KR102158662B1 - Substrate with hard coating film and coating solution for hard coating film - Google Patents

Abstract

It provides a hard coat film portion substrate having anti-blocking properties and inhibiting curling. The hard coat film part base material according to the present invention is a hard coat film part base material comprising a base material and a hard coat film formed on the base material, wherein the hard coat film comprises (i) metal oxide fine particles (A) clusters (CL), (ii) matrix components , And (iii) consisting of a cluster forming agent, at least a part of the cluster CL exists by forming a protrusion on the surface of the hard coat film, and has a protrusion having a height (H 凸) of 15 to 200 nm. In addition, the coating liquid for forming a hard coat film according to the present invention is a coating liquid for forming a hard coat film comprising metal oxide fine particles (A), a matrix forming component, a cluster forming agent, and a dispersion medium, wherein the metal oxide fine particles (A) The concentration (C _A ) is in the range of 0.025 to 48% by weight as a solid content, the concentration (C _M ) of the matrix forming component is in the range of 1 to 59.7% by weight as a solid content, and the concentration (C _CL ) of the cluster forming agent is in the range of solid content. It is characterized in that the metal oxide fine particles (A) in the range of 0.0005 to 6% by weight and the total solid content concentration in the range of 1 to 60% by weight form clusters (CL _P ).

Description

Substrate with hard coating film and coating solution for hard coating film}

The present invention relates to a hard coat film portion base material having excellent anti-blocking properties (hard coat films not in close contact with each other) and also having a curling inhibiting effect, and a coating liquid for forming the hard coat film.

It is known to form a hard coat film on the surface of a substrate to improve scratch resistance on the surface of a substrate such as glass, plastic sheet, plastic lens, resin film, and display device front plate. As such a hard coat film, an organic resin film or an inorganic film is used. It is formed on the surface of glass or plastic. It is being performed to further improve the scratch resistance by blending resin particles or inorganic particles such as silica in the organic resin film or the inorganic film. The resin substrate of such a hard coat film part is sometimes used by being attached to a front plate of a display device.

However, in the case of winding the hard coat film part base material during manufacture, or when the hard coat film part base material is laminated after manufacture, the hard coat film part substrates are in close contact with each other, and it is difficult to peel when used during subsequent processing. There was a problem that defects occurred in the appearance.

In order to increase anti-blocking properties, it is known to design irregularities on the surface of the film. To provide unevenness in order to impart anti-glare properties to the hard coat film, Patent Document 1 (Japanese Patent Laid-Open No. 2007-76055), Patent Document 2 (Japanese Patent Laid-Open No. 2009-169409), and Patent Document 3 (Japanese Patent Publication) 2008-163205), etc.), but this is mentioned in terms of anti-glare property, which is different from the object of the present invention for suppressing adhesion of the transparent film part, and thus, there is a case of a problem of impairing transparency.

On the other hand, Patent Document 4 (Japanese Patent Laid-Open No. 2009-35614) discloses a curable resin composition for a hard coat film layer comprising reactive inorganic fine particles A and organic silicon fine particles B. In this patent document 4, in order to prevent adhesion by overlapping mirror surfaces with each other, reactive inorganic particles A coated with an organic component having excellent dispersibility and binding properties in a binder component, and organic groups that tend to separate from the reactive inorganic particles A It is disclosed that the organic silicon fine particles B are mixed and used to disperse the organic silicon fine particles B on the surface of the binder layer due to the volume exclusion effect of the reactive inorganic fine particles A to form irregularities on the surface.

However, in Cited Literature 4, adhesion to the substrate may decrease and scratch resistance may become insufficient. When the present inventors use a coating solution for forming a hard coat film in which metal oxide particles having a specific range of spherical coefficient are dispersed in a hydrophobic organic resin, the metal oxide fine particles are present by forming recesses on the surface of the hard coat film, and the adhesion is lowered. It discloses that an anti-blocking property can be obtained (Patent Document 5: Japanese Patent Laid-Open No. 2011-68087).

In addition, the inventors of the present invention are able to form recesses of a specific height on the surface of the hard coat film by including metal oxide fine particles having a hydrophilic property in which the refractive index is adjusted and not compatible with the matrix component in the hydrophobic organic resin matrix component. It discloses that the anti-blocking property is improved without the visibility of (Patent Document 6: Japanese Patent Laid-Open No. 2011-136490).

Patent Document 1: Japanese Patent Laid-Open No. 2007-76055 Patent Document 2: Japanese Patent Laid-Open No. 2009-169409 Patent Document 3: Japanese Patent Laid-Open No. 2008-163205 Patent Document 4: Japanese Patent Laid-Open No. 2009-35614 Patent Document 5: Japanese Patent Laid-Open No. 2011-68087 Patent Document 6: Japanese Patent Laid-Open No. 2011-136490

In Patent Documents 5 and 6, particles are unevenly distributed to form concave portions and anti-blocking properties are obtained. Metal oxide fine particles are aggregated and aggregated on the surface as well, so that the anti-blocking properties are not effectively improved. In this case, scratch resistance, The pencil hardness, etc. may become insufficient. In addition, the transparency of the hard coat film may decrease and haze may deteriorate.

