JP6986013B2 - Hardcourt film and its manufacturing method - Google Patents

Description

The present invention relates to a hard coat film in which a hard coat layer containing an ionizing wire curing resin and a leveling agent is provided on an acrylic or cycloolefin polymer-based base film, and a method for producing the same.

With the progress of technology in recent years, in addition to the conventional cathode ray tube display device (CRT), a liquid crystal display device (LCD), a plasma display (PDP), an electroluminescence display (ELD), etc. have been developed and put into practical use. It has been transformed. Among these, LCDs have changed from notebook personal computers (notebook PCs) and monitors to televisions with the technological innovations related to high viewing angles, high definition, high-speed responsiveness, and color reproducibility. It's changing.

A liquid crystal display in which polarizing plates are arranged on both sides of a liquid crystal cell is usually used for the LCD, and the surface of the liquid crystal display is generally hard-coated to prevent the polarizing plate from being scratched. There is. For the hard coat treatment, a method of attaching a hard coat film having high transparency and sufficient hardness to a polarizing plate is often used.

As such a hard coat film, a film in which a hard coat layer is formed on a base film such as a triacetyl cellulose (TAC) film is generally used, but the TAC film has a drawback of being inferior in moisture resistance and heat resistance. It is disclosed that an acrylic base film is used to improve durability (see Patent Documents 1 and 2). Further, it is also disclosed that a cycloolefin polymer-based base film (hereinafter, referred to as “COP-based base film”) is used to improve the durability (see Patent Document 3).

Further, an increasing number of display devices are provided with a touch panel on the visual side of the liquid crystal display, in which a touch panel is attached to the hard coat layer of the hard coat film located on the outermost surface of the liquid crystal display with an adhesive or the like. The hard coat film used for the display device provided with this touch panel needs to have adhesiveness (wetting property) between the hard coat film and the adhesive used for adhering the touch panel, and is patented. It is known that it is effective to use a hard coat film having a low water contact angle on the surface of the hard coat layer as disclosed in Documents 4 and 5.

Japanese Patent No. 5235755 Japanese Patent No. 541452 Japanese Unexamined Patent Publication No. 2013-186236 Japanese Unexamined Patent Publication No. 2013-155219 Japanese Unexamined Patent Publication No. 2001-272503

However, in Patent Documents 1 and 2, when a high flatness (for example, an arithmetic average surface roughness (Ra) of 1 nm or less) is used, the adhesion between the acrylic base film and the hard coat layer is poor. There was the issue of being sufficient. Further, since the COP-based base film is a non-polar resin, there is a problem in the adhesion of the hard coat layer. In Patent Document 3, the adhesion between the COP-based base film and the hard coat layer is tape peeling 1. Only the durability of the dose was obtained, and it was still insufficient.

Further, although the hard coat film disclosed in Patent Documents 4 and 5 has excellent adhesiveness to an adhesive, there is a problem that interference fringes are likely to occur and visibility is likely to be deteriorated.

Therefore, the present invention has excellent adhesion of the hard coat layer even when an acrylic base film is used, and has high adhesiveness (wetting property with the adhesive). It is a first object to provide a hard coat film which prevents the occurrence of interference fringes.
Further, the present invention has excellent adhesion of the hard coat layer even when a COP-based base film is used, and has high adhesiveness (wetting property with the adhesive). A second object is to provide a hard coat film in which the occurrence of interference fringes is prevented.

As a result of diligent studies to solve the above problems, the present inventor has completed the following invention. That is, in order to solve the above problems, the present invention provides the following inventions (1) to (9).

(1) In a hard coat film in which a hard coat layer containing an ionization ray curable resin and a leveling agent is provided on at least one surface of a base film having a water absorption rate of 1.0% or less, the contact angle of water on the surface of the hard coat layer is provided. Is 70 degrees or less, and the contact angle of hexadecane is 20 degrees or less.

(2) The hard coat film according to (1), wherein the base film is an acrylic base film.
(3) The hard-coated film according to (1), wherein the base film is a cycloolefin polymer-based base film.

(4) The hard coat film according to any one of (1) to (3), wherein the leveling agent is a fluorine-based compound.
(5) Any of (1) to (4), wherein the blending amount of the leveling agent is 0.03 part by weight to 3.0 parts by weight with respect to 100 parts by weight of the ionized wire curable resin. The hard coat film described in.

(6) The hard coat film according to any one of (1) to (5), wherein the ionizing wire curable resin contains a polyfunctional acrylate and / or a urethane oligomer.
(7) The hard coat layer is provided on one side of the cycloolefin polymer-based base film via an easy-adhesion layer containing at least a mixture of a polyolefin-based resin and a styrene-acrylic-based resin ((7). The hard coat film according to any one of 3) to (6).

(8) When the area of the peak appearing ^{in 855 to 1325 cm -1 is A and the area of the peak appearing in 1650 to 1800 cm -1} is B in the infrared spectroscopic measurement of the hard coat layer, the peak area ratio (8). The hard-coated film according to any one of (3) to (7), wherein (A / B) × 100) is 450% or more.

(9) A method for producing a hard coat film having a hard coat layer on an acrylic base film having an arithmetic average surface roughness (Ra) of 1 nm or less, wherein the ionization line curing type is applied on the acrylic base film. A hard coat layer coating containing a resin and a leveling agent is applied to form a hard coat layer, and then the hard coat layer is dried at 100 ° C. or higher and then irradiated with ultraviolet rays to obtain the surface of the hard coat layer. A method for producing a hardcourt film, characterized in that the contact angle of water is 70 degrees or less and the contact angle of hexadecane is 20 degrees or less.

According to the present invention, for example, even when an acrylic base film is used, the adhesion of the hard coat layer is excellent, and the adhesive has high adhesiveness (wetting property with the adhesive). It is possible to provide a hard-coated film in which the occurrence of interference fringes is prevented.
Further, according to the present invention, for example, even when a COP-based base film is used, the adhesion of the hard coat layer is excellent, and the adhesive has high adhesiveness (wetting property with the adhesive). At the same time, it is possible to provide a hard coat film in which the occurrence of interference fringes is prevented.
Further, the hard coat film of the present invention is also excellent in scratch resistance.

Hereinafter, embodiments for carrying out the present invention will be described in detail.
The present invention is a hard coat film in which a hard coat layer containing an ionization ray curable resin and a leveling agent is provided on at least one surface of a base film having a water absorption rate of 1.0% or less, and the contact of water on the surface of the hard coat layer is provided. A hard-coated film having an angle of 70 degrees or less and a hexadecane contact angle of 20 degrees or less.

The "water absorption rate" here can be obtained as follows according to the Japanese Industrial Standards JIS K 7209.
First, the weight A of the base film having a size of 100 mm × 100 mm, which has been allowed to stand in an environment of 25 ° C. and 50% for 24 hours, is measured, and then immersed in distilled water adjusted to 23 ° C. for 24 hours so as to be sufficiently immersed.
Immediately after taking it out, the water adhering to the test piece is wiped off, the weight B after immersion is measured, and the water absorption rate (%) can be obtained from the weight difference before and after immersion ((BA) / A × 100).

As the base film having a water absorption rate of 1.0% or less used in the present invention, the above-mentioned acrylic base film or COP base film can be preferably mentioned.
Hereinafter, the case where the acrylic base film is used as the base film will be described as the first embodiment, and the case where the COP base film is used will be described as the second embodiment.

