JP5961947B2 - Hard coat film, polarizing plate, front plate and image display device - Google Patents

Description

The present invention relates to a hard coat film, a polarizing plate, a front plate, and an image display device.

In an image display device such as a cathode ray tube display device (CRT), a liquid crystal display (LCD), a plasma display (PDP), an electroluminescence display (ELD), an electronic paper, etc., an optical laminate for preventing reflection is generally provided on the outermost surface. Is provided. Such an anti-reflection optical laminated body suppresses reflection of an image or reduces reflectance by scattering or interference of light.

Conventionally, a hard coat film in which a hard coat layer is formed on the surface of a triacetyl cellulose (TAC) substrate is known as such an optical laminate.
However, the triacetyl cellulose base material is inferior in heat-and-moisture resistance, and has a drawback in that when a hard coat film is used as a polarizing plate protective film in a high-temperature and high-humidity environment, the polarizing plate function such as polarizing function and hue is deteriorated.
For such a problem, it has been proposed to use a transparent plastic substrate mainly composed of an acrylic resin and / or a methacrylic resin.

However, when a hard coat layer is formed on one or both sides of a transparent plastic base material mainly composed of an acrylic resin and / or a methacrylic resin, there is a problem that the adhesion between the base material and the hard coat layer is poor. .

For such a problem, for example, Patent Document 1 uses a material containing at least one component of polyol acrylate and polyol methacrylate, the drying temperature of the hard coat coating film is 80 to 120 ° C., and the drying time is 1 It is disclosed that the adhesion between the base film and the hard coat layer is improved by performing for 10 minutes.
Further, for example, in Non-Patent Document 1, by using a (meth) acrylate-based photocurable resin, after applying the resin and before irradiating with ultraviolet rays, preheating is performed at 60 ° C. for 10 minutes. It is disclosed to improve the adhesion between the base film and the hard coat layer.
Furthermore, in Patent Document 2, in addition to physical treatment such as corona discharge treatment and oxidation treatment on the base film, after applying a coating called an anchor agent or primer, a hard coat layer is formed, It is disclosed to improve the adhesion between the base film and the hard coat layer.

However, in the method disclosed in Patent Document 1, since the drying temperature is high, there is a problem that the manufacturing cost of the hard coat film is increased, and in the method disclosed in Non-Patent Document 1, the heating time (drying time) is long. Since it becomes long, there is a problem that it takes a long time to produce a hard coat film and the production cost is high, and either method lacks productivity.
In addition, the method disclosed in Patent Document 2 lacks productivity because the number of steps necessary for producing a hard coat film is increased and special treatment is required.

Furthermore, in a hard coat film using a base film mainly composed of an acrylic resin and / or a methacrylic resin, a difference in refractive index occurs between the base film and the hard coat layer, and the hard coat film is used. When the polarizing plate is formed, there is a problem that interference fringes are generated and the appearance is deteriorated.

JP 2009-185282 A JP 2011-81359 A

Adhesion of (meth) acrylate curable resins (Toa Gosei Group Research Annual Report, 2006-9)

In view of the above situation, the present invention has excellent adhesion between the base film and the hard coat layer, does not generate interference fringes, and is excellent in moisture and heat resistance and smoothness, and suitably prevents generation of wrinkles. An object of the present invention is to provide a hard coat film that can be used, a polarizing plate and a front plate using the hard coat film, and an image display device.

As a result of intensive studies, the present inventors have determined that a hard coat layer-forming composition for forming a hard coat layer has a ring structure in the unit structure, and nitrogen and / or oxygen atoms in the ring structure. Even if the base film is made of a (meth) acrylic resin, the base film and the hard coat layer have excellent adhesiveness by using a material including a ring structure component. The inventors have found that interference fringes can be prevented from occurring between these layers, and have completed the present invention.

That is, the present invention is a hard coat film having a base film made of a (meth) acrylic resin and a hard coat layer formed on one surface of the base film, the hard coat layer being It is formed using a composition for a hard coat layer containing a ring structure component having a 5-membered ring structure, and the ring structure component is a maleimide group-containing acrylic polymer, and the hard film of the base film Near the interface on the coat layer side, a compatible layer in which the material constituting the base film and the material constituting the hard coat layer are compatible is formed, and the thickness of the compatible layer is 100 nm to 1 μm. It is a hard coat film characterized by being.

In the hard coat film of the present invention, the ring structure components, a binder resin solid content 100 parts by weight contained in the composition for forming a hard coat layer, to be contained in an amount of 5 0 to 70 parts by weight preferably .

Moreover, this invention is a polarizing plate provided with a polarizing element, Comprising: The polarizing plate characterized by providing the hard coat film of this invention on the surface of the said polarizing element.
Moreover, this invention is also a front plate characterized by hold | maintaining the hard coat film of this invention on the surface.
Furthermore, the present invention is also an image display device comprising the hard coat film of the present invention, the polarizing plate of the present invention, or the front plate of the present invention on the outermost surface.
Hereinafter, the present invention will be described in detail.

