KR20120135486A - Composition for hard coat layer, hard coat film, polarizer, image display device, and method of producing hard coat layer - Google Patents

Abstract

PURPOSE: A composition for a hard coating layer is provided to form a hard coating layer with excellent blocking prevention performance and leveling performance. CONSTITUTION: A composition for a hard coating layer contains a leveling agent, a silica microparticle, and a binder resin. The leveling agent contains a fluorine-based leveling agent which is composed of 10-50 weight% of polypropylene glycol monoacrylate, 10-50 weight% of polyethylene glycol monoacrylate, and 10-50 weight% of 2-(perfluorohexyl)ethylacrylate.

Description

Composition for hard coating layer, hard coating film, polarizing plate, image display device and manufacturing method of hard coating film {COMPOSITION FOR HARD COAT LAYER, HARD COAT FILM, POLARIZER, IMAGE DISPLAY DEVICE, AND METHOD OF PRODUCING HARD COAT LAYER}

The present invention relates to a composition for a hard coating layer, a hard coating film, a polarizing plate, and an image display device.

Image display devices such as cathode ray tube display (CRT), liquid crystal display (LCD), plasma display (PDP), electro luminescence display (ELD), electronic paper, touch panel, tablet PC, organic light emitting diode (OLED) Generally, the optical laminated body for reflection prevention is provided in the outermost surface. Such an antireflection optical laminated body suppresses projection of an image or reduces reflectance by scattering or interference of light.

As said optical laminated body, the hard coat film which provided the hard coat layer on the surface of a transparent base material is known.

Such a hard coat film is produced with a long length from the viewpoint of inexpensiveness and mass production, and is then wound on a roll. However, when the surface of the hard coat film is smooth, adjacent hard coat films are adjacent to each other when the hard coat film is released from the roll. Is attached, a phenomenon called blocking occurs and there is a problem that the yield is lowered.

With respect to the problem of blocking, for example, a method of adding a lubricating agent to the hard coating layer and providing a slipperiness (lubrication ease) to the hard coating layer surface by the lubricating agent present on the surface of the hard coating layer is known. (For example, refer patent document 1).

However, in the conventional method of adding the lubricant, since the lubricant is uniformly dispersed in the hard coating layer, in order to obtain sufficient lubricity, it is necessary to increase the amount of the additive, which causes a problem of high cost. There was also a problem of impairing the transparency of the coating layer.

Moreover, the method of adding a lubricating agent and a leveling agent to a hard coat layer and providing an lubrication ease to a hard coat layer is also known.

Leveling agents to be added to such a hard coat layer is, for example, C8 telomer (perfluoro-octyl (C ₈ F ₁₇ -)) has a fluorine-based leveling agent is known comprising a (for example, see Patent Document 2).

However, the blocking prevention property at the higher level is calculated | required in recent years, and it was impossible to satisfy the blocking prevention property at the high level recently with the hard coat film which used the conventional leveling agent together.

In addition, C8 telomer is a substance which is concerned about the environmental load of human perfluorooctanoic acid produced in the manufacturing process and the effect on the human body, and a hard coat film using a material having a lower environmental load is required.

Japanese Patent Laid-Open No. 2000-249815 Japanese Patent Laid-Open No. 2010-241019

The present invention provides a hard coating layer composition, a hard coating film, a polarizing plate, and an image display device using the hard coating layer composition which can form a hard coating layer having excellent blocking prevention performance and leveling performance in view of the present situation. It aims to do it.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the composition for hard-coat layers containing a silica fine particle and the fluorine-type leveling agent which consists of a specific monomer composition exhibits the outstanding blocking property besides predetermined | prescribed hard coat property when it hardens | cures and it is set as a hard coat layer. It discovered what was possible and came to complete this invention.

That is, this invention is a composition for hard-coat layers containing a leveling agent, a silica fine particle, and binder resin, The said leveling agent is a polypropylene glycol monoacrylate, polyethyleneglycol monoacrylate, and 2- (perfluorohexyl) ethyl. It is a composition for hard-coat layers containing the fluorine-type leveling agent which makes an acrylate the monomer composition.

In the composition for hard coating layers of the present invention, the monomer composition constituting the fluorine-based leveling agent is 10 to 50% by mass of polypropylene glycol monoacrylate, 10 to 50% by mass of polyethylene glycol monoacrylate, and 2- It is preferable that (perfluorohexyl) ethylacrylate is 10-50 mass%.

Moreover, it is preferable that the fluorine atom content rate of the said fluorine-type leveling agent is 7-34 mass%.

Moreover, it is preferable that the weight average molecular weights of the said fluorine-type leveling agent are 11000-25000.

Moreover, it is preferable that the composition for hard-coat layers of this invention contains 5-60 mass parts of said fluorine-type leveling agents with respect to 100 mass parts of said silica fine particles.

The present invention also has a light-transmissive substrate and a hard coat layer, wherein the hard coat layer is also a hard coat film comprising a cured product of the composition for a hard coat layer of the present invention.

It is preferable that the said silica fine particle is localized in the upper layer part on the opposite side to the light transmissive base material side of the said hard coat layer.

Moreover, this invention is a polarizing plate provided with a polarizing element, It is also a polarizing plate characterized by including the hard coat film mentioned above on the surface of the said polarizing element.

Moreover, this invention is also an image display apparatus characterized by including the above-mentioned hard coat film or the above-mentioned polarizing plate.

Moreover, this invention is a manufacturing method of the hard coat film which has a hard coat layer on a light transmissive base material, The process of apply | coating the composition for hard coat layers of this invention to form a coating film on the said light transmissive base material, and hardens the said coating film. It is also a manufacturing method of the hard-coating film characterized by making the fluorine-type leveling agent and silica microparticles localize in the upper layer part on the opposite side to the said light transmissive base material side in the said coating film.

Hereinafter, the present invention will be described in detail.

The composition for hard coating layers of this invention contains a leveling agent, a silica fine particle, and binder resin.

The leveling agent contains a fluorine-based leveling agent having polypropylene glycol monoacrylate, polyethylene glycol monoacrylate and 2- (perfluorohexyl) ethyl acrylate as monomer compositions.

When the said fluorine-type leveling agent forms a hard-coat layer using the composition for hard-coat layers of this invention, by interacting with the binder resin contained in the composition for hard-coat layers of this invention, the upper layer part (light transmittance) of the said hard-coat layer And near the surface on the opposite side to the substrate side). As a result, according to the composition for hard coat layers of this invention, the hard coat layer with favorable planarity can be formed and the hard coat film excellent in the leveling performance can be obtained.