[First Embodiment]
The first embodiment of the present invention is a hard coat film in which a hard coat layer containing an ionization ray curable resin and a leveling agent is provided on at least one side of an acrylic base film, and water on the surface of the hard coat layer is provided. It is a hard coat film characterized by having a contact angle of 70 degrees or less and a hexadecane contact angle of 20 degrees or less.

<Acrylic base film>
In the present invention, the acrylic base film refers to a transparent film base material made of a thermoplastic acrylic resin, and a film having an arithmetic average surface roughness (Ra) of 1 nm or less can be used. For example, when this film is used as a protective film for a polarizing plate (the outermost surface of a display), the appearance quality of the display is greatly improved. Here, the arithmetic mean surface roughness (Ra) is the absolute from the average line of the roughness curve at a certain reference length defined in the Annex of JIS B 0031 (1994) / JIS B 0061 (1994). It is a value obtained by averaging the deviations, that is, the average value of unevenness when the roughness curve portion below the average line is folded back to the positive value side.

In the present invention, as the thermoplastic acrylic resin, for example, a film containing a thermoplastic methacrylic resin is suitable. This methacrylic resin is obtained by polymerizing a monomer mixture containing alkyl methacrylate. Alkyl methacrylates include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, and myristyl. Examples thereof include methacrylate, palmityl methacrylate, stearyl methacrylate, behenyl methacrylate, cyclohexyl methacrylate, and phenyl methacrylate. Of these, alkyl methacrylate having 1 to 4 carbon atoms in the alkyl group is preferable, and methyl methacrylate is particularly preferable. These alkyl metallicates may be used alone or in combination of two or more.

Among them, for example, a (meth) acrylic resin having a lactone ring structure obtained by polymerizing a monomer mixture containing a compound cyclizing the above-mentioned pentyl methacrylate or the like is desirable. Since the (meth) acrylic resin having such a lactone ring structure has low moisture permeability and excellent heat resistance, it is possible to obtain a film having a small change in optical properties even in a high temperature and high humidity environment. can.

Examples of the film forming method include any appropriate film forming method such as a solution casting method (solution casting method), a melt extrusion method, a calendar method, and a compression molding method. The melt extrusion method is preferable. Since the melt extrusion method does not use a solvent, it is possible to reduce the manufacturing cost and the load on the global environment and the working environment due to the solvent.

Examples of the melt extrusion method include a T-die method and an inflation method. The molding temperature is preferably 150 to 350 ° C, more preferably 200 to 300 ° C.

When forming a film by the above T-die method, a T-die is attached to the tip of a known single-screw extruder or twin-screw extruder, and the film extruded into a film is wound to obtain a roll-shaped film. Can be done. At this time, uniaxial stretching is also possible by appropriately adjusting the temperature of the take-up roll and adding stretching in the extrusion direction. Further, by stretching the film in the direction perpendicular to the extrusion direction, simultaneous biaxial stretching, sequential biaxial stretching and the like can be performed.

<Hard coat layer>
Next, the hard coat layer will be described.
In the present invention, the ionized wire (ionizing radiation) curable resin of the hard coat layer is not particularly limited as long as it is a transparent resin that is cured by irradiating with an electron beam or ultraviolet rays, and is not particularly limited, for example, urethane. It can be appropriately selected from an acrylate-based resin, a polyester acrylate-based resin, an epoxy acrylate-based resin, and the like. Among these, the one preferable as the ionization ray-curable resin is from an ultraviolet curable polyfunctional acrylate having two or more (meth) acryloyl groups in the molecule in order to obtain good adhesion to a transparent film substrate. Can be mentioned. Specific examples of the ultraviolet curable polyfunctional acrylate having two or more (meth) acryloyl groups in the molecule include neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and trimethylol. Polycarbonate polyacrylates such as propanetri (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A diglycidyl. Epoxy (meth) acrylates such as ether diacrylates, neopentyl glycol diglycidyl ether diacrylates, di (meth) acrylates of 1,6-hexanediol diglycidyl ethers, polyhydric alcohols and polyvalent carboxylic acids and / or theirs. Urethane (meth) acrylate and poly obtained by reacting polyester (meth) acrylate, polyhydric alcohol, polyvalent isocyanate and hydroxyl group-containing (meth) acrylate, which can be obtained by esterifying anhydride and acrylic acid. Examples thereof include siloxane poly (meth) acrylate. Among these, it is desirable to use urethane acrylate, which is excellent in both hardness and flexibility when the hard coat layer is formed.

The ionized wire curable resin of these hard coat layers may be used alone or in combination of two or more.

In the present invention, the thickness of the hard coat layer is not particularly limited, but is preferably in the range of, for example, 1.0 μm to 12.0 μm. If the coating film thickness is less than 1.0 μm, it becomes difficult to obtain the required surface hardness. Further, when the coating film thickness exceeds 12.0 μm, the curl is strong and the handleability is deteriorated in the cylinder curl manufacturing process, which is not preferable. The thickness of the hard coat layer can be measured by actually measuring it with a micrometer.

In the present invention, the hard coat layer is a polymerization initiator, a defoaming agent, a lubricant, an ultraviolet absorber, a light stabilizer, a polymerization inhibitor, and a wet dispersant, if necessary, in addition to the ionizing wire curable resin and the leveling agent. , Leology control agents, antioxidants, antifouling agents, antistatic agents, conductive agents, other additives, etc. can be blended within a range that does not impair the effects of the present invention, and these can be dissolved in an appropriate solvent. It is formed by applying, drying, and curing a dispersed hard coat paint on a base film.

The solvent that can be used in the present invention may be appropriately selected depending on the solubility of the resin to be blended, and may be a solvent that can uniformly dissolve or disperse at least the solid content (resin, polymerization initiator, other additives). Just do it. Examples of such a solvent include aromatic solvents such as toluene, xylene and n-heptane, aliphatic solvents such as cyclohexane, methylcyclohexane and ethylcyclohexane, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate and acetate. A single known organic solvent such as an ester solvent such as butyl and methyl lactate, a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and an alcohol solvent such as methanol, ethanol, isopropyl alcohol and n-propyl alcohol. Alternatively, it can be used in combination of several types as appropriate.

The coating method of the hard coat layer of the present invention is not particularly limited, but is gravure coating, microgravure coating, fountain bar coating, slide die coating, slot die coating, screen printing method, spray coating method. After coating by a known coating method such as, the solvent is usually removed by drying at a temperature of about 50 to 200 ° C. The drying temperature is particularly preferably 100 ° C. or higher and 140 ° C. or lower. If the temperature is lower than 100 ° C., the fluidity of the ultraviolet curable resin after the solvent volatilizes cannot be obtained, and sufficient adhesion to the film substrate cannot be obtained. Further, if the temperature is higher than 140 ° C., the temperature becomes higher than the glass transition temperature of the film base material, which may impair the flatness of the base material itself, which is not preferable.