Meanwhile, in the conventional hard coat film, there is a problem in that the transparent film portion substrate is curved depending on the thickness of the transparent film or the type and thickness of the substrate. In recent years, in order to reduce weight and improve transparency, substrates with thinner thickness are being sought.

Accordingly, even when a substrate having a thin thickness is used, the above-described anti-blocking property can be obtained, and a transparent film portion substrate capable of suppressing peeling by curling or the like has been required.

In such a situation, it was devised that the conventional problem can be solved by forming clusters and forming irregularities rather than simply manufacturing irregularities using fine particles. The present invention was completed by discovering that a hard coat film portion substrate having anti-blocking properties and suppressing curling can be obtained.

The hard coat film part substrate according to the present invention comprises a substrate and a hard coat film formed on the substrate, and the hard coat film comprises (i) metal oxide fine particles (A) clusters (CL) and (ii) matrix components and (iii) clusters. It is made of a forming agent, and is characterized in that at least a part of the cluster CL exists by forming a protrusion on the surface of the hard coat film, and has a protrusion having a height (H凸) range of 15 to 200 nm.

In addition, the coating liquid for forming a hard coat film according to the present invention includes metal oxide fine particles (A), a matrix forming component, a cluster forming agent, and a dispersion medium, and the concentration (C _A ) of the metal oxide fine particles (A) is 0.025 as a solid content. -48% by weight, the concentration of the matrix forming component (C _M ) is in the range of 1 to 59.7% by weight as a solid content, and the concentration of the cluster forming agent (C _CL ) is in the range of 0.0005 to 6% by weight as the solid content, and the total solid content The concentration is in the range of 1 to 60% by weight and is characterized in that the metal oxide fine particles (A) form clusters (CL _P ).

Provides a hard coat film substrate with excellent adhesion, transparency, abrasion resistance, scratch strength, pencil hardness, etc. with the substrate according to the present invention and excellent anti-blocking properties and curling formation inhibition, and a coating liquid for forming the hard coat film. It can be.

Hereinafter, a description will be given of the hard coat film portion substrate according to the present invention.

[Materials for the hard coat film part]

The hard coat film part substrate according to the present invention comprises a substrate and a hard coat film having irregularities on the surface formed on the substrate.

materials

As the substrate used in the present invention, conventionally known plastic sheets such as glass, polycarbonate, acrylic resin, PET, and TAC, plastic films, and plastic panels can be used, but among them, triacetylcellulose (TAC), which has a low refractive index and requires alkalinity. ) It is preferable to use a substrate, a polyolefin resin substrate such as PET, a polyvinyl alcohol resin substrate, a polyethersulfone resin substrate, and the like.

The thickness of the substrate may be in the range of 20 μm to 5 mm, preferably 20 to 200 μm. In particular, according to the present invention, curling can be suppressed even in a thin substrate and anti-blocking properties can be exhibited.

Hard coat film

The hard coat film is made of metal oxide fine particles (A) clusters CL, a matrix component, and a cluster forming agent. Part of the cluster CL exists by forming a protrusion on the surface of the hard coat film.

(I) Metal oxide fine particles (A) Cluster (CL)

The average particle diameter (D _A ) of the metal oxide fine particles ( _A ) is in the range of 5 to 200 nm, preferably 5 to 150 nm.

When the average particle diameter (D _A ) of the metal oxide fine particles (A) is smaller than the above range, the fine particles may aggregate, the haze of the hard coat film may deteriorate, and the transparency may decrease.

Even when the average particle diameter (D A) of the metal oxide fine particles ( _A ) is large, the haze of the obtained hard coat film may deteriorate and transparency may decrease, and the hard coat film may be damaged by friction or the like.

Examples of the metal oxide fine particles (A) include silica, alumina, zirconia, titanium oxide, antimony pentoxide, boria, antimony-doped tin oxide, indoped tin oxide, tin-doped indium oxide and composite oxides thereof, and fine particles of a mixture.

In the cluster (CL) of the present invention, the cluster (CL _p ) (to be described later) in which the metal oxide particles (A) are relatively weakly agglomerated by the presence of the cluster forming agent in the coating liquid shrinks during dry curing during hard coat film formation It is a particle that is aggregated by doing.

Although the size of the clusters CL in the hard coat film cannot be measured directly, the average particle diameter of the metal oxide fine particles (A) clusters (CL _P ) in the coating solution for forming the hard coat film described later from the size of the convex portions of the surface irregularities ( D _CLP ) is estimated to be in the range of approximately 50 to 2,000 nm in the case of a slight contraction. In addition, ordinary particles do not form irregularities by a conventional method.

(Ii) Cluster forming agent

The cluster forming agent is preferably at least one or more surfactants selected from silicone surfactants, acrylic silicone surfactants, acrylic surfactants, phosphate ester surfactants, and polyoxyethylenealkylamine ether surfactants.