Moreover, when forming a hard coat layer using the composition for hard coat layers of this invention, it is preferable that the said silica fine particle is ubiquitous in the upper layer part of the said hard coat layer. Such a hard coat layer can be more suitably formed in the composition for hard coat layers of the present invention. That is, since the said fluorine-type leveling agent contains polypropylene glycol monoacrylate and polyethyleneglycol monoacrylate as a monomer composition, some hydrophilicity is ensured. For this reason, when a hard-coat layer is formed using the composition for hard-coat layers of this invention, the fluorine-type leveling agent ubiquitous on the said hard-coat layer attracts the said silica microparticles, and the said silica microparticles will be unevenly distributed in the upper layer part of a hard-coat layer. As a result, according to the composition for hard coat layers of this invention, the hard coat film which has the outstanding blocking prevention performance can be obtained.

On the other hand, in the conventional hard coating layer composition containing the silica particle and the conventional leveling agent of the monomer composition different from the fluorine-type leveling agent mentioned above, the said leveling agent is formed in the upper layer part of a hard-coat layer by the compatibility with hydrophilic silica fine particles. Even if it is ubiquitous, since the hydrophilicity of the said leveling agent is inadequate, it does not attract silica microparticles | fine-particles, As a result, silica microparticles | fine-particles are disperse | distributed uniformly to a hard coat layer, It is thought that the blocking prevention performance of a hard coat film becomes inadequate.

That is, in order to give the hard coating film excellent leveling performance and blocking performance, it is necessary to ensure a certain degree of hydrophilicity to the leveling agent added to the hard coating layer composition.

In addition, the silica fine particle localized in the upper layer part of the said hard coat layer can be confirmed by observing the cross section of the thickness direction of the said hard coat layer with a microscope. For example, the hard coat layer formed using the composition for hard coat layers of the present invention may be formed in a region on the side opposite to the light transmissive substrate side than half of the thickness of the hard coat layer at the time of cross-sectional microscope observation in the thickness direction thereof. At least 60% of the silica fine particles are observed.

In the composition for hard coating layers of the present invention, the monomer composition constituting the fluorine-based leveling agent is preferably 10 to 50% by mass of the polypropylene glycol monoacrylate. If it is less than 10 mass%, the degree of hydrophilicity of the upper layer part of a hard coat layer by the said fluorine-type leveling agent may fall, and uneven distribution of silica microparticles | fine-particles may become inadequate, and blocking prevention performance may become inadequate when it is set as a hard coat film. On the other hand, when it exceeds 50 mass%, the fluorine atom content rate of the said fluorine-type leveling agent may become small, and the leveling performance at the time of setting it as a hard coat film may become inadequate.

Moreover, it is preferable that the said polyethyleneglycol monoacrylate is 10-50 mass% in the monomer composition of the said fluorine-type leveling agent. If it is less than 10 mass%, the hydrophilicity of the said fluorine-type leveling agent may fall, and uneven distribution of silica microparticles | fine-particles may become inadequate, and blocking prevention performance may become inadequate when it is set as a hard coat film. On the other hand, when it exceeds 50 mass%, the fluorine atom content rate of the said fluorine-type leveling agent may become small, and the leveling performance at the time of setting it as a hard coat film may become inadequate.

Moreover, it is preferable that the said 2- (perfluorohexyl) ethyl acrylate is 10-50 mass% in the monomer composition of the said fluorine-type leveling agent. If it is less than 10 mass%, the fluorine atom content rate of the said fluorine-type leveling agent may become small, and the leveling performance at the time of using a hard coat film may become inadequate. On the other hand, when it exceeds 50 mass%, the hydrophilicity of the said fluorine-type leveling agent falls, the uneven distribution of silica microparticles | fine-particles may become inadequate, and blocking prevention performance may become inadequate when it is set as a hard coat film.

It is preferable that the fluorine-type leveling agent which consists of the monomer composition mentioned above is 7-34 mass% of fluorine atom content rates. When it is less than 7 mass%, when it is set as a hard coat film, leveling performance may become inadequate. On the other hand, when it exceeds 34 mass%, blocking performance may become inadequate when it is set as a hard coat film. The minimum with more preferable fluorine atom content rate is 10 mass%, and a more preferable upper limit is 30 mass%.

It is preferable that the said fluorine-type leveling agent is 11000-25000 by weight average molecular weight. If it is less than 11000, a silica fine particle cannot be attracted enough, and when it is set as a hard coat film, blocking prevention property may become inadequate, and when it exceeds 25000, sufficient leveling performance may not be obtained. The minimum with more preferable said weight average molecular weight is 13000, and a more preferable upper limit is 20,000.

In addition, the weight average molecular weight of the said fluorine-type leveling agent is a value obtained by the method of a gel permeation chromatography method (GPC method).

Although it is preferable that the composition for hard-coat layers of this invention contains only the fluorine-type leveling agent mentioned above as a leveling agent, as long as it is a range which does not impair the effect of this invention, it may contain the other leveling agent.

As said other leveling agent, well-known things, such as a fluorine-type leveling agent, a silicone-type leveling agent, and an acryl-type leveling agent different from the monomer composition mentioned above, are mentioned, for example.

In addition, when the composition for hard-coat layers of this invention contains a leveling agent other than a fluorine system, sufficient blocking property is not acquired when it is set as a hard coat film. For example, when the composition for a hard coat layer of the present invention contains a silicon leveling agent instead of a fluorine leveling agent, the affinity between the silicon leveling agent and the silica fine particles is strongly and uniformly dispersed, making it difficult to localize on the upper layer. Lose.

In the composition for hard coating layers of this invention, it is preferable to contain 5-60 mass parts of fluorine-type leveling agents mentioned above with respect to 100 mass parts of silica fine particles mentioned later, More preferably, a minimum is 7 mass parts, and a more preferable upper limit is 50 mass parts. It is wealth. When it is less than 5 mass parts, smoothness may not be obtained when it is set as a hard coat film, and when it exceeds 60 mass parts, sufficient blocking prevention performance may not be obtained when it is set as a hard coat film.

The composition for hard coating layers of this invention contains a silica fine particle.

