductive compound. The hard coat layer may also contain nonionic surfactants such as silicone surfactants, fluorine surfactants or polyoxyethers, anionic surfactants, and fluorine-siloxane graft polymers from the viewpoint of applicability and uniform dispersibility of the fine particles. . The fluorine-siloxane graft polymer refers to a polymer of a copolymer obtained by grafting polysiloxane and / or organopolysiloxane including at least siloxane and / or organosiloxane single substance in a fluorine resin. As a commercial item, ZX-022H, ZX-007C, ZX-049, ZX-047-D, etc. made by Fuji Kasei Kogyo Co., Ltd. are mentioned. Moreover, it is preferable to add these components in 0.01-3 mass% with respect to the solid content component in a coating liquid. The hard coat layer may contain inorganic fine particles or organic fine particles as necessary.

Inorganic fine particles include silicon oxide, titanium oxide, aluminum oxide, tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide, magnesium oxide, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, calcium silicate hydrate, aluminum silicate, Magnesium silicate and calcium phosphate. In particular, silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide and the like are preferably used. It is preferable that these inorganic microparticles | fine-particles coat | cover the organic component which has a reactive functional group on a part of surface from the point which abrasion resistance improves, maintaining transparency of a hard coat film. As a method of coating the organic component which has a reactive functional group on a part of surface, the compound containing organic components, such as a silane coupling agent, reacts with the hydroxyl group which exists in the surface of metal oxide fine particles, for example, and a part of the surface has an organic component. The form which couple | bonded, the form which the organic component adhered by interaction with a hydroxyl group etc. which exist on the surface of metal oxide microparticles | fine-particles, etc., the form containing one or two or more inorganic fine particles in a polymer particle, etc. are mentioned. As the organic particles, polymethyl methacrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicone resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, Melamine type resin powder, polyolefin type resin powder, polyester type resin powder, polyamide type resin powder, polyimide type resin powder, polyfluorinated ethylene resin powder, etc. can be added. Preferred fine particles include crosslinked polystyrene particles (e.g., SX-130H, SX-200H, SX-350H), polymethylmethacrylate-based particles (e.g., MX150, MX300, manufactured by Sokengagaku), fluorine Containing acrylic resin microparticles | fine-particles are mentioned. As fluorine-containing acrylic resin microparticles | fine-particles, commercial items, such as Nippon Paint: FS-701, are mentioned, for example. Moreover, as an acrylic particle, Nippon Paint-made: S-4000, For example, Nippon Paint-made: S-1200, MG-251, etc. are mentioned as an acrylic particle. Although the average particle diameter of these fine particle powders is not specifically limited, 0.01-5 micrometers is preferable, Furthermore, it is especially preferable that it is 0.01-1.0 micrometer. Moreover, you may contain 2 or more types of microparticles | fine-particles from which a particle diameter differs. The average particle diameter of microparticles | fine-particles can be measured, for example by the laser diffraction type particle size distribution measuring apparatus.

The ratio of the ultraviolet-curable resin composition to the fine particles is preferably 10 to 400 parts by mass, more preferably 50 to 200 parts by mass, per 100 parts by mass of the resin composition.

(Hardness)

The pencil hardness of the hard coat film of this invention which is an index of hardness is H or more, More preferably, it is 3H or more. If it is 3H or more, it is difficult to be scratched when used as a display device and exhibits excellent film strength even when used as a surface protection film of a large liquid crystal display device or a liquid crystal display device for digital signage, which is often used for outdoor use. . The pencil hardness was measured by following the pencil hardness evaluation method prescribed by JISK5400 using a test pencil prescribed by JIS S 6006 after humidifying the produced hard coat film under conditions of a temperature of 23 ° C. and a relative humidity of 55% for 2 hours. Value.

(Surface shape)

The hard coat layer is a method of forming surface irregularities by the addition of the inorganic or organic fine particles described above, a method of forming surface irregularities using phase separation by spinodal decomposition, or a method of forming protrusions on a surface by pressing a mold. Anti-glare property can also be given. As a casting roll, the fine unevenness | corrugation and a coarse thing can be selected suitably, and it can use, and the shape, mat shape, lenticular lens shape, and spherical unevenness | corrugation can be used regularly or randomly arranged. Anti-glare means blurring the outline of the image reflected on the surface to reduce the visibility of the reflection image so that the projection of the reflection image or light is not disturbed when the display device or the like is used.

The arithmetic mean roughness Ra (JIS B0601: 1994) of surface irregularities of the hard coat layer is preferably 1 to 300 nm. In order to make said arithmetic mean roughness Ra, 10 nm-4 micrometers of height of protrusion shape are preferable. Moreover, the width | variety of protrusion shape is 50 nm-300 micrometers, Preferably it is 50 nm-100 micrometers. The 10-point average roughness Rz is preferably 10 times or less of the centerline average roughness Ra, and the average valley distance Sm is preferably 5 to 150 µm, more preferably 20 to 100 µm, from the uneven core. The standard deviation of the height of the convex portion is preferably 0.5 μm or less, the standard deviation of the average valley distance Sm from the center line is 20 μm or less, and the plane having an inclination angle of 0 to 5 degrees is preferably 10% or more. By such a design, a white turbidity suppression effect is easy to be acquired. Said arithmetic mean roughness (Ra, Sm, Rz) is the value measured with the optical interference type surface roughness meter (for example, RST / PLUS, the product made by WYKO) according to JISB0601: 1994. The kurtosis (Rku) is preferably 3 or less. Kurtosis (Rku) is a parameter that defines the shape of the convex portion of the surface irregularities, and as the value of the kurtosis Rku increases, the shape of the convex portion of the surface irregularities becomes sharp like a needle. Beyond the kurtosis (Rku) 3, white turbidity is likely to occur. The kurtosis (Rku) of the antiglare layer is more preferably 1.5 to 2.8. Moreover, it is preferable that the absolute value of the surface distortion degree Rsk is 1 or less. The skewness degree Rsk is a parameter representing the ratio of the convex portion and the concave portion with respect to the average surface of the uneven shape. If the uneven shape has more convex portions than the average surface, the distortion degree Rsk becomes a positive value. On the other hand, when there are many concave parts, it becomes a negative value and is large. When the absolute value of the distortion degree Rsk exceeds 1, white turbidity is likely to occur. The absolute value of the distortion degree Rsk is preferably 0.01 to 0.5. In addition, the kurtosis (Rku) and the skewness (Rsk) can be measured using the optical interference surface roughness meter. In addition, the image sharpness (transmission filamentousness) according to JIS-K7105 is preferably 5% to 90% when measured with an optical comb width of 0.5 mm.

<Base film>

The base film is at least 1 selected from an acrylic resin film, a polycarbonate resin film, a polypropylene resin film, a cycloolefin resin film, and a polyester resin film in terms of easy manufacturing, transparency, and good adhesion with an easy adhesion layer. It is a feature of being a species.

First, an acrylic resin film is demonstrated. An acrylic resin film is a film containing resin which has a skeleton derived from acrylic acid or methacrylic acid. Although it does not specifically limit as an example of acrylic resin, Poly (meth) acrylic acid ester, such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid copolymer, methyl methacrylate- (meth) acrylic acid ester copolymer, meta Methyl methacrylate- (meth) acrylic acid copolymer, methyl (meth) acrylate-styrene copolymer, polymer having an alicyclic hydrocarbon group (for example, methyl methacrylate-cyclohexyl copolymer, methacrylic) Methyl acid- (meth) acrylic acid norbornyl copolymer), and the like. Among these acrylic resins, poly (meth) acrylate C1-6 alkyl such as methyl poly (meth) acrylate is preferable, and methyl methacrylate resin is more preferable. As a commercial item of acrylic resin, Delpet 60N, 80N (made by Asahi Chemical Co., Ltd.), diamond BR52, BR80, BR83, BR85, BR88 (made by Mitsubishi Rayon), KT75 (Denki Chemical Co., Ltd.) Production). Acrylic resin can also use 2 or more types together.

A polycarbonate resin film is demonstrated. As a polycarbonate resin type film, it is a film containing resin comprised from the compound called poly-4,4'-isopropylidene- diphenyl carbonate. This polycarbonate resin can be produced from bisphenol A and carbonyl chloride in the interfacial polycondensation method and from bisphenol A and diphenyl carbonate in the transesterification method. The polypropylene resin is a film containing a resin having a skeleton derived from propylene. Although it does not specifically limit as an example of polypropylene resin, The homopolymer of propylene or the copolymer of 1 or more types of monomers chosen from the group which consists of propylene, ethylene, and C4-12 alpha-olefin, etc. are mentioned.

As a cycloolefin resin film, it is a film containing resin which has frame | skeleton derived from cycloolefin. Examples of cycloolefin-based resins are not particularly limited, but resins or hydrogen-norbornene-based monomers which are hydrogenated after performing ring-opening (co) polymers of norbornene-based monomers, such as maleic acid addition and cyclopentadiene addition, are optionally modified. The resin which carried out addition polymerization, the resin which carried out addition polymerization of the norbornene-type monomer and olefinic monomers, such as ethylene and alpha-olefin, etc. are mentioned.

