JP5245688B2 - Hard coat film and method for producing the same - Google Patents

Description

  The present invention relates to a hard coat film having a hard coat layer and a method for producing the same, and more particularly to a hard coat film suitable for use as an optical film and a method for producing the same.

  For the liquid crystal display device, for example, optical films such as a protective film for polarizing plate, an optical compensation film, a viewing angle improving film, an antiglare film, an antireflection film, an antistatic film, a conductive film, and an antireflection film are used. Yes. As such an optical film, it is known to use a hard coat film in which a hard coat layer is formed on the surface of a film substrate from the viewpoint of scratch resistance.

  As a manufacturing method of a hard coat film, after apply | coating the ultraviolet curable resin composition containing a specific (meth) acrylate on a transparent base material, it is a 1st irradiation process to the obtained coating film from the air. A method has been proposed in which ultraviolet rays are irradiated from the transparent substrate side in a state of low oxygen to cure the ultraviolet curable resin composition, and in the second irradiation step, ultraviolet irradiation from the coating film side is performed at least once. (Patent Document 1).

However, in the conventional method for producing a hard coat film, although a hard coat film having a relatively high surface hardness can be obtained, since the flatness of the surface is lowered, it is impossible to achieve both excellent surface hardness and flatness. There was a problem. The above problem also occurred when a low refractive index layer was formed on the surface of the hard coat film. In particular, the above problem is more remarkable when the width of the substrate is wide and the thickness of the base material is thin.
JP 2007-262281 A

  An object of the present invention is to provide a hard coat film sufficiently excellent in both surface hardness and flatness and a method for producing the same.

  An object of the present invention is to provide a hard coat film that is sufficiently excellent in both surface hardness and flatness even when the width of the substrate is relatively wide and the thickness of the substrate is relatively thin, and a method for producing the same. .

The present invention is a method for producing a hard coat film in which ultraviolet rays are irradiated in two or more steps after forming a hard coat layer coating film on a substrate,
The illuminance of ultraviolet rays in the first ultraviolet irradiation step is 50 to 150 mW / cm ² , and the light amount is 50 to 200 mJ / cm ² .
The illuminance of ultraviolet rays in each ultraviolet irradiation step after the second time is 50 mW / cm ² or more, and the amount of light is 50 mJ / cm ² or more.
The present invention relates to a method for producing a hard coat film, wherein the total amount of ultraviolet rays in the total ultraviolet irradiation step is 100 to 500 mJ / cm ² , and the hard coat film produced by the method.

  According to the present invention, a hard coat film that is sufficiently excellent in both surface hardness and flatness can be produced. Moreover, even if the width of the substrate is relatively wide and the thickness of the substrate is relatively thin, it is possible to produce a hard coat film that is sufficiently excellent in both surface hardness and flatness.

  In the method for producing a hard coat film according to the present invention, after forming a hard coat layer coating film on a substrate, ultraviolet rays are irradiated in two or more steps. Hereafter, each process implemented in this invention is demonstrated in detail. In the present specification, “HC” means a hard coat layer. The first ultraviolet irradiation process is referred to as “first UV process”, the second ultraviolet irradiation process is referred to as “second UV process”, and the third ultraviolet irradiation process is referred to as “third UV process”.

(HC coating process)
The HC coating film is formed by applying an HC composition containing an ultraviolet curable compound on a substrate. The coating method is not particularly limited as long as it can form a uniform thickness coating film, for example, extrusion coating method, gravure coating method, dip coating method, reverse coating method, wire bar coating method, die coating method, or spray coating method, Examples include an inkjet coating method. It is preferable to perform application | coating continuously with respect to the base material conveyed. The film thickness of the HC coating film is not particularly limited, and may be, for example, a range in which the final dry film thickness of HC in the hard coat film is 0.1 to 30 μm, preferably 1 to 20 μm. The HC coating film is cured by the UV process described later, and HC having a refractive index of 1.49 to 2.2 at 23 ° C. and a wavelength of 550 nm is formed.

  The ultraviolet curable compound constituting the HC coating film is a compound that can be cured by ultraviolet rays, and those conventionally used in the field of the hard coat layer of the film can be used. Examples of HC ultraviolet curable compounds include polyfunctional (meth) acrylates and monofunctional radical polymerizable monomers. The HC composition preferably contains at least a polyfunctional (meth) acrylate. In the present specification, (meth) acrylate is meant to include acrylate and methacrylate.

  The polyfunctional (meth) acrylate is a compound having two or more acryloyloxy groups and / or methacryloyloxy groups in the molecule. The polyfunctional (meth) acrylate is a group consisting of pentaerythritol polyfunctional (meth) acrylate, dipentaerythritol polyfunctional (meth) acrylate, pentaerythritol polyfunctional (meth) acrylate, and dipentaerythritol polyfunctional (meth) acrylate. Is preferably selected from.

  Specific examples of the polyfunctional (meth) acrylate include, for example, ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, tetra Methylolmethane triacrylate, tetramethylolmethane tetraacrylate, pentaglycerol triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, glycerin triacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol Pentaacrylate, dipen Erythritol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetra Methylol methane trimethacrylate, tetramethylol methane tetramethacrylate, pentaglycerol trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerol trimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol te La methacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexa methacrylate, isobornyl acrylate, multifunctional urethane (meth) acrylate preferably. These compounds are used alone or in admixture of two or more. It may be an oligomer such as a dimer or trimer of the above monomer.

  A monofunctional radically polymerizable monomer is a compound having one radically polymerizable group in the molecule. Specific examples of the monofunctional radical polymerizable monomer include, for example, styrene monomers such as styrene, p-methylstyrene, p-chloromethylstyrene, or vinyltoluene; methyl (meth) acrylate, ethyl (meth) acrylate , N-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (Meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, phenyl (meth) acrylate, or benzyl (meth) acrylate (Meth) acrylate monomers having a hydrocarbon group such as a rate; (meth) acrylate monomers in which hydrogen atoms of these (meth) acrylate monomers are substituted with fluorine atoms, chlorine atoms, bromine atoms, or the like Monomer; vinyl ester monomer such as vinyl acetate, vinyl benzoate, or vinyl ester of branched monocarboxylic acid (Beova: manufactured by Shell Chemical Co., Ltd.); acrylonitrile monomer such as acrylonitrile or methacrylonitrile Vinyl ether monomers such as ethyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, or cyclohexyl vinyl ether; acrylamide monomers such as (meth) acrylamide, dimethyl (meth) acrylamide, or diacetone acrylamide; N, N-dimethylaminoe Ru (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, 4- (N, N-dimethylamino) styrene, or N- {2- (meth) acryloyloxy Ethyl} piperidine and other basic nitrogen-containing vinyl compound monomers; epoxy group-containing vinyl compounds such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and 3,4-epoxyvinylcyclohexane Monomer; (meth) acrylic acid, angelic acid, crotonic acid, maleic acid, 4-vinylbenzoic acid, p-vinylbenzenesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, or mono {2- (meta ) Acidic vinyl compounds such as acryloyloxyethyl} acid phosphate Monomers: p-hydroxymethylstyrene, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, di-2-hydroxyethyl fumarate, polyethylene glycol or polypropylene glycol mono (meth) acrylate, or their ε-caprolactone adduct, (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, Addition product of α, β-ethylenically unsaturated carboxylic acid such as itaconic acid or citraconic acid and ε-caprolactone, hydroxyalkyl esters of the above α, β-ethylenically unsaturated carboxylic acid, or α, β -Ethylenically unsaturated cal Hydroxyl-containing vinyl compound monomers such as adducts of boric acid and epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, branched carboxylic acid glycidyl ester (Cardura E; manufactured by Shell Chemical Co., Ltd.); vinyl trimethoxy Silane compound monomers such as silane, γ-methacryloxyethyltrimethoxysilane, γ-methacryloxyethylmethyldimethoxysilane; olefin monomers such as ethylene and propylene; vinyl chloride, vinylidene chloride, vinyl bromide, fluorine Halogenated olefin monomers such as vinyl fluoride, tetrafluoroethylene, or chlorotrifluoroethylene; and other maleimides and vinyl sulfones. These monomers may be used alone or in admixture of two or more, and a (meth) acrylate type is preferably used mainly from the viewpoint of copolymerization. It may be an oligomer such as a dimer or trimer of the above monomer.

  In the composition for HC (hereinafter also referred to as HC coating liquid), the content of the ultraviolet curable compound is preferably 50% by mass or more and less than 98% by mass in the solid content. In particular, the polyfunctional (meth) acrylate is preferably used in an amount of 50% by mass to 100% by mass with respect to the total amount of the ultraviolet curable compound.

  The HC composition preferably contains a photopolymerization initiator to accelerate the curing of the ultraviolet curable compound. It is preferable that content of a photoinitiator is mass ratio and is photoinitiator: UV curable compound = 20: 100-0.01: 100.

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

  The HC composition may contain additives such as a leveling agent, a refractive index adjusting agent, an organic solvent, an antioxidant, a conductive agent, and a color tone adjusting agent.

  By including a leveling agent, the planarity can be further improved.

  The leveling agent is a compound having an HLB value of 3 to 18, and preferably has an HLB value of 8 to 14 from the viewpoint of excellent scratch resistance after wet heat treatment. The HLB value is Hydrophile-Lipophile-Balance, hydrophilic-lipophilic-balance, and is a value indicating the hydrophilicity or lipophilicity of a compound. The smaller the HLB value, the higher the lipophilicity, and the higher the value, the higher the hydrophilicity.

  The HLB value can be obtained by the following calculation formula.

HLB = 7 + 11.7Log (Mw / Mo)
In the formula, Mw represents the molecular weight of the hydrophilic group, Mo represents the molecular weight of the lipophilic group, and Mw + Mo = M (molecular weight of the compound).

  Alternatively, according to the Griffin method, it can be obtained by using HLB value = 20 × total formula weight of hydrophilic part / molecular weight (J. Soc. Cosmetic Chem., 5 (1954), 294).

  Specific compounds of the leveling agent are listed below, but the present invention is not limited thereto. Figures in parentheses indicate HLB values.