Examples of the silicone-based surfactant include Daze Faron LS-220, LS-240, LS-260, LS-280, LS-460, LS-480, 1711EF, etc. manufactured by Kusumoto Chemical Co., Ltd.

Examples of the acrylic silicone-based surfactant include Days Faron LHP-810, NSH-8430HF, UVX-270, UVX-271, UVX-272, UVX-2280, UVX-2285 manufactured by Kusumoto Chemical Co., Ltd.

Examples of the acrylic surfactant include Days Faron UVX-3750 UVX-35, UVX-36, UVX-39 manufactured by Kusumoto Chemical Co., Ltd.

As a phosphate ester surfactant, Daiichi Kogyo Pharmaceutical Co., Ltd. fly-safe A-212E, AL, etc. are mentioned.

As a polyoxyethylene alkylamine ether type surfactant, Daiichi Kogyo Pharmaceutical Co., Ltd. Amirazine C-1802 etc. are mentioned.

The metal oxide fine particles (A) are aggregated to a suitable size by the cluster forming agent to form a cluster (CL). In addition, clusters are unevenly distributed on the surface of the transparent film by the cluster forming agent, thereby forming a desired protrusion on the surface, resulting in a transparent film having excellent anti-blocking properties.

Metal oxide fine particles (B)

In the present invention, in addition to the metal oxide fine particles (A), the metal oxide fine particles (B) treated with a surfactant may be further included. When the metal oxide fine particles (B) are contained in the hard coat film, a hard coat film portion base material having further excellent anti-blocking properties and scratch resistance can be obtained. The reason is not clear, but the metal oxide particles (B) form a cluster that is finer than the clusters (CL) of the metal oxide particles (A), and exist between the clusters (CL) of the metal oxide particles (A), so that the cluster (CL) gap It is thought to have a function as a bonding material that can fill in.

The average particle diameter of the metal oxide fine particles (B) is in the range of 5 to 300 nm, preferably 5 to 150 nm. When the average particle diameter of the metal oxide fine particles (B) is smaller than the above range, it varies depending on the presence or absence of a surface treatment to be described later, but the fine particles may aggregate, so that the haze of the hard coat film may deteriorate or the transparency may decrease. Even if the average particle diameter of the metal oxide fine particles (B) is too large, it varies depending on the content of the metal oxide fine particles (B), but the haze of the obtained hard coat film may deteriorate or the transparency may decrease, and the hard coat film may be damaged by friction. .

As the metal oxide fine particles (B), the same fine particles as the metal oxide fine particles (A) are used. It is preferable that the metal oxide fine particles (B) are surface-treated with a surfactant.

Surfactants used in the surface treatment of the metal oxide fine particles (B) include at least one selected from cationic surfactants, anionic surfactants, complex ionic surfactants, and nonionic surfactants.

Specifically, cationic surfactants include lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, octyldimethylethylammonium ethylsulfate, lauryldimethylethylammonium ethylsulfate, palmityldimethylethylammonium ethylsulfate, dide Sildimethylammonium chloride, bisdiaryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, stearyldimethylhydroxyethylammoniumparatoluenesulfonate, stearyldimethylaminopropylamide, tributylbenzylammonium chloride, 1,4-bis( 2-ethylhexyl)sulfosuccinate sodium dioctylsulfosuccinate, etc. are mentioned.

As anionic surfactants, polyoxyethylene alkyl ether phosphate, polyoxyalkylene alkyl phosphate, polyoxyalkylene alkyl phenyl ether phosphate, polyoxyethylene tridecyl ether phosphate, polyoxyethylene alkyl phosphate, polyoxyethylene Alkyl ether phosphate monoethanolamine salt, polyoxyethylene lauryl ether phosphate, polyoxyethylene trilauryl ether phosphate monoethanolamine salt, polyoxyethylene styrenated phenyl ether phosphate, alkyl phosphate sodium, alkyl phosphate Monoethanolamine salt, sodium polyoxyethylene lauryl ether acetate, sodium lauryl sulfosuccinate, sodium polyoxyethylene sulfosuccinate, sodium polyoxyethylene alkyl sulfosuccinate, polyoxystyrene phenyl ether ammonium sulfate, polyethoxyalkyl Sodium renbundidecyl ether sulfate, ammonium polyoxyethylene isodecyl ether sulfate, sodium polyoxyethylene tridecyl ether sulfate, sodium polyoxyethylene lauryl ether sulfate, ammonium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, polyoxyethylene Ammonium oleyl cetyl ether sulfate, sodium polyoxyethylene oleyl cetyl ether sulfate, sodium alkylbenzene sulfonate, alkylbenzene sulfonic acid, sodium alpha-olefin sulfonate, phenol sulfonic acid, sodium dioctyl sulfosuccinate, sodium lauryl sulfate, and the like.

Examples of the complex ionic surfactant include lauryl dimethylamino acetate pentane, lauryl acid amide propyl pentane, octanoic acid amide propyl pentane, and lauryl dimethyl amine oxide.