As a norbornene-type monomer used in order to obtain the ring-opening (co) polymer of a norbornene-type monomer, for example, norbornene, 2-norbornene, 5-methyl-2-norbornene, 5, 5-dimethyl- 2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-cyano-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5-phenyl-2-norbornene, 5-phenyl-5-methyl-norbornene, etc. Can be mentioned. As a polymerization catalyst used for this ring-opening polymerization, tungsten, molybdenum, and a chromium-type catalyst called a metathesis polymerization catalyst are used preferably. Moreover, as a commercial item of a cycloolefin resin type film, a zeonor film (made by Nippon Xeon Co., Ltd.), an aton film (made by JSR Co., Ltd.), etc. are mentioned.

A polyester resin film is demonstrated. The polyester resin film is preferably a biaxially stretched polyester resin film from thermal and mechanical stability. The biaxially stretched polyester film is a polyester resin film which is stretched in two directions and heat treated as necessary. As dicarboxylic acid used for polyester resin, terephthalic acid, naphthalenedicarboxylic acid, isophthalic acid, diphenyl carboxylic acid, diphenyl sulfone dicarboxylic acid, diphenoxy ethane dicarboxylic acid, 5-sodium sulfondica Alicyclic compounds such as aromatic dicarboxylic acids such as carboxylic acid and phthalic acid, aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid, dimer acid, maleic acid and fumaric acid, and cyclohexanedicarboxylic acid Oxycarboxylic acids, such as dicarboxylic acid and paraoxybenzoic acid, can be used. Examples of the glycols used in the polyester resin include aliphatic glycols such as ethylene glycol, propanediol, butanediol, pentanediol, hexanediol and neopentyl glycol, and polyoxyalkylenes such as diethylene glycol, polyethylene glycol, and polypropylene glycol. Alicyclic glycols, such as glycol and cyclohexane dimethanol, aromatic glycols, such as bisphenol A and bisphenol S, etc. can be used. In consideration of mechanical strength, weather resistance, chemical resistance, transparency, and the like, it is preferable to use terephthalic acid or naphthalenedicarboxylic acid as dicarboxylic acids and ethylene glycol as glycols.

As a specific polyester resin type film, a polyethylene terephthalate film etc. are mentioned.

Moreover, it is preferable to use an alkaline earth metal compound, a manganese compound, a cobalt compound, an aluminum compound, an antimony compound, a titanium compound, a germanium compound etc. as a catalyst at the time of superposition | polymerization. These dicarboxylic acids, glycols, and a catalyst may use 2 or more types together, respectively.

Among the base films described above, a polyester resin film is preferable in view of better heat resistance, mechanical strength, dimensional stability, and the object effect of the present invention.

(Property of base film)

10 micrometers or more and 350 micrometers or less are preferable, and, as for the thickness of a base film, 20 micrometers or more and 200 micrometers or less are more preferable. By making the thickness of a base film 10 micrometers or more, appropriate intensity | strength and rigidity are obtained, it becomes possible to carry out film manufacture stably and easily, and the handleability at the time of forming an easily bonding layer also becomes favorable. Moreover, the line speed at the time of manufacture, productivity, controllability, etc. become high by making thickness of a base film into 350 micrometers or less.

As for the width | variety of a base film, the thing of 1-4 m is used. When it exceeds 4m, conveyance becomes difficult. Moreover, 500-10000m are preferable, and, as for the length of a base film, 1000m-7000m are more preferable. By setting it as the range of the said length, it is excellent in the processing titration in application | coating and the handleability of the base film itself.

(Matte processing)

The base film usually has an arithmetic mean surface roughness Ra of 2 nm to 10 nm, more preferably 2 nm to 6 nm.

In addition, a base film can perform a mat process as needed. By performing a mat process, the flaw generation prevention property and handling property in the process after film base material manufacture improve.

Arithmetic mean surface roughness (Ra) of the base film which performed this mat process becomes like this. Preferably it is 2 nm or more, 2 micrometers or less, More preferably, it is 2 nm or more and 1 micrometer or less. As microparticles | fine-particles added in order to carry out a mat process, 0.005-3 micrometers of average particle diameters are preferable. Examples of the fine particles include inorganic fine particles such as silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, kaolin, talc, calcined calcium silicate, calcium silicate hydrate, aluminum silicate, magnesium silicate, calcium phosphate, and crosslinked polymers. Especially, silicon dioxide is used preferably at the point which can suppress the handleability and the haze increase of a base film.

(Optical characteristics)

It is preferable that a total light transmittance of a base film is 90% or more, More preferably, it is 92% or more. Moreover, as a realistic upper limit, it is about 99%. Moreover, 2% or less of haze value is preferable, More preferably, it is 1.5% or less. The total light transmittance and the haze value can be measured according to JIS K7361 and JIS K7136.

In order to achieve transparency excellent in the said haze value and total light transmittance in a base film, it is effective to remove the foreign material in a polymer by high precision filtration, and to reduce the spread and absorption of the light inside a film.

Moreover, as for in-plane retardation Ro of a base film, the range whose 0-200 nm and retardation Rth of a thickness direction are -150-150 nm is preferable. Ro and Rth of optical retardation are the values defined by following formula (I) and (II).

Formula (I) Ro = (nx-ny) × d

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

(Wherein nx is the refractive index in the slow axis direction in the film plane, ny is the refractive index in the direction orthogonal to the slow axis in the base film surface, nz is the refractive index in the thickness direction of the film, and d is the thickness of the film (nm )being)

The retardation can be obtained, for example, using a KOBRA-21ADH (Ojige Sokugiki Co., Ltd.) at a wavelength of 590 nm under an environment of 23 ° C and 55% RH.

When a base film has the said retardation, when it is used for a liquid crystal display device, it suppresses the conversion effect of the polarization direction of a transmission light ray, and is excellent in the optimization and controllability of the polarization of the polarizer to the transmission axis direction.

(Manufacturing method)

Although the manufacturing method of a base film is not specifically limited, For example, additives, such as a flake raw material of a synthetic resin, a plasticizer, can be mixed by a well-known mixing method, and can be prepared after making it a thermoplastic resin composition previously.

This thermoplastic resin composition is obtained by, for example, preblending with a mixer such as an omni mixer and then extruding and kneading the obtained mixture. In this case, the kneading machine used for extrusion kneading is not specifically limited, For example, well-known kneading machines, such as an extruder, such as a single screw extruder and a twin screw extruder, and a pressurized kneader, can be used.

As a method of molding into a base film, a known method such as a solution casting method (solution casting method), a melt extrusion method, a calender method, a compression molding method can be used. Among these, the solution casting method (solution casting method) and the melt extrusion method are preferable at the point of productivity.

When forming a film, a thermoplastic resin composition kneaded in advance may be used, and other additives such as a synthetic resin and a plasticizer are separately dissolved in a solvent to form a uniform mixed solution, followed by solution casting (solution casting method) or melt extrusion. It can also shape | mold by the method.

As a solvent used for the solution casting method (solution casting method), For example, Chlorine solvents, such as chloroform and dichloromethane; Aromatic solvents such as toluene, xylene, benzene and mixed solvents thereof; Alcohol solvents such as methanol, ethanol, isopropanol, n-butanol and 2-butanol; Methyl cellosolve, ethyl cellosolve, butyl cellosolve, dimethylformamide, dimethyl sulfoxide, dioxane, cyclohexanone, tetrahydrofuran, acetone, methyl ethyl ketone (MEK), ethyl acetate, diethyl ether; And the like. Only 1 type may be used for these solvents and they may use 2 or more types together. As an apparatus for performing the solution casting method (solution casting method), a drum type casting machine, a band type casting machine, a spin coater, etc. are mentioned, for example.

Examples of the melt extrusion method include a T-die method and an inflation method. The molding temperature of the film at the time of melt extrusion becomes like this. Preferably it is 150 degreeC or more and 350 degrees C or less, More preferably, it is 200 degreeC or more and 300 degrees C or less.

When film-forming by the T-die method, a T die is provided in the front-end | tip of a well-known single screw extruder or a twin screw extruder, it extrudes to a film shape, a film can be wound up, and a film can be obtained in a roll shape. At this time, it is also possible to set it as the uniaxial stretching process by adjusting the temperature of a winding roll suitably, and extending | stretching in an extrusion direction. Moreover, it is also possible to add processes, such as sequential biaxial stretching and simultaneous biaxial stretching, by adding the process of extending | stretching a film to the direction perpendicular | vertical to an extrusion direction.

The base film may be an unstretched film or a stretched film. When extending | stretching, it may be a uniaxial stretched film or a biaxially stretched film may be sufficient as it. When it is set as a biaxially stretched film, it may be simultaneous biaxially stretched and may be successively biaxially stretched. In the case of biaxial stretching, the mechanical strength is improved and the film performance is improved.