  Made by Kao Corporation: Emulgen 102KG (6.3), Emulgen 103 (8.1), Emulgen 104P (9.6), Emulgen 105 (9.7), Emulgen 106 (10.5), Emulgen 108 (12. 1), Emulgen 109P (13.6), Emulgen 120 (15.3), Emulgen 123P (16.9), Emulgen 147 (16.3), Emulgen 210P (10.7), Emulgen 220 (14.2) , Emulgen 306P (9.4), Emulgen 320P (13.9), Emulgen 404 (8.8), Emulgen 408 (10.0), Emulgen 409PV (12.0), Emulgen 420 (13.6), Emulgen 430 (16.2), Emulgen 705 (10.5), Emulgen 707 (12.1), Emulgen 7 9 (13.3), Emulgen 1108 (13.5), Emulgen 1118S-70 (16.4), Emulgen 1135S-70 (17.9), Emulgen 2020G-HA (13.0), Emulgen 2025G (15. 7), Emulgen LS-106 (12.5), Emulgen LS-110 (13.4), Emulgen LS-114 (14.0), Emulgen MS-110 (12.7), Emulgen A-60 (12. 8), Emulgen A-90 (14.5), Emulgen A-500 (18.0), Emulgen B-66 (13.2), Latemul PD-420 (12.6), Latemul PD-430 (14. 4), Latemul PD-430S (14.4), Latemuru PD-450 (16.2), Rhedol SP-L10 (8.6), Rhedol SP- 10 (6.7), Rhedol SP-S10V (4.7), Rhedol SP-S20 (4.4), Rhedol SP-O10V (4.3), Rheodor Super SP-L10 (8.6), Rheodor AS10V (4.7), Rhedol AO-10V (4.3), Rheodor AO-15V (3.7), Emazole L-10V (8.6), Emazole P-10V (6.7), Emazole S- 10V (4.7), Emazole O-10V (4.3), Rheodor TW-L120 (16.7), Rhedol TW-L106 (13.3), Rheodor TW-P120 (15.6), Rhedol TW- S120V (14.9), Rheodor TW-S106V (9.6), Rheodor TW-S320V (10.5), Rheodor TW-O120V (15.0), R Odol TW-O106V (10.0), Rheodor TW-O320V (11.0), Rheodor Super TW-L120 (16.7), Rheodor 430V (10.5), Rheodor 440V (11.8), Rheodor 460V (13.8), Rhedol MS-60 (3.5), Rhedol MS-165V (11.0), Excel T-95 (3.8), Excel VS-95 (3.8), Excel O-95R (3.5), Excel 200 (3.5), Excel 122V (3.5), Emanon 1112 (13.7), Emanon 4110 (11.6), Emanon CH-25 (10.7), Emanon CH -40 (12.5), Emanon CH-60 (K) (14.0), Emanon CH-80 (15.0), Amit 102 (6.3), A 105 (9.8), Amite 105A (10.8), Amite 302 (5.1), Amite 320 (15.4), Aminone PK-02S (5.5), Aminone L-02 (5. 8), manufactured by Nissin Chemical Industry Co., Ltd .: Surfinol 104E (4), Surfinol 104H (4), Surfinol 104A (4), Surfinol 104BC (4), Surfinol 104DPM (4), Surfinol 104PA ( 4), Surfinol 104PG-50 (4), Surfinol 104S (4), Surfinol 420 (4), Surfinol 440 (8), Surfinol 465 (13), Surfinol 485 (17), Surfinol SE (6), Surfinol SE-F (6), Surfinol 61 (6), Surfinol 6 4 (8), Surfinol 2502 (8), Surfinol 82 (4), Surfinol DF110D (3), Surfinol CT111 (8-11), Surfinol CT121 (11-15), Surfinol CT136 (13) , Surfynol TG (9), Surfynol GA (13), Orphine STG (9-10), Olphine E1004 (7-9), Olphine E1010 (13-14), Shin-Etsu Chemical Co., Ltd .: X-22 4272 (7), X-22-6266 (8), KF-351 (12), KF-352 (7), KF-353 (10), KF-354L (16), KF-355A (12), KF -615A (10), KF-945 (4), KF-618 (11), KF-6011 (12), KF-6015 (4), K F-6004 (5).

  The leveling agent is preferably used in an amount of 0.005 mass% or more and less than 50 mass% in the solid content of the HC composition. Two or more leveling agents may be used in combination.

  As the refractive index adjusting agent, inorganic fine particles and organic fine particles are used to adjust the refractive index and slipperiness of the hard coat layer.

  Specific examples of inorganic fine particles include, for example, silicon oxide, titanium oxide, aluminum oxide, tin oxide, indium oxide, ITO, zinc oxide, zirconium oxide, magnesium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined silica. Mention may be made of calcium hydrate, hydrated calcium silicate, 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.

  Specific examples of organic fine particles include, for example, polymethacrylate methyl acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicon resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, melamine Examples thereof include a resin resin powder, a polyolefin resin powder, a polyester resin powder, a polyamide resin powder, a polyimide resin powder, and a polyfluoroethylene resin powder. Particularly preferred are cross-linked polystyrene particles (for example, SX-130H, SX-200H, SX-350H, manufactured by Soken Chemical), polymethyl methacrylate-based particles (for example, MX150, MX300, manufactured by Soken Chemical), and fluorine-containing acrylic resin fine particles. . Examples of the fluorine-containing acrylic resin fine particles include commercial products such as FS-701 manufactured by Nippon Paint. Examples of the acrylic particles include Nippon Paint: S-4000, and examples of the acrylic-styrene particles include Nippon Paint: S-1200, MG-251.

  The average particle size of the inorganic fine particles and the organic fine particles is preferably 0.01 to 5 μm, more preferably 0.1 to 5.0 μm, and particularly preferably 0.1 to 4.0 μm. Moreover, it is preferable to contain 2 or more types of microparticles | fine-particles from which a particle size differs. As for content of a refractive index regulator, 0.1-30 mass parts is desirable with respect to 100 mass parts of ultraviolet curable compounds.

  Examples of the organic solvent include hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone), esters (methyl acetate, (Ethyl acetate, methyl lactate), glycol ethers, and other organic solvents can be appropriately selected or used by mixing them. Propylene glycol monoalkyl ether (1 to 4 carbon atoms of the alkyl group) or propylene glycol monoalkyl ether acetate ester (1 to 4 carbon atoms of the alkyl group) is 5% by mass or more, more preferably 5 to 80%. It is preferable to use the organic solvent containing at least mass%. The content of the organic solvent is preferably such that the solid concentration in the HC composition forming the HC coating film is 30 to 80% by mass.

  As the antioxidant, a compound that does not suppress the photocuring reaction of the hard coat layer can be selected and used. Examples include hindered phenol derivatives, thiopropionic acid derivatives, phosphite derivatives, and the like. Specifically, for example, 4,4′-thiobis (6-tert-3-methylphenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) mesitylene, di-octadecyl-4- Examples thereof include hydroxy-3,5-di-tert-butylbenzyl phosphate.

  After forming the HC coating film in this step, drying is usually performed at 40 to 150 ° C. for 10 seconds to 5 minutes.

(UV process)
The UV process is performed in two or more processes and under specific irradiation conditions described later. In the present invention, curing by UV irradiation can be preferentially caused near the surface of the hard coat layer coating film. Therefore, even if curing occurs inside the coating film by subsequent UV irradiation, the surface is hardly affected by the distortion due to internal curing. As a result, good flatness can be ensured, so that a hard coat film sufficiently excellent in both surface hardness and flatness can be produced. Moreover, such an effect can be effectively obtained even when the width of the substrate is relatively wide and the thickness of the substrate is relatively thin. Further, by performing the UV irradiation in two or more steps, heat generated by the UV irradiation can be once released between the UV steps, so that it is possible to prevent a decrease in flatness due to film softening. The number of UV irradiation steps is not particularly limited as long as it is 2 or more, and is preferably divided into 2-3 steps from the viewpoint of productivity. In this specification, the term “UV process” means all the UV processes.

In the first UV step, the illuminance of ultraviolet rays is 50 to 150 mW / cm ² , and preferably 60 to 120 mW / cm ² from the viewpoint of the balance of surface hardness, flatness, and productivity. Quantity of ultraviolet light is 50~200mJ / cm ^2, surface hardness, preferably in terms of planarity and productivity of balance 60~180mJ / cm ^2, more preferably 80~150mJ / cm ^2. If the illuminance or light intensity is too small in the first UV process, the HC coating surface is not sufficiently cured, so that distortion appears on the surface during the internal curing in the second and subsequent UV processes, and the flatness is lowered. If the illuminance or the amount of light is too large, curing occurs not only on the surface of the HC coating film but also on the inside in the first UV process, so that distortion appears on the surface and flatness decreases.

  The illuminance and light quantity of the ultraviolet light can be easily controlled by adjusting the output of the irradiation unit in the ultraviolet irradiation device, the distance between the hard coat coating film surface and the light source, the irradiation time, and the like.

  The irradiation time in the first UV step is not particularly limited as long as it is a time for achieving the light amount within the above range with the ultraviolet light having the above illuminance.

Each UV step the second and subsequent (e.g., second 2UV step and the 3UV step) in the illuminance of ultraviolet rays 50 mW / cm ² or more, particularly a 50~200mW / cm ^2, preferably from the viewpoint of surface hardness 70～200MW / cm ² . Quantity of ultraviolet light is 50 mJ / cm ² or more, in particular at 50~200mJ / cm ^2, preferably from the viewpoint of surface hardness is 80~200mJ / cm ^2. If the illuminance or the amount of light is too small in the UV process after the second UV process, the surface hardness decreases because the curing inside the HC coating is not sufficient. The illuminance and light intensity in each UV process after the second time may be selected and set within the above range independently for each UV process.

For example, when the UV step is performed in two steps, the illuminance of ultraviolet rays in the second UV step is preferably 70 to 200 mW / cm ² , more preferably 80 to 200 mW / cm ² , and the light amount of ultraviolet rays is 80 to 200 mJ / cm 2. ² is preferable, and more preferably 100 to 200 mJ / cm ² . The illuminance and light intensity in the second UV step are preferably larger than the illuminance and light amount in the first UV step, respectively, from the viewpoint of further improving the surface hardness and flatness.

For example, when the UV step is performed in three steps, the illuminance of ultraviolet rays in the second UV step is preferably 70 to 200 mW / cm ² , more preferably 80 to 200 mW / cm ² , and the light amount of ultraviolet rays is 80 to 200 mJ / cm ² is preferable, and 100 to 200 mJ / cm ² is more preferable. In the third UV step, the illuminance of ultraviolet rays is preferably 80 to 200 mW / cm ² , more preferably 90 to 200 mW / cm ² , and the amount of ultraviolet rays is preferably 90 to 200 mJ / cm ² , more preferably 110 to 200 mJ / cm 2. ² . The illuminance and light intensity in the second UV process are larger than the illuminance and light intensity in the first UV process, respectively, and the illuminance and light intensity in the third UV process are larger than those in the second UV process, respectively. It is preferable from the viewpoint of improvement.

  The irradiation time in each UV process after the second time is not particularly limited as long as it is a time for achieving the light quantity within the above range with the ultraviolet light having the above illuminance.

Integrated quantity of ultraviolet light in the entire ultraviolet irradiation step is 100 to 500 mJ / cm ^2, preferably from the viewpoint of productivity of the balance between surface hardness 180~500mJ / cm ^2, more preferably 200~500mJ / cm ^2. If the integrated light quantity is too small, the surface hardness decreases because the curing inside the HC coating is not sufficient. If the integrated amount of light is too large, the flatness deteriorates due to the occurrence of strain and the shrinkage of the base material inside the hard coat film.

  The cumulative amount of ultraviolet light in the total ultraviolet irradiation process is the sum of the amounts of ultraviolet light irradiated in all the UV processes.

  In the UV step, UV irradiation may be performed from the HC coating film forming surface side, or from the opposite side when the substrate has transparency. From the viewpoint of transportability and flatness, UV irradiation is performed from the HC coating film forming surface side.

  The ultraviolet light source in the UV process can be used without limitation as long as it is a light source that generates ultraviolet light. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.

  When irradiating UV in the UV process, it is preferably performed while applying tension in the transport direction of the film, more preferably while applying tension in the width direction. The tension to be applied is preferably 30 to 500 N / m. The method for applying tension is not particularly limited, and tension may be applied in the transport direction on the back roll, or tension may be applied in the width direction or biaxial direction by a tenter.

  Specific examples of the execution order of the HC coating film forming process and the UV process are illustrated below.

(1) HC coating film forming process-first UV process-second UV process; or (2) HC coating film forming process-first UV process-second UV process-third UV process.