The said silica fine particle is a material which functions as an antiblocking agent (lubricating agent), and when it contains a said silica fine particle to make a hard coat film, suitable antiblocking performance is obtained.

As said silica microparticles | fine-particles, the spherical particle which does not have a reactor and whose average primary particle diameter is 100-600 nm is mentioned suitably. If it is less than 100 nm, there exists a possibility that blocking prevention property may not be exhibited in the hard coat film formed using the composition for hard-coat layers of this invention. When it exceeds 600 nm, there exists a possibility that the haze of the said hard coat film may become high. As for the said average primary particle diameter, it is more preferable that it is 100-350 nm.

In addition, the said average primary particle diameter is a value obtained by measuring by the laser diffraction scattering method particle size distribution measuring apparatus in the state of 5 weight% of methyl isobutyl ketone dispersion liquid. In addition, the average primary particle diameter of the said silica fine particle can also be computed as an average value of the diameter of the silica fine particle measured by microscope observation, such as SEM, when it is set as a hard coat film.

Moreover, since the said silica fine particle is spherical, the raise of the haze of the hard-coat layer to form can be suppressed.

It is preferable that content of the said silica fine particle is 1-4 mass parts with respect to 100 mass parts of resin solid content of the composition for hard-coat layers of this invention. If it is less than 1 mass part, there exists a possibility that blocking prevention property may not be exhibited in the hard coat film formed using the composition for hard-coat layers of this invention. If it exceeds 4 parts by mass, the optical properties of the hard coat film formed by using the composition for hard coating layer of the present invention is increased, the dispersibility is remarkably deteriorated, resulting in agglomeration and gelation. As a result, there is a possibility that the defects in the appearance of the surface of the hard coat film and the rise of haze may be connected. As such, the silica fine particles are preferably not aggregated.

The composition for hard coating of this invention contains binder resin.

It is preferable that it is transparent as said binder resin, For example, ionizing radiation curable resin which is resin hardened | cured by an ultraviolet-ray or an electron beam, ionizing radiation curable resin, and a solvent-drying resin (such as a thermoplastic resin, adjusting solid content at the time of application | coating construction) And a thermosetting resin, or a mixture with a resin to form a film only by drying the solvent added for the purpose. More preferably, it is an ionizing radiation hardening type resin. In addition, in this specification, "resin" is a concept also containing resin components, such as a monomer and an oligomer.

As said ionizing radiation curable resin, the compound which has one or two or more unsaturated bonds, such as a compound which has an acrylate-type functional group, is mentioned, for example. As a compound which has one unsaturated bond, ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methyl styrene, N-vinylpyrrolidone, etc. are mentioned, for example. As a compound which has two or more unsaturated bonds, For example, polymethylol propane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acryl Latex, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, neopentylglycol di (meth) acrylate and the like and these The polyfunctional compound modified | denatured with the seed (EO) etc., or reaction products (for example, poly (meth) acrylate ester of polyhydric alcohol), such as said polyfunctional compound and (meth) acrylate, etc. are mentioned. In addition, in this specification, "(meth) acrylate" refers to methacrylate and acrylate.

A polyether resin, an acrylic resin, an epoxy resin, a urethane resin, an alkyd resin, a spiroacetal resin, a polybutadiene resin, a polythiol polyene resin and the like having an unsaturated double bond, It can be used as a curable resin.

The said ionizing radiation curable resin can also be used in combination with solvent drying type resin. By using solvent dry type resin together, the coating defect of an application surface can be prevented effectively. The solvent-drying resin that can be used in combination with the ionizing radiation curable resin is not particularly limited, and generally a thermoplastic resin can be used.

It does not specifically limit as said thermoplastic resin, For example, styrene resin, (meth) acrylic-type resin, vinyl acetate type resin, vinyl ether type resin, halogen containing resin, alicyclic olefin resin, polycarbonate resin, Polyester resin, polyamide resin, a cellulose derivative, silicone resin, rubber | gum, an elastomer, etc. are mentioned. The thermoplastic resin is preferably amorphous and soluble in an organic solvent (in particular, a common solvent capable of dissolving a plurality of polymers or curable compounds). In particular, styrene resins, (meth) acrylic resins, alicyclic olefin resins, polyester resins, cellulose derivatives (such as cellulose esters) and the like are preferable from the viewpoint of film forming property, transparency and weather resistance.

As the thermosetting resin that can be used as the binder resin, a phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea ball Condensation resin, a silicon resin, polysiloxane resin, etc. are mentioned.

Moreover, in the composition for hard-coat layers of this invention, what is marketed can also be used for the said binder resin, For example, the beam set DT3 (a mixture of an acrylate monomer, an acrylate acrylate oligomer, and an acrylate polymer, Arakawa) Kagaku High School).

Moreover, in the composition for hard-coat layers of this invention, it is preferable that the said binder resin contains urethane (meth) acrylate which has an isocyanur skeleton. By containing the urethane (meth) acrylate which has the said isocyanur skeleton, the hard coat film formed using the composition for hard-coat layers of this invention can be made to have high hardness and excellent resilience.

Here, the "high hardness" is specifically "3H" or more in the pencil hardness test prescribed by JIS K5600-5-4 (1999).

As a urethane (meth) acrylate which has the said isocyanurate skeleton, the urethane (meth) acrylate which made the polyfunctional monomer react with the isocyanate group of the terminal of the isocyanurate which consists of diisocyanate is mentioned.

Examples of the polyfunctional monomers include pentaerythritol tri (meth) acrylate, dipentaerythritol pentaacrylate (DPPA), dipentaerythritol tetra (meth) acrylate, and the like.

It is preferable that the number of functional groups of the urethane (meth) acrylate which has the said isocyanuric skeleton is 9 or more. If the number of the said functional groups is less than 9, there exists a possibility that sufficient hardness may not be obtained. As for the said functional group number, it is more preferable that it is 12 or more, and it is still more preferable that it is 15.

It is preferable that the weight average molecular weights of the urethane (meth) acrylate which has the said isocyanuric skeleton are 1500-3000.

If it is less than 1500, there is a fear that sufficient hardness cannot be obtained. When it exceeds 3000, the viscosity of the composition for hard coating layers of the present invention may increase, making coating difficult, or inhibiting the hardening reaction of the formed hard coating layer, and there is a possibility that sufficient hardness may not be obtained.

As for the said weight average molecular weight, it is more preferable that it is 1800-2500.