Nonionic surfactants include polyoxyalkylene decyl ether, polyoxyethylene tridecyl ether, polyoxyalkylene tridecyl ether, polyoxyalkylene alkyl ether, polyoxyethylene isodecyl ether, polyoxyalkylene lauryl ether, poly Oxyethylene styrenated phenyl ether, polyoxyethylene naphthyl ether, phenoxyethanol, polyoxyethylene phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene lauryl ether, polyoxyethylene oleyl cetyl ether, polyoxyethylene Oleic acid ester, polyoxyethylene stearic acid ester, polyoxyethylene sorbitan monococoate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, isostearic acid polyoxyethylene glycerol, polyoxyethylene alkylamine, Octyl polyglucoside, butyl polyglycoside, etc. are mentioned.

Among them, cationic surfactants, anionic surfactants, and nonionic surfactants are preferred.

Specifically, octyl dimethyl ethyl ammonium ethyl sulfate, lauryl dimethyl ethyl ammonium ethyl sulfate, palmityl dimethyl ethyl ammonium ethyl sulfate, stearyl dimethyl hydroxyethyl ammonium paratoluene sulfonate, etc. are mentioned as a cationic surfactant.

As anionic surfactants, polyoxyethylene alkyl ether phosphate, polyoxyalkylene alkyl phosphate, polyoxyalkylene alkyl phenyl ether phosphate, polyoxyethylene tridecyl ether phosphate, polyoxyethylene alkyl phosphate, polyoxyethylene Alkyl ether phosphate monoethanolamine salt, polyoxyethylene lauryl ether phosphate, polyoxyethylene trilauryl ether phosphate monoethanolamine salt, polyoxyethylene styrenated phenyl ether phosphate, polyoxyethylene lauryl ether sodium acetate , Sodium lauryl polyoxyethylene sulfosuccinate, sodium polyoxyethylene alkyl sulfosuccinate, ammonium polyoxystyrene phenyl ether sulfate, sodium polyoxyalkylene branched decyl ether sulfate, polyoxyethylene isodecyl ether ammonium sulfate, polyoxyethylene tridecyl Sodium ether sulfate, sodium polyoxyethylene lauryl ether sulfate, ammonium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, ammonium polyoxyethylene oleyl cetyl ether sulfate, sodium polyoxyethylene oleyl cetyl ether sulfate, and the like. .

Nonionic surfactants include polyoxyalkylene decyl ether, polyoxyethylene tridecyl ether, polyoxyalkylene tridecyl ether, polyoxyalkylene alkyl ether, polyoxyethylene isodecyl ether, polyoxyalkylene lauryl ether, poly Oxyethylene styrenated phenyl ether, polyoxyethylene naphthyl ether, polyoxyethylene phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene lauryl ether, polyoxyethylene oleyl cetyl ether, polyoxyethylene oleic acid ester, poly Oxyethylene stearester, polyoxyethylene sorbitan monococoate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, isostearic acid polyoxyethylene glycerin, polyoxyethylene alkylamine, and the like.

Particularly, a surfactant having an ethylene oxide-modified skeleton is preferable. Specifically, octyldimethylammonium ethyl sulfate (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.: Catiogen ES-O), stearyldimethylhydroxy Ethyl ammonium paratoluene sulfonate (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.: Catiogen D2), and the like.

In addition, polyoxyalkylene alkylphenyl ether phosphate ester (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.: FlySafe A-212E) as anionic surfactant, sodium polyoxyethylene tridecyl ether sulfate (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.: High tenol 330T), polyoxyethylene alkyl (C8) ether phosphoric acid ester (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.: FlySafe A-208F), polyoxyalkylene styrenated phenyl ether phosphoric acid ester (Daiichi Kogyo Pharmaceutical Co., Ltd.) Manufacturing: Flysafe AL), etc. are mentioned. Nonionic surfactants include polyoxyethylene tridecyl ether (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.: Neugen TDS-80), polyoxyethylene sorbitan monostearate (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.: Sorugen TW). -60), etc. are mentioned.

The content of the surfactant in the metal oxide fine particles (B) treated with the surfactant varies depending on the average particle diameter, but is in the range of 0.5 to 30% by weight, preferably 1 to 25% by weight.

If the content of the surfactant is low, the dispersibility of the matrix-forming component dispersion medium described later is insufficient or agglomerates in the coating solution, and the agglomerated particles form protrusions on the surface of the film, resulting in a decrease in scratch resistance and transparency, and sufficient anti-blocking properties. There are cases where it cannot be obtained. Even if the content of the surfactant is too large, the amount of surfactant freed from the particles in the coating liquid increases, and the resulting hard coat film haze occurs, or the hardness, scratch resistance, etc. may become insufficient.

The metal oxide fine particles (B) treated with a surfactant can be prepared by dispersing the metal oxide fine particles (B) in a solvent and adding a predetermined amount of surfactant to the metal oxide fine particles (B) to adsorb the surfactant to the metal oxide fine particles (B). . Further, the surfactant may be used by dissolving in a solvent in advance.