(LR coating film forming process)
In the present invention, a coating film for a low refractive index layer may be formed. In the present specification, “LR” means a low refractive index layer. The LR coating film forming process may be performed after the first UV process, and may be performed between, for example, each UV process, or may be performed after the last UV process. In the UV process after the LR coating is formed, the UV passes through the LR coating to reach the HC coating, and the curing of the HC coating is achieved. At the same time, the curing of the LR coating is also achieved if desired. The

  For example, when the first UV process and the second UV process are performed as the UV process, the LR coating film forming process may be performed after the first UV process and before the second process, or after the second process. May be.

  For example, when the first UV process, the second UV process, and the third UV process are performed as the UV process, the LR coating film forming process may be performed after the first UV process and before the second UV process, or the second UV process. It may be performed after the process and after the third UV process, or may be performed after the third UV process.

  Specific examples of the execution order of the above steps will be exemplified below.

(3) HC coating film forming process-first UV process-LR coating film forming process-second UV process;
(4) HC coating film forming process-first UV process-second UV process-LR coating film forming process;
(5) HC coating film forming process-first UV process-second UV process-LR coating film forming process-third UV process; or (6) HC coating film forming process-first UV process-LR coating film forming process-second UV process. -3rd UV process. The preferred execution order is order (5) and (6).

  The LR coating film forming process will be described in detail.

  The LR coating film contains a curable compound and / or a non-curable compound. When the curable compound is included, the LR coating film is cured, and when the curable compound is not included, the refractive index is higher than the base material by drying without being cured. Is a low layer. LR is preferably a refractive index of 1.20 to 1.45 at 23 ° C. and a wavelength of 550 nm.

  The LR coating film is formed by applying a composition for LR containing a curable compound and / or a non-curable compound on HC. The coating method is not particularly limited as long as a coating film having a uniform thickness can be formed, and examples thereof include the same coating method as that used when forming the HC coating film. It is preferable to perform application | coating continuously with respect to the base material conveyed. The film thickness of the LR coating film is not particularly limited, and may be, for example, a range in which the final dry film thickness of LR in the hard coat film is 5 nm to 0.5 μm, preferably 10 nm to 0.3 μm.

  The curable compound constituting the LR coating film is selected from the group consisting of a thermosetting polycondensation type compound, a heat and / or photocurable cationic polymerization type compound and a heat and / or photocurable radical polymerization type compound. These compounds. A preferred LR coating film contains a thermosetting polycondensation type compound or a heat and / or photosetting cationic polymerization type compound.

  The thermosetting polycondensation type compound is a compound that can be polycondensed by heat, and those conventionally used in the field of the low refractive index layer of the film can be used. Examples of such a thermosetting polycondensation compound include an organosilicon compound, a hydrolyzate thereof, or a polycondensate thereof.

  Examples of the organosilicon compound include an organosilane compound represented by the general formula (1), a hydrolyzate thereof, or a polycondensate thereof.

R ¹ _n SiX ¹ _4-n Formula (1)
In the formula, R ¹ is a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, X ¹ is a hydroxyl group or a hydrolyzable substituent, and n is an integer of 0 to 3.

  Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, s-butyl group, hexyl group, decyl group, hexadecyl group and the like. Examples of the aryl group include a phenyl group and a naphthyl group.

Examples of the hydrolyzable substituent for X ¹ include an alkoxy group, a halogen group, and a carboxyl group.

  Specific examples of the organic silane compound represented by the general formula (1) include, for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, and phenyltrimethoxy. Silane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, isobutyltrimethoxysilane, trifluoropropyltrimethoxysilane, vinyltri Methoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyl Pyrtriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyl Dimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropylmethyldimethoxysilane, 2-aminoethyl-3-aminopropyltrimethoxysilane, N-2-aminoethyl-3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-1,3-dimethylbutylidenepropylamine, N-phenyl -3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-isocyanatopropyltriethoxysilane, p-styryltrimethoxysilane, diethylsilane, etc. Or 2 or more types are mixed and used.

  The heat and / or ultraviolet curable cationic polymerization type compound is a compound that can be cationically polymerized by ultraviolet light and / or heat, and those conventionally used in the field of the low refractive index layer of the film can be used. Examples of such cationically polymerizable compounds include oxetane compounds, epoxy compounds, and fluorine-containing cationically polymerizable compounds.

  An oxetane compound is a compound having at least one oxetane ring in the molecule. As such an oxetane compound, various compounds can be used, and preferred compounds include compounds represented by the following general formula (2), general formula (3), and general formula (4).

(Wherein R ² represents hydrogen, fluorine, an alkyl group, a fluoroalkyl group, an allyl group, an aryl group, or a furyl group, m represents an integer of 1 to 4, Z represents oxygen or sulfur, and R ³ Represents a monovalent to tetravalent organic group depending on the value of m.)

(In the formula, R ⁴ and R ⁵ each independently represent hydrogen, fluorine, an alkyl group, a fluoroalkyl group, an allyl group, an aryl group, or a furyl group.)

(Wherein R ⁶ represents hydrogen, fluorine, an alkyl group, a fluoroalkyl group, an allyl group, an aryl group, or a furyl group, R ⁷ represents hydrogen or an inert monovalent organic group, and R ⁸ represents water Represents a decomposable functional group, n represents an integer of 1 to 5, and p represents an integer of 0 to 2.)
In the general formulas (2) to (4), when R ² , R ⁴ , R ⁵ , and R ⁶ are alkyl groups, the number of carbon atoms can be about 1 to 6, specifically, methyl, Examples include ethyl, prokyl, butyl and the like. The fluoroalkyl group can also have about 1 to 6 carbon atoms. Furthermore, the aryl group is typically phenyl or naphthyl, which may be substituted with other groups.

The organic group represented by R ³ in the general formula (2) is not particularly limited. For example, when m is 1, an alkyl group, a phenyl group, or the like, and when m is 2, the number of carbon atoms is 1 to 1. When 12 linear or branched alkylene groups, linear or branched poly (alkyleneoxy) groups, and the like are 3 or 4, similar polyfunctional groups are exemplified.

The inactive monovalent organic group represented by R ⁷ in the general formula (4) typically includes an alkyl group having 1 to 4 carbon atoms, and is hydrolyzable represented by R ^8. Examples of the functional group include an alkoxy group having 1 to 5 carbon atoms including methoxy and ethoxy, and a halogen atom such as a chlorine atom and a bromine atom.

  In addition to these, an oxetanyl group was introduced into an epoxy acrylate resin having an OH residue (such as “epoxy ester” (trade name) manufactured by Kyoeisha Chemical Co., Ltd., “lipoxy” (trade name) manufactured by Showa Polymer Co., Ltd.) via an isocyanate group. The number average molecular weight (polystyrene equivalent number average molecular weight measured by the GPC method) of 20,000 or less is a urethane acrylate resin obtained by polyaddition of various isocyanates and oxetanyl group-containing monomers having a hydroxyl group or the like through a urethane bond. These oligomers can also be preferably used.

  Furthermore, a (co) polymer containing a monomer having a hydrogen bond-forming group as required, and a reactive polymer having an oxetanyl group in the main chain or side chain and having a number average molecular weight of 20,000 or more is preferably used. it can. These reactive polymers can be synthesized by, for example, the technique disclosed in JP-A-07-309856.

  The epoxy compound is a monomer having at least one epoxy group in the molecule, and includes both a high molecular compound and a low molecular compound as the compound, and can be cured by cationic polymerization. Can also be used. For example, phenyl glycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, vinyl cyclohexene dioxide, 1,2,8,9-diepoxy limonene, 3,4-epoxy cyclohexyl methyl, 3 ', 4'-epoxy cyclohexane A silane coupling agent having an epoxy group such as carboxylate, bis (3,4-epoxycyclohexyl) adipate, an alkoxysilane compound having an epoxy group, or γ-glycidoxypropyltrimethoxysilane can be used.

  As an alkoxysilane compound (silane coupling agent) having an epoxy group, an organosilicon compound represented by the following general formula (a), a hydrolyzate thereof, or a polycondensate thereof is preferably contained.

R2 _m SiX2 _4-m (a)
In the formula, R2 is an epoxy group, X2 is a hydroxyl group or a hydrolyzable substituent, and m is an integer of 0 to 3.

  R2 of the alkoxysilane compound having an epoxy group represented by the general formula (a) is not particularly limited, but examples thereof include 2-glycidoxyethyl group, 3-glycidoxypropyl group, 3-glycidoxybutyl group and the like. Glycidoxy C1-C4 alkyl group, preferably glycidoxy C1-C3 alkyl group, glycidyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxycyclohexyl) propyl group, 2- (3 Oxiranes such as 4-epoxycycloheptyl) ethyl group, 2- (3,4-epoxycyclohexyl) propyl group, 2- (3,4-epoxycyclohexyl) butyl group, 2- (3,4-epoxycyclohexyl) pentyl group And a C1-C3 alkyl group substituted with a C5-C8 cycloalkyl group having a group. Among these, a 2-glycidoxyethyl group, a 3-glycidoxypropyl group, and a 2- (3,4-epoxycyclohexyl) ethyl group are preferable. Preferred specific examples of the compound that can be used as the compound of the general formula (1) having these substituents R2 include 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, and 3-glycidide. Xylpropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4) -epoxycyclohexylethyltriethoxysilane and the like. These may be used alone or in combination of two or more.

The alkoxysilane compound used in the present invention can be produced, for example, by the method described in JP-A-10-324749 and JP-A-6-298940. As described in JP-A-2006-348061, it can also be obtained by (co) condensation of an alkoxysilane compound of the general formula (a) under a base catalyst. In that case, water can be added as needed to promote (co) condensation. The amount of water added is usually 0.05 to 1.5 mol, preferably 0.1 to 1.2 mol, with respect to 1 mol of alkoxy groups in the entire reaction mixture. The catalyst used for the condensation reaction is not particularly limited as long as it is basic, but an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc. Organic bases such as ammonia, triethylamine, diethylenetriamine, n-butylamine, dimethylaminoethanol, triethanolamine, and tetramethylammonium hydroxide can be used. Among these, an inorganic base or ammonia is preferable because the catalyst can be easily removed from the product. The addition amount of the catalyst is usually 5 × 10 ^{−4 to} 7.5 mass%, preferably 1 × 10 ^{−3 to} 5 mass%, based on the amount of the alkoxysilane compound. The condensation reaction can be carried out without a solvent or in a solvent. There is no restriction | limiting in particular as a solvent in the case of using a solvent, if it is a solvent which melt | dissolves an alkoxysilane compound. Examples of such solvents include nonpolar solvents such as dimethylformamide, dimethylacetamide, tetrahydrofuran, methyl ethyl ketone, and methyl isobutyl ketone, and aromatic hydrocarbons such as toluene and xylene, preferably methyl ethyl ketone and methyl isobutyl ketone. .

  As the epoxy compound used in the present invention, an oligomer having a molecular weight of 20,000 or less or a polymer having a molecular weight of 20,000 or more can be used as in the case of the oxetane compound. The polymer can be synthesized, for example, by the technique disclosed in JP-A-07-247313.

As the oxetane compound or epoxy compound, a compound having a refractive index lowered by containing a fluorine atom may be used. For example, methylene (CF ₂ ) _n having a fluorine atom may be introduced into the compound.

  The fluorine-containing cationic polymerizable compound is represented by the following general formula (5).

^{_{R 9 -R 11 - (CF 2}} ) n -R 12 -R 10 formula (5)
(Wherein R ⁹ and R ¹⁰ are reactive groups that can be bonded / unbonded to each other by heat and / or photoreaction, and R ¹¹ and R ¹² are single bonds or 2 having 1 to 5 carbon atoms) Valent hydrocarbon, oxygen, or sulfur, and n represents an integer of 1 to 30.)
In the general formula (5), R ⁹ and R ¹⁰ may be the same or different as long as they are photoreactive groups that can be bonded to each other by irradiation with ultraviolet rays. Examples of the photoreactive group include those in which the reaction proceeds by a reaction form such as photocationic polymerization.