The present invention is a hard coat film having a base film made of a (meth) acrylic resin and a hard coat layer formed on one surface of the base film.
The hard coat film of the present invention provided with the base film made of the (meth) acrylic resin is superior in moisture and heat resistance and smoothness as compared with the hard coat film provided with the base film made of TAC. Can be suitably prevented.
In the present specification, “(meth) acryl” means “acryl” and “methacryl”.

In the present invention, the base film is made of an acrylic resin.
As acrylic resin which comprises such a base film, it is preferable that it is acrylic resin which has a ring structure, for example.
Although it does not specifically limit as acrylic resin which has the said ring structure, For example, the (meth) acrylic resin which has a lactone ring structure or the (meth) acrylic resin which has an imide ring structure is used suitably. The base film made of these (meth) acrylic resins is superior in mechanical strength and smoothness to the base film made of TAC, has low moisture permeability, and has high heat resistance in a high temperature environment. It is excellent in durability such as moisture resistance in a humid environment.

As thickness of the said base film, it is preferable that it is 20-300 micrometers, More preferably, an upper limit is 200 micrometers and a minimum is 30 micrometers. When the thickness of the base film is less than 20 μm, wrinkles may occur in the hard coat film of the present invention. On the other hand, when the thickness exceeds 300 μm, the hard coat film of the present invention becomes thick and light transmittance, etc. Inferior optical properties.

The hard coat film of the present invention has a hard coat layer on one surface of the substrate film.
The hard coat layer is formed using a composition for a hard coat layer containing a ring structure component having a five-membered ring structure, and the ring structure component has a unit structure of nitrogen atoms and / or oxygen atoms. It contains at least one inside.
When the hard coat layer composition contains the ring structure component, the hard coat film of the present invention has excellent adhesion between the base film and the hard coat layer, and the refractive index between these layers. Generation of interference fringes due to the difference can be suitably prevented. This is because the hard coat layer composition containing the ring structure component is applied on one side of the base film to form a hard coat layer, so that the base film is near the interface on the hard coat layer side. This is considered to be because a compatible layer is formed in which the material constituting the base film described later and the material constituting the hard coat layer are compatible. In addition, when the above-mentioned ring structure component does not contain a 5-membered ring structure (for example, has a 6-membered ring structure) or does not contain a nitrogen atom and / or oxygen atom in the unit structure, Compared with the invention, the adhesion between the base film and the hard coat layer is inferior.

It is preferable that the said ring structure component is contained in the ratio of 30-70 mass parts in 100 mass parts of binder resin solid content contained in the said composition for hard-coat layers. If it is less than 30 parts by mass, the adhesion between the base film and the hard coat layer of the hard coat film of the present invention and the interference fringe prevention property may be insufficient. On the other hand, when it exceeds 70 parts by mass, the hardness as a hard coat film such as pencil hardness and scratch resistance may be insufficient.

In the hard coat film of the present invention, the ring structure component has a 5-membered ring structure containing at least one nitrogen atom and / or oxygen atom in the unit structure. Suitable examples of such a ring structure component include maleimide group-containing acrylic polymers, maleimide group-containing acrylic monomers, oxazolidone acrylate, N-vinyl-2-pyrrolidone, γ-butyrolactone acrylate, and polyvinylpyrrolidone.
By forming the hard coat layer using the hard coat layer composition containing these compounds, the hard coat film of the present invention has extremely excellent adhesion between the base film and the hard coat layer. .
The said ring structure component may be used independently and 2 or more types may be used together.

The hard coat layer composition preferably contains a binder resin other than the ring structure component (hereinafter also referred to as other binder resin).
The other binder resin is preferably a transparent one, for example, an ionizing radiation curable resin, an ionizing radiation curable resin and a solvent drying resin (thermoplastic resin or the like, which is a resin curable by ultraviolet rays or electron beams). It is possible to use a mixture with a resin that becomes a film only by drying a solvent added to adjust the solid content during the process, or a thermosetting resin. More preferred is an ionizing radiation curable resin.
In the present specification, “resin” is a concept including resin components such as monomers and oligomers.

Examples of the ionizing radiation curable resin include compounds having one or more unsaturated bonds such as compounds having an acrylate functional group. Examples of the compound having one unsaturated bond include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, and the like. Examples of the compound having two or more unsaturated bonds include polymethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri ( Polyfunctional compounds such as (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, or the above polyfunctional compound and (meth) acrylate And the like (for example, poly (meth) acrylate esters of polyhydric alcohols).

In addition to the above compounds, relatively low molecular weight polyester resins having unsaturated double bonds, polyether resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, etc. It can be used as an ionizing radiation curable resin.

The ionizing radiation curable resin can be used in combination with a solvent-drying resin. By using the solvent-drying resin in combination, film defects on the coated surface can be effectively prevented. The solvent-drying resin that can be used in combination with the ionizing radiation curable resin is not particularly limited, and a thermoplastic resin can be generally used.
The thermoplastic resin is not particularly limited. For example, a styrene resin, a (meth) acrylic resin, a vinyl acetate resin, a vinyl ether resin, a halogen-containing resin, an alicyclic olefin resin, a polycarbonate resin, or a polyester resin. Examples thereof include resins, polyamide-based resins, cellulose derivatives, silicone-based resins, rubbers, and elastomers. The thermoplastic resin is preferably amorphous and soluble in an organic solvent (particularly a common solvent capable of dissolving a plurality of polymers and curable compounds). In particular, from the viewpoints of film forming properties, transparency and weather resistance, styrene resins, (meth) acrylic resins, alicyclic olefin resins, polyester resins, cellulose derivatives (cellulose esters, etc.) and the like are preferable.