In addition, the said weight average molecular weight is the value calculated | required in polystyrene conversion by the gel permeation chromatography (GPC) method.

As a urethane (meth) acrylate which has the said isocyanur skeleton, it is a dipenta to three terminal isocyanate of the isocyanurate which formed the isocyanur skeleton from the trimer of hexamethylene diisocyanate (HDI), especially The urethane acrylate to which erythritol pentaacrylate (DPPA) was made to react is preferable. Since the urethane acrylate has a large number of functional groups, has a certain size in molecular weight, and has an isocyanur skeleton as a skeleton, it can not only realize high hardness but also have elasticity as a characteristic of the urethane acrylate. For example, restorability, such as recovery of the recessed part of the surface by the pencil hardness test of a hard coat film, can also be realized.

It is preferable that content of the urethane (meth) acrylate which has the said isocyanuric skeleton is 30-50 mass% in solid content among the binder resin components of the composition for hard-coat layers. If it is less than 30 mass%, there exists a possibility that sufficient hardness may not be obtained. When it exceeds 50 mass%, there exists a possibility that curling of a hard coat film may arise easily. As for the said content, it is more preferable that it is 35-50 mass%.

In addition, curling of the hard coat film is a phenomenon in which a curing shrinkage occurs due to an ultraviolet curing reaction during formation of a hard coat layer, and the coating film shrinks, so that a stress difference occurs between the coating film (hard coating layer) and the substrate and the film curls on the coating film side. Say

When the urethane (meth) acrylate having the isocyanur skeleton is contained as the binder resin, it is preferable to further contain pentaerythritol tri (meth) acrylate.

By containing pentaerythritol tri (meth) acrylate, when it is set as a hard coat film, the blocking such as adhesion of the said hard coat films can be prevented more suitably. In addition, the occurrence of curling of the hard coat film may be appropriately prevented.

It is preferable that content of the said pentaerythritol tri (meth) acrylate is 15-35 mass% in solid content among the said binder resin components. If it is less than 15 mass%, sufficient hardness may not be obtained, and when it exceeds 35 mass%, curling may generate | occur | produce or blocking may occur when it is set as a hard coat film. As for the said content, it is more preferable that it is 20-35 mass%.

It is preferable that the said composition for hard-coat layers contains urethane (meth) acrylate whose number of functional groups is 6 or less as binder resin further.

In addition to the urethane (meth) acrylate having the isocyanuric skeleton described above, by using a urethane (meth) acrylate with a relatively small number of functional groups, curling can be prevented while maintaining a high pencil hardness and making a hard coating film. Can be.

As a urethane (meth) acrylate with the number of the said functional groups 6 or less, it is a urethane (meth) acrylate which consists of hexamethylene diisocyanate (HDI) and / or isophorone diisocyanate (IPDI), and the number of functional groups is 2-3. It is preferable to add a functional acrylate monomer.

It is preferable that content of the urethane (meth) acrylate whose number of the said functional groups is 6 or less is 15-35 mass% in solid content among the binder resin components of the composition for hard-coat layers. If it is less than 15 mass%, curling at the time of using a hard coat film may arise. When it exceeds 35 mass%, there exists a possibility that sufficient hardness may not be obtained.

As said binder resin, it is preferable to contain a (meth) acryl polymer other than the resin component mentioned above. Curing and damage of a hard coat film can be prevented by containing the said (meth) acryl polymer other than the urethane (meth) acrylate which has the said isocyanur skeleton.

The damage is a heat generated by the ultraviolet curing reaction when forming the hard coating layer, or rapidly heated by the heat generated, and suddenly cooled by the end of ultraviolet irradiation, so that the hard coating layer and the substrate in the flow direction along with curing shrinkage The phenomenon of waving.

It is preferable that the weight average molecular weights of the said (meth) acryl polymer are 10,000-30,000. If the said weight average molecular weight is less than 10,000, there exists a possibility that sufficient hardness may not be obtained. When it exceeds 30,000, there exists a possibility that coating film adhesiveness may fall, the viscosity of the composition for hard-coat layers rises, a coating surface may worsen, or handling may worsen. It is preferable that a minimum is 10,000, and, as for the said weight average molecular weight, it is preferable that an upper limit is 20,000.

The said weight average molecular weight is a value obtained by the method of a gel permeation chromatography method (GPC method).

The (meth) acryl polymer has an acrylic double bond equivalent of 200 to 300. It is also difficult to synthesize | combine that the said acrylic double bond equivalent is less than 200, and glass transition temperature will fall. When it exceeds 300, there are few double bonds, and the hardness and scratch resistance of the hard coat layer obtained by hardening fall.

It is preferable that the minimum is 210, and, as for the said acrylic double bond equivalent, it is preferable that an upper limit is 270.

The said acrylic double bond equivalent is the value calculated | required by the double bond amount and the weight average molecular weight computed from the mix | blended monomer.

It is preferable that ratio (weight average molecular weight / acrylic double bond equivalent) of the said (meth) acrylic polymer with the said weight average molecular weight and the said acrylic double bond equivalent is 50-80.

If the said ratio is less than 50, there exists a possibility that hardness and abrasion resistance may deteriorate. When it exceeds 80, there exists a possibility that adhesiveness may deteriorate.

It is more preferable that the said minimum is 50, and an upper limit is 70.

It is preferable that the said (meth) acryl polymer is 40-100 degreeC of glass transition temperature Tg. If glass transition temperature is less than 40 degreeC, there exists a possibility that hardness and scratch resistance may become inadequate. When it exceeds 100 degreeC, the viscosity of the composition for hard-coat layers may rise, or the said composition may gelatinize. It is more preferable that it is 50 degreeC, and, as for the minimum of the said glass transition temperature, it is more preferable that it is 70 degreeC.

The said glass transition temperature is a value obtained by the method of calculating from Tg of the monomer which comprises a polymer.

It is preferable that the said (meth) acryl polymer has an acid value of 1 mgKOH / g or less. If the acid value exceeds 1 mgKOH / g, there is a fear that a hard coat layer having a desired hardness may not be obtained. Moreover, there exists a possibility that a blocking prevention property may be inferior.

As for the said acid value, it is more preferable that it is 0.8 mgKOH / g or less.