As a method of applying on a base film (acrylic base film) and curing the hard coat paint from which the solvent has been removed, a method of irradiating with an electron beam or ultraviolet rays can be used. The irradiation conditions may be appropriately adjusted according to, for example, an electron beam curable resin to be used and various other chemicals to be added. For example, when ultraviolet rays are used, the wavelength range is preferably in the range of 200 to 400 nm, and the illuminance is 80. It is desirable that the irradiation amount is ~ 120 mW / cm ² and the irradiation amount is 70 to 500 mJ / cm ^2. As the ultraviolet irradiation device, for example, an irradiation device equipped with a lamp light source such as a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, an excimer lamp, a pulse such as an argon ion laser or a helium neon laser, or a continuous laser light source is used. Is possible. It should be noted that the curing reaction can be carried out by lowering the oxygen concentration, such as in a nitrogen gas atmosphere.

The coating thickness of the hard coat layer formed on the hard coat film can be measured by a known method such as measurement using a micrometer.

<Leveling agent>
In the present invention, examples of the leveling agent contained in the hard-coded layer include fluorine-based, acrylic-based, and siloxane-based leveling agents. Among these, a type in which the leveling agent contains a hydroxyl group in order to lower the water contact angle on the surface of the hard coat layer is preferable, and it is particularly effective to use a specific fluorine-based leveling agent.

The specific fluorine-based leveling agent referred to here is, for example, a fluorine-based leveling agent containing at least a hexafluoropropene oligomer derivative. The fluorine-based leveling agent containing such a hexafluoropropene oligomer derivative is a compound having a double bond in the molecule and having a molecular structure of perfluoroalkenyl having a branched whole.

The fluorine-based leveling agent not only improves the leveling property, but also has good orientation to the surface of the hard coat layer, and has an excellent surface modification effect even when added in a small amount, such as the wettability of the hard coat layer.

Specific examples of the fluorine-based leveling agent preferably used in the present invention include commercially available Futergent 681 (trade name) (manufactured by Neos Co., Ltd.) and Futergent 602A (trade name) (manufactured by Neos Co., Ltd.). Can be mentioned.

In the present invention, the above-mentioned fluorine-based, acrylic-based, siloxane-based and other leveling agents can be used in combination as long as the desired effect is not impaired.

In the present invention, the preferable blending amount of the leveling agent is in the range of 0.03 part by weight to 3.0 parts by weight with respect to 100 parts by weight of the ionized wire curable resin. If the blending amount of the leveling agent is less than 0.03 part by weight, a sufficient surface adjusting action cannot be obtained and the improvement of the interference fringes is inferior. On the other hand, when the blending amount of the leveling agent exceeds 3.0 parts by weight, it is difficult to obtain sufficient hard coat property because the content of the uncured component contained in the hard coat layer is high, and the hard coat layer is also difficult to obtain. Since the abundance of the leveling agent on the surface becomes too high, the surface property satisfying the present invention may not be obtained.

In the present invention, the water contact angle on the surface of the hard coat layer is 70 degrees or less. When the water contact angle of the hard coat layer is 70 degrees or less, the wet spread with respect to the highly hydrophilic resin is good, which is preferable.

Further, in the present invention, the hexadecane contact angle on the surface of the hard coat layer is 20 degrees or less. When the hexadecane contact angle of the hard coat layer is 20 degrees or less, it is preferable that the wet spread with respect to the highly lipophilic resin is good.

The hard coat film of the present embodiment having the contact angle defined by the above water and hexadecane has a wide and good wettability to an adhesive used for a touch panel or the like, and therefore has a touch panel on the surface of the hard coat layer. Even when such materials are bonded together via an adhesive, there is no wet repelling, and therefore good adhesiveness can be exhibited.

As described above, according to the present embodiment, even when the acrylic base film is used, the adhesion of the hard coat layer is excellent, and the adhesiveness to the adhesive (wetting property to the adhesive) is high. It is possible to provide a hard coat film which has, prevents the occurrence of interference fringes, and is also excellent in scratch resistance.

The present invention also provides the above-mentioned method for producing a hard-coated film. That is, it is a method for producing a hard coat film having a hard coat layer on an acrylic base film having an arithmetic average surface roughness (Ra) of 1 nm or less, and is an ionization ray curable resin on the acrylic base film. And a paint for a hard coat layer containing a leveling agent is applied to form a hard coat layer, and then the hard coat layer is dried at 100 ° C. or higher and then irradiated with ultraviolet rays to obtain water on the surface of the hard coat layer. This is a method for producing a hard-coated film, characterized in that the contact angle of the film is 70 degrees or less and the contact angle of hexadecane is 20 degrees or less. According to such a method for producing a hard-coated film, a hard-coated film having the above-mentioned excellent properties can be obtained.

<Second embodiment>
A second embodiment of the present invention is a hard coat film in which a hard coat layer containing an ionization ray curable resin and a leveling agent is provided on at least one side of a COP-based base film, and water on the surface of the hard coat layer is provided. It is a hard coat film characterized by having a contact angle of 70 degrees or less and a hexadecane contact angle of 20 degrees or less.

<COP-based base film>
In the present invention, the COP-based base film is a polymer in which cycloolefin units are alternately or randomly polymerized in a polymer skeleton and has an alicyclic structure in the molecular structure, and is a norbornene-based compound or a monocyclic cyclic olefin. , Cycloolefin copolymer film or cycloolefin polymer film, which is a (co) polymer containing at least one compound selected from cyclic conjugated diene and vinyl alicyclic hydrocarbons, is appropriately selected and used. To.

Further, in the present invention, the thickness of the COP-based base film is appropriately selected depending on the application in which the hardcoat film is used, but is in the range of 10 μm to 300 μm from the viewpoint of mechanical strength, handleability, and the like. It is preferably in the range of 20 μm to 200 μm.

In the present invention, regarding the heat resistance of the COP-based base film, when used for a hard coat film application, a thermogravimetric measurement (TG) method for measuring the thermal change when a temperature change is applied to the sample or a differential scanning method is used. It is preferable to use a film having a glass transition temperature of about 120 ° C. to 170 ° C. as measured by a calorimetric measurement (DSC) method or the like.

In the present invention, the COP-based base film is a film obtained by kneading a cycloolefin resin and an ultraviolet absorber for the purpose of preventing deterioration of the coating film and poor adhesion due to ultraviolet rays when used for a hard coat film application. A film may be formed in the form of a film, or a film coated with a paint obtained by mixing a thermoplastic or thermosetting resin and an ultraviolet absorber on one or both sides of a cycloolefin film may be used. Regarding the ultraviolet ray blocking property, it is preferable that the transmittance at a wavelength of 380 nm by a spectrophotometer is 10% or less. More preferably, it is 7% or less.

<Easy adhesive layer>
In the present embodiment, in order to improve the adhesion of the hard coat layer, the hard coat layer can be provided on the COP-based base film via the easy-adhesion layer. As such an easy-adhesion layer, it is necessary to contain at least a mixture of a polyolefin-based resin and a styrene-acrylic-based resin.

In the present embodiment, the polyolefin-based resin constituting the easy-adhesion layer is a resin blended for the purpose of imparting adhesion between the COP-based base film and the hard coat layer. As a result of diligent studies on a resin for an easy-adhesion layer having excellent adhesion to both a COP-based base film and a hardcourt layer, the present inventors have found that a polyolefin-based resin having excellent flexibility is suitable.