It is preferable to perform extending | stretching temperature in the case of performing an extending process in the vicinity of the glass transition temperature of the thermoplastic resin composition of a film raw material, and it is preferable to carry out at (glass transition temperature -30) degreeC-(glass transition temperature +100) degreeC specifically, More preferably, they are (glass transition temperature-20) degreeC-(glass transition temperature +80) degreeC. If the stretching temperature is lower than (glass transition temperature -30) ° C, since a sufficient stretching ratio cannot be obtained, it is not preferable. If the stretching temperature is higher than (glass transition temperature +100) ° C., a flow (flow) of the resin is generated, which is not preferable because stable stretching cannot be performed. The draw ratio defined by the area ratio is preferably 1.1 times or more and 25 times or less, and more preferably 1.3 times or more and 10 times or less. If the draw ratio is smaller than 1.1 times, it is not preferable because it does not lead to the improvement of the toughness due to the draw. If the draw ratio is larger than 25 times, the effect of increasing the draw ratio is not recognized. The stretching speed (one direction) is preferably in the range of 10 to 20000% / min, more preferably in the range of 100 to 10000% / min. If it is slower than 10% / min, it takes time to obtain a sufficient draw ratio and it is not preferable because the manufacturing cost becomes high. When it is faster than 20000% / min, since breakage of a stretched film, etc. may occur, it is unpreferable. Moreover, heat treatment (annealing) etc. can also be performed after an extending | stretching process in order to stabilize the optical isotropy and a mechanical characteristic of a base film.

Moreover, it can also be used for drying, after apply | coating the easily bonding layer mentioned later as an aqueous coating material for the amount of heat applied at the time of extending | stretching or heat processing (annealing).

When winding up the original fabric of the produced film base material, both ends of the width direction of a film can be embossed (knurling process), and blocking can also be prevented. When a knurling process is performed to a film, since the process location of the both ends of a film becomes unavailable, the part is cut and discarded generally. In addition, in the winding operation of a film, you may mask with a protective film in order to prevent a scratch.

(Other additives)

In order to improve the fluidity | liquidity and flexibility of a composition, you may add a plasticizer to the resin composition which forms a film base material as needed. Although it does not specifically limit as a plasticizer, The compound which has a functional group which can interact by synthetic resin, a hydrogen bond, etc. is preferable so that the haze of a base film may not generate | occur | produce or bleed out or volatilizes from a base film. Examples of such plasticizers include, but are not particularly limited to, phosphate ester plasticizers, phthalate ester plasticizers, trimellitic acid ester plasticizers, pyromellitic acid plasticizers, polyhydric alcohol plasticizers, glycolate plasticizers, citric acid ester plasticizers, and fatty acid ester compounds. Plasticizers, carboxylic acid ester plasticizers, polyester plasticizers, and sugar esterified products (preferably, compounds having a furanose structure and / or a pyranose structure). These plasticizers can also be used in combination. The plasticizer is preferably added in an amount of 0.5 to 30 parts by mass based on 100 parts by mass of the base film. The base film may contain the ultraviolet absorber described in the hard coat layer. Here, among the ultraviolet absorbers, the ultraviolet absorbent having a molecular weight of 400 or more is preferable because it is difficult to volatilize at a high boiling point and hardly to scatter even at high temperature molding. Moreover, in order to improve the thermal decomposition property and thermochromic property at the time of shaping | molding process, various antioxidant can also be added to a base film. In addition, an antistatic agent may be added. A base film can also add a phosphorus flame retardant. As the phosphorus flame retardant, one or two or more selected from triaryl phosphate ester, diaryl phosphate ester, monoaryl phosphate ester, condensed aryl phosphate ester, halogenated alkyl phosphate ester, halogen-containing condensed phosphate ester, halogen-containing phosphite ester and the like And mixtures.

(fault)

It is preferable that the fault of 5 micrometers or more in diameter inside a film plane is 1/10 cm square or less in a base film. If the number of defects is larger than 1/10 cm square, for example, when tension is applied to the film during processing in a subsequent step, the film may break at the defect and the productivity may decrease. Moreover, when the diameter of a fault becomes 5 micrometers or more, it can visually confirm by observing a polarizing plate etc., and a bright point may generate | occur | produce when used as an optical member. In addition, in the measurement based on JIS-K7127-1999, it is preferable that the breaking elongation of at least one direction is 10% or more, More preferably, it is 20% or more.

The upper limit of the breaking elongation is not particularly limited, but in reality, it is about 250%. In order to increase the elongation at break, it is effective to suppress defects in a film caused by foreign matter or foaming.

<Easy adhesion layer>

(Suzy)

Next, an easily bonding layer is demonstrated. The easy adhesion layer which concerns on this invention shows the layer formed in order to improve the interlayer adhesion of a base film and a hard-coat layer, Specifically, it is compared with JISK 5400 (JIS K5600) rather than the case where a base film and a hard-coat layer directly adhere | attach. A layer having a function of improving the adhesion in the adhesion evaluation defined by the crosscut method to be used is represented, and at least one resin selected from the group consisting of polyester resins, acrylic resins and urethane resins is characterized by containing do.

Among these resins, polyester-based resins are preferred from the viewpoint that the objective effects of the present invention are easily exhibited, and it is preferable to use 50-% by mass or more of polyester-based resins with respect to the components constituting the easy bonding layer. Next, each resin is demonstrated. Polyester-based resin is manufactured by esterifying (ester exchange) and dicondensing dicarboxylic acid and diol according to a well-known method. Examples of the dicarboxylic acid include aromatic dicarboxylic acids or esters thereof such as terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid, and aliphatic dicarboxylic acids such as adipic acid, succinic acid, sebacic acid and dodecanedioic acid. And hydroxycarboxylic acids such as hydroxybenzoic acid or esters thereof can be used. As the diol, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, bisphenols and the like can be used. As polyester resin, in addition to the said dicarboxylic acid and diol, the component which has a hydrophilic group can also be copolymerized and can provide hydrophilicity. Examples of the component having such a hydrophilic group include dicarboxylic acid components such as 5-sodium sulfoisophthalic acid and diol components such as ethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol. It is preferable to use together two or more resin from which a glass transition point differs from a viewpoint of the objective effect of this invention and prevention of precipitation of an oligomer by heating among polyester resin. It is preferable to use together the polyester resin (X) whose glass transition point (Tg) is 105 degreeC or more and less than 135 degreeC, and the polyester resin (Y) whose glass transition point (Tg) is 65 degreeC or more and less than 95 degreeC. . As polyester resin (X) whose glass transition point (Tg) is 105 degreeC or more and less than 135 degreeC, what used 2, 6- naphthalenedicarboxylic acid and / or sodium sulfonate isophthalic acid as an acid component is preferable. More preferably, sodium sulfonate isophthalic acid is used as the acid component. Moreover, as a content molar ratio of sodium sulfonate isophthalic acid, when the whole acid component of polyester resin (X) is set to 50, 15/50 or less is preferable, More preferably, it is 10/50 or less.

As polyester resin (Y) whose glass transition point (Tg) is 65 degreeC or more and less than 95 degreeC, it is preferable to use terephthalic acid and / or trimellitic acid for an acid component, More preferably, it is preferable to use trimellitic acid. As a content molar ratio of trimellitic acid, when the whole acid component of a polyester resin (Y) is set to 50, 20/50 or less are preferable, More preferably, it is 15/50 or less. Ethylene glycol is preferable as a diol component of polyester resin (X) and polyester resin (Y).

Acrylic resin can be synthesized by polymerizing a reactive polymer having a skeleton derived from acrylic acid or methacrylic acid. Examples of such reactive polymers include those having carboxyl groups such as acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, and carboxyphenyl acrylate, 2-hydroxyethyl (meth) acrylate, and 3-hydroxybutyl (meth) acrylic. Having hydroxyl groups such as acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth ) Having amide groups such as acrylamide, N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, having glycidyl groups such as glycidyl (meth) acrylate, 7- P-chlorostyrene, chloromethylstyrene, divinylbenzene, 4-vinylpyridine, in addition to having amino groups such as amino-3, 7-dimethyloctyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; , Vinyloxazoline, maleic anhydride, etc. .

Examples of the copolymer components other than those constituting the acrylic resin include acrylic esters, methacrylic esters, propylene, vinyl chloride, cellulose, ethylene, ethyleneimine, vinyl alcohol, peptide, vinylpyridine, and diene. Although a type | system | group, a fluorine series, an acrylonitrile series, etc. are mentioned, It is preferable to contain an acrylic acid ester type and a methacrylic acid ester type from a viewpoint of versatility, coatability, etc. The component which comprises these acrylic resin can be used individually or in combination of multiple types.

The urethane-based resin can be synthesized from a low molecular weight chain extender containing at least two hydrogen atoms reacting with a polyhydroxyl compound, diisocyanate and diisocyanate by a known method. For example, after synthesize | combining a comparatively high molecular weight polyurethane in a solvent, it adds water little by little and makes it phase-emulsify, and removes a solvent by pressure reduction, The urethane preliminary which introduce | transduced polyethyleneglycol, a carboxyl group, etc. as a hydrophilic group in a polymer. After dissolving or dispersing a polymer in water, there is a method of adding a chain extender and reacting.