It is preferable that the said (meth) acryl polymer is contained 5-20 mass% in solid content in binder resin of the composition for hard-coat layers. If it is less than 5 mass%, there is a possibility that the marking mark residue cannot be prevented. When it exceeds 20 mass%, there exists a possibility that the hardness of a hard coat layer may fall. As for content of the said (meth) acryl polymer, it is more preferable that it is 10-20 mass%.

It is preferable that the composition for hard-coat layers of this invention contains a photoinitiator.

The photopolymerization initiator is not particularly limited as long as it is known, and examples thereof include acetophenones (for example, 1-hydroxycyclohexyl-phenyl-ketone manufactured by Ciba Specialty Chemicals, Inc. Cure 907, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1-one by Ciba Specialty Chemicals Co., Ltd.), benzophenones, thioxanthones, benzoin, benzo Phosphorus methyl ether, aromatic diazonium salt, aromatic sulfonium salt, aromatic iodonium salt, metaceron compound, benzoin sulfonic acid ester, etc. are mentioned. Especially, it is preferable that they are acetophenones.

It is preferable that content of the said photoinitiator is 1-7 mass parts with respect to 100 mass parts of resin solid content in the composition for hard-coat layers of this invention. If it is less than 1 mass part, the quantity of a photoinitiator will run short and there exists a possibility that it may become hardening. When it exceeds 7 mass parts, a photoinitiator will become excess, and the difference of the photoinitiation reaction by the excess may arise, and it may cause the hardness shortage or the fault by melt residue rather.

As for content of the said photoinitiator, it is more preferable that it is 2-5 mass parts with respect to 100 mass parts of said resin solid content.

The said hard-coat layer composition may further contain other components as needed other than the component mentioned above.

As said other component, a thermal polymerization initiator, a ultraviolet absorber, a light stabilizer, a crosslinking agent, a hardening | curing agent, a polymerization accelerator, a viscosity modifier, an antistatic agent, antioxidant, an antifouling agent, a slip agent, a refractive index regulator, a dispersing agent, etc. are mentioned. These can use a well-known thing.

The composition for hard coating layers of this invention can be manufactured by mixing and disperse | distributing the above-mentioned leveling agent, a silica fine particle, binder resin, and a photoinitiator, and other components in a solvent as needed.

The mixing and dispersion may be performed using a known apparatus such as a paint shaker, bead mill, kneader or the like.

The solvent may be water, alcohol (e.g. methanol, ethanol, propanol, isopropanol, n-butanol, s-butanol, t-butanol, benzyl alcohol, PGME, ethylene glycol), ketone (e.g. acetone, methyl ethyl ketone, methyl Isobutyl ketone, cyclopentanone, cyclohexanone, heptanone, diisobutyl ketone, diethyl ketone), aliphatic hydrocarbons (e.g. hexane, cyclohexane), halogenated hydrocarbons (e.g. methylene chloride, chloroform, carbon tetrachloride), aromatic Hydrocarbons (e.g. benzene, toluene, xylene), amides (e.g. dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ethers (e.g. diethyl ether, dioxane, tetrahydrofuran), ether alcohol ( Examples include 1-methoxy-2-propanol) and esters such as methyl acetate, ethyl acetate, butyl acetate and isopropyl acetate.

Among them, methyl isobutyl ketone and / or methyl ethyl ketone are preferable as the solvent can dissolve or disperse the above-described resin component and other additives and apply the composition for the hard coating layer of the present invention appropriately. Do.

It is preferable that the composition for hard-coat layers of this invention is 30 to 45% of total solids. If it is less than 30%, a residual solvent may remain and whitening may arise. When it exceeds 45%, the viscosity of the composition for hard-coat layers of this invention becomes high, coating property falls and there exists a possibility that a stain and a streak may arise on the surface, or interference streaks may arise. As for the said solid content, it is more preferable that it is 35 to 45%.

After apply | coating the composition for hard-coat layers of this invention on the light transmissive base material mentioned later, and forming a coating film, it is made to dry as needed, and a hard-coat layer can be formed by hardening the said coating film.

As a method of apply | coating the composition for hard-coat layers of this invention, and forming a coating film, for example, a spin coating method, an immersion method, a spray method, a die coating method, a bar coating method, a roll coater method, a meniscus coater method, a platter Various well-known methods, such as a flexographic printing method, the screen printing method, the bead coater method, are mentioned.

Moreover, it is preferable that application amount (dry application amount) is 3-15 g / m <2>. If it is less than 3 g / m <2>, there exists a possibility that the hard coat layer of desired hardness may not be obtained. When it exceeds 15 g / m <2>, there exists a possibility that prevention of curling and damage may become inadequate. As for the said application amount, it is more preferable that it is 4-9 g / m <2>.

Although it does not specifically limit as said drying method, Generally, what is necessary is just to dry for 3 to 120 second at 30-120 degreeC.

What is necessary is just to select a well-known method suitably according to the content etc. of the composition for hard-coat layers of this invention as a method of hardening the said coating film. For example, what is necessary is just to harden by irradiating an ultraviolet-ray to a coating film, when the resin component contained in the composition for hard-coat layers of this invention is an ultraviolet curable type.

When irradiating the said ultraviolet-ray, it is preferable that the amount of ultraviolet irradiation is 80 mJ / cm <2> or more, It is more preferable that it is 100 mJ / cm <2> or more, It is more preferable that it is 130 mJ / cm <2> or more.

The hard coat layer preferably has a layer thickness of 3 to 15 µm.

If it is less than 3 micrometers, there exists a possibility that hardness may become inadequate. When it exceeds 15 micrometers, a residual solvent may remain and coating film adhesiveness may fall. As for the layer thickness of the said hard-coat layer, it is more preferable that it is 4-9 micrometers.

The layer thickness is a value obtained by measuring the cross section of the hard coat layer with an electron microscope (SEM, TEM, STEM).

It is preferable that the said light transmissive base material has smoothness and heat resistance, and is excellent in mechanical strength.

Specific examples of the material for forming the light-transmissive substrate include polyester (polyethylene terephthalate, polyethylene naphthalate), cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, polyamide, polyimide, polyether sulfone, polysulfone And thermoplastic resins such as polypropylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal, polyether ketone, polymethyl methacrylate, polycarbonate, or polyurethane, and preferably polyester (polyethylene Terephthalate, polyethylene naphthalate), triacetyl cellulose, and polymethyl methacrylate.