(Iii) matrix component

As the matrix component, an organic resin is preferably used.

As the organic resin matrix component, specifically, all known thermosetting resins, thermoplastic resins, and the like can be used as resins for paints. For example, polyester resin, polycarbonate resin, polyamide resin, polyphenylene oxide resin, thermoplastic acrylic resin, vinyl chloride resin, fluororesin, vinyl acetate resin, thermoplastic resin such as silicone rubber, urethane resin, melamine And thermosetting resins such as resins, silicone resins, butylanol resins, reactive silicone resins, phenol resins, epoxy resins, unsaturated polyester resins, and thermosetting acrylic resins. In addition, two or more types of copolymers and modified products of these resins may be used.

Such a resin may be an emulsion resin, a water-soluble resin, or a hydrophilic resin. Further, in the case of a thermosetting resin, an ultraviolet curable resin or an electron beam curable resin may be used, and in the case of a thermosetting resin, a curing catalyst may be included.

Among them, it has a functional group such as a vinyl group, a urethane group, an epoxy group, a (meth)acryloyl group, and a CF ₂ group. It is preferable that it is at least 1 type selected from functional (meth)acrylic acid ester resin. More specifically, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetraacrylate, ditrimethylpropane tetra(meth)acrylate, dipentaerythritol hexaacrylate, methyl Methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl acrylate, n-stearyl acrylate, 1,6 -Hexanediol dimethacrylate, perfluorooctylethyl methacrylate, trichloroethyl methacrylate, urethane acrylate, and the like, and mixtures thereof are preferably used.

Among them, urethane acrylate oligomer resins can be preferably used because they are excellent in anti-blocking properties, have moderate hardness, and can obtain a hard coat film that is also excellent in the curling inhibitory effect.

Composition of hard coat film

The content (W _A ) of the metal oxide fine particles (A) in the hard coat film is in the range of 0.5 to 80% by weight, preferably 1 to 70% by weight, as a solid content.

If the content (W _A ) of the metal oxide fine particles (A) in the hard coat film is small, it varies depending on the thickness, but the anti-blocking property may be insufficient, and the curling inhibiting effect may be insufficient. Even if the content (W _A ) is too large, the haze of the hard coat film may deteriorate or the transparency may decrease, and the scratch resistance and adhesion to the substrate may be insufficient.

The content (W _M ) of the matrix component in the hard coat film is in the range of 20 to 99.5% by weight, preferably 30 to 99% by weight as solid content.

If the content (W _M ) of the matrix component is small, the haze of the hard coat film may deteriorate or the transparency may decrease, and the scratch resistance and adhesion to the substrate may be insufficient. Even if the content (W _M ) is too large, depending on the thickness, the anti-blocking property may be insufficient, and the curling inhibiting effect may be insufficient.

The content (W _CL ) of the cluster forming agent in the hard coat film is in the range of 0.01 to 10% by weight, preferably 0.02 to 5% by weight, as a solid content. If the amount of the cluster forming agent (W _CL ) in the hard coat film is small, it varies depending on the thickness, but the anti-blocking property may be insufficient. Even if the content (W _CL ) is too large, the haze of the hard coat film may deteriorate or the transparency may decrease, and the scratch resistance and adhesion to the substrate may be insufficient.

(W _CL )/(W _A ) is in the range of 0.0005 to 1, preferably 0.0001 to 0.5. If it is in this range, the particulate (A) can form a cluster of a desired size. Also becomes smaller when to adjust the size of the clusters, the _{(W CL) / (W A} ) when the zoom increases (W _CL) / small (W _A).

In the case of including the metal oxide fine particles (B) surface-treated with a surfactant, if necessary, the content (W _B ) of the surface-treated metal oxide fine particles (B) of the hard coat film is 30% by weight or less as a solid content, preferably 1 It is in the range of -20% by weight.

When the content of the metal oxide fine particles (B) (W _B ) in the hard coat film is within the above range, a hard coat film portion substrate having excellent anti-blocking properties and scratch resistance can be obtained.

In the hard coat film of the present invention, a portion of the clusters CL forms a protrusion on the surface of the hard coat film, and the height of the protrusion (H 凸) is in the range of 10 to 200 nm, preferably 15 to 150 nm.

When the height of the protrusion (H凸) is small, the anti-blocking property may be insufficient. Even if the height of the protrusion (H 凸) is too large, the haze of the hard coat film may be deteriorated or the transparency may be lowered, and the scratch resistance and adhesion to the substrate may be insufficient.

The height of the protrusion (H凸) can be adjusted by dissolving or dispersing a polymerization initiator or the like described later. The average thickness of the hard coat film is appropriately selected depending on the purpose and is in the range of 0.5 to 20 µm, preferably 1 to 10 µm.

When the average thickness of the hard coat film is in the above range, stress can be sufficiently absorbed, so that the scratch resistance is high and curling during drying is reduced. In the present invention, the average thickness of the hard coat film is measured by photographing a stylus-type step gauge or a vertical cross-sectional transmission electron microscope (TEM) of the hard coat film. In addition, the height of the protrusion (H 凸) (Rmax) is measured with an atomic force microscope (AFM) (manufactured by Bruker Co., Ltd.: Dimension 3100).