As an example of the polyhydroxyl compound used for manufacture of a urethane-type resin, Carboxylic acids, such as a phthalic acid, adipic acid, dimerized linolenic acid, maleic acid; Glycols such as ethylene glycol, propylene glycol, butylene glycol and diethylene glycol; Polyester polyols obtained by a dehydration condensation reaction from trimethylolpropane, hexanetriol, glycerin, trimethylolethane, pentaerythritol, and the like; Inorganic acids such as polyoxypropylene glycol, polyoxybutylene glycol, polytetramethylene glycol, polyoxypropylene triol, polyoxyethylene polyoxypropylene triol, sorbitol, pentaerythritol, sucrose, starch and phosphoric acid as initiators Polyether polyols such as polyoxypropylene polyol and polyoxypropylene polyoxyethylene polyol; And acrylic polyols, castor oil derivatives, tall oil derivatives, and other hydroxyl compound compounds. These polyhydroxyl compounds can be used individually or in combination of multiple types.

Examples of the diisocyanate used in the production of the urethane resin include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylenedi isocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, Tetramethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4'-dicyclohexyl methane di Isocyanate, 3,3'-dimethyl-4,4'-biphenylenediisocyanate, 3,3'-dimethoxy-4,4'-biphenylenediisocyanate, 3,3'-dichloro-4,4'-ratio Phenylene diisocyanate, 1, 5- naphthalene diisocyanate, 1, 5- tetrahydro naphthalene diisocyanate, etc. are mentioned. These diisocyanate can be used combining single or multiple types. Examples of chain extenders used in the production of urethane resins include ethylene glycol, 1,4-butanediol, trimethylolpropane, triisopropanolamine, N, N-bis (2-hydroxypropyl) aniline, hydroquinone-bis (β-hydroxy Polyols such as ethyl) ether, resorcinol-bis (β-hydroxyethyl) ether, ethylenediamine, propylenediamine, hexamethylenediamine, phenylenediamine, tolylenediamine, diphenyldiamine, diaminodiphenylmethane, And polyamines such as diaminodiphenylmethane, diaminodicyclohexylmethane, piperazine, isophoronediamine, diethylenetriamine and dipropylenetriamine, hydrazines and water. These chain extenders can be used individually or in combination of multiple types.

The synthesis reaction in the production of the urethane-based resin can be carried out in the presence of a catalyst such as an organic tin compound, organic bismuth, or an amine, and particularly preferably in the presence of an organic tin compound. Specific examples of the organotin compound include stannous carboxylates such as stannous acetate, stannous octanoate, stannous laurate and stannous oleate; Dialkyl tin salts of carboxylic acids such as dibutyltin acetate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin di-2-ethylhexate, dilauryl tin diacetate, and dioctyl tin diacetate ; Trialkyl tin hydroxides such as trimethyl tin hydroxide, tributyl tin hydroxide, and trioctyl hydroxide; Dialkyl tin oxides such as dibutyltin oxide, dioctyl tin oxide and dilauryl tin oxide; Dialkyl tin chlorides such as dibutyltin dichloride and dioctyl dichloride; and the like, and these may be used alone, or two or more thereof may be used in combination.

(Manufacturing method)

An easily bonding layer can be formed by apply | coating resin selected from polyester resin, acrylic resin, and urethane resin to a base film as aqueous emulsion or aqueous solution (henceforth "aqueous emulsion etc."), and drying. Moreover, after apply | coating an aqueous emulsion or aqueous solution to a base film, it can also form by extending | stretching and drying with a base film.

Solid content, such as aqueous emulsion, is 10 mass% or more and 50 mass% or less normally. Water is used as a main solvent such as an aqueous emulsion, and a small amount of an organic solvent miscible with water may be used. Examples of such organic solvents include lower alcohols, polyhydric alcohols, alkyl ethers and alkyl esters thereof, and the like. Aqueous emulsion etc. are apply | coated to a base film using well-known dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, extrusion coating method (die coating method), etc. can do. Subsequently, an easily bonding layer can be formed by drying the apply | coated aqueous emulsion etc.

(Other additives)

It is preferable to add a crosslinking agent as needed, for an aqueous emulsion for forming an easily bonding layer. Examples of the crosslinking agent include melamine type, oxazoline type, aldehyde, N-methylol compound, dioxane derivative, active vinyl compound, active halogen compound, isoxazole, dialdehyde starch, isocyanate compound, and silane coupling agent. . These crosslinking agents may be used independently and may use two or more types together. 0.1 mass% or more and 20 mass% or less are preferable with respect to hydrophilic resin whole quantity, and, as for the addition amount of a crosslinking agent, 0.5 mass% or more and 15 mass% or less are more preferable. Aqueous emulsions for forming an easy adhesion layer include, if necessary, other resin components such as amino group-containing resins, surfactants, sliding agents, dyes, ultraviolet absorbers, and mat agents (silica, colloidal silica, etc., with an average particle diameter of 0.005 to 3 µm). Preservatives, thickeners, film forming aids, antistatic agents, antioxidants and the like.

(Optical characteristics)

90% or more of the total light transmittance of the base film which provided the easily bonding layer is preferable, More preferably, it is 91% or more. 2% or less is preferable and, as for the haze of the base film in which the easily bonding layer was formed, More preferably, it is 1.5% or less. When the total light transmittance is less than 90%, when used in a display device, the luminance may be reduced or the original color of the article may appear dark. In addition, when the haze greatly exceeds 2%, it is not preferable when the article is used for a display device because the article appears whitish and may damage the original appearance of the article such as an image of a flat panel display or a home appliance.

<Functional layer>

In the hard coat film of this invention, functional layers, such as an antireflection layer and a transparent conductive thin layer, can be formed.

<Antireflection layer>

The hard coat film which concerns on this invention can be used as an anti-reflective film which has an anti-reflective layer apply | coated and provided in the upper layer of a hard coat layer.

The antireflection layer is preferably 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 anti-reflection layer is comprised combining the low refractive index layer which has a lower refractive index than the protective film which is a support body, or the high refractive index layer and its low refractive index layer which is higher than a protective film which is a support body. Particularly preferably, it is an antireflection layer composed of three or more refractive index layers, and the three layers having different refractive indices from the support side are made of a medium refractive index layer (a layer having a higher refractive index than the support and having a lower refractive index than the high refractive index layer) / high refractive index layer / low What is laminated | stacked in order of the refractive index layer is used preferably. Alternatively, an antireflection layer having a four or more layer structure in which two or more high refractive index layers and two or more low refractive index layers are alternately stacked is also preferably used. Although the following structures can be considered as a laminated constitution of an antireflection film, It is not limited to this.

Easy adhesion layer / base film / easy adhesion layer / hard coat layer / low refractive index layer

Easy adhesion layer / base film / easy adhesion layer / hard coat layer / high refractive index layer / low refractive index layer

<Low Refractive Index Layer>

It is preferable that the low refractive index layer contains silica fine particles, and the refractive index thereof is preferably in the range of 1.30 to 1.45 by 23 ° C and wavelength 550 nm measurement.

It is preferable that the film thickness of a low refractive index layer is 5 nm-0.5 micrometer, It is more preferable that it is 10 nm-0.3 micrometer, It is most preferable that it is 30 nm-0.2 micrometer.

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 outer layers and the inside of which are porous or hollow are hollow silica-based particles.

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

(OSi-1): Si (OR) ₄

In the organosilicon compound represented by the above formula, 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 hardening | curing agent, surfactant, etc. can also be added as needed. Moreover, you may contain the compound which has the thermosetting and / or photocurable which consists mainly of the fluorine-containing compound which contains a fluorine atom in the range of 35-80 mass%, and contains a crosslinkable or a polymerizable functional group. Specifically, it is a fluorine-containing polymer or a fluorine-containing sol-gel compound. As the fluorine-containing polymer, for example, in addition to the hydrolyzate or dehydrating condensate of a perfluoroalkyl group-containing silane compound [for example, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane], The fluorine-containing copolymer which makes a fluorine-containing monomeric unit and a crosslinking reactive unit a structural unit is mentioned. In addition, a solvent, a silane coupling agent, a hardening | curing agent, surfactant, etc. can also be added as needed.

<High refractive index layer>

As for the refractive index of a high refractive index layer, it is preferable to adjust a refractive index in the range of 1.4-2.2 by 23 degreeC and wavelength 550nm measurement. Further, the thickness of the high refractive index layer is preferably 5 nm to 1 m, more preferably 10 nm to 0.2 m, and most preferably 30 nm to 0.1 m. The means for adjusting the refractive index can be achieved by adding metal oxide fine particles or the like. It is preferable that it is 1.80-2.60, and, as for the refractive index of the metal oxide fine particle which also uses metal oxidation, it is more preferable that it is 1.85-2.50.