As a photocationic polymerization reactive group, for example, R ⁹ and R ¹⁰ in the above general formula (5) are both represented by the following general formula (6);

(In the formula, R ¹³ is hydrogen, fluorine, an alkyl group, or a fluoroalkyl group.)
Or an epoxy group represented by the following general formula (7):

(In the formula, R ¹⁴ represents hydrogen, fluorine, an alkyl group having 1 to 10 carbon atoms, or a fluoroalkyl group.)
And cyclic ethers such as oxetanyl group, thioether, and vinyl ether groups. Among these, cyclic ether groups such as an epoxy group, a thioether group, and an oxetanyl group have advantages such as small shrinkage accompanying the polymerization reaction, easy availability of compounds having various structures, high degree of polymerization, and low toxicity. .

  These fluorine-containing cationic polymerizable compounds having a cationic photopolymerizable reactive group are used in combination with the above-described epoxy compound and / or oxetane compound, so that they can be uniformly incorporated into LR, curing acceleration, coating film Realizes flexibility and elasticity and low refractive index.

In the above general formula (5), different combinations of R ⁹ and R ¹⁰ that can be bonded to each other specifically include a combination of an epoxy group and an oxetanyl group.

As a method for synthesizing the fluorine-containing cationic polymerizable compound represented by the above formula (1), for example, there is a method derived from a fluorinated diiodoalkane. For example, when R ⁹ and R ¹⁰ are both an epoxy group and n is 4, octafluoro-1,4-diiodobutane is used as a starting material, and known methods such as Japanese Patent Publication No. 54-11284 and Japanese Patent Publication No. 59 -22712, JP-B-6-60116, and J.H. Fluorine Chem. , 73, 151 (1995) and the like, and can be synthesized via a diol derivative.

When both R ⁹ and R ¹⁰ are oxetanyl groups, the above diol derivative is converted to an alkali metal alcoholate with reference to a known method, for example, a method described in JP-A-2000-336082, It can be synthesized by a sulfonic acid esterification reaction of 3-hydroxymethyloxetanes.

  The heat and / or photo-curable radically polymerizable compound is a compound that can be radically polymerized by heat and / or ultraviolet light, and those conventionally used in the field of low refractive index layers of films can be used. Examples of such heat and / or photo-curable radical polymerization type compounds include di (meth) acrylates such as ethylene glycol di (meth) acrylate and pentaerythritol di (meth) acrylate monostearate; trimethylolpropane tri (meta ) Acrylates, tri (meth) acrylates such as pentaerythritol tri (meth) acrylate, polyfunctional (meth) acrylates such as pentaerythritol tetra (meth) acrylate derivatives and dipentaerythritol penta (meth) acrylate, and EO modification of the above-mentioned products Goods etc. can be illustrated.

  The non-curable compound that constitutes the LR coating film does not cause curing by heat or ultraviolet rays, but is a compound that can constitute a low refractive index layer simply by drying after coating. As such a non-curable compound, a non-curable compound conventionally used as a binder or the like in the field of a low refractive index layer of a film can be used. Specific examples of the non-curable compound include, for example, acrylic resins such as polyvinyl alcohol, polyester, polyurethane, and polymethyl methacrylate, and cellulose ester resins.

  When a curable compound is contained in the LR composition, it usually further contains a polymerization initiator or a catalyst. A polymerization initiator and a catalyst are appropriately selected and used depending on the type of the curable compound. For example, when using a thermosetting polycondensation type compound, a catalyst is further contained. Further, for example, when a heat and / or photocurable cationic polymerization type compound is used, a thermal cationic polymerization initiator and / or an ultraviolet cationic polymerization initiator are further contained. For example, when using a heat and / or photocurable radical polymerization type compound, a thermal radical polymerization initiator and / or an ultraviolet radical polymerization initiator are further contained.

  Catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, organic acids such as oxalic acid, acetic acid, formic acid and methanesulfonic acid, inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia, and organic acids such as triethylamine and pyridine. Examples include bases, metal alkoxides such as triisopropoxyaluminum and tetrabutoxyzirconium, metal chelate compounds described later, and the like. Among them, acid catalysts and metal chelate compounds are preferably used.

  As the acid catalyst, hydrochloric acid, sulfuric acid, oxalic acid, acetic acid, phthalic acid and the like are preferably used. As the metal chelate compound, a chelate compound having a metal selected from Zr, Ti, and Al as a central metal can be suitably used without particular limitation.

  Specific examples include tri-n-butoxyethyl acetoacetate zirconium, di-n-butoxybis (ethyl acetoacetate) zirconium, n-butoxy tris (ethyl acetoacetate) zirconium, tetrakis (n-propyl acetoacetate) zirconium, tetrakis ( Zirconium chelate compounds such as acetylacetoacetate) zirconium and tetrakis (ethylacetoacetate) zirconium, diisopropoxybis (ethylacetoacetate) titanium, diisopropoxybis (acetylacetate) titanium, diisopropoxybis (acetylacetone) titanium and the like Titanium chelate compound, diisopropoxyethyl acetoacetate aluminum, diisopropoxyacetylacetonate aluminum , Isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetonatobis (ethylacetoacetate) aluminum, etc. Examples of the aluminum chelate compound. Of these metal chelate compounds, tri-n-butoxyethyl acetoacetate zirconium, diisopropoxyethyl acetoacetate aluminum, and tris (ethyl acetoacetate) aluminum are particularly preferably used. These metal chelate compounds can be used either alone or in combination.

  The content of the catalyst is preferably 0.01 to 30 parts by mass, particularly preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the curable compound.

As a thermal cationic polymerization initiator, for example, SbF ₆ ^- sulfonium salts and the like can be used.

  As the ultraviolet cationic polymerization initiator, for example, diazonium salt, diphenyliodonium salt, triphenylsulfonium salt, sulfonic acid ester, iron arene complex, milanol / aluminum complex and the like can be used.

  Further, when an alkoxysilane compound having an epoxy group is contained in the LR composition, it is preferable to contain a photocationic polymerization initiator that promotes polymerization. Examples of the photocationic polymerization initiator include known acids and A photo acid generator can be mentioned. Examples of the photoacid generator include a cationic polymerization photoinitiator, a dye photodecoloring agent, a photochromic agent, a known compound used in a microresist, and a mixture thereof. Specific examples include onium compounds, organic halogen compounds, and disulfone compounds, and onium compounds are preferable. As the onium compound, diazonium salts, sulfonium salts, iodonium salts and the like represented by the following formulas are preferably used.

ArN ₂ ⁺ Z ⁻ ,
(R) ₃ S ⁺ Z ⁻ ,
(R) ₂ I ⁺ Z ⁻
In the formula, Ar represents an aryl group, R represents an aryl group or an alkyl group having 1 to 20 carbon atoms, and when R appears multiple times in one molecule, they may be the same or different, and Z ⁻ Represents a non-basic and non-nucleophilic anion.

In each of the above formulas, the aryl group represented by Ar or R is also typically phenyl or naphthyl, and these may be substituted with an appropriate group. Specific examples of the anion represented by Z ⁻ include tetrafluoroborate ion (BF ₄ ⁻ ), tetrakis (pentafluorophenyl) borate ion (B (C ₆ F ₅ ) ₄ ⁻ ), and hexafluorophosphate ion. (PF ₆ ⁻ ), hexafluoroarsenate ion (AsF ₆ ⁻ ), hexafluoroantimonate ion (SbF ₆ ⁻ ), hexachloroantimonate ion (SbCl ₆ ⁻ ), hydrogen sulfate ion (HSO ₄ ⁻ ), perchloric acid Ion (ClO ₄ ⁻ ) and the like.

  Examples of other onium compounds include ammonium salts, iminium salts, phosphonium salts, arsonium salts, selenonium salts, boron salts and the like. For example, as described in JP-A-2002-29162, paragraph numbers [0058] to [0059] Compounds and the like.

  Of these, diazonium salts, iodonium salts, sulfonium salts, and iminium salts are preferable from the viewpoint of the material stability of the compound.

  Specific examples of onium salts that can be suitably used include, for example, an amylated sulfonium salt described in paragraph No. [0035] of JP-A No. 9-268205, and paragraph Nos. Of JP-A No. 2000-71366. Diaryl iodonium salts or triarylsulfonium salts described in [0010] to [0011], sulfonium salts of thiobenzoic acid S-phenyl ester described in paragraph [0017] of JP-A-2001-288205, JP-A-2001-133696 Onium salts and the like described in paragraph numbers [0030] to [0033] of the publication.

  Other examples of the acid generator include organometallic / organic halides described in JP-A-2002-29162, paragraphs [0059] to [0062], and a photoacid generator having an o-nitrobenzyl type protecting group. And compounds such as compounds that generate photosulfonic acid to generate sulfonic acid (iminosulfonate, etc.). Since many of these compounds are commercially available, such commercially available products can be used. Commercially available initiators include, for example, “Syracure UVI-6990” (trade name) sold by Dow Chemical Japan Co., Ltd., and “Adekaoptomer SP-150” (available from ADEKA Corporation) Product name), “Adekaoptomer SP-300” (trade name), “RHODORSIL PHOTOINITIAOR 2074” (trade name) sold by Rhodia Japan Co., Ltd., and the like.

  As the acid, Bronsted acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or the like, or organic acid such as acetic acid, formic acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, dibutyltin dilaurate, Examples thereof include Lewis acids such as dibutyltin diacetate, dibutyltin dioctate, triisopropoxyaluminum, tetrabutoxyzirconium, and tetrabutoxytitanate.

  Aromatic polycarboxylic acids such as pyromellitic acid, pyromellitic anhydride, trimellitic acid, trimellitic anhydride, phthalic acid, phthalic anhydride, or anhydrides thereof, maleic acid, maleic anhydride, succinic acid, succinic anhydride Aliphatic polyvalent carboxylic acid or anhydride thereof such as

  As an acid, only 1 type may be used and 2 or more types may be used together.

  These acids and photoacid generators are preferably added in a proportion of 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, with respect to 100 parts by mass of the cationic polymerizable compound. is there. When the addition amount is in the above range, it is preferable from the viewpoint of stability of the curable composition, polymerization reactivity, and the like.

  As the ultraviolet radical polymerization initiator, for example, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone and the like and derivatives thereof can be used.

  Content of a polymerization initiator is 0.01-30 mass parts with respect to 100 mass parts of sclerosing | hardenable compounds, Especially 0.1-20 mass parts is preferable.

  The composition for LR may contain additives such as a refractive index adjusting agent, an organic solvent, a fluorine-based compound, a silicone-based surfactant, a conductive agent, and a leveling agent.

  As the refractive index adjusting agent for LR, in addition to the inorganic fine particles and organic fine particles exemplified as the refractive index adjusting agent that may be contained in the HC composition, hollow silica-based particles can be used. Among these, hollow silica particles are preferably used.

  Hollow silica-based particles are particles having an outer shell layer and porous or hollow inside. Specific examples of the hollow silica-based particles include (1) composite particles composed of porous particles and a coating layer provided on the surface of the porous particles, or (2) a cavity inside, and the content is a solvent, Cavity particles filled with gas or porous material. A hollow particle is a particle having a cavity inside, and the cavity is surrounded by a particle wall. The cavity is filled with contents such as a solvent, a gas, or a porous material used at the time of preparation.