In addition, in the present invention, the thickness of the hard coat layer does not take into account the height of the protrusion (H 凸) (Rmax). The refractive index difference between the refractive index (n _B ) of the substrate and the refractive index (n _H ) of the hard coat film is 0.3 or less, preferably 0.2 or less. If the difference between the refractive index of the hard coat film and the refractive index of the substrate exceeds 0.3, there is a problem that interference fringes occur.

Such a hard coat film can be formed by applying, drying, and curing the following coating liquid for forming a hard coat film according to the present invention.

Hereinafter, a coating liquid for forming a hard coat film according to the present invention will be described.

[Coating liquid for hard coat film formation]

The coating liquid for forming a hard coat film according to the present invention includes the metal oxide particles (A), a matrix forming component (before curing polymerization of the matrix component of the hard coat film), a cluster forming agent, and a dispersion medium. In addition, the metal oxide fine particles (B) may be included if necessary.

The metal oxide fine particles (A) form clusters (CL _P ) in the coating liquid. The cluster (CL _P ) is a relatively weak aggregation of metal oxide particles (A) in the coating liquid due to the presence of a cluster forming agent.

Dispersion medium

The dispersion medium used in the present invention is particularly limited as long as it is capable of dissolving or dispersing the metal oxide fine particles (A), the matrix forming component, the cluster forming agent, the metal oxide fine particles (B) used as needed, and a polymerization initiator. Is absent, and a conventionally known solvent can be used.

Specifically, alcohols such as methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, hexylene glycol, and isopropylene glycol; Esters such as methyl acetate, ethyl acetate, and butyl acetate; Diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol isopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol Ethers such as monoethyl ether; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl butyl ketone, cyclohexanone, methyl cyclohexanone, dipropyl ketone, methyl pentyl ketone, diisobutyl ketone, isoformone, acetylacetone, and acetacetic acid ester, Toluene, xylene, etc. are mentioned. These may be used alone or in combination of two or more.

The concentration of the coating liquid for forming a hard coat film is in the range of 1 to 60% by weight, preferably 2 to 50% by weight as the total solid content.

When the total solid concentration is low, clusters of the desired size (CL _P ) may not be formed, and for this reason, when forming the hard coat film, the desired irregularities may not be formed, and anti-blocking properties may not be obtained. In some cases, it is difficult to obtain a hard coat film having a desired thickness in one application. In addition, when repeated application and drying are repeated, a predetermined protrusion may not be formed.

If the total solid content concentration is too high, the cluster (CL _P ) may become too large, so that the surface irregularities become too large, and the haze of the hard coat film may deteriorate or the transparency may decrease. Also, scratch resistance and adhesion to the substrate may be insufficient. In addition, the viscosity of the coating liquid may increase, so that the coating property may decrease, the haze of the resulting hard coat film may increase, or the scratch resistance may be insufficient.

The concentration (C _A ) of the metal oxide fine particles (A) in the coating liquid for forming a hard coat film is in the range of 0.025 to 48% by weight, preferably 0.05 to 42% by weight as a solid content. The concentration (C _A) of the metal oxide fine particles (A) small, anti-blocking property becomes insufficient, it is possible to suppress the curling effect is insufficient. The hard coat film haze value is the concentration (C _A) of the metal oxide fine particles (A) is too high yield may be deteriorated, or the decrease in transparency, it can also be brought into intimate contact with the scratch resistance, and the substrate is insufficient.

The concentration (C _B ) of the metal oxide fine particles (B) or surface-treated metal oxide fine particles (B) used in accordance with the need of the hard coat film forming coating liquid is 18% by weight or less as a solid content, preferably Preferably, it is in the range of 0.05 to 18% by weight, more preferably 0.1 to 12% by weight.

When the concentration (C _B ) is in the above range, a hard coat film portion substrate excellent in anti-blocking properties and scratch resistance can be obtained.

In addition, when the metal oxide fine particles (B) are used, the total concentration with the metal oxide particles (A) is used so that the solid content is in the range of 0.075 to 48% by weight.

The concentration (C _M ) of the matrix forming component in the coating liquid for forming a hard coat film is in the range of 0.1 to 59.7% by weight, preferably 1 to 54% by weight, as a solid content. If the concentration (C _M ) of the matrix forming component is too low, the haze of the obtained hard coat film may deteriorate or the transparency may decrease, and the scratch resistance and adhesion to the substrate may be insufficient. Even if the concentration C _M ) of the matrix forming component is too high, it may vary depending on the thickness, but the anti-blocking property may be insufficient, and the curling inhibiting effect may be insufficient.

Polymerization initiator

In the present invention, a photopolymerization initiator may be used as needed.

Known polymerization initiators may be used without particular limitation, and examples include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)2, 4,4- Trimethylpentylphosphine oxide, 2-hydroxy-methyl-2-methyl-phenyl-propane-1-ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclo Hexyl-phenyl-ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-monopropan-1-one, and the like.