The kind of metal oxide fine particles is not particularly limited, and is selected from Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S. Metal oxides having at least one element can be used, and these metal oxide fine particles may be doped with a small amount of atoms such as Al, In, Sn, Sb, Nb, a halogen element, and Ta. It may also be a mixture thereof. In the present invention, at least one metal oxide fine particle selected from zirconium oxide, antimony oxide, tin oxide, zinc oxide, indium tin oxide (ITO), antimony-doped tin oxide (ATO), and zinc antimonate is used as a main component. It is especially preferable to use. It is particularly preferable to contain zinc antimonate particles.

The average particle diameter of the primary particles of these metal oxide fine particles is in the range of 10 nm to 200 nm, and particularly preferably 10 to 150 nm. The average particle diameter of metal oxide fine particles can be measured from the electron micrograph with a scanning electron microscope (SEM). Measurement can also be made by a particle size distribution meter or the like using a dynamic light scattering method or a static light scattering method. If the particle size is too small, it becomes easy to aggregate and the dispersibility is deteriorated. If the particle size is too large, the haze rises remarkably, which is not preferable. The shape of the metal oxide fine particles is preferably rice grains, spherical, cubic, fusiform, acicular or indefinite.

Metal oxide fine particles can also be surface-treated with an organic compound. By surface-modifying the surface of the metal oxide fine particles with an organic compound, dispersion stability in an organic solvent can be improved, control of dispersion particle diameter can be facilitated, and aggregation and sedimentation with time can also be suppressed. Therefore, the surface modification amount in a preferable organic compound is 0.1 mass%-5 mass% with respect to a metal oxide particle, More preferably, they are 0.5 mass%-3 mass%. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents and titanate coupling agents. Especially, a silane coupling agent is preferable. You may combine 2 or more types of surface treatment. Further, the high refractive index layer may contain a π conjugated conductive polymer. The (pi) conjugated conductive polymer can be used as long as the main chain is an organic polymer composed of a (pi) conjugated system. For example, polythiophene, polypyrroles, polyaniline, polyphenylene, polyacetylene, polyphenylene vinylene, polyacene, polythiophene vinylene, and these copolymers are mentioned. In view of ease of polymerization and stability, polythiophenes, polyanilines, and polyacetylenes are preferable.

Although the π-conjugated conductive polymer has sufficient conductivity or solubility in binder resin even in an unsubstituted state, functional groups such as alkyl group, carboxyl group, sulfo group, alkoxy group, hydroxy group and cyano group can be introduced to improve conductivity and solubility. It may be.

It may also contain an ionic compound. Ionic compounds include imidazole ryumgye, pyridinium-based, alicyclic amine-based, aliphatic amine, aliphatic phosphonium nyumgye positive and BF ₄ ^-, PF ₆ ^-, etc. of the inorganic ^{_{ionic, CF 3 SO 2 -, (}} CF 3 ^{_{SO 2) 2 N -, CF}} 3 CO 2 - can be given as the compound comprises a fluorine-containing anion, such as. As for the ratio of the said polymer and a binder, 10-400 mass parts of binders are preferable with respect to 100 mass parts of polymers, Especially preferably, it is 100-200 mass parts of binders with respect to 100 mass parts of polymers.

<Transparent conductive thin layer>

It is also possible to form a transparent conductive thin layer on the hard coat layer of the hard coat film.

As the transparent conductive thin layer formed, a generally known transparent conductive material can be used. For example, transparent conductive materials 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 coat film by vacuum deposition, sputtering, ion plating, solution coating, or the like. Moreover, it is also possible to form a transparent conductive thin layer using the organic electroconductive material which is said (pi) conjugated system conductive polymer. In particular, a transparent conductive material containing any one of indium oxide, tin oxide, and indium tin oxide, which is excellent in transparency and conductivity and is obtained at a relatively low cost, can be preferably used. Although the thickness of the transparent conductive thin film is different depending on the material to be applied, it cannot be said uniformly. However, the thickness of the transparent conductive thin film is 1000 Ω or less, preferably 500 Ω or less in terms of surface resistivity. As mentioned above, the range of 80 nm or less, Preferably 70 nm or less is suitable. In such a thin film, interference fringes of visible light due to thickness unevenness of the transparent conductive thin layer are hardly generated.

<Image Display Device>

The hard coat film of this invention is preferable at the point which the performance excellent in visibility (clearness) is exhibited by using for an image display apparatus. Examples of the image display apparatus include a reflective, transmissive, and transflective liquid crystal display device, or liquid crystal display devices of various driving methods such as TN type, STN type, OCB type, VA type, IPS type, ECB type, organic EL display device, plasma display, and the like. Can be mentioned. Among these image display apparatuses, when the hard coat film of this invention is used for the touch panel member of the liquid crystal display device containing a touch panel, it is preferable at the point which is excellent in high visibility and durability with respect to pen input (scratches by a sliding movement, etc.). Do.

Next, an example in the case of using for a touch panel is shown in FIG. A transparent conductive thin film 12 is formed on the transparent hard coat film 11 of the present invention, and the glass substrate 13 on which the transparent conductive thin film 15 is formed is opposed to each other at regular intervals such that the transparent conductive thin films face each other. In this way, the resistive touch panel 10 can be configured. The electrode which is not shown in figure is arrange | positioned at the edge part of the hard-coat film 11 and the glass substrate 13. When the user presses the hard coat film 11 having the transparent conductive thin film 12 attached with a finger or a pen, the transparent conductive thin film 12 contacts the transparent conductive thin film 15 on the glass substrate 13. The pressed position is detected by electrically detecting this contact via the electrode at the end. On the transparent conductive thin film 15 of the glass substrate 13, the dot-shaped spacer 14 is arrange | positioned as needed. Moreover, as shown in FIG. 2, the touch panel 10 of FIG. 2 is mounted on the color liquid crystal display panel 20, and the liquid crystal display device with a touch panel can be comprised.

<Examples>

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

Example 1

<Preparation of the base film 1 with an easily bonding layer>

The polyethylene terephthalate containing no filler was melt-extruded at 280 degreeC, and cast on the cast drum of 20 degreeC applied electrostatically, and the non-stretched sheet was produced. This sheet was preheated at 100 ° C. and stretched three times in the longitudinal direction by stretching the roll at this temperature. Then, the easily-adhesive layer water-based coating material 1 adjusted to 4.5% of concentration was apply | coated to both of said sheet | seats. After application | coating, it extended | stretched 3.5 times in the width direction at 120 degreeC, and heat-processed at 220 degreeC. After the heat treatment, a knurling process having a width of 10 mm and an average height of 5 μm was applied to both ends, and wound up. Base film 1 was obtained.

(Easily Bonded Water-Based Coating 1)

The following materials were stirred and mixed and adjusted to a solid content concentration of 4.5% with pure water to obtain an aqueous emulsion of a polyester resin.

19 mass parts of polyester resins (X) of Tg of 120 degreeC and the molar ratio of sodium sulfonate isophthalic acid 7/50

Polyester resin (Y) whose Tg is 80 degreeC and the molar ratio 12/50 of trimellitic acid

                                                  45 parts by mass

27 parts by mass of melamine resin

7 mass parts of oxazoline group containing polymer (the crosslinking agent, the Nippon Shokubai company make)

2 parts by mass of colloidal silica having a particle diameter of 150 nm

<Production of Base Film 2 with Adhesive Easy Layer>

In preparation of the base film 1, the coating amount of the easily bonding layer water-based coating material 2 was adjusted so that the film thickness of the easily bonding layer was 150 nm, and the easily bonding layer water-based coating material 1 was changed to the easily bonding layer water-based coating material 2 in the same manner. And the base film 2 with an easily bonding layer was obtained.

(Easily Bonded Water-Based Paint 2)

The following materials were stirred and mixed and adjusted to a solid content concentration of 4.5% with pure water to obtain an aqueous emulsion of a polyester resin.

15 mass parts of polyester resins (X) whose Tg is 110 degreeC and the ratio 12/50 of sodium sulfonate isophthalic acid

Polyester resin (Y) whose Tg is 70 degreeC and the molar ratio of trimellitic acid 16/50.

                                                 62 parts by mass

18 parts by mass of melamine resin

3 mass parts of oxazoline group containing polymer (crosslinking agent, the Nippon Shokubai company make)

2 parts by mass of colloidal silica having a particle diameter of 150 nm

<Preparation of base film 3 with easy bonding layer>

In preparation of the base film 1, the coating amount of the easily bonding layer water-based coating material 3 was adjusted so that the film thickness of the easily bonding layer was 150 nm, and the easily bonding layer water-based coating material 1 was changed to the easily bonding layer water-based coating material 3 in the same manner. To obtain a base film 3 with an easy adhesion layer.

(Easily adhesive layer water based paint 3)

The following materials were stirred and mixed, and the pure water concentration was adjusted to 4.5% with pure water to obtain an aqueous emulsion of acrylic resin.