The polyolefin-based resin used for the easy-adhesion layer in the present embodiment is not particularly limited, but examples thereof having excellent adhesion to the substrate include ethylene-propylene copolymers and propylene-butene copolymers. It is preferable that the copolymer is composed of more than one kind of monomer, and it is particularly preferable that the copolymer contains a propylene monomer. The molecular weight thereof is not particularly limited, but those having a weight average molecular weight in the range of 10,000 to 200,000 are preferable in terms of the balance between flexibility and adhesion. Examples of such polyolefin-based resins include commercially available Unistor (trade name: manufactured by Mitsui Chemicals, Inc.), Surfren (trade name: manufactured by Mitsubishi Chemical Corporation), and Arrow Base (trade name: manufactured by Unitika Co., Ltd.). , Auloren (trade name: manufactured by Nippon Paper Co., Ltd.) and the like.

Further, in the present embodiment, the styrene-acrylic resin contained in the easy-adhesion layer is a polymer in which acrylic monomers and styrene monomers are alternately or randomly contained in the constituent units. This styrene-acrylic resin is a resin that is relatively hard and has little elongation because it is a resin that is blended for the purpose of reducing the shrinkage difference between the easy-adhesion layer and the hardcoat layer and preventing the occurrence of cracks under heat-resistant conditions. Is required. In the present invention, it is desirable to use a resin having a glass transition temperature of 50 ° C. or higher as a guide. Examples of such a styrene acrylic resin include commercially available ARUFON resin (trade name: manufactured by Toagosei Co., Ltd.) and Acryt resin (trade name: manufactured by Taisei Fine Chemical Co., Ltd.).

In the present embodiment, the blending ratio (part by weight) of the polyolefin resin and the styrene acrylic resin contained in the easy-adhesion layer is preferably in the range of 95/5 to 40/60.

When the blending ratio of the polyolefin resin exceeds 95 parts by weight, the easily adhesive layer to be formed is soft and easily stretchable. ), There is a problem that cracks are likely to occur, and there is a problem that the hardness of the coating film (pencil hardness) is likely to decrease when the hard coat layer is formed on the easy-adhesion layer. On the other hand, when the blending ratio of the polyolefin resin is less than 40 parts by weight, the shrinkage difference between the easy-adhesion layer and the hardcoat layer becomes small and cracks do not occur under heat-resistant conditions, which is good. There is a problem that the adhesion to the base film is lowered.

The thickness of the coating film of the easy-adhesion layer is not particularly limited, but is within a range that does not adversely affect the adhesion between the COP-based base film and the hard coat layer or the pencil hardness of the hard coat layer. It is preferably 0.1 μm to 1.0 μm, and more preferably 0.2 μm to 0.6 μm. If the thickness of the easy-adhesion layer is less than 0.1 μm, the adhesion to the hard coat layer is lowered, which is not preferable. On the other hand, when the thickness of the easy-adhesion layer exceeds 1.0 μm, an easy-adhesion layer made of a resin layer having a low hardness is formed under the hard coat layer, and the pencil hardness of the hard coat film decreases (for example). , Pencil hardness H decreases to pencil hardness HB), and cracks are likely to occur under heat-resistant conditions, which is not preferable.

A leveling agent can be added to the easy-adhesion layer for the purpose of improving coatability, and known leveling agents such as fluorine-based, acrylic-based, siloxane-based, and adducts or mixtures thereof can be used. Is. The blending amount can be, for example, blended in the range of 0.03 parts by weight to 3.0 parts by weight with respect to 100 parts by weight of the resin component of the easy-adhesion layer.

In addition, a benzotriazole-based ultraviolet absorber and a benzophenone-based ultraviolet absorber can be added to the easy-adhesion layer for the purpose of imparting light adhesion (preventing poor adhesion due to ultraviolet rays). The blending amount is preferably 0.05 parts by weight to 10.0 parts by weight with respect to 100 parts by weight of the resin component of the easy-adhesion layer. Particularly preferably, it is 1.0 part by weight to 5.0 parts by weight.

In addition, as other additives to be added to the easy-adhesion layer, a defoaming agent, an antifouling agent, an antioxidant, an antistatic agent, a light stabilizer, etc. may be added as needed, as long as the effects of the present invention are not impaired. It may be blended.

In the present embodiment, in the easy-adhesion layer, in addition to the polyolefin resin and the styrene acrylic resin, a paint obtained by dissolving and dispersing other additives and the like in an appropriate organic solvent is applied onto the COP base film. It is formed by coating, drying, or then curing. In this case, the organic solvent can be appropriately selected depending on the solubility of the above-mentioned resin contained therein, and must be a solvent capable of uniformly dissolving or dispersing at least the solid content (resin and other additives), and at the time of coating. From the viewpoint of workability and drying property, it is preferable to use an organic solvent having a boiling point of 50 ° C to 160 ° C. Examples of such a solvent include aromatic solvents such as toluene, xylene and n-heptane, aliphatic solvents such as cyclohexane, methylcyclohexane and ethylcyclohexane, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate and acetate. Known organic solvents such as ester solvents such as butyl and methyl lactate, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol and butanol. Can be used alone or in combination of several types as appropriate.

In the present embodiment, as a method of applying the above-mentioned paint for an easy-adhesion layer on a COP-based base film, gravure coating, microgravure coating, fountain bar coating, slide die coating, slot die coating, etc. It can be applied by a known coating method such as a screen printing method or a spray coating method. The paint applied on the COP-based base film is usually dried at a temperature of about 50 to 120 ° C. to remove the solvent, and then cured by applying thermal energy or external energy such as ultraviolet rays or electron beams to form a coating film. To form.

<Hard coat layer>
Next, the hard coat layer will be described.
In the present embodiment, the ionized wire (ionized radiation) curable resin of the hard coat layer is a transparent resin that is cured by irradiating with an electron beam, ultraviolet rays, or the like as in the case of the first embodiment. The present invention is not particularly limited, and for example, a urethane acrylate-based resin, a polyester acrylate-based resin, an epoxy acrylate-based resin, or the like can be appropriately selected. Among these, the one preferable as the ionization ray-curable resin is from an ultraviolet curable polyfunctional acrylate having two or more (meth) acryloyl groups in the molecule in order to obtain good adhesion to a transparent film substrate. Can be mentioned. Specific examples of the ultraviolet curable polyfunctional acrylate having two or more (meth) acryloyl groups in the molecule include neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and trimethylol. Polycarbonate polyacrylates such as propanetri (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A diglycidyl. Epoxy (meth) acrylates such as ether diacrylates, neopentyl glycol diglycidyl ether diacrylates, di (meth) acrylates of 1,6-hexanediol diglycidyl ethers, polyhydric alcohols and polyvalent carboxylic acids and / or theirs. Urethane (meth) acrylate and poly obtained by reacting polyester (meth) acrylate, polyhydric alcohol, polyvalent isocyanate and hydroxyl group-containing (meth) acrylate, which can be obtained by esterifying anhydride and acrylic acid. Examples thereof include siloxane poly (meth) acrylate. Among these, it is desirable to use urethane acrylate, which is excellent in both hardness and flexibility when the hard coat layer is formed. The ionized wire curable resin of these hard coat layers may be used alone or in combination of two or more.

In this embodiment, an acrylic containing the As such ionizing radiation-curable resin, showing a peak in 1350～1390Cm ^-1 and 715～745Cm ^-1 in the infrared spectrum in the uncured state (meth) acryloyl groups It is preferable that it contains a based resin. It is preferable because the peak area ratio of the hard coat layer described later is 450% or more.