Thermosetting resins that can be used as the other binder resins include phenolic resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, and melamine-urea. A condensation resin, a silicon resin, a polysiloxane resin, etc. can be mentioned.

The hard coat layer composition preferably further contains a leveling agent.
By containing the leveling agent, the flatness of the hard coat layer can be improved and blocking of the hard coat film can be prevented.
Examples of the leveling agent include known ones such as a fluorine leveling agent, a silicone leveling agent, and an acrylic leveling agent. Among these, a fluorine-based leveling agent is preferable in that the stability of the ink and the stability of the coated surface can be ensured with a small addition amount.

It is preferable that content of the said leveling agent is 0.1-1 mass part with respect to 100 mass parts of binder resin solid content of the composition for hard-coat layers. If the amount is less than 0.1 parts by mass, the flatness of the hard coat layer is deteriorated, haze and unevenness are likely to occur, and the anti-blocking property may not be sufficiently exhibited. On the other hand, if it exceeds 1 part by mass, the dispersibility and pot life of the hard coat layer composition are likely to deteriorate, and the haze of the hard coat layer may increase due to the aggregation of the anti-blocking agent described below and the adverse effect on the coating film. is there.

The hard coat layer composition may also contain an antiblocking agent.
Examples of the anti-blocking agent include particles such as silicon or styrene having no reactive group and an average primary particle size of 100 to 600 nm.
If the average primary particle size is less than 100 nm, the anti-blocking property may not be exhibited. If it exceeds 600 nm, the haze may be increased. The average primary particle size is more preferably 100 to 350 nm.
The average primary particle size is a value obtained by measuring with a laser diffraction scattering method particle size distribution measuring apparatus in a 5% by weight dispersion of methyl isobutyl ketone.

It is preferable that content of the said blocking inhibitor is 0.5-3 mass parts with respect to 100 mass parts of binder resin solid content of the composition for hard-coat layers. If it is less than 0.5 parts by mass, the anti-blocking property may not be exhibited. If it exceeds 3 parts by mass, the dispersibility is remarkably deteriorated, causing aggregation and gelation, and as a result, there is a possibility of leading to defects in the appearance of the hard coat film surface and an increase in haze.

The hard coat layer composition preferably further contains a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it is a known one. For example, acetophenones (for example, trade name Irgacure 184, 1-hydroxy-cyclohexyl-phenyl-ketone manufactured by Ciba Specialty Chemicals, Inc. Name Irgacure 907, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one), benzophenones, thioxanthones, benzoin, benzoin methyl ether, manufactured by Ciba Specialty Chemicals, Aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, metathelone compounds, benzoin sulfonic acid esters and the like can be mentioned. Of these, acetophenones are preferable.

It is preferable that content of the said photoinitiator is 1-7 mass parts with respect to 100 mass parts of binder resin solid content in the composition for hard-coat layers. If the amount is less than 1 part by mass, the amount of the photopolymerization initiator may be insufficient, resulting in insufficient curing. When the amount exceeds 7 parts by mass, the photopolymerization initiator becomes excessive, and a difference in the photopolymerization reaction due to the excess is caused.
The content of the photopolymerization initiator is more preferably 2 to 5 parts by mass with respect to 100 parts by mass of the resin solid content.

The composition for hard coat layers may further contain other components as necessary in addition to the components described above.
Examples of the other components include a thermal polymerization initiator, an ultraviolet absorber, a light stabilizer, a crosslinking agent, a curing agent, a polymerization accelerator, a viscosity modifier, an antistatic agent, an antioxidant, an antifouling agent, a slip agent, A refractive index adjusting agent, a dispersing agent, etc. can be mentioned. These can use a well-known thing.

The hard coat layer composition preferably has a total solid content of 20 to 50%. If it is lower than 20%, residual solvent may remain or whitening may occur. If it exceeds 50%, the viscosity of the composition for hard coat layer is increased, the coating property is lowered and unevenness and streaks may appear on the surface, or interference fringes may be generated. The solid content is more preferably 30 to 45%.

The hard coat layer composition can be prepared by mixing and dispersing the binder resin, leveling agent, anti-blocking agent, photopolymerization initiator, and other components in a solvent.
The mixing and dispersing may be performed using a known apparatus such as a paint shaker, a bead mill, a kneader.

Examples of the solvent include water, alcohol (eg, methanol, ethanol, propanol, isopropanol, n-butanol, s-butanol, t-butanol, benzyl alcohol, PGME, ethylene glycol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl). Ketone, cyclopentanone, cyclohexanone, heptanone, diisobutyl ketone, diethyl ketone), aliphatic hydrocarbon (eg, hexane, cyclohexane), halogenated hydrocarbon (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic hydrocarbon (Eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether Ether alcohols (e.g., 1-methoxy-2-propanol) and the like.
Among these, methyl isobutyl ketone, cyclohexanone, and dimethylformamide are particularly preferably used because a compatible layer described later can be suitably formed on the base film.