30 parts by mass of a copolymer of 70% by mass of 2-hydroxyethyl acrylate and 30% by mass of methyl acrylate

3 mass parts of diacrylates of hydroxy pivalic acid ester neopentyl glycol

Urethane acrylate oligomer ("KAYARAD" UX-4101 "made by Nippon Kayaku Co., Ltd.)

                                                    3 parts by mass

0.3 parts by mass of benzoyl peroxide

Isocyanate compound ("Sumijule N-75" made by Sumika Bayer urethane Co., Ltd.)

                                                    1.5 parts by mass

2 parts by mass of colloidal silica having a particle diameter of 150 nm

<Production of Base Film 4 with Adhesive Easy Layer>

In preparation of the base film 1, the coating amount of the easily bonding layer water-based coating material 4 was adjusted so that the film thickness of the easily bonding layer was 150 nm, and the easily bonding layer water-based coating material 1 was changed to the easily bonding layer water-based coating material 4 in the same manner. To obtain a base film 4 with an easy adhesion layer.

(Easy adhesion layer water-based paint 4)

The following materials were stirred and mixed, adjusted to a solid content concentration of 4.5% with pure water, and then reacted at about 70 ° C for 3 hours to obtain an aqueous emulsion of urethane resin.

25 parts by mass of aqueous urethane (`` Aron Neotan UE-1300 '' manufactured by Toagosei Chemical Co., Ltd.)

5 parts by mass of hydroxyethyl methacrylate

0.2 parts by mass of potassium persulfate

2 parts by mass of colloidal silica having a particle diameter of 150 nm

<Production of Base Film 5 with Adhesive Easy Layer>

In preparation of the base film 1, the coating amount of the easily bonding layer water-based coating material 5 was adjusted so that the film thickness of the easily bonding layer was set to 150 nm, and the easily bonding layer water-based coating material 1 was changed to the easily bonding layer water-based coating material 5 similarly. The obtained base film 5 with an easily bonding layer was obtained.

(Easy adhesion layer water-based paint 5)

The following materials were stirred and mixed and adjusted to a solid content concentration of 4.5% with pure water to obtain an aqueous emulsion of an epoxy resin.

Copolymer of 70 mass% glycidyl acrylate and 30 mass% of vinyl propionate

                                                      30 parts by mass

3 mass parts of diacrylates of hydroxy pivalic acid ester neopentyl glycol

Urethane acrylate oligomer ("KAYARAD" UX-4101 "made by Nippon Kayaku Co., Ltd.)

                                                      3 parts by mass

0.3 parts by mass of benzoyl peroxide

Isocyanate compound ("Sumijule N-75" made by Sumika Bayer urethane Co., Ltd.)

                                                      1.5 parts by mass

2 parts by mass of colloidal silica having a particle diameter of 150 nm

<Production of Base Film 6 with Adhesive Easy Layer>

A norbornene-based polymer was synthesized, and a cycloolefin film having a norbornene ring was produced by the following method.

(Synthesis of norbornene-based polymer 1)

NBOAc: 5-norbornene-2-ylacetate (bicyclo [2.2.1] hepto-5-en-2-ylacetate)

Norbornene (NB): Norbornylene or bicyclo [2.2.1] hepto-5-ene was purchased from Aldrich.

150 parts by mass of toluene and 152 parts by mass of NBOAc were placed in a reaction vessel. Dimethylanilinium tetrakispenta dissolved in 0.018 parts by mass of allyl palladium chloride dimer (manufactured by Tokyo Kasei Co., Ltd.), 0.028 parts by mass of tricyclohexylphosphine (manufactured by Streme Corporation), and 5 parts by mass of methylene chloride. 0.12 mass part of fluorophenyl borate (made by Strem Corporation), and 0.33 mass part of allyl tributyl tin (made by Aldrich) melt | dissolved in 10 mass parts of toluene were thrown into the reaction container. When heating started and reached 90 degreeC, 130 mass parts of NB melt | dissolved in 20 mass parts of toluene was dripped over 1 hour. This mixture was reacted at 90-100 degreeC for 6 hours. In addition, toluene was appropriately added with the raise of the viscosity of the reaction solution in the meantime. 10 mass parts of 1-hexene (made by Wako Pure Chemical Industries, Ltd.) was dripped, and it was made to react further for 1 hour. The obtained reaction solution was thrown in excess methanol, and the polymer was precipitated. This precipitate was collected, washed with methanol, and vacuum dried at 110 ° C for 6 hours. The obtained polymer (norbornene-based polymer 1) was dissolved in tetrahydrofuran, and the molecular weight was measured by gel permeation chromatography. As a result of measuring mass average molecular weight (Mw), number average molecular weight (Mn) was 100200, mass average molecular weight (Mw) was 256300, and molecular weight distribution (Mw / Mn) was 2.56.

(Production of norbornene dope liquid)

The following materials were sequentially placed in a sealed container, the temperature in the container was raised from 20 ° C to 80 ° C, and then stirred for 3 hours while maintaining the temperature at 80 ° C to completely dissolve the norbornene-based polymer 1. Silicon oxide microparticles | fine-particles were disperse | distributed and added in the solvent and the solution of a small amount of cellulose esters added beforehand. This dope was filtered using filter paper (manufactured by Azumi Filtration Co., Ltd., Azumi filter paper No. 244) to obtain a norbornene dope liquid.

(Norbornene dope)

Norbornene-based polymer 1 100 parts by mass

Silicon oxide fine particles (Aerosil R972V, product made by Nippon Aerosol Co., Ltd.)

                                                 0.1 parts by mass

400 parts by mass of methylene chloride

40 parts by mass of ethanol

Butanol 5 parts by mass

The above-mentioned materials were mixed to prepare a dope liquid, and the obtained dope liquid was cast from a casting die on a support having a temperature of 35 ° C. made of a stainless steel endless belt to form a web. Subsequently, the web was dried on the support, and the web was peeled from the support by a peeling roll in a step where the amount of residual solvent of the web became 100% by mass. Subsequently, the easily-adhesive layer water-based coating material 1 was applied to the peeled web so as to adjust the coating amount of the water-based paint so that the film thickness of the easily-adhesive layer was 150 nm and applied to both surfaces of the web. After application | coating, it conveyed, drying at 120 degreeC, and after holding both ends of a web with a tenter, it extended | stretched so that it might become 1.4 times as it was before extending | stretching to 150 degreeC in the width direction (TD). After extending | stretching by a tenter, it further dried at 160 degreeC. After drying, a knurling process having a width of 10 mm and an average height of 5 μm was applied to both ends and wound, and the base film 6 with an easy adhesion layer, which is a cycloolefin film having a norbornene ring having a width of 1.5 m, a film thickness of 80 μm, and a length of 6000 m, was obtained. Got it.

<Production of Base Film 7 with Adhesive Easy Layer>

In preparation of the base film 6, the base film 7 with an easily bonding layer in which the base film contains an acrylic film was produced similarly except having changed norbornene dope liquid into the following acrylic dope liquid.

(Acrylic dope liquid)

The following materials were sequentially placed in a sealed container, the temperature in the container was raised from 20 ° C to 80 ° C, and then stirred for 3 hours while maintaining the temperature at 80 ° C to completely dissolve the methyl methacrylate / methyl acrylate copolymer. . Silicon oxide microparticles | fine-particles were disperse | distributed and added in the solvent and the solution of a small amount of cellulose esters added beforehand. This dope was filtered using filter paper (manufactured by Azumi Filtration Co., Ltd., Azumi filter paper No. 244) to obtain dope solution 2.

100 parts by mass of methyl methacrylate / methyl acrylate copolymer (molar ratio 9: 1)

1 part by mass of [2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole]

400 parts by mass of methylene chloride

100 parts by mass of methanol

Silicon oxide fine particles (Aerosil R972V, product made by Nippon Aerosol Co., Ltd.)

                                                    0.1 parts by mass

<Preparation of base film 8 with easy bonding layer>

A propylene / ethylene random copolymer (Sumitomo Noblen W151, manufactured by Sumitomo Chemical Co., Ltd.) containing about 5% of an ethylene unit is melt-extruded at 240 ° C, cast on an electrostatically applied cast drum at 20 ° C, and not stretched. It was set as a sheet. This was preheated at 120 degreeC and it extended | stretched twice in the longitudinal direction by roll extending | stretching at this temperature. Then, the easily bonding layer water-based coating material 1 was apply | coated to both surfaces of said film. After application | coating, it extended | stretched 3.7 times in the width direction at 130 degreeC, and heat-processed at 180 degreeC. After the heat treatment, a kneading process having a width of 10 mm and an average height of 5 μm was applied to both ends, and wound. 8 was obtained.

<Production of base film 9>

In the preparation of the base film 1 with an easy adhesion layer, a polyethylene terephthalate film was produced in the same manner except that the easy adhesion layer water-based coating material 1 was not formed.