As the light transmissive substrate, an amorphous olefin polymer (Cyclo-Olefin-Polymer: COP) film having an alicyclic structure can also be used. These are substrates in which norbornene-based polymers, monocyclic cyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon-based polymer resins, and the like are used. ), Sumitomo Bakelite company Sumilite FS-1700, JSR company Aton (modified norbornene-based resin), Mitsui Chemicals Co., Ltd. Apel (cyclic olefin copolymer), Ticona company Topas (cyclic olefin) Copolymer), the Hitachi Kasei Co., Ltd. optlets OZ-1000 series (alicyclic acrylic resin), etc. are mentioned. Moreover, the FV series (low birefringence and low photoelasticity film) by Asahi Kasei Chemicals Co., Ltd. is also preferable as an alternative base material of triacetyl cellulose.

It is preferable to use the thermoplastic resin as a film-rich body having flexibility as the light-transmissive base material, but it is also possible to use the plates of these thermoplastic resins depending on the use form in which curability is required, or the plate-shaped body of the glass plate. You may use it.

As thickness of the said transparent base material, it is preferable that it is 5-300 micrometers, More preferably, an upper limit is 200 micrometers and a minimum is 30 micrometers. In the case where the light transmissive substrate is a plate-like body, a thickness exceeding these thicknesses may be used.

In addition, when forming an anti-glare layer on the said light-transmissive base material, in addition to physical treatments, such as a corona discharge process and an oxidation process, in order to improve adhesiveness, you may apply the coating material called an anchor agent or a primer beforehand.

The hard coat film which has the above-mentioned light-transmissive base material and a hard coat layer, and the said hard coat layer consists of hardened | cured material of the composition for hard coat layers of this invention is also one of this invention.

It is preferable that it is 3H or more in a pencil hardness test (load 4.9N) by JISK5600-5-4 (1999), and, as for the hard coat film of this invention, it is more preferable that it is 4H or more.

It is preferable that the total light transmittance of the hard coat film of this invention is 90% or more. If it is less than 90%, when mounted on the display surface, it may not only damage color reproducibility and visibility, but also a desired contrast may not be obtained. As for the said total light transmittance, it is more preferable that it is 91% or more.

The said total light transmittance can be measured by the method based on JISK-7361 using the haze meter (made by Murakami Shikisai Kijutsu Co., Ltd., product number; HM-150).

Moreover, it is preferable that haze is 1% or less of the hard coat film of this invention. When it exceeds 1%, a desired optical characteristic will not be obtained, and the visibility at the time of installing the hard coat film of this invention on the image display surface falls.

The said haze can be measured by the method based on JISK-7136 using a haze meter (made by Murakami Shikisai Kijutsu Co., Ltd., product number; HM-150).

The hard coat film of this invention has a hard coat layer formed using the composition for hard coat layers of this invention containing a specific leveling agent and a silica microparticle as mentioned above. Therefore, the hard coat film of this invention has the outstanding leveling property and antiblocking property.

Moreover, the hard coat film of this invention can be made to have high hardness and excellent resilience by containing urethane (meth) acrylate which has an isocyanur skeleton as binder resin.

The method for producing such a hard coat film of the present invention is also one of the present invention.

That is, the manufacturing method of the hard coat film of this invention is a manufacturing method of the hard coat film which has a hard coat layer on a light transmissive base material, The coating composition is formed by apply | coating the composition for hard coat layers of this invention on the said light transmissive base material, And a step of curing the coating film to form the hard coating layer, wherein the fluorine-based leveling agent and the silica fine particles are localized in the upper layer on the side opposite to the light-transmitting substrate side in the coating film.

As a process of forming the said hard coat layer, it can carry out similarly to the method of forming a hard coat layer mentioned above.

Moreover, it is a polarizing plate provided with a polarizing element, It is one of this invention also to equip the surface of the said polarizing element with a light-transmitting base material, etc., and to provide the hard-coating film of this invention.

It does not specifically limit as said polarizing element, For example, the polyvinyl alcohol film, the polyvinyl formal film, the polyvinyl acetal film, the ethylene-vinyl acetate copolymerization saponification film etc. which were dyed with iodine etc. and extended | stretched can be used. . In the lamination process of the said polarizing element and the hard coat film of this invention, it is preferable to perform a saponification process to a light transmissive base material. Adhesiveness improves by saponification process.

This invention is also an image display apparatus provided with the said hard coat film or the said polarizing plate. Examples of the image display apparatus include LCD, PDP, FED, ELD (organic EL, inorganic EL), CRT, touch panel, electronic paper, and the like.

The LCD includes a transmissive display and a light source device for irradiating the transmissive display from the back side. When the image display apparatus of this invention is LCD, the hard coat film of this invention or the polarizing plate of this invention is formed in the surface of this transmissive display body.

In the case of the liquid crystal display device having the hard coat film of the present invention, the light source of the light source device is irradiated from the bottom side (base side) of the hard coat film. In addition, in the STN type liquid crystal display device, a retardation plate may be inserted between the liquid crystal display element and the polarizing plate. An adhesive layer can be provided between each layer of this liquid crystal display device as needed.

The said PDP is provided with the back glass substrate arrange | positioned so that discharge gas may be sealed between the surface glass substrate and the said surface glass substrate. When the image display apparatus of the present invention is a PDP, the above-mentioned hard coat film may also be provided on the surface of the surface glass substrate or the front plate (glass substrate or film substrate) thereof.

The other image display device deposits a light emitting material such as zinc sulfide or a diamine substance, which emits light when a voltage is applied to the glass substrate, and converts the ELD device or the electric signal to display the light by controlling the voltage applied to the substrate, An image display device such as a CRT that generates an image visible to the human eye may be used. In this case, the above-described hard coat film is provided on the outermost surface of each display device or the front plate thereof.

The hard coat film of this invention can be used for display indication of a television, a computer, etc. in any case. In particular, it can use suitably for the surface of high-definition image displays, such as a liquid crystal panel, PDP, ELD, a touch panel, and an electronic paper.

Since the composition for hard-coat layers of this invention consists of a structure mentioned above, the hard coat film provided with the hard-coat layer which has the outstanding leveling performance and blocking performance can be obtained. For this reason, the hard coat film of this invention using the composition for hard coat layers of this invention is a cathode ray tube display apparatus (CRT), a liquid crystal display (LCD), a plasma display (PDP), an electroluminescence display (ELD). , Electronic paper and the like, in particular, high-definition display can be used suitably.