The hard coat layer composition can be applied on the base film to form a coating film, dried as necessary, and then cured to form a hard coat layer. The hard coat film of the present invention can be produced.
Here, since the composition for a hard coat layer contains the ring structure component described above, by forming a hard coat layer on the base film, the hard coat layer side interface of the base film is formed. A compatible layer in which the material constituting the base film and the material constituting the hard coat layer are compatible is formed. The reason for this is assumed to be as follows.
That is, in the present invention, as the (meth) acrylic resin constituting the base film, those having a ring structure such as a lactone ring or an imide ring are preferably used, but the (meth) acrylic resin having such a ring structure is used. When the hard coat layer composition is applied on a base film made of resin, the surface of the base film made of the (meth) acrylic resin is caused by the ring structure component contained in the hard coat layer composition. Eroded and dissolved. And the said ring structure component with a structure close | similar to the ring structure in the said (meth) acrylic resin osmose | permeates the said base film, As a result, the (meth) acrylic resin and ring structure which comprise a base film It is presumed that a compatible layer in which the components are compatible is formed.

By forming the compatible layer, the hard coat film of the present invention has excellent adhesion between the base film and the hard coat layer, and also generates interference fringes due to the difference in refractive index between these layers. Can be prevented.
The compatible layer preferably has a thickness of 100 nm to 1 μm. When the thickness is less than 100 nm, the above-described effects of the present invention may not be sufficiently obtained. On the other hand, when the thickness exceeds 1 μm, hard coat properties such as pencil hardness may be lowered, and haze may be increased.

In the hard coat film of the present invention, the ring structure component constituting the binder resin of the hard coat layer penetrates into the base film to form a compatible layer. For this reason, the hard coat film of the present invention has a concentration gradient of the ring structure component in the thickness direction.

Examples of a method for forming a coating film by applying the hard coat layer composition include, for example, a spin coating method, a dip method, a spray method, a die coating method, a bar coating method, a roll coater method, a meniscus coater method, and a flexographic printing method. And various known methods such as a screen printing method and a bead coater method.

Moreover, it is preferable that the application quantity (dry application quantity) of the said composition for hard-coat layers is 5-15 g / m < ² >. If it is less than 5 g / m ² , a hard coat layer having a desired hardness may not be obtained. If it exceeds 15 g / m ² , curling and damage may be insufficiently prevented. The coating amount is more preferably 6 to 10 g / m ² .

Although it does not specifically limit as said drying method, Generally, it is good to carry out at drying temperature 30-80 degreeC, and drying time 3 to 120 second. When the drying temperature is less than 30 ° C., it takes a long time to produce the hard coat film, and the production cost may increase. On the other hand, when the drying temperature exceeds 80 ° C., there is a problem that the production cost of the hard coat film is increased, and there is a possibility that an initiator, a solvent, etc. adhere to the inside of the drying furnace and deteriorate the appearance.
If the drying time is less than 3 seconds, a sufficiently thick compatible layer is not formed, and the adhesion between the base film and the hard coat layer may be inferior, or interference fringes may occur. There is. On the other hand, when the drying time exceeds 120 seconds, it takes a long time to dry the coating film, which may increase the production cost.

As a method for curing the coating film, a known method may be appropriately selected according to the contents of the hard coat layer composition. For example, if the binder resin contained in the hard coat layer composition is of an ultraviolet curable type, the coating film may be cured by irradiating with ultraviolet rays.
When irradiating the ultraviolet light is preferably ultraviolet irradiation amount is 80 mJ / cm ² or more, more preferably 100 mJ / cm ² or more, more preferably 130 mJ / cm ² or more.

The hard coat layer preferably has a layer thickness of 5 to 15 μm.
If it is less than 5 μm, the hardness may be insufficient. If it exceeds 15 μm, residual solvent may remain or coating film adhesion may be reduced. The lower limit of the thickness of the hard coat layer is more preferably 5 to 10 μm.
The layer thickness is a value obtained by measuring the cross section of the hard coat layer with an electron microscope (SEM, TEM, STEM).

The hardness of the hard coat film of the present invention is preferably 3H or more, and more preferably 4H or more, in a pencil hardness test (load 4.9 N) according to JIS K5600-5-4 (1999).

The hard coat film of the present invention preferably has a total light transmittance of 90% or more. If it is less than 90%, color reproducibility and visibility may be impaired when mounted on the display surface, and a desired contrast may not be obtained. The total light transmittance is more preferably 91% or more.
The total light transmittance can be measured by a method based on JIS K-7361 using a haze meter (manufactured by Murakami Color Research Laboratory, product number: HM-150).