<Production of hard coat film 1>

What filtered the following hard coat layer composition 1 on the produced base film 1 with the polypropylene filter of 0.4 micrometers of pore diameters was apply | coated using an extrusion coater, and it is the constant drying section temperature of 80 degreeC, and the reduction ratio drying section temperature of 80 degreeC. After drying, the irradiated area was 100 mW / cm ² and the irradiation amount was set to 0.3 J / cm ² using an ultraviolet lamp while purging nitrogen so that the oxygen concentration was 1.0 vol% or less, and the coating layer was cured, and the dry film thickness The hard-coat layer 1 of 8 micrometers was formed and wound up, and the roll-shaped hard coat film 1 was produced.

(Hard Coat Layer Composition 1)

The following materials were stirred and mixed to obtain a hard coat layer coating composition 1.

65 parts by mass of pentaerythritol tree / tetraacrylate

(NK ester A-TMM-3L, Shinnakamura Gakuku Kogyo Co., Ltd. product)

35 parts by mass of tris (2-acryloyloxyethyl) isocyanurate

(NK ester A-9300, Shinnakamura Gakuku Kogyo Co., Ltd. product)

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

2 parts by mass of polyether modified silicone (KF-614A, Shin-Etsu Chemical Co., Ltd.)

10 parts by mass of propylene glycol monomethyl ether

20 parts by mass of methyl acetate

70 parts by mass of methyl ethyl ketone

<Production of hard coat film 2>

The hard coat film 2 was produced similarly except having changed into the following hard-coat layer composition 2 on the produced base film 1.

(Hard Coat Layer Composition 2)

The following materials were stirred and mixed to obtain a hard coat layer coating composition 2.

100 parts by mass of pentaerythritol tree / tetraacrylate

(NK ester A-TMM-3L, Shinnakamura Gakuku Kogyo Co., Ltd. product)

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

2 parts by mass of polyether modified silicone (KF-614A, Shin-Etsu Chemical Co., Ltd.)

10 parts by mass of propylene glycol monomethyl ether

20 parts by mass of methyl acetate

70 parts by mass of methyl ethyl ketone

<Production of hard coat film 3>

The hard coat film 3 was produced similarly except having changed into the following hard-coat layer coating composition 3 on the produced base film 1.

(Hard Coat Layer Composition 3)

The following materials were stirred and mixed to obtain a hard coat layer coating composition 3.

65 parts by mass of pentaerythritol tree / tetraacrylate

(NK ester A-TMM-3L, Shinnakamura Gakuku Kogyo Co., Ltd. product)

35 parts by mass of tris (2-acryloyloxyethyl) isocyanurate

(Aronix M-315, manufactured by Toagosei Co., Ltd.)

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

2 parts by mass of polyether modified silicone (KF-614A, Shin-Etsu Chemical Co., Ltd.)

10 parts by mass of propylene glycol monomethyl ether

20 parts by mass of methyl acetate

70 parts by mass of methyl ethyl ketone

<Production of hard coat film 4>

The hard coat film 4 was produced similarly except having changed into the following hard-coat layer coating composition 4 on the produced base film 1.

(Hard Coat Layer Composition 4)

The following materials were stirred and mixed to obtain a hard coat layer coating composition 4.

65 parts by mass of pentaerythritol tree / tetraacrylate

(NK ester A-TMM-3L, Shinnakamura Gakuku Kogyo Co., Ltd. product)

35 parts by mass of isocyanuric acid ethoxy-modified diacrylate

(Aronix M-215, manufactured by Toagosei Co., Ltd.)

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

2 parts by mass of polyether modified silicone (KF-614A, Shin-Etsu Chemical Co., Ltd.)

10 parts by mass of propylene glycol monomethyl ether

20 parts by mass of methyl acetate

70 parts by mass of methyl ethyl ketone

<Production of Hard Coat Films 5 to 14>

In the production of the hard coat film 1, the hard coat films 5 to 14 were produced in the same manner except that the hard coat layer coating composition and the base film with an easy adhesion layer were changed as described in Table 1.

"evaluation"

The following content was evaluated about the hard coat films 1-14 produced above. The obtained results are shown in Table 1.

a. My blocking ability

The produced roll-shaped hard coat films 1 to 14 were wrapped in an aluminum moisture proof sheet and stored for 10 days in a constant temperature bath at 80 ° C. and a relative humidity of 80%, assuming long-term transportation. After storage for 10 days, the aluminum moisture proof sheet was peeled off and the blocking property was evaluated based on the following criteria by visual observation from the surface. The results are shown in Table 1.

◎: 0% cling area, no blocking

○: The sticking area was less than 2% and some blocking occurred.

(Triangle | delta): Although the sticking area | region is 2% or more and less than 10% and blocking generate | occur | produced, the level which is satisfactory practically.

×: cling area is 10% or more and less than 40%, blocking occurs

××: cling area is 40% or more, which is very problematic in practical use

b. Flexibility

(Durability test)

The produced hard coat films 1 to 14 are cut out into 10 cm x 10 cm sizes, and are assumed to be used outdoors, and cycle cycles (-40 ° C. for 30 minutes, and then 85 ° C. for 30 minutes are alternately 500 cycles). ), And stored for 500 hours in a thermostatic chamber of 80% relative humidity 90%.

After hardening each hard coat film 1-14 after a durability test for 12 hours in the atmosphere of 23 degreeC 55% RH, it is flexible by the cylindrical mandrel method using a type 1 test apparatus by the method according to JISK5600-5-1. Was evaluated. The lower the value of the diameter of the mandrel, the better the flexibility.

In addition, triic (2-acryloyloxyethyl) isocyanurate which is an active energy ray hardening type isocyanurate derivative of the hard coat layer resin of Table 1 is called TAIC, and isocyanurate ethoxy modified diacrylate is called DAIC. Described. In addition, an easily bonding layer and a base film abbreviation are as follows.

(Easy Adhesive Layer)

PES: Polyester Resin

ACP: Acrylic Resin

PUP: Urethane Resin

EPP: Epoxy Resin

(Substrate film)

PET: polyethylene terephthalate film

COF: cycloolefin film

ACF: acrylic film

PP: propylene film

As can be seen from the results in Table 1, polyester resins, acrylic resins, and urethane resins are formed on both surfaces of at least one base film selected from an acrylic resin film, a polypropylene resin film, a cycloolefin resin film, and a polyester resin film. The hard coat film of the present invention comprising a constitution in which the easy-adhesive layer and the hard coat layer containing at least one resin selected from the group contains an active energy ray-curable isocyanurate derivative has blocking resistance and flexibility. It can be seen that it is excellent.

Among the hard coat films of the present invention, the base film comprises a polyester resin film, and the easy-to-adhesive layer has a glass transition point (Tg) of 105 ° C. or higher and less than 135 ° C., and the sodium sulfonate isophthalic acid is an acid component. The hard coat film comprised from the polyester resin (X) and glass transition point (Tg) containing from less than 65 degreeC and less than 95 degreeC, and is comprised from the polyester resin (Y) which contains trimellitic acid in an acid component is especially Since it has the outstanding blocking resistance and flexibility, it turns out that it is a especially preferable structure.

Example 2

In the preparation of the hard coat film 1 of Example 1, tris (2-acryloyloxyethyl) isocyanurate (A) and isosi which are active energy ray-curable isocyanurate derivatives of the hard coat layer coating composition 1 It carries out except having changed the content mass ratio of active energy ray hardening type resin (pentaerythritol tri / tetraacrylate) (B) other than an anurate derivative into the hard coat layer coating compositions 5-8 which changed as shown in Table 2. In the same manner as in Example 1, hard coat films 15 to 18 were produced.

Subsequently, about the obtained hard coat films 15-18 and the hard coat film 1 produced in Example 1, the shelf life of the blocking resistance was changed to 15 days, and the shelf life of the flexible durability test was changed to 750 hours. Evaluation was performed similarly to 1. The obtained results are shown in Table 2.

As can be seen from the results in Table 2, under the severer conditions of the durability test, tris (2-acryloyloxyethyl) isocyanurate (A) and isocyanurate which are active energy ray-curable isocyanurate derivatives It is more preferable to set the content mass ratio of the active energy ray-curable resin (pentaerythritol tri / tetraacrylate) other than the derivative (B) to (A) :( B) = 10: 90 to 50:50 to achieve the desired effect of the present invention. It is preferable because it exhibits well.

Example 3

<Production of hard coat film 19>

The following hard coat layer coating composition 9 was filtered on a polypropylene filter having a pore diameter of 0.4 μm on the base film 1 with an easy adhesion layer to prepare a hard coat layer coating liquid, and applied using an extrusion coater. After drying, the coating layer was cured with an irradiance of 80 mW / cm ² and an irradiation amount of 50 mJ / cm ² using an ultraviolet lamp to form a hard coat layer 1 having a dry film thickness of 1 μm. Subsequently, the hard coat layer coating composition 1 is extruded onto the hard coat layer 1 and coated with a coater, dried at 80 ° C., and purged with nitrogen using an ultraviolet lamp while purging with nitrogen so as to have an oxygen concentration of 1.0% by volume or less. The roughness was 100 mW / cm ² , the irradiation amount was 0.3 J / cm ² , the coating layer was cured, a hard coat layer 2 having a dry film thickness of 7 μm was formed and wound up to prepare a roll-shaped hard coat film 19.