  The average particle diameter of the hollow silica particles is 5 to 200 nm, preferably 10 to 70 nm. The particle size of the hollow silica particles is preferably monodispersed with a coefficient of variation of 1 to 40%. The average particle diameter of the hollow silica-based particles can be measured from an electron micrograph taken with a scanning electron microscope (SEM) or the like. You may measure by the particle size distribution meter etc. which utilize a dynamic light scattering method, a static light scattering method, etc.

  The average particle diameter of the hollow silica-based particles is appropriately selected according to the thickness of the transparent film of the low refractive index layer to be formed, and is 3/2 to 1/10, preferably 2/3, of the film thickness of the transparent film. 1/10 is desirable. These hollow silica particles are preferably used in a state of being dispersed in an appropriate medium in order to form a low refractive index layer. As the dispersion medium, water, alcohol (for example, methanol, ethanol, isopropyl alcohol), ketone (for example, methyl ethyl ketone, methyl isobutyl ketone), ketone alcohol (for example, diacetone alcohol), propylene monomethyl ether, propylene glycol monomethyl ether acetate and the like are preferable. .

  The thickness of the coating layer of the composite particles or the thickness of the particle walls of the hollow particles is 1 to 40 nm, preferably 1 to 20 nm, more preferably 2 to 15 nm. For example, in the case of composite particles, when the thickness of the coating layer is less than 1 nm, the particles may not be completely covered, and the coating liquid component easily enters the inside of the composite particles and the internal porosity May decrease, and the effect of lowering the refractive index may not be sufficiently obtained. In addition, when the thickness of the coating layer exceeds 20 nm, the coating liquid component does not enter the inside, but the porosity (pore volume) of the composite particles is lowered and the effect of lowering the refractive index cannot be sufficiently obtained. Sometimes. For example, in the case of hollow particles, if the particle wall thickness is less than 1 nm, the particle shape may not be maintained, and even if the thickness exceeds 20 nm, the effect of lowering the refractive index may not be sufficiently exhibited. There is.

The coating layer of the composite particles or the particle wall of the hollow particles is preferably composed mainly of silica. Moreover, components other than silica may be contained, specifically, Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , _{sb 2 O 5, SbO 2,} MoO 3, ZnO 2, WO 3 and the like.

Examples of the porous particles constituting the composite particles include those made of silica, those made of silica and an inorganic compound other than silica, and those made of CaF ₂ , NaF, NaAlF ₆ , MgF, and the like. Among these, porous particles made of a composite oxide of silica and an inorganic compound other than silica are particularly preferable. As inorganic compounds other than silica, Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , Sb ₂ O ₅ , SbO ₂ , MoO ₃ , ZnO ₂ , or WO ₃ and two or more. In such porous particles, the molar ratio when the silica is represented by SiO ₂ and the inorganic compound other than silica is represented by oxide (MOx): MOx / SiO ₂ is 0.0001 to 1.0, preferably Is preferably in the range of 0.001 to 0.3.

A porous particle having a molar ratio of MOx / SiO ₂ of less than 0.0001 is difficult to obtain, and even if obtained, a pore volume is small and particles having a low refractive index cannot be obtained. Further, when the molar ratio of the porous particles: MOx / SiO ₂ exceeds 1.0, the ratio of silica decreases, so that the pore volume increases and it may be difficult to obtain a material having a lower refractive index.

  The pore volume of such porous particles is desirably in the range of 0.1 to 1.5 ml / g, preferably 0.2 to 1.5 ml / g. When the pore volume is less than 0.1 ml / g, particles having a sufficiently reduced refractive index cannot be obtained, and when the pore volume exceeds 1.5 ml / g, the strength of the particles is lowered and the strength of the resulting coating may be lowered. is there.

  The pore volume of the porous particles can be determined by a mercury intrusion method.

  Examples of the contents of the hollow particles include a solvent, a gas, and a porous substance used at the time of particle preparation. The solvent may contain an unreacted particle precursor used when preparing the hollow particles, the catalyst used, and the like. As a porous substance, what consists of a compound illustrated by the porous particle is mentioned. These contents may be composed of a single component or may be a mixture of a plurality of components.

  The refractive index of the hollow silica particles is as low as less than 1.42. Such hollow silica-based particles are presumed to have a low refractive index because the porosity inside the porous particles is maintained or the inside is hollow.

  The hollow silica-based particles can be suitably produced by the method for preparing composite oxide colloidal particles disclosed in, for example, paragraphs [0010] to [0033] of JP-A-7-133105, or as a commercially available product. It can also be obtained.

  As a commercially available product of hollow particles, for example, ELCOM V-8209 (manufactured by Catalyst Kasei Kogyo Co., Ltd.) can be used.

  The content of the refractive index adjusting agent, particularly the hollow silica-based particles, is preferably 1 to 400 parts by mass, particularly 25 to 120 parts by mass with respect to 100 parts by mass of the curable compound or the non-curable compound.

  Specific examples of the organic solvent include alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester (eg, methyl acetate, ethyl acetate, acetic acid). Propyl, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic carbonization Hydrogen (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1 Methoxy-2-propanol), propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate. Of these, toluene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethanol, isopropanol, and propylene glycol monomethyl ether are particularly preferable.

  The content of the organic solvent is preferably such that the solid content concentration in the LR composition forming the LR coating film is 1 to 4% by mass. By setting the solid content concentration to 4% by mass or less, coating unevenness hardly occurs, and by setting it to 1% by mass or more, the drying load is reduced.

  The fluorine-based compound is a monomer, oligomer, or polymer containing a perfluoroalkyl group as a mother nucleus, and includes derivatives such as polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene, and the like. Examples of commercially available products include Surflon “S-381”, “S-382”, “SC-101”, “SC-102”, “SC-103”, and “SC-104” (all manufactured by Asahi Glass Co., Ltd.). FLORARD “FC-430”, “FC-431”, “FC-173” (all manufactured by Fluorochemicals-Sumitomo 3M), F-top “EF352”, “EF301”, “EF303” (all Shin-Akita Kasei Co., Ltd.) Company made), Schwegower "8035", "8036" (both made by Schwegman), "BM1000", "BM1100" (both made by BM Himmy), Megafuck "F-171", "F -470 "(all manufactured by Dainippon Ink & Chemicals, Inc.).

  The content of the fluorine-based compound is preferably 0.1 to 30 parts by mass, particularly 1 to 20 parts by mass with respect to 100 parts by mass of the curable compound or the non-curable compound. One or two or more fluorine compounds can be used in combination.

  The silicone-based surfactant is a surfactant obtained by substituting a part of the methyl group of dimethyl silicone oil with a hydrophilic group. The position of substitution may be a side chain of silicone oil, both ends, one end, both end side chains, or the like. Examples of the hydrophilic group include groups derived from polyether, polyglycerin, pyrrolidone, betaine, sulfate, phosphate, quaternary salt and the like.

  As the silicone-based surfactant, a nonionic surfactant having a hydrophobic group composed of dimethylpolysiloxane and a hydrophilic group composed of polyoxyalkylene is preferable.

  Specific examples of the silicone-based nonionic surfactant include, for example, silicone surfactants SILWET L-77, L-720, L-7001, L-7002, L-7604, Y-7006, FZ- 2101, FZ-2104, FZ-2105, FZ-2110, FZ-2118, FZ-2120, FZ-2122, FZ-2123, FZ-2130, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164, FZ-2166, FZ-2191, SUPERSILWET SS-2801, SS-2802, SS-2803, SS-2804, SS-2805, etc. are mentioned.

  The silicone-based nonionic surfactant is more preferably a linear block copolymer in which dimethylpolysiloxane structural portions and polyoxyalkylene chains are alternately and repeatedly bonded. It is preferable from unevenness suppression and leveling properties when a coating composition for forming a low refractive index layer is applied. Specific examples of such silicone-based nonionic surfactants include silicone surfactants ABN SILWET FZ-2203, FZ-2207, FZ-2208, and FZ-2222 manufactured by Toray Dow Corning.

  Reactive silicone-based nonionic surfactants can also be used. Reactive silicone-based nonionic surfactant is a reactive type modified silicone resin in which amino, epoxy, carboxyl, hydroxyl, methacryl, mercapto, phenol, etc. are substituted on the side chain, one end or both ends of polysiloxane. . As amino-modified silicone resins, specifically, KF-860, KF-861, X-22-161A, X-22-161B (above, manufactured by Shin-Etsu Chemical Co., Ltd.), FM-3311, FM-3325 (above, Chisso Corporation), epoxy-modified silicone resins such as KF-105, X-22-163A, X-22-163B, KF-101, KF-1001 (above, Shin-Etsu Chemical Co., Ltd.), polyether-modified X-22-4272, X-22-4952 as silicone resins, X-22-3701E, X-22-3710 (above, manufactured by Shin-Etsu Chemical Co., Ltd.) as carboxyl-modified silicone resins, and carbinol-modified silicone resins KF-6001, KF-6003 (Shin-Etsu Chemical Co., Ltd.), methacryl-modified silicone X-22-164C (made by Shin-Etsu Chemical Co., Ltd.) as the resin, KF-2001 (made by Shin-Etsu Chemical Co., Ltd.) as the mercapto-modified silicone resin, and X-22-1821 as the phenol-modified silicone resin (The above is manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the hydroxyl group-modified silicone resin include FM-4411, FM-4421, FM-DA21, FM-DA26 (manufactured by Chisso Corporation). In addition, X-22-170DX, X-22-2426, X-22-176F (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like are also included.

  The content of the silicone surfactant is preferably 0.1 to 30 parts by mass, particularly 1 to 20 parts by mass with respect to 100 parts by mass of the curable compound or the non-curable compound.

  After forming the LR coating film in this step, drying is usually performed at 40 to 150 ° C. for 10 seconds to 5 minutes.

(Surface treatment process)
In the present invention, the surface treatment step may be performed on HC before the LR coating film forming step. Thereby, the adhesion between HC and LR can be improved.

  Specifically, the surface treatment process is performed after the first UV process and before the LR coating film forming process.

  Specifically, for example, when the execution order (1) is adopted, the surface treatment process may be performed between the first UV process and the second UV process, or may be performed after the second UV process. Good.

  For example, when the implementation order (2) is adopted, the surface treatment process may be performed between the first UV process and the second UV process, or may be performed between the second UV process and the third UV process. Or may be performed after the third UV step.

  For example, when the said execution order (3) or (6) is employ | adopted, a surface treatment process is implemented between a 1st UV process and a LR coating-film formation process.

  Further, for example, when the execution order (4) or (5) is adopted, the surface treatment process may be performed between the first UV process and the second UV process, or the second UV process and the LR coating film formation. You may implement between processes.

  Examples of the surface treatment method include a cleaning method, an alkali saponification treatment method, a plasma treatment method, an electron beam method, an ion beam method, a sputtering method, an acid treatment, a corona treatment method, and an atmospheric pressure glow discharge plasma method. From the viewpoint of durable adhesion, it is preferable to employ an alkali saponification method.

  The alkali saponification treatment is generally carried out in a cycle in which the film is immersed in an alkali solution, washed with water and dried. Further, after the alkali treatment, neutralization in an acidic water step may be performed, followed by washing with water and drying. Examples of the alkaline solution include potassium hydroxide solution and sodium hydroxide solution, and the prescribed concentration of hydroxide ions is preferably 0.1 to 3N, and more preferably 0.5N to 2N. Adhesiveness between the hard coat layer and the low refractive index layer can be obtained by setting the content in the above range. The temperature of the alkaline solution is preferably in the range of 25 to 90 ° C., more preferably 40 to 70 ° C., from the viewpoint of precipitation of the alkaline solution. The alkali treatment time is 5 seconds to 5 minutes, preferably 30 seconds to 3 minutes.