The hard coat film of the present invention preferably has a haze of 1% or less. If it exceeds 1%, the desired optical properties cannot be obtained, and the visibility when the hard coat film of the present invention is placed on the image display surface is lowered.
The haze can be measured by a method based on JIS K-7136 using a haze meter (manufactured by Murakami Color Research Laboratory, product number: HM-150).
The hard coat film of the present invention may also contain other layers (antiglare layer, antistatic layer, low refractive index layer, antifouling layer, adhesive layer) as necessary within the range where the effects of the present invention are not impaired. , Other hard coat layers, etc.) can be appropriately formed. Among these, it is preferable to have at least one of an antiglare layer, an antistatic layer, a low refractive index layer, and an antifouling layer. These layers may be the same as those of a known antireflection laminate.

The hard coat film of the present invention can be suitably used for a polarizing plate.
Examples of the polarizing plate using the hard coat film of the present invention include a polarizing plate provided with a polarizing element and the surface of the polarizing element provided with the hard coat film of the present invention.
A polarizing plate using such a hard coat film of the present invention is also one aspect of the present invention.

The polarizing element is not particularly limited, and for example, a polyvinyl alcohol film, a polyvinyl formal film, a polyvinyl acetal film, an ethylene-vinyl acetate copolymer saponified film, etc. dyed and stretched with iodine or the like can be used. In laminating the polarizing element and the hard coat film of the present invention, it is preferable to saponify the light-transmitting substrate. By the saponification treatment, the adhesiveness is improved and an antistatic effect can be obtained.

The present invention is also an image display device comprising the hard coat film of the present invention, the polarizing plate of the present invention, or the front plate of the present invention on the outermost surface.
Examples of the image display device include LCD, PDP, FED, ELD (organic EL, inorganic EL), CRT, touch panel, and electronic paper.

The LCD includes a transmissive display body and a light source device that irradiates the transmissive display body from the back. When the image display device of the present invention is an LCD, the hard coat film, the polarizing plate or the front plate of the present invention is formed on the surface of the transparent display body.

When the present invention is a liquid crystal display device having the hard coat film, the light source of the light source device is irradiated from the lower side (base material side) of the hard coat film. Note that in the STN liquid crystal display device, a retardation plate may be inserted between the liquid crystal display element and the polarizing plate. An adhesive layer may be provided between the layers of the liquid crystal display device as necessary.

The PDP includes a front glass substrate and a rear glass substrate disposed with a discharge gas sealed between the front glass substrate and the front glass substrate. When the image display device of the present invention is a PDP, the surface of the surface glass substrate or the front plate (glass substrate or film substrate) is provided with the hard coat film described above.
The front plate holding the hard coat film of the present invention on its surface is also one aspect of the present invention.

Other image display devices are ELD devices that emit light when zinc is applied, such as zinc sulfide or diamine substances, deposited on a glass substrate, and display the voltage by controlling the voltage applied to the substrate. It may be an image display device such as a CRT that generates an image visible to human eyes. In this case, the hard coat film described above is provided on the outermost surface of each display device as described above or the surface of the front plate.

In any case, the hard coat film of the present invention can be used for display display of a television or a computer. In particular, it can be suitably used for the surface of a high-definition image display such as a liquid crystal panel, PDP, ELD, touch panel, and electronic paper.

In the hard coat film of the present invention, the hard coat layer provided on one surface of the base film is formed using the hard coat layer composition containing the ring structure component described above. The adhesion between the material film and the hard coat layer is excellent, and the generation of interference fringes due to the difference in refractive index between these layers can be suitably prevented. For this reason, the hard coat film of the present invention is used for displays such as cathode ray tube display (CRT), liquid crystal display (LCD), plasma display (PDP), electroluminescence display (ELD), and electronic paper, particularly high definition display. It can be preferably used.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples and comparative examples.
In the text, “part” or “%” is based on mass unless otherwise specified.

Example 1
4 parts by mass of Irgacure 184 (photopolymerization initiator, manufactured by BASF Japan Ltd.) was added to 15 parts by mass of methyl isobutyl ketone (MIBK), and dissolved by stirring to prepare a solution having a final solid content of 40% by mass. .
In this solution, pentaerythritol triacrylate (PETA) and Aronix UVT-302 (manufactured by Toa Gosei Co., Ltd., maleimide group-containing polymer) as a resin component in a solid content ratio, PETA: UVT-302 = 70 parts by mass: 30 It added and stirred so that it might become a mass part.
To this solution, 0.2 parts by mass of a leveling agent (product name: Megafac F-477, manufactured by DIC) was added and stirred, and further, silica fine particles (SIRMIBK15WT% -E65, manufactured by CIK Nanotech). ) Was added at a solid content ratio of 2 parts by mass and stirred to prepare a composition for a hard coat layer.
The composition for hard coat layer was applied on an acrylic substrate (thickness 40 μm, Tg = 125 ° C.) by slit reverse coating to form a dry coating amount of 8 g / m ² to form a coating film. After drying the obtained coating film at 70 ° C. for 1 minute, the coating film was cured by irradiating with ultraviolet rays at an ultraviolet irradiation amount of 150 mJ / cm ² to form a hard coat layer having a thickness of 7 μm. A coated film was obtained.

(Example 2)
The blending amount of pentaerythritol triacrylate (PETA) and Aronix UVT-302 (manufactured by Toagosei Co., Ltd., maleimide group-containing polymer) is such that PETA: UVT-302 = 50 parts by mass: 50 parts by mass in solid content ratio. Except for the above, a hard coat layer composition was prepared in the same manner as in Example 1, and a hard coat film of Example 2 was obtained in the same manner as in Example 1 by using the hard coat layer composition.