In the present embodiment, the thickness of the hard coat layer is not particularly limited, but is preferably in the range of, for example, 1.0 μm to 12.0 μm. If the coating film thickness is less than 1.0 μm, it becomes difficult to obtain the required surface hardness. Further, when the coating film thickness exceeds 12.0 μm, the curl is strong and the handleability is deteriorated in the cylinder curl manufacturing process, which is not preferable. The thickness of the hard coat layer can be measured by actually measuring it with a micrometer.

In the present embodiment, in addition to the ionizing wire curable resin and the leveling agent, the hard coat layer includes a polymerization initiator, a defoaming agent, a lubricant, an ultraviolet absorber, a light stabilizer, a polymerization inhibitor, and a wet dispersion, if necessary. Agents, rhologic control agents, antioxidants, antifouling agents, antioxidants, conductive agents, other additives, etc. can be blended within a range that does not impair the effects of the present invention, and these can be dissolved in an appropriate solvent. , The dispersed hard coat paint is applied on the base film, dried and cured to form.

The solvent that can be used for the above-mentioned hard coat paint can be appropriately selected depending on the solubility of the resin to be blended, and at least the solid content (resin, polymerization initiator, other additives) can be uniformly dissolved or dispersed. It may be a solvent. Examples of such a solvent include aromatic solvents such as toluene, xylene and n-heptane, aliphatic solvents such as cyclohexane, methylcyclohexane and ethylcyclohexane, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate and acetate. A single known organic solvent such as an ester solvent such as butyl and methyl lactate, a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and an alcohol solvent such as methanol, ethanol, isopropyl alcohol and n-propyl alcohol. Alternatively, it can be used in combination of several types as appropriate.

The coating method of the hard coat layer is not particularly limited as in the case of the first embodiment, but is gravure coating, microgravure coating, fountain bar coating, slide die coating, and slot die coating. After coating by a known coating method such as a screen printing method or a spray coating method, the solvent is usually removed by drying at a temperature of about 50 to 120 ° C.

As in the case of the first embodiment described above, as a method of coating on a base film (COP-based base film) and curing the hard coat paint from which the solvent has been removed, electron beam or ultraviolet rays are irradiated. The method can be used. The irradiation conditions and the like may be appropriately adjusted according to the electron beam curable resin to be used and various other chemicals to be added. It should be noted that the curing reaction can be carried out by lowering the oxygen concentration, such as in a nitrogen gas atmosphere.

In the present embodiment, in the hardcourt layer obtained as described above, the area of the peak appearing at ^{855 to 1325 cm -1} in the infrared spectroscopic measurement is defined as A, and the area of the peak appearing at ^{1650 to 1800 cm -1.} When B is, the peak area ratio ((A / B) × 100) is preferably 450% or more. When the peak area ratio of the hard coat layer satisfies this range, the effect of the present invention can be further obtained. Further, even if the easy-adhesion layer is not provided, there is an effect that the adhesion of the hard coat layer is improved.

The coating thickness of the hard coat layer formed on the hard coat film can be measured by a known method such as measurement using a micrometer.

<Leveling agent>
In the present embodiment, examples of the leveling agent contained in the hard-coded layer include fluorine-based, acrylic-based, and siloxane-based leveling agents as in the case of the first embodiment. Among these, a type in which the leveling agent contains a hydroxyl group in order to lower the water contact angle on the surface of the hard coat layer is preferable, and it is particularly effective to use a specific fluorine-based leveling agent.

The specific fluorine-based leveling agent referred to here is, for example, a fluorine-based leveling agent containing at least a hexafluoropropene oligomer derivative. The fluorine-based leveling agent containing such a hexafluoropropene oligomer derivative is a compound having a double bond in the molecule and having a molecular structure of perfluoroalkenyl having a branched whole.

The fluorine-based leveling agent not only improves the leveling property, but also has good orientation to the surface of the hard coat layer, and has an excellent surface modification effect even when added in a small amount, such as the wettability of the hard coat layer.

Specific examples of the fluorine-based leveling agent preferably used in the present embodiment include commercially available Futergent 681 (trade name) (manufactured by Neos Co., Ltd.) and Futergent 602A (trade name) (manufactured by Neos Co., Ltd.). Listed in.

Also in this embodiment, the above-mentioned fluorine-based, acrylic-based, siloxane-based and other leveling agents can be used in combination as long as the desired effect is not impaired.

Also in this embodiment, the preferable blending amount of the leveling agent is in the range of 0.03 part by weight to 3.0 parts by weight with respect to 100 parts by weight of the ionized wire curable resin. If the blending amount of the leveling agent is less than 0.03 part by weight, a sufficient surface adjusting action cannot be obtained and the improvement of the interference fringes is inferior. On the other hand, when the blending amount of the leveling agent exceeds 3.0 parts by weight, it is difficult to obtain sufficient hard coat property because the content of the uncured component contained in the hard coat layer is high, and the hard coat layer is also difficult to obtain. Since the abundance of the leveling agent on the surface becomes too high, the surface property satisfying the present invention may not be obtained.

In the present embodiment, the water contact angle on the surface of the hard coat layer is 70 degrees or less. When the water contact angle of the hard coat layer is 70 degrees or less, the wet spread with respect to the highly hydrophilic resin is good, which is preferable.

Further, in the present embodiment, the hexadecane contact angle on the surface of the hard coat layer is 20 degrees or less. When the hexadecane contact angle of the hard coat layer is 20 degrees or less, it is preferable that the wet spread with respect to the highly lipophilic resin is good.

The hard coat film of the present embodiment having the contact angle defined by the above water and hexadecane has a wide and good wettability to an adhesive used for a touch panel or the like, and therefore has a touch panel on the surface of the hard coat layer. Even when such materials are bonded together via an adhesive, there is no wet repelling, and therefore good adhesiveness can be exhibited.

As described above, according to the present embodiment, even when the COP-based base film is used, the adhesion of the hard coat layer is excellent, and the adhesiveness to the adhesive (wetting property to the adhesive) is high. It is possible to provide a hard coat film which has, prevents the occurrence of interference fringes, and is also excellent in scratch resistance.

Hereinafter, the present invention will be described with reference to specific examples, but the present invention is not limited to the following embodiments.
The following Examples 1 to 11 are examples corresponding to the above-mentioned first embodiment of the present invention.

(Preparation of acrylic base film)
The pellets made of a methacrylic resin were sufficiently vacuum dried and then supplied, melt-kneaded at 250 ° C., extruded from a T-die, cooled with water with a cooling roll, and taken up to obtain a film having a thickness of 100 μm. After that, the film is a biaxially stretched film having a thickness of 40 μm, which is obtained by sequentially stretching 1.8 times (heating temperature 140 ° C.) and then 2.4 times laterally (heating temperature 140 ° C.) using a sequential twin-screw extruder. An acrylic base film ((meth) acrylic resin film) having a surface roughness (Ra) of 0.7 nm and a water absorption of 0.5% was obtained.

<Example 1>
A resin composition for forming a hard coat layer having the following composition is applied to one surface of an acrylic base film using a bar coater, and dried in a drying oven at 100 ° C. for 20 seconds to form a hard coat layer having a film thickness of 5 μm. Formed. ^{This was cured at a UV irradiation amount of 100 mJ / cm 2} using a UV irradiation device set at a height of 60 mm from the coated surface to prepare a hard coat film.