In addition, the concentration (C _CL ) of the cluster forming agent is in the range of 0.0005 to 6% by weight, preferably 0.001 to 3% by weight as a solid content. When the concentration (C _CL ) of the cluster forming agent is less than 0.0005% by weight as a solid content, it varies depending on the thickness, but the anti-blocking property may be insufficient. Even if the concentration of the cluster forming agent (C _CL ) exceeds 6% by weight as a solid content, the haze of the obtained hard coat film may be deteriorated or the transparency may be lowered, and also scratch resistance and adhesion to the substrate may be insufficient.

Ratio _{(C CL) / (C A} ) of the solid content of _(A C) as a solid content as the concentration (C _CL) and the metal oxide fine particles (A) of said cluster agent is 0.0005 to 1, preferably 0.0001 to 0.5 Is the range of.

If the concentration ratio (C _CL )/(C _A ) fails to form a cluster, it may vary depending on the film thickness, but the anti-blocking property may be insufficient. Even if the concentration ratio (C _CL )/(C _A ) is large, the haze of the obtained hard coat film may deteriorate or the transparency may decrease, and there may be cases where the scratch resistance and adhesion to the substrate are insufficient.

The average particle diameter (D _CLP ) of the clusters (CL _P ) in the coating solution for forming a hard coat film is in the range of 50 to 2,000 nm, preferably 50 to 1500 nm. If the average particle diameter (D _CLP ) of the clusters CL _{P in the} coating liquid for forming a hard coat film is too small, it may vary depending on the thickness, but the anti-blocking property may be insufficient. Even if the average particle diameter (D _CLP ) of the clusters (CL _P ) in the coating liquid for forming the hard coat film is too large, the haze of the obtained hard coat film may deteriorate or the transparency may decrease, and the scratch resistance and adhesion to the substrate may be insufficient. have.

In the present invention, the average particle diameter (D _CLP ) of the cluster (CL _P ) of the coating solution for forming a hard coat film can be measured using ZetaSizer Nano ZS manufactured by Spactless Co., Ltd. in the prepared coating solution.

In addition, it is impossible to form predetermined irregularities with ordinary monodisperse particles. The cluster of the present invention is a kind of agglomerated particles, and in the case of irregular and unspecified aggregated particles, the hard coat property is not exhibited.

A hard coat film can be formed by applying such a coating liquid to the above-described substrate by a known method such as a dipping method, a spray method, a spinner method, and a roll coating method, and curing by dry heat treatment or ultraviolet irradiation.

The present invention will be described in more detail by the following examples, but the present invention is not limited by these examples.

(Example 1)

Preparation of metal oxide fine particles (A-1) dispersion

To 1000 g of silica organosol (manufactured by Nikki Shokubai Chemical Co., Ltd.: Cataloid SI-30; average particle diameter 12 nm, SiO ₂ concentration 40.5% by weight, dispersion medium: water, particle refractive index 1.46), 6000 g of ion-exchanged water was added, and then 800 g of a cation exchange resin (manufactured by Mitsubishi Chemical Co., Ltd.: SK-1BH) was added, and the mixture was stirred for 1 hour, followed by dealkalization treatment.

Subsequently, after separating the cation exchange resin, 400 g of an anion exchange resin (manufactured by Mitsubishi Chemical Co., Ltd.: SANUPC) was added, followed by stirring for 1 hour to perform deanionic treatment. Then, 400 g of a cation exchange resin (manufactured by Mitsubishi Chemical Co., Ltd.: SK-1BH) was added again, followed by stirring for 1 hour to deal with alkalizing treatment to prepare a silica particle (A) dispersion having a SiO ₂ concentration of 5% by weight.

This dispersion was solvent-substituted with methanol using an ultrafiltration membrane to obtain a methanol dispersion having a solid content concentration of 40% by weight.

Then, 5.84 g of γ-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd.: KBM-503, SiO ₂ component 81.2% by weight) was mixed with 100 g of the methanol dispersion, and 4.2 g of ultrapure water was added thereto. The mixture was stirred at °C for 6 hours to obtain a surface-treated silica fine particle dispersion having a solid content of 40.5% by weight.

Thereafter, the solvent is substituted with methyl isobutyl ketone (MIBK) in a rotary evaporator to obtain a surface-treated silica fine particle MIBK dispersion having a solid content of 40.5% by weight.

Then, to 100 g of surface-treated silica fine particles MIBK dispersion having a solid content of 40.5% by weight, 1.61 g of an acrylic-silicone surfactant (manufactured by Kusumoto Chemical Co., Ltd.: Days Faron LHP-810, 10% by weight of solid content) was added to 50 The mixture was stirred at °C for 20 hours to prepare a dispersion of fine metal oxide particles (A-1) made of silica having a solid content of 40.0% by weight.