(Example 3)
The blending amount of pentaerythritol triacrylate (PETA) and Aronix UVT-302 (manufactured by Toagosei Co., Ltd., maleimide group-containing polymer) is, as a solid content ratio, PETA: UVT-302 = 30 parts by mass: 70 parts by mass. Except for the above, a hard coat layer composition was prepared in the same manner as in Example 1, and a hard coat film of Example 3 was obtained in the same manner as in Example 1 by using the hard coat layer composition.

( Reference Example 4)
A hard coat layer was obtained in the same manner as in Example 1 except that NVP (Nippon Shokubai Co., Ltd., N-vinyl-2-pyrrolidone) was used instead of Aronix UVT-302 (manufactured by Toagosei Co., Ltd., maleimide group-containing polymer). A hard coat film of Reference Example 4 was obtained in the same manner as in Example 1 using the composition for hard coat layer.

( Reference Example 5)
A hard coat layer was obtained in the same manner as in Example 2 except that NVP (manufactured by Nippon Shokubai Co., Ltd., N-vinyl-2-pyrrolidone) was used instead of Aronix UVT-302 (manufactured by Toagosei Co., Ltd., maleimide group-containing polymer). A hard coat film of Reference Example 5 was obtained in the same manner as in Example 1 using the composition for hard coat layer.

( Reference Example 6)
Hard coat layer in the same manner as in Example 3 except that NVP (Nippon Shokubai Co., Ltd., N-vinyl-2-pyrrolidone) was used instead of Aronix UVT-302 (manufactured by Toagosei Co., Ltd., maleimide group-containing polymer). A hard coat film of Reference Example 6 was obtained in the same manner as in Example 1 using the composition for hard coat layer.

(Example 7)
For the hard coat layer as in Example 1, except that a mixed solvent of 12 parts by mass of methyl isobutyl ketone (MIBK) and 3 parts by mass of dimethylformamide (DMF) was used as the solvent for the composition for the hard coat layer. A composition was prepared, and a hard coat film of Example 7 was obtained in the same manner as Example 1 using the composition for hard coat layer.

(Example 8)
A hard coat layer composition was prepared in the same manner as in Example 2 except that M145 (manufactured by Toagosei Co., Ltd., Arrayimide acrylate) was used instead of Aronix UVT-302 (manufactured by Toagosei Co., Ltd., maleimide group-containing polymer). The hard coat film of Example 8 was obtained in the same manner as in Example 1 using the composition for hard coat layer.

Example 9
A hard coat layer composition was prepared in the same manner as in Example 2 except that MT1000 (manufactured by Toa Gosei Co., Ltd., oxazolidone acrylate) was used instead of Aronix UVT-302 (manufactured by Toagosei Co., Ltd., maleimide group-containing polymer). And the hard coat film of Example 9 was obtained like Example 1 using this composition for hard-coat layers.

(Example 10)
A hard coat layer composition was prepared in the same manner as in Example 1 except that dipentaerythritol hexaacrylate (DPHA) was used instead of pentaerythritol triacrylate (PETA). In the same manner as in Example 1, the hard coat film of Example 10 was obtained.

(Example 11)
For the hard coat layer as in Example 1, except that a mixed solvent of 12 parts by mass of methyl isobutyl ketone (MIBK) and 3 parts by mass of dimethylformamide (DMF) was used as the solvent for the composition for the hard coat layer. A composition was prepared, and a hard coat film of Example 11 was obtained in the same manner as Example 10 using the composition for hard coat layer.

(Reference Example 1)
The blending amount of pentaerythritol triacrylate (PETA) and Aronix UVT-302 (manufactured by Toagosei Co., Ltd., maleimide group-containing polymer) is, as a solid content ratio, PETA: UVT-302 = 80 parts by mass: 20 parts by mass Except for the above, a hard coat layer composition was prepared in the same manner as in Example 1, and a hard coat film of Reference Example 1 was obtained in the same manner as in Example 1 using the hard coat layer composition.

(Reference Example 2)
The blending amount of pentaerythritol triacrylate (PETA) and Aronix UVT-302 (manufactured by Toagosei Co., Ltd., maleimide group-containing polymer) is such that PETA: UVT-302 = 20 parts by mass: 80 parts by mass in solid content ratio. Except for the above, a hard coat layer composition was prepared in the same manner as in Example 1, and a hard coat film of Reference Example 2 was obtained in the same manner as in Example 1 using the hard coat layer composition.

(Comparative Example 1)
Hard coat layer in the same manner as in Example 1 except that BS577 (Arakawa Chemical Industries, IPDP derivative hexafunctional urethane acrylate) was used instead of Aronix UVT-302 (manufactured by Toagosei Co., Ltd., maleimide group-containing polymer). A hard coat film of Comparative Example 1 was obtained in the same manner as in Example 1 using the composition for hard coat layer.