(Resin composition for forming a hard coat layer)
100 parts by weight of urethane acrylate (trade name: DIC-17-806, manufactured by DIC Corporation, polyfunctional polymer having 2 or more functional groups), photopolymerization initiator (trade name: Irgacure 184, manufactured by BASF Corporation), 5 weights , Fluorine-based leveling agent (trade name: Futergent 681, manufactured by Neos Co., Ltd.) 0.1 part by weight,> N-CH ₃ type hindered amine-based photostabilizer (trade name: Chinubin 292, manufactured by BASF Corporation) ) 3.2 parts by weight was stirred and diluted with ethyl acetate so that the volatile content was 50% to obtain a paint for a hard coat layer.

<Example 2>
A hardcourt film was prepared in the same manner as in Example 1 except that the number of parts of the fluorine-based leveling agent compounded in Example 1 was 0.25 parts by weight.

<Example 3>
A hardcourt film was prepared in the same manner as in Example 1 except that the number of parts of the fluorine-based leveling agent compounded in Example 1 was 0.5 parts by weight.

<Example 4>
A hardcourt film was prepared in the same manner as in Example 1 except that the number of parts of the fluorine-based leveling agent compounded in Example 1 was 1.0 part by weight.

<Example 5>
A hardcourt film was prepared in the same manner as in Example 1 except that the number of parts of the fluorine-based leveling agent compounded in Example 1 was 3.0 parts by weight.

<Example 6>
100 parts by weight of the urethane acrylate used in Example 2 (trade name: DIC-17-806, manufactured by DIC Corporation, polyfunctional resin having 2 or more functional groups) was used as pentaerythritol triacrylate (trade name: light acrylate PE-). 3A, manufactured by Kyoeisha Chemical Co., Ltd., number of functional groups: 3) A hard coat film was produced in the same manner as in Example 2 except that the number was changed to 100 parts by weight.

<Example 7>
100 parts by weight of the urethane acrylate used in Example 2 (trade name: DIC-17-806, manufactured by DIC Corporation, a polyfunctional resin having 2 or more functional groups) is used as dipentaerythritol pentaacrylate (trade name: light acrylate DPE). -6A, manufactured by Kyoeisha Chemical Co., Ltd., number of functional groups: 6) A hard coat film was produced in the same manner as in Example 2 except that the number was changed to 100 parts by weight.

<Example 8>
100 parts by weight of urethane acrylate used in Example 2 (trade name: DIC-17-806, manufactured by DIC Corporation, polyfunctional resin having 2 or more functional groups) is used as polypropylene dimethacrylate (trade name: NK ester 9PG, new). A hard coat film was produced in the same manner as in Example 2 except that the number of functional groups was changed to 100 parts by weight, manufactured by Nakamura Chemical Co., Ltd.

<Example 9>
A hard coat film was produced in the same manner as in Example 2 except that the fluorine-based leveling agent of Example 2 was changed to a fluorine-based leveling agent (trade name: Futergent 602A, manufactured by Neos Co., Ltd.).

<Example 10>
The hardcourt layer-forming resin composition was applied using a bar coater and dried in a drying oven at 140 ° C. for 20 seconds to form a hardcourt layer having a film thickness of 5 μm. I got a film.

<Example 11>
The hardcourt film was applied in the same manner as in Example 2 except that the resin composition for forming a hardcoat layer was applied using a bar coater and dried in a drying oven at 90 ° C. for 20 seconds to form a hardcoat layer having a film thickness of 5 μm. Got

<Comparative Example 1>
A hardcourt film was prepared in the same manner as in Example 1 except that the fluorine-based leveling agent of Example 1 was not blended.

<Comparative Example 2>
A hardcourt film was prepared in the same manner as in Example 1 except that the number of parts of the fluorine-based leveling agent compounded in Example 1 was 5.0 parts by weight.

<Comparative Example 3>
A hard-coated film was produced in the same manner as in Example 1 except that the leveling agent of Example 1 was changed to 0.25 parts by weight of a siloxane-based leveling agent (trade name: BYK310, manufactured by Big Chemie Japan Co., Ltd.).

<Comparative Example 4>
A hardcourt film was produced in the same manner as in Example 1 except that the leveling agent of Example 1 was changed to an acrylic leveling agent (trade name: Disparon LF-1984, manufactured by Kusumoto Kasei Co., Ltd.) by 0.25 parts by weight. ..

<Evaluation>
The hard-coated films of Examples and Comparative Examples produced as described above were evaluated for the following items, and the results are summarized in Table 1.

<Adhesion>
The adhesion of the hard coat layer was evaluated according to the cross-cut method of JIS K5600.
^{That is, 100 1 mm 2} cross-cut masses were prepared using a grid peeling test jig, and Sekisui Chemical Co., Ltd.'s adhesive tape No. 252 was attached onto it, pressed uniformly with a spatula, and then peeled off in the 90-degree direction to evaluate the residual ratio (residual number / 100) of the hardcoat layer. The evaluation criteria are as follows, and if it is ◎ or ○, it is judged that the adhesion is good.
⊚: Residual rate of cross-cut mass is 100%
◯: Residual rate of cross-cut mass is 90% or more and less than 100% Δ: Residual rate of cross-cut mass is 80% or more and less than 90% ×: Residual rate of cross-cut mass is less than 80%

<Film flatness>
The hard coat film was visually observed under a fluorescent lamp, and the hard coat film was compared with the (meth) acrylic resin film having an arithmetic mean surface roughness (Ra) of 1 nm or less produced by the method described in Example 1. , The state of flatness of the film was evaluated. The evaluation criteria are as follows, and ○ and △ were accepted.
◯: Flatness is equivalent to that of a film having an arithmetic mean roughness (Ra) of 1 nm or less.
Δ: Arithmetic mean roughness (Ra) is slightly uneven and inferior in flatness as compared with a film having an average roughness (Ra) of 1 nm or less.
X: Compared with a film having an arithmetic mean roughness (Ra) of 1 nm or less, unevenness is observed and the flatness is significantly inferior.

<Measurement of water contact angle and hexadecane contact angle>
Using a fully automatic contact angle meter DM-701 manufactured by Kyowa Interface Science Co., Ltd., 1 μL of water or hexadecane was dropped, and the contact angle after 30 seconds was measured.

<Evaluation of interference fringes (iris-like color)>
The hardcourt films obtained in Examples and Comparative Examples were cut into an area of 10 cm × 15 cm to prepare a sample film. A black glossy tape is attached to the surface of the sample film opposite to the hard coat layer, and the hard coat surface is turned to the upper surface, and a three-wavelength neutral white fluorescent lamp (National Palook, FL 15EX-N 15W) is used as a light source. , The reflected light was visually observed from diagonally above. The evaluation criteria are as follows.
◯: No interference fringes are seen.
Δ: There are slight interference fringes, but there is no problem in practical use.
×: Interference fringes are very noticeable.

<Evaluation of scratch resistance>
A 3-wavelength neutral white fluorescent lamp that shows the scratched state of the hard coat surface when it is reciprocated 10 times while pressing steel wool # 0000 (manufactured by Nippon Steel Wool Co., Ltd.) with a diameter of 25 mm against the hard coat surface of the hard coat film at 1000 gf. (National Palook, FL 15EX-N 15W) was used as a light source, and the reflected light was visually observed from diagonally above. The evaluation criteria are as follows.
◯: No scratches are seen.
Δ: There are scratches, but there is no problem in practical use.
×: The scratches are very noticeable.