(Hard Coat Layer Coating Composition 9)

The following materials were stirred and mixed to obtain a hard coat layer coating composition 9.

50 parts by mass of pentaerythritol tree / tetraacrylate

(NK ester A-TMM-3L, Shinnakamura Gakuku Kogyo Co., Ltd. product)

50 parts by mass of tris (2-acryloyloxyethyl) isocyanurate

(NK ester A-9300, Shinnakamura Gakuku Kogyo Co., Ltd. product)

UV absorber (TINUVIN 109) 3 parts by mass

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

1 mass part of polyether modified silicone (KF-351A, Shin-Etsu Chemical Co., Ltd. make)

10 parts by mass of cyclohexanone

93 parts by mass of methyl ethyl ketone

<Production of hard coat film 20>

In the production of the production of the hard coat film 19, the hard coat film 20 was similarly produced except that the hard coat layer coating composition 9 was changed to the hard coat layer coating composition 10.

(Hard Coat Layer Coating Composition 10)

The following materials were stirred and mixed to obtain a hard coat layer coating composition 10.

50 parts by mass of pentaerythritol tree / tetraacrylate

(NK ester A-TMM-3L, Shinnakamura Gakuku Kogyo Co., Ltd. product)

50 parts by mass of tris (2-acryloyloxyethyl) isocyanurate

(NK ester A-9300, Shinnakamura Gakuku Kogyo Co., Ltd. product)

UV absorber (TINUVIN 405) 3 parts by mass

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

1 mass part of polyether modified silicone (KF-351A, Shin-Etsu Chemical Co., Ltd. make)

10 parts by mass of cyclohexanone

93 parts by mass of methyl ethyl ketone

Next, about the obtained hard coat films 19 and 20 and the hard coat film 1 produced in Example 1, the shelf life of blocking resistance evaluation was changed to 15 days, a flexible durability test was changed to the following conditions, and also the adhesive evaluation Evaluation was performed similarly to Example 1 except having performed the following. In addition, the obtained results are shown in Table 3.

b. Flexibility

(Durability test)

The hard coat films 1 and 20 produced in the hard coat films 19 and 20 and Example 1 were cut out to a size of 10 cm x 10 cm, and the cycle thermograms were left at -40 ° C for 30 minutes, followed by 85 ° C for 30 minutes. After being charged into the cycle), the resultant was stored in a thermostatic chamber at 80 ° C and a relative humidity of 90% for 1000 hours, and further irradiated with a light tester (i.e., a UV tester, manufactured by Iwasaki Denki Co., Ltd.) for 200 hours.

c. A close evaluation

(Weather resistance test)

The hard coat films 1 and 20 produced in the hard coat films 19 and 20 and Example 1 were cut out of each 10 cm x 10 cm size sample, and the heat shock test (-40 ° C. for 30 minutes, then assumed to be used outdoors) was continued. 500 cycles were put into 85 degreeC * 30 minute alternation, and then, it irradiated for 168 hours with the light test machine (AiShi UV tester, the Iwasaki Denki Co., Ltd. make).

After hardening the hard coat films 1 and 20 produced in the weather resistance test and the hard coat films 1 prepared in Example 1 for 12 hours in an atmosphere of 23 ° C. 55% RH, 11 perforations were cut in the length and width at 1 mm intervals in accordance with JISK5400. 1 square, 100 checkerboard eyes were prepared, and the number of checkerboard eyes remaining without peeling off by peeling off at a 90 degree angle by attaching cellophane tape was counted and evaluated by the following criteria.

◎: No peeling at all

(Circle): The area ratio which peeled was less than 5%.

(Triangle | delta): The peeled area ratio was less than 10%.

X: The area ratio which peeled was 10% or more.

As can be seen from the results in Table 3, the hard coat film of the present invention contains the ultraviolet absorber in the hard coat layer, thereby exhibiting the objective effect of the present invention even in a more severe endurance test and having more excellent adhesion. It is preferable because of that.

Example 4

<Production of the conductive hard coat film 1>

In the manufacture of the hard coat film 1, the hard coat film was produced similarly except having apply | coated the hard coat layer composition 1 on both surfaces. A transparent conductive thin film of indium tin oxide (ITO) having a surface resistivity of about 400 Ω was formed on one side of the produced hard coat film by sputtering to prepare a conductive hard coat film 1 shown in FIG. 3.

<Production of conductive hard coat film 2>

In the manufacture of the hard coat film 2, the hard coat film was similarly produced except having apply | coated the hard coat layer composition 2 on both surfaces. A transparent conductive thin film of indium tin oxide (ITO) having a surface resistivity of about 400 Ω was formed on one side of the produced hard coat film by using a sputtering method to prepare a conductive hard coat film 2.

<Production of Resistive Touch Panel Liquid Crystal Display Device 1>

The conductive hard coat film of the resistive touch panel liquid crystal display device (product name: LCD-USB10XB-T, IO DATA company made in the market) which is marketed is peeled off, and the produced conductive hard coat film 1 is made as shown in FIG. It bonded so that it might become a viewing side, and the resistive film system touch panel liquid crystal display device 1 was produced.

<Production of Resistive Touch Panel Liquid Crystal Display 2>

In the production of the resistive touch panel liquid crystal display device 1, except that the conductive hard coat film 1 was changed to the conductive hard coat film 2, the liquid crystal display device 2 of the resistive touch panel was produced in the same manner, and the following items were evaluated. Was performed.

"evaluation"

a. Visibility (clear) evaluation

The liquid crystal display of a resistive touch panel is placed in a ceiling with 10 sets of primary color fluorescent fluorescent lamps (manufactured by FLR40S, D / MX Panasonic Co., Ltd.) 40 W × 2 at 1.5 m intervals from various angles. It observed and evaluated visibility on the following references | standards.

(Circle): A fluorescent lamp looks straight.

X: A fluorescent lamp looks bent.

b. Pen Slip Movement

On the surface of the hard coat layer of each conductive hard coat film used for the liquid crystal display device of the resistive touch panel, a straight line 40 mm was used at a load of 250 g and a pen sliding speed of 100 mm / sec using a polyacetal pen having a tip of 0.08 mmφ. Scratches and peeling of the hard coat layer in the sliding part after the round trip were evaluated visually.

As a result of evaluation, both the visibility and the pen sliding resistance of the liquid crystal display device of the resistive touch panel using the conductive hard coat film 1 of this invention were favorable.

10: touch panel
11: hard coat film of the present invention
12: transparent conductive thin film
13: glass substrate
14: Spacer
20: color liquid crystal display panel
30: base film with adhesion easy layer
31: hard coat layer
32: ITO layer (transparent conductive thin film)
40: conductive hard coat film

Claims (10)

It has an easily bonding layer on both surfaces of at least 1 type of base film selected from an acrylic resin film, a polypropylene resin film, a cycloolefin resin film, and a polyester resin film, and a hard-coat layer is laminated | stacked on at least one surface of the said easily bonding layer. WHEREIN: The said easily bonding layer contains at least 1 sort (s) chosen from polyester-based resin, acrylic resin, and urethane-type resin, and the said hard-coat layer contains an active energy ray hardening type isocyanurate derivative. Hard coat film, characterized in that. The hard coat film according to claim 1, wherein the base film is a polyester resin film. The hard coat film according to claim 1 or 2, wherein the easily bonding layer comprises a polyester resin. The hard coat film of any one of Claims 1-3 in which the polyester resin of the said easily bonding layer contains 2 or more types of polyester resin from which a glass transition point differs. The polyester resin (X) and the glass transition point (A) according to any one of claims 1 to 4, wherein the polyester resin of the easily bonding layer has a glass transition point (Tg) of at least 105 ° C and less than 135 ° C. Tg) contains polyester resin (Y) which is 65 degreeC or more and less than 95 degreeC, The hard coat film characterized by the above-mentioned. The said polyester resin (X) is a polyester resin as described in any one of Claims 1-5 containing sodium sulfonate isophthalic acid in an acid component, and the said polyester resin (Y) is an acid. It is a polyester resin containing trimellitic acid in a component, The hard coat film characterized by the above-mentioned. 7. The hard coat layer according to any one of claims 1 to 6, wherein the hard coat layer contains an active energy ray curable isocyanurate derivative (A) and an active energy ray curable resin (B) other than an isocyanurate derivative. And the mass ratio of the active energy ray-curable isocyanurate derivative (A) and the active energy ray-curable resin (B) other than the isocyanurate derivative is 10:90 to 50:50. film. The hard coat film according to any one of claims 1 to 7, wherein the hard coat layer contains an ultraviolet absorber. An image display device comprising the hard coat film of any one of claims 1 to 8. An image display apparatus according to claim 9, wherein the image display apparatus comprises a touch panel, wherein the hard coat film according to any one of claims 1 to 8 is used as a constituent member of the touch panel.

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