(Comparative Example 2)
Instead of Aronix UVT-302 (manufactured by Toa Gosei Co., Ltd., maleimide group-containing polymer), U-15HA (manufactured by Shin-Nakamura Chemical Co., Ltd., isocyanuric skeleton-containing 15-functional urethane acrylate) was used in the same manner as in Example 1. A hard coat layer composition was prepared, and a hard coat film of Comparative Example 2 was obtained in the same manner as in Example 1 using the hard coat layer composition.

(Comparative Example 3)
A hard coat layer composition was prepared in the same manner as in Example 2 except that ACMO (manufactured by Kojin Co., Ltd., acryloylmorpholine) was used instead of Aronix UVT-302 (manufactured by Toagosei Co., Ltd., maleimide group-containing polymer). And the hard coat film of the comparative example 3 was obtained like Example 2 using this composition for hard-coat layers.

(Comparative Example 4)
Only 10 parts by mass of pentaerythritol triacrylate (PETA) was added as a resin component, and a mixed solvent of 12 parts by mass of methyl isobutyl ketone (MIBK) and 3 parts by mass of dimethylformamide (DMF) was used as a solvent. Then, a hard coat layer composition was prepared in the same manner as in Example 1, and a hard coat film of Comparative Example 4 was obtained in the same manner as in Example 1 using the hard coat layer composition.

(Comparative Example 5)
Only 10 parts by mass of dipentaerythritol hexaacrylate (DPHA) was added as a resin component, and a mixed solvent of 12 parts by mass of methyl isobutyl ketone (MIBK) and 3 parts by mass of dimethylformamide (DMF) was used as a solvent. Prepared the composition for hard-coat layers similarly to Example 1, and obtained the hard-coat film of the comparative example 5 like Example 1 using this composition for hard-coat layers.

(Comparative Example 6)
As the resin component, pentaerythritol triacrylate (PETA) and D41 (manufactured by Hitachi Chemical Co., Ltd., acrylic acrylate polymer) are used, and the blending amount thereof is, as a solid content ratio, PETA: D41 = 70 parts by mass: 30 parts by mass A composition for a hard coat layer was prepared in the same manner as in Example 1 except that a mixed solvent of 12 parts by mass of methyl isobutyl ketone (MIBK) and 3 parts by mass of methyl ethyl ketone (MEK) was used as the solvent. And the hard coat film of the comparative example 6 was obtained like Example 1 using this composition for hard-coat layers.

(Comparative Example 7)
Hard coat layer in the same manner as in Example 2 except that FA-511AS (manufactured by Hitachi Chemical Co., Ltd., dicyclopentanyl acrylate) was used instead of Aronix UVT-302 (manufactured by Toagosei Co., Ltd., maleimide group-containing polymer). A hard coat film of Comparative Example 7 was obtained in the same manner as in Example 1 using the composition for hard coat layer.

(Comparative Example 8)
Hard coat in the same manner as in Example 2 except that FA-512AS (manufactured by Hitachi Chemical Co., Ltd., dicyclopentenyloxyethyl acrylate) was used instead of Aronix UVT-302 (manufactured by Toagosei Co., Ltd., maleimide group-containing polymer). A layer composition was prepared, and a hard coat film of Comparative Example 8 was obtained in the same manner as in Example 1 using the hard coat layer composition.

(Comparative Example 9)
The hard coat layer composition was the same as in Example 2 except that FA-BZA (Hitachi Chemical Co., Ltd., benzyl acrylate) was used instead of Aronix UVT-302 (manufactured by Toagosei Co., Ltd., maleimide group-containing polymer). A hard coat film of Comparative Example 9 was obtained in the same manner as in Example 1 using the composition for hard coat layer.

(Comparative Example 10)
A hard coat layer composition was prepared in the same manner as in Example 2 except that DMAA (manufactured by Kojin Co., Ltd., dimethylacrylamide) was used instead of Aronix UVT-302 (manufactured by Toagosei Co., Ltd., maleimide group-containing polymer). And the hard coat film of the comparative example 10 was obtained like Example 1 using this composition for hard-coat layers.

(Comparative Example 11)
Hard coat layer composition in the same manner as in Example 2, except that DMAPAA (manufactured by Kojin Co., Ltd., dimethylaminopropylacrylamide) was used instead of Aronix UVT-302 (manufactured by Toagosei Co., Ltd., maleimide group-containing polymer). A hard coat film of Comparative Example 11 was obtained in the same manner as in Example 1 using the composition for hard coat layer.

(Comparative Example 12)
A hard coat layer composition was prepared in the same manner as in Example 2 except that NIPAM (manufactured by Kojin Co., Ltd., isopropylacrylamide) was used instead of Aronix UVT-302 (manufactured by Toagosei Co., Ltd., maleimide group-containing polymer). And the hard coat film of the comparative example 12 was obtained like Example 1 using this composition for hard-coat layers.

(Comparative Example 13)
Instead of Aronix UVT-302 (manufactured by Toagosei Co., Ltd., maleimide group-containing polymer), a hard coat layer composition was prepared in the same manner as in Example 2 except that HEAA (manufactured by Kojin Co., Ltd., hydroxyethylacrylamide) was used. The hard coat film of Comparative Example 13 was obtained in the same manner as in Example 1 using the composition for hard coat layer.