  The alkali saponification treatment may be performed by applying an alkali solution to the hard coat layer surface, and for example, the methods described in JP-A Nos. 2003-313326 and 2007-332253 may be used.

  Examples of the plasma treatment include flame plasma treatment, atmospheric pressure plasma treatment, and atmospheric pressure plasma treatment.

  As the plasma processing method, plasma processing techniques disclosed in JP-A Nos. 2004-352777, 2004-352777, 2007-314707, and the like can be referred to.

  As a processing apparatus, AP-T series etc. which are the atmospheric pressure plasma processing apparatus by Sekisui Chemical Co., Ltd. can be used.

  The corona treatment can be performed by using a device commercially available from a corona treatment having a multi-knife electrode of SOFTAL (Sophthal), Kasuga Electric Co., Ltd., Toyo Electric Co., Ltd. or the like. The intensity of the corona discharge treatment depends on the distance between the electrodes, the output per unit area, and the generator frequency.

As one electrode (A electrode) of the corona treatment apparatus, a commercially available one can be used, but the material can be selected from aluminum, stainless steel and the like. The other is an electrode (B electrode) for holding a plastic film, and is a roll electrode installed at a certain distance from the A electrode so that the corona treatment is carried out stably and uniformly. A commercially available one can also be used, and the material is preferably a roll made of ceramic, silicon, EPT rubber, hyperon rubber or the like on a roll made of aluminum, stainless steel, or a metal thereof. It is done. The frequency used for the corona treatment is a frequency of 20 kHz or more and 100 kHz or less, and a frequency of 30 kHz to 60 kHz is preferable. When the frequency is lowered, the uniformity of the corona treatment is deteriorated and unevenness of the corona treatment occurs. In addition, when the frequency is increased, there is no particular problem when performing high-output corona treatment, but when performing low-output corona treatment, it is difficult to perform stable processing, resulting in uneven processing. Will occur. The output of the corona treatment is 10 to 500 W · min. / M ² but 20 to 400 W · min. An output of / m ² is preferred. The distance between the electrode and the film is 5 mm or more and 50 mm or less, preferably 10 mm or more and 35 mm or less. When the gap opens, a higher voltage is required to maintain a constant output, and unevenness is likely to occur. On the other hand, if the gap is too narrow, the applied voltage becomes too low and unevenness is likely to occur. Furthermore, when the film is transported and continuously processed, the film contacts the electrode and scratches are generated.

(BC coating film formation process)
In the present invention, a coating film for a backcoat layer may be formed. In the present specification, “BC” means a backcoat layer. The BC coating film forming process may be performed after the first UV process regardless of whether the LR coating film forming process or the surface treatment process is performed. If desired, the BC coating film may be cured in the UV process after the present process is performed.

  The BC coating film is formed on the surface of the substrate opposite to the side on which HC is provided. The BC coating film is provided in order to correct the curl generated by providing HC. That is, the degree of curling can be balanced by imparting the property of curling with the surface on which the BC coating film is provided facing inward. The BC coating film is preferably applied also as an anti-blocking layer, and in that case, it is preferable that fine particles are added to the BC coating composition in order to provide an anti-blocking function.

  As fine particles added to the composition for BC coating, examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, oxidized Mention may be made of tin, indium oxide, zinc oxide, ITO, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. These fine particles include, for example, Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.), Seahoster KE-P10, KE-P30, KE- P50, KE-P100, KE-P150, and KE-P250 (above, manufactured by Nippon Shokubai Co., Ltd.) are commercially available and can be used. Examples of the polymer include silicone resin, fluororesin, and acrylic resin. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120, and 240 (manufactured by Toshiba Silicone Co., Ltd.) Are commercially available and can be used.

  Among these fine particles, Aerosil 200V, Aerosil R972V, Seahoster KE-P30, KE-P50, and KE-P100 are particularly preferably used because they have a large anti-blocking effect while keeping haze low.

  The fine particles contained in the BC coating film are 0.1 to 50% by mass, preferably 0.1 to 10% by mass, based on the binder.

  Examples of the solvent used for forming the BC coating film include dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylformamide, methyl acetate, ethyl acetate, trichloroethylene, methylene chloride, ethylene chloride, tetrachloroethane, trichloroethane, Chloroform, water, methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butanol, cyclohexanone, cyclohexanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, or hydrocarbons (toluene, xylene) Are used in appropriate combinations.

  Examples of the resin used as a binder for the BC coating film include vinyl chloride-vinyl acetate copolymer, vinyl chloride resin, vinyl acetate resin, vinyl acetate-vinyl alcohol copolymer, partially hydrolyzed vinyl chloride-vinyl acetate copolymer. Polymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer, ethylene-vinyl alcohol copolymer, chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, etc. Vinyl polymer or copolymer, nitrocellulose, cellulose acetate propionate (preferably acetyl group substitution degree 1.8-2.3, propionyl group substitution degree 0.1-1.0), diacetyl cellulose, cellulose Cellulose derivatives such as acetate butyrate resin, maleic acid and / or Crylic acid copolymer, acrylic ester copolymer, acrylonitrile-styrene copolymer, chlorinated polyethylene, acrylonitrile-chlorinated polyethylene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylic resin, polyvinyl Alcohol resin, polyvinyl acetal resin, polyvinyl butyral resin, urethane resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, styrene-butadiene resin, butadiene-acrylonitrile resin, etc. However, it is not limited to these. From the viewpoint of adhesion and transparency, a cellulose derivative, particularly cellulose acetate propionate is preferred.

  These coating compositions are preferably applied to the surface of the transparent resin film with a wet film thickness of 1 to 100 μm using a gravure coater, dip coater, reverse coater, wire bar coater, die coater, spray coating, ink jet coating or the like. Is particularly preferably 5 to 30 μm.

  After forming the BC coating film in this step, drying is usually performed at 40 to 150 ° C. for 10 seconds to 5 minutes.

(Post-processing process)
After performing the said process in this invention, it is preferable to heat-process as a post-processing process. The HC formed in the above process, and optionally the layers such as LR and BC, are stabilized by heat treatment.

  The heat treatment is usually performed at 80 to 150 ° C. for 10 seconds to 3 minutes.

(Base material)
The base material used in the present invention is not particularly limited, and it can be used from a sheet-like material having a thickness of about 0.2 to 5 mm to a film-like material having a thickness of 20 to 200 μm. In the present invention, it is preferable that the film base material is unwound from a state of being wound in a roll shape with a width of 1 m or more, and is continuously wound up in a roll shape after performing the above-described steps continuously. The width of the substrate is usually 1 to 4 m.

  The substrate thickness / substrate width is not particularly limited, but is preferably 10 to 100 ppm, particularly preferably 10 to 80 ppm. When a substrate having a thickness / width within the above range is used, it is difficult to achieve both the hardness and flatness of the film surface. In the present invention, even in such a case, the hardness and flatness of the film surface This is because it can be sufficiently improved.

  The formation width of the HC coating film on the substrate is more preferably 75% or more, particularly 80 to 99%, relative to the substrate width. If it is less than 75%, the yield is lowered and the efficiency is poor, and if it is more than 99%, the back of the liquid film is generated, resulting in a problem in transportability.

  The material which comprises a base material in particular is not restrict | limited, What is optically isotropic is preferable. For example, triacetyl cellulose film, cellulose acetate propionate ionate film, cellulose diacetate film, cellulose ester film such as cellulose acetate butyrate film, polyester film such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate film, polyarylate Film, polysulfone (including polyethersulfone) film, polyethylene film, polypropylene film, cellophane, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, norbornene resin film, polymethyl Pentene film, polyetherketone film, poly Chromatography ether ketone imides film, polyamide film, fluorocarbon resin film, nylon film, cycloolefin polymer films, there may be mentioned polymethyl methacrylate film or an acrylic film or the like, but are not limited to. Among these, cellulose ester films (for example, Konica Minoltak KC8UX2M, KC4UX2M, KC4UY, KC8UT, KC5UN, KC12UR, KC8UCR-3, KC8UCR-4 (above, manufactured by Konica Minolta Opto), polycarbonate film, cycloolefin A polymer film and a polyester film are preferable, and in the present invention, a cellulose ester film is particularly preferable in terms of production, cost, isotropy, adhesiveness, and object effects of the present invention.

  The cellulose ester film preferable as the substrate film will be described in detail.

  The cellulose ester is preferably a lower fatty acid ester of cellulose. The lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms. For example, cellulose acetate, cellulose propionate, cellulose butyrate and the like, and JP-A Nos. 10-45804 and 08-231761 , Mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate as described in US Pat. No. 2,319,052 can be used. Among the above descriptions, the lower fatty acid esters of cellulose particularly preferably used are cellulose triacetate and cellulose acetate propionate. These cellulose esters can be used alone or in combination.

  In the case of cellulose triacetate, those having an average degree of acetylation (bound acetic acid amount) of 54.0 to 62.5% are preferably used, and more preferably an average degree of acetylation of 58.0 to 62.5%. Cellulose triacetate. When the average degree of acetylation is small, the dimensional change is large, and the polarization degree of the polarizing plate is lowered. When the average degree of acetylation is large, the solubility in a solvent is lowered and the productivity is lowered. Preferred cellulose esters other than cellulose triacetate have an acyl group having 2 to 4 carbon atoms as a substituent, and when the substitution degree of acetyl group is X and the substitution degree of propionyl group or butyryl group is Y, the following formula ( It is a cellulose ester containing the cellulose ester which satisfy | fills I) and (II) simultaneously.

Formula (I) 2.6 ≦ X + Y ≦ 3.0
Formula (II) 0 ≦ X ≦ 2.5
Of these, cellulose acetate propionate is preferably used, and it is particularly preferable that 1.9 ≦ X ≦ 2.5 and 0.1 ≦ Y ≦ 0.9. The portion that is not substituted with an acyl group usually exists as a hydroxyl group. These can be synthesized by known methods. The measuring method of the substitution degree of an acyl group can be measured according to ASTM-D817-96.

  The molecular weight of the cellulose ester is preferably a number average molecular weight (Mn) of 60,000 to 300,000, more preferably 70,000 to 200,000, particularly preferably 100,000 to 200,000. The cellulose ester used in the present invention preferably has a weight average molecular weight (Mw) / number average molecular weight (Mn) ratio of 4.0 or less, more preferably 1.4 to 2.3.

  Since the average molecular weight and molecular weight distribution of the cellulose ester can be measured using high performance liquid chromatography, the number average molecular weight (Mn) and the weight average molecular weight (Mw) can be calculated using this, and the ratio can be calculated.

  The measurement conditions are as follows.

Solvent: Methylene chloride Column: Shodex K806, K805, K803G (Used by connecting three Showa Denko Co., Ltd.)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (GL Science Co., Ltd.)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0 ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation)
A calibration curve with 13 samples from Mw = 1,000,000 to 500 was used. The 13 samples are preferably used at approximately equal intervals.

  As the cellulose ester, a cellulose ester synthesized using cotton linter, wood pulp, kenaf or the like as a raw material can be used alone or in combination. In particular, it is preferable to use a cellulose ester synthesized from cotton linter (hereinafter sometimes simply referred to as linter) alone or in combination.

  The cellulose ester film can be produced by a so-called solution casting method or melt casting method. At that time, the cellulose ester film may contain additives such as a plasticizer, an ultraviolet absorber, and inorganic fine particles.