Although an Example and a comparative example are given to the following and this invention is demonstrated in more detail, this invention is not limited only to these Examples and a comparative example.

In addition, it is a mass reference | standard unless there is particular notice that it is "part" or "%" in this specification.

(Example 1)

4 parts by mass of Irgacure 184 (photopolymerization initiator, manufactured by BASF Japan Co., Ltd.) was added to a mixed solvent of methyl ethyl ketone (MEK) / methyl isobutyl ketone (MIBK), stirred, and dissolved to obtain a final solid of 40 mass%. The solution was prepared. Pentaerythritol triacrylate (PETA) and U-4HA (4-functional urethane oligomer, weight average molecular weight 600, made by Shin-Nakamura Chemical Co., Ltd.) and U-15HA (15 functional urethane oligomer, weight average molecular weight) as a resin component to this solution. 25 parts by mass: 25 parts by mass: 40 parts by mass: 10 parts by mass of 2300, manufactured by Shinnakamura Kagaku Co., Ltd., and a polymer (7975-D41, acrylic double bond equivalent 250, weight average molecular weight 15000, Hitachi Kasei Kogyo Co., Ltd.). It added so that it might add and stirred. 0.2 mass part of leveling agents (product name: Megafax F-477, DIC make) are added to this solution by solid content, and it stirred, and 2 mass parts of silica fine particles (SIRMIBK15WT% -E65, CIK Nanotech Co., Ltd.) were added by solid content. The mixture was stirred to prepare a composition for a hard coating layer.

This composition for hard-coat layers was apply | coated so that it might become a dry application amount of 8 g / m <2> by slit reverse coating on the triacetyl cellulose (TAC) base material (brand name KC4UAW, thickness 40 micrometers, the product made by Konica Minolta Opto Corporation), and the coating film was formed. After drying the obtained coating film for 1 minute at 70 degreeC, the ultraviolet-ray was irradiated with the ultraviolet irradiation amount 150mJ / cm <2>, the coating film was hardened, the hard-coat layer of thickness 7micrometer was formed, and the hard coat film of Example 1 was obtained.

In addition, "Megafax F-477" is a fluorine-type leveling agent which uses polypropylene glycol monoacrylate, polyethyleneglycol monoacrylate, and 2- (perfluorohexyl) ethyl acrylate as a monomer composition.

(Example 2)

In the composition for hard coating layers of Example 1, the hard coating layer was formed on the TAC base material similarly to Example 1 except having set the compounding quantity of a leveling agent to 0.1 mass part, and the hard coat film was obtained.

(Example 3)

In the composition for hard coating layers of Example 1, the hard coating layer was formed on the TAC base material similarly to Example 1 except having set the compounding quantity of a leveling agent to 0.6 mass parts, and the hard coat film was obtained.

(Example 4)

In the composition for hard coating layers of Example 1, the hard coating layer was formed on the TAC base material similarly to Example 1 except having made the compounding quantity of a silica fine particle into 1 mass part, and the hard coat film was obtained.

(Example 5)

In the composition for hard coat layers of Example 1, the hard coat layer was formed on the TAC base material in the same manner as in Example 1, except that the compounding amount of the silica fine particles was 1.5 parts by mass to obtain a hard coat film.

(Example 6)

In the composition for hard coating layers of Example 1, the hard coating layer was formed on the TAC base material similarly to Example 1 except having made the compounding quantity of a silica fine particle 3 mass parts, and the hard coat film was obtained.

(Example 7)

In the composition for hard coating layers of Example 1, a hard coating layer was formed on a TAC substrate in the same manner as in Example 1 except that the blending amount of the leveling agent was 0.6 parts by mass, and the blending amount of the silica fine particles was 1.3 parts by mass, A coating film was obtained.

(Example 8)

In the composition for hard coating layers of Example 1, 100 parts by mass of the beam set DT3 (a mixture of an acrylic monomer, an acrylic acrylate oligomer, and an acrylic acrylate polymer, manufactured by Arakawa Chemical Industries, Ltd.) is used as a resin component. Except having made the compounding quantity 1.5 mass parts, the hard coat layer was formed on the TAC base material similarly to Example 1, and the hard coat film was obtained.

(Comparative Example 1)

In the composition for a hard coat layer of Example 1, except that a leveling agent (product name: Megafax F-444, manufactured by DIC Corporation) was used instead of a leveling agent (product name: MegaFax F-477, manufactured by DIC Corporation). In the same manner, a hard coat layer was formed on the TAC substrate to obtain a hard coat film.

In addition, "Megafax F-444" is a fluorine-type leveling agent which consists of a compound represented by following formula (1).

&Lt; Formula 1 >

(Comparative Example 2)

In the composition for a hard coat layer of Example 1, except that a leveling agent (product name: Megafax F-554, DIC Corporation) was used instead of a leveling agent (product name: Megafax F-477, DIC Corporation) In the same manner, a hard coat layer was formed on the TAC substrate to obtain a hard coat film.

In addition, "Megafax F-554" is a fluorine-type leveling agent which uses polyisobutylene glycol monoacrylate and 2- (perfluorohexyl) ethyl acrylate as a monomer composition.

(Comparative Example 3)

In the composition for a hard coat layer of Example 1, except that a leveling agent (product name: Megafax F-552, manufactured by DIC) was used instead of a leveling agent (product name: MegaFax F-477, manufactured by DIC) In the same manner, a hard coat layer was formed on the TAC substrate to obtain a hard coat film.

In addition, "Megafax F-552" is a fluorine-type leveling agent whose monomer composition is methyl methacrylate, octadecyl acrylate, and 2- (perfluorohexyl) ethyl acrylate.

(Comparative Example 4)

In the composition for a hard coating layer of Example 1, except that a leveling agent (product name: MegaFax MCF-350, manufactured by DIC Corporation) was used instead of a leveling agent (product name: MegaFax F-477, manufactured by DIC Corporation). In the same manner, a hard coat layer was formed on the TAC substrate to obtain a hard coat film.

In addition, "Megafax MCF-350" is represented by methyl methacrylate, hydroxyethyl methacrylate (HEMA), tolylene diisocyanate (TDI), 2- (perfluorooctyl) ethyl acrylate and the following formula (2) It is a fluorine-type leveling agent which is a C8 telomer which has a compound as a monomer composition.

<Formula 2>

(Reference Example 1)

In the composition for hard coat layers of Example 1, the hard coat layer was formed on the TAC base material in the same manner as in Example 1 except that the compounding amount of the leveling agent was 0.05 parts by mass, to obtain a hard coat film.