(Comparative Example 14)
Instead of Aronix UVT-302 (manufactured by Toagosei Co., Ltd., maleimide group-containing polymer), PPZ (manufactured by Kyoeisha Chemical Co., Ltd., 2,2,4,4,6,6-hexa {2- (methacryloyloxy) -ethoxy} -1,3,5-triaza-2,4,6-triphosphorin), a hard coat layer composition was prepared in the same manner as in Example 2, and the hard coat layer composition was used. A hard coat film of Comparative Example 14 was obtained in the same manner as Example 1.

The obtained hard coat film was evaluated in the following items. The evaluation results are shown in Table 1.

(Compatible layer thickness)
The thickness of the compatible layer formed at the interface on the hard coat layer side of the base film was measured by cross-sectional SEM observation of the hard coat layer.

(Adhesion)
In accordance with JIS K5600, cross cut CCJ-1 (manufactured by Cortec Co., Ltd.) is used to make a grid-like cut on the surface of the hard coat layer to produce 100 squares of 1 mm square. Nichiban Industrial 24mm wide cello tape (registered trademark) is applied on the grid, and then it is rubbed back and forth 10 times with a spatula to make it come in close contact and rapidly peel off in the direction of 150 °, and the same operation is repeated 5 times. Count the number of remaining squares. Using the number of remaining squares as the numerator and the total number of squares as the denominator, the following criteria were used for evaluation.
A: 100/100
B: 50/100 to 99/100
C: 0/100 to 49/100

(Interference fringes)
Black tape was bonded to the back surface of each hard coat film (the surface opposite to the hard coat layer on the base film side), interference fringes were confirmed under a dark room fluorescent lamp, and the following criteria were evaluated.
○: Interference fringes are not observed ×: Interference fringes are observed

(Pencil hardness test)
Each hard coat film is conditioned for 2 hours under conditions of a temperature of 25 ° C. and a relative humidity of 60%, and then specified by JISK5600-5-4 (1999) using a test pencil specified by JIS-S-6006. According to the pencil hardness evaluation method, the pencil hardness of the surface on which the hard coat layer was formed was measured with a load of 4.9 N, and evaluated according to the following criteria.
○: Pencil hardness is B or more ×: Pencil hardness is less than B

From Table 1, as for the hard coat film which concerns on an Example, all have the compatible layer formed in the hard coat layer side interface vicinity of a base film, It is excellent in adhesiveness and the prevention of an interference fringe, Furthermore, the surface hardness was also excellent.
Since the hard coat film according to Comparative Examples 1 to 3 has a ring structure component including a ring structure including a nitrogen atom and / or an oxygen atom in the unit structure in the hard coat layer, a compatible layer is formed to prevent interference fringes. However, since the ring structure component had a 6-membered ring structure, the formed compatible layer was few and the adhesion was poor.
Moreover, in the hard coat films according to Comparative Examples 4 to 14, no compatible layer was formed in the vicinity of the hard coat layer side interface of the base film, and the adhesion and interference fringe prevention properties were poor. It was.
In addition, the hard coat film according to Reference Example 1 has a five-membered ring structure in the hard coat layer and has a ring structure component containing a nitrogen atom and / or an oxygen atom in the unit structure, so that a compatible layer is formed. Further, although the PETA having a sufficient content was excellent in pencil hardness, the compatibility layer formed with a small content of the ring structure component was few and inferior in adhesion.
Further, the hard coat film according to Reference Example 2 has a 5-membered ring structure in the hard coat layer, has a large content of ring structure components containing nitrogen atoms and / or oxygen atoms in the unit structure, and has sufficient compatibility. Although the layer was formed and was excellent in adhesion and interference fringe prevention property, the PETA content was small and the pencil hardness was inferior.

The hard coat film of the present invention is suitable for a cathode ray tube display (CRT), a liquid crystal display (LCD), a plasma display (PDP), an electroluminescence display (ELD), a touch panel, an electronic paper or the like, particularly a high definition display. Can be used for

Claims (5)

A hard coat film having a base film made of a (meth) acrylic resin and a hard coat layer formed on one surface of the base film,
The hard coat layer is formed using a composition for a hard coat layer containing a ring structure component having a five-membered ring structure,
The ring structure component is a maleimide group-containing acrylic polymer,
Near the interface on the hard coat layer side of the base film, a compatible layer in which the material constituting the base film and the material constituting the hard coat layer are compatible is formed,
The thickness of the said compatible layer is 100 nm-1 micrometer, The hard coat film characterized by the above-mentioned. Ring component, a hard coat film of a hard binder resin solid content 100 parts by weight contained in the coating layer forming composition, 5 0-70 parts by claim 1, wherein it contains a proportion of. A polarizing plate comprising a polarizing element,
A polarizing plate comprising the hard coat film according to claim 1 or 2 on a surface of the polarizing element. Front plate, characterized in that for holding the hard coat film according to claim 1 or 2, wherein the surface. The hard coat film according to claim 1 or 2, wherein the outermost surface, or the polarizing plate according to claim 3, or an image display apparatus, characterized in that it comprises a front plate of claim 4 wherein.