(Hard coat film)
The hard coat film of the present invention obtained by the above method achieves a pencil hardness of 3H or more, preferably 4H or more.

  The pencil hardness is a pencil specified by JIS K 5400 using a test pencil specified by JIS S 6006 after the prepared antireflection film sample is conditioned at a temperature of 23 ° C. and a relative humidity of 55% for 2 hours or more. It is the value measured according to the hardness evaluation method.

(Use)
The hard coat film of the present invention is particularly suitable for use as an optical film such as an antireflection film.

  When the antireflection film of the present invention is used as, for example, a polarizing plate protective film, the thickness of the protective film is preferably 10 to 500 μm. In particular, it is preferably 20 μm or more, more preferably 35 μm or more. Moreover, 150 micrometers or less, Furthermore 120 micrometers or less are preferable. Most preferably, it is 25 or more and 90 micrometers. If the antireflection film is thicker than the above region, the polarizing plate after polarizing plate processing becomes too thick, and is not suitable for the purpose of thin and light in liquid crystal displays used for notebook personal computers and mobile electronic devices. On the other hand, if it is thinner than the above-mentioned region, it is not preferable because it becomes difficult to develop retardation, the moisture permeability of the film becomes high, and the ability to protect the polarizer from humidity decreases.

  A polarizing plate using the antireflection film of the present invention will be described. The polarizing plate can be produced by a general method. The back surface side of the antireflection film of the present invention is subjected to alkali saponification treatment, and a completely saponified polyvinyl alcohol aqueous solution is used on at least one surface of a polarizing film prepared by immersing and stretching the treated antireflection film in an iodine solution. It is preferable to bond them together. The antireflection film may be used on the other surface, or another polarizing plate protective film may be used. With respect to the antireflection film of the present invention, the polarizing plate protective film used on the other surface has an in-plane retardation Ro of 590 nm, an optical compensation film having a phase difference of 20 to 70 nm and Rt of 70 to 400 nm. It is preferable to use a retardation film. These can be prepared, for example, by the methods described in JP-A No. 2002-71957 and Japanese Patent Application No. 2002-155395. Alternatively, it is preferable to use a polarizing plate protective film that also serves as an optical compensation film having an optically anisotropic layer formed by aligning a liquid crystal compound such as a discotic liquid crystal. For example, the optically anisotropic layer can be formed by the method described in JP-A-2003-98348. Alternatively, a non-oriented film having a retardation Ro of 590 nm of 0 to 5 nm and an Rt of -20 to +20 nm described in JP-A No. 2003-12859 is also preferably used.

  By using it in combination with the antireflection film of the present invention, a polarizing plate having a stable viewing angle expansion effect can be obtained.

  As a polarizing plate protective film used on the back side, as a commercially available cellulose ester film, KC8UX2MW, KC4UX, KC5UX, KC4UY, KC8UY, KC12UR, KC4UEW, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC4FR-1, KC4F-1, -2, KC8UE, KC4UE (manufactured by Konica Minolta Opto Co., Ltd.) and the like are preferably used.

  The polarizing film, which is the main component of the polarizing plate, is an element that transmits only light having a polarization plane in a certain direction. A typical polarizing film known at present is a polyvinyl alcohol polarizing film, which is a polyvinyl alcohol film. There are ones in which iodine is dyed on a system film and ones in which a dichroic dye is dyed, but it is not limited to this. As the polarizing film, a polyvinyl alcohol aqueous solution is formed and dyed by uniaxially stretching or dyed, or uniaxially stretched after dyeing, and then preferably subjected to a durability treatment with a boron compound. A polarizing film having a thickness of 5 to 30 μm, preferably 8 to 15 μm, is preferably used. On the surface of the polarizing film, one side of the antireflection film of the present invention is bonded to form a polarizing plate. It is preferably bonded with an aqueous adhesive mainly composed of completely saponified polyvinyl alcohol or the like.

  By incorporating a polarizing plate produced using the antireflection film of the present invention into a display device, various image display devices having excellent visibility can be produced.

  The antireflection film of the present invention is incorporated in the polarizing plate, and is a reflection type, transmission type, transflective liquid crystal display device or TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS. It is preferably used in liquid crystal display devices of various drive systems such as a type and an OCB type.

  The antireflection film of the present invention is also preferably used for various image display devices such as a plasma display, a field emission display, an organic EL display, an inorganic EL display, and electronic paper.

(Production of film substrate 1)
(Dope 1)
The following materials were sequentially put into a sealed container, the temperature in the container was raised from 20 ° C. to 80 ° C., and the mixture was stirred for 3 hours while maintaining the temperature at 80 ° C. to completely dissolve the cellulose ester. . The silicon oxide fine particles were added dispersed in a solution of a solvent to be added in advance and a small amount of cellulose ester. The dope was filtered using a filter paper (Azumi filter paper No. 244, manufactured by Azumi Filter Paper Co., Ltd.) to obtain a dope 1.

Cellulose triacetate (acetyl group substitution degree 2.95) 100 parts by weight Trimethylolpropane tribenzoate 5 parts by weight Ethylphthalylethyl glycolate 5 parts by weight Fine particles of silicon oxide 0.2 parts by weight (Aerosil R972V, manufactured by Nippon Aerosil Co., Ltd.)
Tinuvin 109 (manufactured by Ciba Japan) 1 part by weight Tinuvin 171 (manufactured by Ciba Japan) 1 part by weight Methylene chloride 300 parts by weight Ethanol 40 parts by weight Butanol 5 parts by weight Next, the obtained dope 1 was heated to 35 ° C. A web was formed by passing the casting die kept warm to a support of 35 ° C. made of a stainless steel endless belt. Next, the web was dried on the support, and the web was peeled from the support with a peeling roll when the residual solvent amount of the web reached 80% by mass.

The web after peeling is transported while being dried with 90 ° C drying air in a transport drying process using a plurality of rolls arranged on the top and bottom, and then grips both ends of the web with a tenter and then stretches in the width direction at a temperature of 130 ° C. The film was stretched to 1.1 times the previous size. After stretching with a tenter, the web was dried with a drying air at a temperature of 135 ° C. in a transport drying process using a plurality of rolls arranged vertically. Then, it cooled to room temperature and wound up and produced the elongate film base material 1 of width 1330mm, film thickness 80 micrometers, length 4000m, and refraction 1.49. Moreover, the film base material 1 was wound by giving a knurling process with a width of 1 cm and an average height of 10 μm at both ends. The draw ratio in the web conveyance direction immediately after peeling calculated from the rotational speed of the stainless steel band support and the operating speed of the tenter was 1.1 times.
(Production of film substrate 2)
The film substrate 2 was produced by the same method as the production of the film substrate 1 except that the thickness of the film substrate was 40 μm by adjusting the flow rate of the dope.
(Production of film substrate 3)
The film substrate 3 was produced by the same method as the production of the film substrate 1 except that the thickness of the film substrate was 40 μm by adjusting the flow rate of the dope and the substrate width was 2300 mm.
(Production of film substrate 4)
The film substrate 4 was produced by the same method as the production of the film substrate 1 except that the thickness of the film substrate was 40 μm by adjusting the flow rate of the dope and the substrate width was 3000 mm.
(Production of film substrate 5)
A film substrate 5 was produced by the same method as the production of the film substrate 1 except that the thickness of the film substrate was 150 μm by adjusting the flow rate of the dope.
<Example 1; Production of antireflection film 1>
The following hard coat layer composition 1 was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a hard coat layer coating solution. This was applied to the surface of the film substrate 1 using an extrusion coater and dried at a temperature of 80 ° C. (HC coating film forming step). Thereafter, using an ultraviolet lamp, the coating layer was cured by irradiating ultraviolet rays from the hard coat coating surface side at an illuminance of 80 mW / cm ² and an amount of light of 80 mJ / cm ² of the irradiated portion (UV process A). Next, the following back coat layer composition 1 was applied to the surface opposite to the surface of the film substrate 1 on which the hard coat layer was applied with an extrusion coater so that the wet film thickness was 14 μm, and the temperature was 50 ° C. It dried and created the film 1 (BC formation process).

(Hard coat layer composition 1)
The following materials were stirred and mixed to obtain hard coat layer composition 1.

90 parts by mass of dipentaerythritol hexaacrylate (NK ester A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.)
Pentaerythritol triacrylate 20 parts by mass Pentaerythritol tetraacrylate 60 parts by mass Urethane acrylate 10 parts by mass (trade name U-4HA manufactured by Shin-Nakamura Chemical Co., Ltd., polyfunctional acrylate)
Irgacure 184 8 parts by mass (Ciba Japan Co., Ltd.)
Irgacure 907 10 parts by mass (Ciba Japan Co., Ltd.)
9 parts by mass of polyether-modified silicone compound (trade name; KF-355A, manufactured by Shin-Etsu Chemical Co., Ltd., leveling agent)
Propylene glycol monomethyl ether 10 parts by weight Ethyl acetate 80 parts by weight Methyl ethyl ketone 100 parts by weight (Backcoat layer composition 1)
Acetone 54 parts by weight Methyl ethyl ketone 24 parts by weight Methanol 22 parts by weight Cellulose acetate propionate 0.6 parts by weight (acetyl group substitution degree 1.9, propionyl group substitution degree 0.8)
0.2 parts by mass of ultrafine silica 2% acetone dispersion (Aerosil 200V manufactured by Nippon Aerosil Co., Ltd.)
Next, the hard coat layer of the produced film 1 was surface-treated by alkali saponification treatment. Specifically, the produced film 1 is immersed in a 1N aqueous sodium hydroxide solution heated to 50 ° C. for 2 minutes, subjected to alkali treatment, washed with water, and then washed with a 0.5% -H ₂ SO ₄ aqueous solution at 25 ° C. for 30 seconds. It was immersed, neutralized, washed with water, and dried to produce an alkali saponified film 1 (surface treatment step).

The film 1 subjected to the alkali saponification treatment was irradiated with ultraviolet rays again from the hard coat layer application surface side using an ultraviolet lamp at an illuminance of 100 mW / cm ² and a light amount of 160 mJ / cm ² (UV process B). The following low refractive index layer composition 1 was continuously applied onto the hard coat layer surface by extrusion coating, and dried at 100 ° C. for 1 minute (LR coating film forming step). From the hard coat layer application surface side, ultraviolet rays were irradiated again with an illuminance of 100 mW / cm ² and a light amount of 160 mJ / cm ² (UV process C). Furthermore, after heat-treating the film at 130 ° C. for 1 minute (post-treatment step), the film was wound into a roll. Subsequently, the anti-reflective film 1 was manufactured by heat-aging at 60 degreeC for 2 days. The dry thickness of the hard coat layer was 12 μm, and the dry thickness of the low refractive index layer was 85 nm.

(Low refractive index layer composition 1; polycondensation type)
Propylene glycol monomethyl ether 200 parts by mass Isopropyl alcohol 660 parts by mass Tetraethoxysilane hydrolyzate A 120 parts by mass γ-methacryloxypropyltrimethoxysilane 4 parts by mass (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.)
30 parts by mass of isopropyl alcohol-dispersed hollow silica particle sol (solid content 20%, silica sol manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name: ELCOM V-8209)
Aluminum ethyl acetoacetate / diisopropylate 2 parts by mass Silicone surfactant (FZ-2207, manufactured by Nippon Unicar Co., Ltd.) 10% propylene glycol monomethyl ether solution 3 parts by mass Acetic acid 4 parts by mass (Tetraethoxysilane hydrolyzate A Manufacturing of)
By mixing 205 g of tetraethoxysilane, 25 g of tridecafluorooctyltrimethoxysilane, and 440 g of ethanol and adding 120 g of 2% aqueous acetic acid solution thereto, the mixture is stirred for 20 hours in a water bath at a temperature of 25 ° C. Hydrolyzate A was prepared.
<Examples 2-6, 9-12 / Comparative Examples 1-6>
An antireflection film is produced in the same manner as in Example 1, except that a predetermined film substrate is used, a predetermined low refractive index layer coating composition is used, and a UV process is performed under predetermined conditions. did.