(Reference Example 2)

In the composition for hard coating layers of Example 1, a hard coat layer was formed on a TAC substrate in the same manner as in Example 1 except that the compounding quantity of the silica fine particles was 0.5 parts by mass, to obtain a hard coat film.

(Reference Example 3)

In the composition for hard coating layers of Example 1, a hard coating layer was formed on a TAC substrate in the same manner as in Example 1 except that the compounding amount of the leveling agent was 0.7 parts by mass, and the compounding amount of the silica fine particles was 1 part by mass, A coating film was obtained.

(Reference Example 4)

In the composition for hard coating layers of Example 1, the hard coating layer was formed on the TAC base material similarly to Example 1 except having set the compounding quantity of silica microparticles to 5 mass parts, and the hard coat film was obtained.

(Reference Example 5)

In the composition for hard coating layers of Example 1, a hard coat layer was formed on a TAC substrate in the same manner as in Example 1 except that only pentaerythritol triacrylate (PETA) was used as the resin component at 100 parts by mass, and the hard coating film Got.

(Reference Example 6)

In the composition for hard coating layers of Example 1, a hard coating layer was formed on a TAC substrate in the same manner as in Example 1 except that the compounding amount of the leveling agent was 0.4 parts by mass, and the compounding amount of the silica fine particles was 5 parts by mass. A coating film was obtained.

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

<Pencil hardness test>

After each hard-coating film was humidified for 2 hours under conditions of a temperature of 25 ° C. and a relative humidity of 60%, JIS K5600-5-4 (with hardness HB to 3H) specified in JIS-S-6006 was used. According to the pencil hardness evaluation method prescribed by 1999), the pencil hardness of the surface on which the hard coat layer was formed was measured under a load of 4.9 N.

<Antiblocking>

Two hard coating films were prepared, and each hard coating layer was rubbed with each other, and the slipperiness | lubricacy was evaluated on the following reference | standard.

◎: sliding well

○: slippery

△: slightly slippery

×: non-slip

<Leveling property>

The hard coat film was visually evaluated by transmitting and reflecting under a fluorescent lamp.

○: no problems at all

X: Deterioration of appearance due to lack of leveling agent such as unevenness, stripes, whitening or haze or excessiveness or poor compatibility

From Table 1, the hard coat film of the Example using the composition for hard-coat layers containing the fluorine-type leveling agent which made polypropylene glycol monoacrylate, polyethyleneglycol monoacrylate, and 2- (perfluorohexyl) ethylacrylate the monomer composition. Silver pencil hardness test, blocking prevention property, and leveling property were all favorable results.

On the other hand, the hard coat film of the comparative example using the composition for hard-coat layers containing the fluorine-type leveling agent which does not make polypropylene glycol monoacrylate, polyethylene glycol monoacrylate, and 2- (perfluorohexyl) ethyl acrylate as a monomer composition is In all cases, the antiblocking property was inferior.

In addition, the hard coat film of the reference example 1 using the composition for hard coat layers with few content of a fluorine-type leveling agent, and the hard coat film of the reference example 2 with little content of a silica fine particle were inferior to blocking prevention property compared with an Example. . In addition, since the bubble of the composition for whitening and a hard-coat layer generate | occur | produced the hard coat film of the reference example 3 with many content of a leveling agent, the evaluation of leveling property fell, and the hard coat film of the reference example 4 with much content of silica microparticles | fine-particles The higher the haze, the lower the leveling was. In addition, the hard-coating film of Reference Example 5 using only PETA as the resin component was inferior in pencil hardness. Moreover, even if the hard coat film of the reference example 6 with many content of a silica fine particle mix | blended many leveling agents, haze was high and leveling property evaluation was inferior.

The hard coat film using the composition for a hard coat layer of the present invention is a display such as cathode ray tube display (CRT), liquid crystal display (LCD), plasma display (PDP), electro luminescence display (ELD), touch panel, electronic paper, etc. In particular, it can be suitably used for high-definition display.

Claims (11)

It is a composition for hard-coat layers containing a leveling agent, a silica fine particle, and binder resin,
The leveling agent contains a fluorine-based leveling agent having polypropylene glycol monoacrylate, polyethylene glycol monoacrylate and 2- (perfluorohexyl) ethyl acrylate as monomer compositions.
Hard coating layer composition, characterized in that. The monomer composition constituting the fluorine-based leveling agent is 10 to 50% by mass of polypropylene glycol monoacrylate, 10 to 50% by mass of polyethylene glycol monoacrylate, and 2- (perfluorohexyl ) Composition for hard coating layers whose ethyl acrylate is 10-50 mass%. The hard coating layer composition of Claim 1 or 2 whose fluorine atom content rate of a fluorine-type leveling agent is 7-34 mass%. The composition for hard coating layers according to any one of claims 1 to 3, wherein the weight average molecular weight of the fluorine-based leveling agent is 11000 to 25000. The composition for hard coating layers according to any one of claims 1 to 4, which contains 5 to 60 parts by mass of the fluorine-based leveling agent with respect to 100 parts by mass of the silica fine particles. The composition for hard coating layers according to any one of claims 1 to 5, wherein the silica fine particles are not aggregated. Having a light transmissive substrate and a hard coating layer,
The said hard coat layer consists of hardened | cured material of the composition for hard coat layers in any one of Claims 1-6.
Hard coating film, characterized in that. The hard coat film according to claim 7, wherein the silica fine particles are ubiquitous in the upper layer portion on the side opposite to the light transmissive substrate side of the hard coat layer. It is a polarizing plate provided with a polarizing element,
The hard coat film of Claim 7 or 8 is provided in the surface of the said polarizing element, The polarizing plate characterized by the above-mentioned. The hard coat film of Claim 7 or 8, or the polarizing plate of Claim 9 is provided, The image display apparatus characterized by the above-mentioned. It is a manufacturing method of the hard coat film which has a hard coat layer on a transparent base material,
It has a process of apply | coating the composition for hard-coat layers in any one of Claims 1-6 on the said transparent base material, forming a coating film, hardening the said coating film, and forming the said hard coating layer,
In the coating film, the fluorine-based leveling agent and the silica fine particles are localized on the upper layer portion opposite to the light transmissive substrate side.
Method for producing a hard coat film, characterized in that.