<Resin wettability>
0.7 g of U-2110 (manufactured by Chemistat) was dropped onto the hard coat layer of the hard coat film as a resin for an adhesive made of an ultraviolet curable acrylic monomer, and the diameter of the droplet after 5 minutes was measured. The evaluation criteria are as follows.
◯: Droplet diameter is 35 mm or more (sufficient adhesive strength can be obtained)
Δ: The diameter of the droplet is 30 to 34 mm (the adhesive strength varies).
×: Droplet diameter is less than 30 mm (adhesive strength is insufficient)

According to the present invention, as is clarified in Examples 1 to 10 shown in Table 1, the acrylic base film also has excellent adhesion, the hard coat layer contains a leveling agent, and the hard coat layer. A hard coat film with a surface water contact angle of 70 degrees or less and a hexadecane contact angle of 20 degrees or less has good wettability between the hard coat layer and the resin, has no problem with interference fringes, and has sufficient scratch resistance. A hard-coated film having a property can be obtained. Further, the hard-coated film of Example 11 has slightly inferior adhesion, but has good characteristics as an overall evaluation.
On the other hand, in Comparative Examples 1 to 4, it is difficult to obtain a hard coat film having good properties in all evaluations of adhesion, interference fringes, scratch resistance, and wettability of the adhesive resin.

The following Examples 12 to 21 are examples corresponding to the above-mentioned second embodiment of the present invention.
<Preparation of easy-adhesion layer paint>
First, 60 parts of the styrene acrylic resin "ARUFON UG-4070 (trade name)" (solid content 100%, manufactured by Toa Synthetic Co., Ltd., glass transition temperature 58 ° C.) was stirred into 140 parts of ethyl acetate using a stirrer. While adding little by little, the resin was dissolved to prepare a solution having a concentration of 30%.

Next, 70 parts of the polyolefin resin "Surflen P-1000 (trade name)" (solid content 20%, manufactured by Mitsubishi Chemical Corporation) and the above-mentioned styrene acrylic resin "ARUFON UG-4070 (trade name)" (solid content 30). %) 20 parts were mixed and diluted with butyl acetate / toluene = 85/15 (% by weight) until the solid content concentration became 5% to prepare an easy-adhesion layer paint.

<Resin composition for forming a hard coat layer>
100 parts by weight of urethane acrylate (trade name: DIC-17-806, manufactured by DIC Corporation, polyfunctional polymer having 2 or more functional groups), photopolymerization initiator (trade name: Irgacure 184, manufactured by BASF Corporation), 5 weights , Fluorine-based leveling agent (trade name: Futergent 681, manufactured by Neos Co., Ltd.) 0.1 part by weight,> N-CH ₃ type hindered amine-based photostabilizer (trade name: Chinubin 292, manufactured by BASF Corporation) ) 3.2 parts by weight was stirred and diluted with ethyl acetate so that the volatile content was 50% to obtain a paint for a hard coat layer.

<Example 12>
The above-mentioned easy-adhesive layer paint is applied to one side of Zeonoa film ZF14 (manufactured by Nippon Zeon Co., Ltd., water absorption rate 0.01%) having a thickness of 60 μm as a cycloolefin film using a bar coater, and a drying furnace at 90 ° C. The film was dried and solidified by hot air for 1 minute to form an easily adhesive layer having a coating film thickness of 0.3 μm, and a film with an easy adhesive layer was obtained.

Next, the above-mentioned hard coat layer paint was applied onto the easy-adhesive layer of the film with the easy-adhesive layer using a bar coater, and dried with hot air in a drying oven at 80 ° C. for 1 minute to obtain a coating film thickness of 5. A 0 μm coating layer was formed. ^{This was cured at a UV irradiation amount of 150 mJ / cm 2} using a UV irradiation device set at a height of 60 mm from the coated surface to form a hard coat layer, and a hard coat film of this example was produced.

<Example 13>
A hardcourt film was prepared in the same manner as in Example 12 except that the number of parts of the fluorine-based leveling agent compounded in Example 12 was 0.25 parts by weight.

<Example 14>
A hardcourt film was prepared in the same manner as in Example 12 except that the number of parts of the fluorine-based leveling agent compounded in Example 12 was 0.5 parts by weight.

<Example 15>
A hardcourt film was prepared in the same manner as in Example 12 except that the number of parts of the fluorine-based leveling agent compounded in Example 12 was 1.0 part by weight.

<Example 16>
A hardcourt film was prepared in the same manner as in Example 12 except that the number of parts of the fluorine-based leveling agent compounded in Example 12 was 3.0 parts by weight.

<Example 17>
100 parts by weight of the urethane acrylate used in Example 13 (trade name: DIC-17-806, manufactured by DIC Corporation, polyfunctional resin having 2 or more functional groups) was used as pentaerythritol triacrylate (trade name: light acrylate PE-). 3A, manufactured by Kyoeisha Chemical Co., Ltd., number of functional groups: 3) A hard coat film was produced in the same manner as in Example 13 except that the number was changed to 100 parts by weight.

<Example 18>
100 parts by weight of the urethane acrylate used in Example 13 (trade name: DIC-17-806, manufactured by DIC Corporation, polyfunctional resin having 2 or more functional groups) is used as dipentaerythritol pentaacrylate (trade name: light acrylate DPE). -6A, manufactured by Kyoeisha Chemical Co., Ltd., number of functional groups: 6) A hard coat film was produced in the same manner as in Example 13 except that the number was changed to 100 parts by weight.

<Example 19>
100 parts by weight of urethane acrylate used in Example 13 (trade name: DIC-17-806, manufactured by DIC Corporation, polyfunctional resin having 2 or more functional groups) is used as polypropylene dimethacrylate (trade name: NK ester 9PG, new). A hard coat film was produced in the same manner as in Example 13 except that the number of functional groups was changed to 100 parts by weight, manufactured by Nakamura Chemical Co., Ltd.

<Example 20>
A hard coat film was produced in the same manner as in Example 13 except that the fluorine-based leveling agent of Example 13 was changed to a fluorine-based leveling agent (trade name: Futergent 602A, manufactured by Neos Co., Ltd.).

<Example 21>
As the resin composition for forming the hard coat layer, the main agent is the urethane acrylate-based ultraviolet curable resin composition "TOMAX FA-3246" (solid content 40%, manufactured by Nippon Kako Paint Co., Ltd.), and Irgacure 184 (photopolymerization initiator, BASF) (3 parts by weight with respect to the solid content of the resin composition) is diluted with butyl acetate until the solid content concentration in the UV-curable resin paint becomes 30%, and the mixture is sufficiently stirred to make the hard coat layer paint 2 (Other components (fluorine-based leveling agent, light stabilizer, etc.) are the same as the hard coat layer paint used in Example 13), and the above-mentioned Zeonoa film "ZF14" (Nippon Zeon Co., Ltd.) is prepared as a cycloolefin film. A hard coat film was produced in the same manner as in Example 13 except that the easy-adhesion layer was omitted and the hard coat layer paint 2 was directly coated on one side thereof using a bar coater.