  In Table 1, “-” in the row of the low refractive index layer indicates that the LR coating film forming step was not performed.

In each UV process column, “-” indicates that the UV process was not performed.
<Example 7>
Without subjecting the hard coat layer of the film 1 produced in the same manner as in Example 1 to surface treatment, the following low refractive index layer composition 2 was applied to the hard coat layer surface by extrusion coating and dried at 100 ° C. for 1 minute. (LR coating film forming step). From the hard coat layer application surface side, ultraviolet rays were irradiated at an illuminance of 100 mW / cm ² and a light amount of 160 mJ / cm ² (UV process B), and left for 1 minute. Furthermore, ultraviolet rays were irradiated from the hard coat layer application surface side with an illuminance of 100 mW / cm ² and a light amount of 160 mJ / cm ² (UV process C). The thickness of the low refractive index layer was 85 nm. Furthermore, after heat-treating the film at 130 ° C. for 1 minute (post-treatment step), the film was wound into a roll. Subsequently, the film was subjected to heat aging treatment at 60 ° C. for 2 days to produce an antireflection film.

(Low refractive index layer composition 2; cationic polymerization type)
(Cationically polymerizable compound)
[1- (3-Ethyl-3-oxetanyl) methyl] ether 6.5 parts by mass 3,4-epoxy-6-methylcyclohexylmethylcarboxylate 0.5 parts by mass Fluorine-containing epoxy compound 1 2 parts by mass (cationic polymerization property) Initiator)
Triallylsulfonium hexafluorophosphine salt 0.2 parts by mass (fine particles)
Isopropyl alcohol-dispersed hollow silica fine particle sol 6.9 parts by mass (solid content 20%, silica sol manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name: ELCOM V-8209)
(Additive)
0.9% by mass of 10% propylene glycol monomethyl ether solution of a silicone compound (FZ-2207, Nippon Unicar Co., Ltd.) (solvent)
Methyl isobutyl ketone 90 parts by mass Methyl ethyl ketone 30 parts by mass (Production of fluorine-containing epoxy compound 1)
81.03 g of 1,3-dihydroxyhexafluoroisopropylbenzene and 185 g of epichlorohydrin were mixed, 16.27 g of sodium hydroxide and 40 ml of water were added, and the mixture was heated to reflux with stirring. After reacting at 130 ° C. for 3 hours, the mixture was naturally cooled, and the produced sodium chloride was removed by suction filtration. The obtained filtrate was extracted with chloroform-water, and the organic layer was dried.
95.7g of fluorine-containing epoxy compound 1 was obtained by filtering and concentrating.
<Example 8>
Without subjecting the hard coat layer of film 1 produced in the same manner as in Example 1 to surface treatment, the following low refractive index layer composition 3 was applied to the hard coat layer surface by extrusion coating and dried at 100 ° C. for 1 minute. (LR coating film forming step). From the hard coat layer application surface side, ultraviolet rays were irradiated at an illuminance of 100 mW / cm ² and a light amount of 160 mJ / cm ² (UV process B), and left for 1 minute. Furthermore, ultraviolet rays were irradiated from the hard coat layer application surface side with an illuminance of 100 mW / cm ² and an amount of light of 200 mJ / cm ² (UV process C). The thickness of the low refractive index layer was 90 nm. Furthermore, after heat-treating the film at 130 ° C. for 1 minute (post-treatment step), the film was wound into a roll. Subsequently, the film was subjected to heat aging treatment at 60 ° C. for 2 days to produce an antireflection film.

(Low refractive index layer composition 3; cationic polymerization type)
(Cationically polymerizable compound)
Alkoxysilane compound A-1 having an epoxy group 6.5 parts by mass [1- (3-ethyl-3-oxetanyl) methyl] ether 0.5 parts by mass Fluorine-containing epoxy compound 1 2 parts by mass (cationic polymerizable initiator)
Triallylsulfonium hexafluorophosphine salt 0.2 parts by mass (fine particles)
Isopropyl alcohol-dispersed hollow silica fine particle sol 6.9 parts by mass (solid content 20%, silica sol manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name: ELCOM V-8209)
(Additive)
0.9% by mass of 10% propylene glycol monomethyl ether solution of a silicone compound (FZ-2207, Nippon Unicar Co., Ltd.) (solvent)
90 parts by mass of methyl isobutyl ketone 30 parts by mass of methyl ethyl ketone (production of alkoxysilane compound A-1 having an epoxy group)
A reaction vessel was charged with 94.5 parts of γ-glycidoxypropyltrimethoxysilane, 89.1 parts of methyl isobutyl ketone, and 10.8 parts of a 0.1% by weight aqueous potassium hydroxide solution, heated to 80 ° C. and heated for 5 hours. Reacted. After completion of the reaction, the recommendation was repeated using a 0.5 mass% aqueous acetic acid solution until the washing solution became neutral, and then the solvent was removed under reduced pressure to obtain 67 parts of a silicon compound (A-1). The obtained epoxy equivalent was 164 g / eq and refractive index 1.472.

<Evaluation>
(Pencil hardness)
Pencil hardness was measured for the surface on the hard coat layer forming side of the antireflection film after the wet heat treatment. Specifically, the antireflection film was conditioned at a temperature of 23 ° C. and a relative humidity of 55% for 24 hours, and then the pencil hardness was evaluated by the following method. Using a test pencil stipulated by JIS-S6006, according to the pencil hardness evaluation method stipulated by JIS-K5400, a 500 g weight is used to repeatedly scratch a given surface with a pencil of each hardness 5 times, up to one scratch. The hardness of was measured. The higher the number, the higher the hardness. The hardness is 3H or higher, which is a practically acceptable range, and the preferred range is 4H or higher.
(Flatness)
The flatness of the surface on the hard coat layer forming side of the antireflection film was evaluated. Specifically, the reflection image of the fluorescent lamp on the hard coat layer forming surface was observed and evaluated as follows.

◎: There is no distortion in the reflected image of the fluorescent lamp. ○: The distortion of the reflected image of the fluorescent lamp is slight and there is no practical problem. ×: The distortion of the reflected image of the fluorescent lamp is very large and there is a practical problem. (Scratch resistance after accelerated light resistance test)
The scratch resistance after the accelerated light resistance test was evaluated on the low refractive index layer-formed surface in the antireflection film produced in Examples 3, 7, and 8. Specifically, on the surface of the antireflection film produced in Examples 3, 7, and 8, using a super xenon weather meter (SX120, manufactured by Suga Test Instruments Co., Ltd.), the light quantity is 100 W / m ² ; 300 to 400 nm, black A UV irradiation test was conducted under the conditions of a panel temperature of 50 ° C., a humidity of 65%, and a test time of 200 hours. Thereafter, a scratch resistance test was conducted.

The prepared antireflection film sample was cut out to a size of 5 cm × 10 cm, and a load of 500 g / cm ² was applied to steel wool (SW) of Bonster # 0000 manufactured by Nippon Steel Wool Co., Ltd. The number of wounds was measured. Note that the number of scratches is measured at a place where the number of scratches is the largest among the portions to which a load is applied. The smaller the number of scratches, the better the scratch resistance.

A: The number of scratches is 0 to 5 / cm
○: The number of scratches is 5 to 10 / cm
Δ: Number of scratches 10-20 / cm
×: 21 / cm or more

Claims (15)

A method for producing a hard coat film comprising forming a hard coat layer coating film on a substrate and then irradiating with ultraviolet rays in two or more steps,
The illuminance of ultraviolet rays in the first ultraviolet irradiation step is 50 to 150 mW / cm ² , and the light amount is 50 to 200 mJ / cm ² .
The illuminance of ultraviolet rays in each ultraviolet irradiation step after the second time is 50 mW / cm ² or more, and the amount of light is 50 mJ / cm ² or more.
The manufacturing method of the hard coat film characterized by the total light quantity of the ultraviolet-ray in an all-ultraviolet irradiation process being 100-500 mJ / cm < ² >. The manufacturing method of the hard coat film of Claim 1 which irradiates with an ultraviolet-ray divided into 2 or 3 processes. 2 and subsequent illumination 50~200mW / cm ² of ultraviolet in the ultraviolet irradiation step, the production method of the hard coat film according to claim 1 or 2 light quantity is 50~200mJ / cm ^2. The manufacturing method of the hard coat film in any one of Claims 1-3 which implements each process in the following orders.
(1) Hard coat layer coating film forming process (HC coating film forming process) -first ultraviolet light process (first UV process) -second ultraviolet light process (second UV process); or (2) HC coating film forming process-second 1UV process-2nd UV process-3rd UV process It is a manufacturing method of the hard coat film in any one of Claims 1-4 which form the coating film for low refractive index layers (LR coating film) after the 1st ultraviolet irradiation process (1st UV process), The manufacturing method of the hard coat film which implements a process in the following orders.
(3) HC coating film forming process-first UV process-LR coating film forming process-second UV process;
(4) HC coating film forming process-first UV process-second UV process-LR coating film forming process;
(5) HC coating film forming process-first UV process-second UV process-LR coating film forming process-third UV process; or (6) HC coating film forming process-first UV process-LR coating film forming process-second UV process. -3rd UV process The method for producing a hard coat film according to any one of claims 1 to 5, wherein the substrate width is 1000 mm or more and the substrate thickness / substrate width is 10 to 100 rpm. The method for producing a hard coat film according to any one of claims 1 to 6, wherein a ratio of the coating formation width for the hard coat layer to the substrate width is 75% or more. The method for producing a hard coat film according to any one of claims 1 to 7, wherein the substrate is a cellulose ester film. The manufacturing method of the hard coat film in any one of Claims 1-8 in which the coating film for hard-coat layers contains the ultraviolet curable compound containing polyfunctional (meth) acrylate. The method for producing a hard coat film according to claim 5, wherein the coating film for the low refractive index layer contains a curable compound and becomes a layer having a refractive index lower than that of the substrate by curing. The curable compound contained in the coating film for the low refractive index layer is selected from the group consisting of a thermosetting polycondensation type compound, a heat and / or photocurable cationic polymerization type compound, and a heat and / or photocurable radical polymerization type compound. The method for producing a hard coat film according to claim 10, wherein the compound is one or more selected compounds. The curable compound contained in the coating film for low refractive index contains an organosilicon compound represented by the following general formula (5), a hydrolyzate thereof, or a polycondensate thereof. A method for producing a hard coat film.
R2mSiX2 _4-m (5)
In the formula, R2 is an epoxy group, X2 is a hydroxyl group or a hydrolyzable substituent, and m is an integer of 0 to 3. The manufacturing method of the hard coat film in any one of Claims 10-12 in which the coating film for low refractive indexes contains a photocationic polymerization initiator. The method for producing a hard coat film according to claim 13, wherein the cationic photopolymerization initiator is any compound selected from an onium compound, an organic halogen compound, and a disulfone compound. The hard coat film manufactured with the manufacturing method of the hard coat film in any one of Claims 1-11.