<Comparative Example 5>
A hardcourt film was prepared in the same manner as in Example 12 except that the fluorine-based leveling agent of Example 12 was not blended.

<Comparative Example 6>
A hardcourt film was prepared in the same manner as in Example 12 except that the number of parts of the fluorine-based leveling agent compounded in Example 12 was 5.0 parts by weight.

<Comparative Example 7>
A hardcourt film was produced in the same manner as in Example 12 except that the leveling agent of Example 12 was changed to 0.25 parts by weight of a siloxane-based leveling agent (trade name: BYK310, manufactured by Big Chemie Japan Co., Ltd.).

<Comparative Example 8>
A hardcourt film was produced in the same manner as in Example 12 except that the leveling agent of Example 12 was changed to an acrylic leveling agent (trade name: Disparon LF-1984, manufactured by Kusumoto Kasei Co., Ltd.) by 0.25 parts by weight. ..

<Evaluation>
The hard-coated films of Examples and Comparative Examples produced as described above were evaluated for the following items, and the results are summarized in Table 2.

<Adhesion>
The adhesion of the hard coat layer was evaluated according to the cross-cut method of JIS K5600.
^{That is, 100 1 mm 2} cross-cut masses were prepared using a grid peeling test jig, and Sekisui Chemical Co., Ltd.'s adhesive tape No. 252 was attached onto it, pressed evenly with a spatula, and then peeled off in the 90 degree direction. After repeating the operation 5 times, the residual ratio (remaining number / 100) of the hard coat layer was evaluated. The evaluation criteria are as follows, and if it is ◎ or ○, it is judged that the adhesion is good.
⊚: Residual rate of cross-cut mass is 100%
◯: Residual rate of cross-cut mass is 90% or more and less than 100% Δ: Residual rate of cross-cut mass is 80% or more and less than 90% ×: Residual rate of cross-cut mass is less than 80%

<Peak area ratio>
The infrared spectroscopic spectrum (infrared absorption spectrum) was measured by the ATR method on the surface of the hard coat layer of the hard coat film using an infrared spectrophotometer. An FT-IR Spectrometer Spectram 100 (manufactured by PerkinElmer Japan Co., Ltd.) was used as an infrared spectrophotometer. On the spectral chart with the obtained horizontal axis as the wave number (cm ^-1 ) and the vertical axis as the absorbance ^{, baselines are drawn at 855 to 1325 cm -1} and 1650 ^{to 1800 cm -1} , respectively, and the baseline and the spectral curve are used. The areas surrounded by are A and B, respectively, and the ratio (A / B) × 100 is defined as the peak area ratio.

<Measurement of water contact angle and hexadecane contact angle>
Using a fully automatic contact angle meter DM-701 manufactured by Kyowa Interface Science Co., Ltd., 1 μL of water or hexadecane was dropped, and the contact angle after 30 seconds was measured.

<Evaluation of interference fringes (iris-like color)>
The hardcourt films obtained in Examples and Comparative Examples were cut into an area of 10 cm × 15 cm to prepare a sample film. A black glossy tape is attached to the surface of the sample film opposite to the hard coat layer, and the hard coat surface is turned to the upper surface, and a three-wavelength neutral white fluorescent lamp (National Palook, FL 15EX-N 15W) is used as a light source. , The reflected light was visually observed from diagonally above. The evaluation criteria are as follows.
◯: No interference fringes are seen.
Δ: There are slight interference fringes, but there is no problem in practical use.
×: Interference fringes are very noticeable.

<Evaluation of scratch resistance>
A 3-wavelength neutral white fluorescent lamp that shows the scratched state of the hard coat surface when it is reciprocated 10 times while pressing steel wool # 0000 (manufactured by Nippon Steel Wool Co., Ltd.) with a diameter of 25 mm against the hard coat surface of the hard coat film at 1000 gf. (National Palook, FL 15EX-N 15W) was used as a light source, and the reflected light was visually observed from diagonally above. The evaluation criteria are as follows.
◯: No scratches are seen.
Δ: There are scratches, but there is no problem in practical use.
×: The scratches are very noticeable.

<Resin wettability>
0.7 g of U-2110 (manufactured by Chemistat) was dropped onto the hard coat layer of the hard coat film as a resin for an adhesive made of an ultraviolet curable acrylic monomer, and the diameter of the droplet after 5 minutes was measured. The evaluation criteria are as follows.
◯: Droplet diameter is 35 mm or more (sufficient adhesive strength can be obtained)
Δ: The diameter of the droplet is 30 to 34 mm (the adhesive strength varies).
×: Droplet diameter is less than 30 mm (adhesive strength is insufficient)

According to the present invention, as will be clarified in Examples 12 to 21 shown in Table 2, the COP-based base film also has excellent adhesion, the hard coat layer contains a leveling agent, and the hard coat layer. A hard coat film with a surface water contact angle of 70 degrees or less and a hexadecane contact angle of 20 degrees or less has good wettability between the hard coat layer and the resin, has no problem with interference fringes, and has sufficient scratch resistance. A hard-coated film having a property can be obtained. Further, the hard coat film of Example 21 does not have an easy-adhesion layer because the peak area ratio of the hard coat layer is 450% or more, but the adhesion of the hard coat layer is good.
On the other hand, in Comparative Examples 5 to 8, it is difficult to obtain a hard coat film having good properties in all evaluations of adhesion, interference fringes, scratch resistance, and wettability of the adhesive resin.

Claims (6)

In a hard coat film in which a hard coat layer containing an ionization ray curable resin and a leveling agent is provided on at least one side of a base film having a water absorption rate of 1.0% or less.
The base film is a cycloolefin polymer-based base film.
The hard coat layer is provided via an easy-adhesion layer containing at least a mixture of a polyolefin resin and a styrene acrylic resin on one side of the cycloolefin polymer-based base film.
A hard coat film characterized in that the contact angle of water on the surface of the hard coat layer is 70 degrees or less and the contact angle of hexadecane is 20 degrees or less. The hard coat film according to claim 1, wherein the leveling agent is a fluorine-based compound. The hard coat film according to claim 1 or 2 , wherein the blending amount of the leveling agent is 0.03 part by weight to 3.0 parts by weight with respect to 100 parts by weight of the ionized wire curable resin. The hard coat film according to any one of claims 1 to 3 , wherein the ionizing wire curable resin contains a polyfunctional acrylate and / or a urethane oligomer. When the area of the peak appearing ^{in 855 to 1325 cm -1 is A and the area of the peak appearing in 1650 to 1800 cm -1} is B in the infrared spectroscopic measurement of the hard coat layer, the peak area ratio ((A /). B) The hard-coated film according to any one of claims 1 to 4 , wherein × 100) is 450% or more. A method for producing a hardcoat film having a hardcoat layer on an acrylic base film having an arithmetic average surface roughness (Ra) of 1 nm or less.
A paint for a hard coat layer containing a leveling agent composed of an ionizing wire curable resin containing a polyfunctional acrylate and / or a urethane oligomer and a fluorine-based compound is applied onto the acrylic base film to form a hard coat layer. Next, the hard coat layer is dried at 100 ° C. or higher, and then irradiated with ultraviolet rays. The contact angle of water on the surface of the hard coat layer is 70 degrees or less, and the contact angle of hexadecane is 20 degrees or less. A method for manufacturing a hard-coated film.