Hard coat film Preparation of forming coating liquid (1)

Urethane acrylate oligomer resin (manufactured by Shinnakamura Chemical Co., Ltd.: NK oligo UA-33H average molecular weight with 56.81 g of a dispersion of metal oxide particles (A-1) composed of silica having a solid content of 40.0% by weight and an acrylate resin having 9 functional groups. =4,000) 13.58g and dimethylloyl-tricyclodecanediacrylate (manufactured by Gongyoung Chemical Co., Ltd.; Light acrylate DCP-A) 1.51g and photopolymerization initiator (manufactured by Chiba Japan Co., Ltd.: Iruga Cure 184) 0.91 g of PGME and 16.86 g of PGME and 9.43 g of acetone were sufficiently mixed to prepare a coating solution (1) for forming a hard coat film having a solid content of 37.74% by weight.

In the coating liquid (1) for forming a hard coat film, the average particle diameter of the clusters (CL _P ) was measured, and the results are shown in the table.

Hard coat shogunate Preparation of base (1)

Coating liquid (1) for forming a hard coat film was applied to a PET film (manufactured by Toyo Co., Ltd.: Cosmoshine A4300, thickness: 188㎛) by a bar coater method (# 8), dried at 80℃ for 120 minutes, and then 300mJ/ It was cured by irradiating with ultraviolet rays of cm ² to form a hard coat film portion substrate (1). The average thickness of the hard coat film was 4 µm. In addition, the height of the protrusion (H 凸) was 27 nm.

The total light transmittance, haze, curling property, anti-blocking property, adhesion, pencil hardness, and scratch resistance of the hard coat film portion substrate (1) were measured by the following methods, and the results are shown in the table. The total light transmittance and haze were measured with a haze meter (NDH-5000 manufactured by Nippon Electric Co., Ltd.). In addition, the total light transmittance of the uncoated PET film was 92.0% and the haze was 0.9%.

Curling evaluation

After applying the hard coat film forming coating solution (1) to the 14cm × 25cm × 40㎛ (thick) TAC film substrate so that a 7㎛-thick hard coat film can be formed and allowed to stand for 20 hours, the film is 10cm × 10cm Cut to size, the film was placed on a flat plate with the coated surface facing down, and the height of the floating substrate was measured at the apex slab by curling (curving), and the evaluation was performed according to the following criteria.

(Evaluation standard)

Less than 10mm: ◎

Less than 10-20mm: ○

Less than 20-30mm: △

30mm or more: ×

Anti - Blocking

A part of the hard coat film part (1) is cut into two, and another hard coat film part (substrate + hard coat film) is stacked on one hard coat film part base material (substrate + hard coat film), and a load of 10 kg per 1 cm ² is applied. After loading the weight so as to stand for 24 hours, the degree of difficulty of peeling was evaluated based on the following criteria.

Very easy to peel: ◎

Peeling can be easily done: ○

Peeling is slightly difficult: △

Unable or difficult to peel: ×

Pencil hardness measurement

It measured with a pencil hardness tester according to JIS-K-5600.

Scratch resistance Measure

Using #0000 steel wool, it was slid 10 times with a load of 1 kg/cm ² , and the surface of the film was visually observed, and evaluated according to the following criteria.

Evaluation standard :

Surface damage is not recognized: ◎

Damage to the surface is evaluated slightly: ○

Many damage to the surface is recognized: △

The surface is entirely cut: ×

Adhesion

The surface of the transparent film substrate (1) is damaged by 11 parallel damages with a knife at intervals of 1 mm horizontally and vertically, making 100 damaged trees, attaching cellophane tape to them, and then peeling off the cellophane tape. The number of was classified into the following 4 steps to evaluate the adhesion. Table 1 shows the results.

Evaluation standard :

100 trees remaining: ◎

90-99 remaining trees: ○

85-89 remaining trees: △

84 or less remaining trees: ×

(Example 2)

Preparation of metal oxide fine particles (A-2) dispersion

In Example 1, a dispersion of metal oxide particles (A-2) made of silica having a solid content concentration of 40.0% by weight was prepared in the same manner as 0.54 g of surfactant was added.

Hard coat film Preparation of forming coating liquid (2)

In Example 1, a coating solution (2) for forming a hard coat film having a solid content of 37.74% by weight was prepared in the same manner except that metal oxide particles (A-2) made of silica having a solid content of 40.0% by weight were used. The average particle diameter of the cluster (CL _P ) with respect to the coating liquid for hard coat film formation (2) was measured, and the result is shown in the table.

Hard coat shogunate Preparation of base (2)

In the same manner as in Example 1, except that the coating liquid for hard coat film formation (2) was used, the hard coat film portion substrate (2) was formed. The average thickness of the hard coat film was 4 µm. In addition, the height of the protrusion (H 凸) was 23 nm. The total light transmittance, haze, curling property, anti-blocking property, adhesion, pencil hardness, and scratch resistance were measured for the obtained hard coat film part substrate (2), and the results are shown in the table.

(Example 3)

Preparation of metal oxide fine particles (A-3) dispersion

In Example 1, a dispersion of metal oxide fine particles (A-3) made of silica having a solid content of 40.0% by weight was prepared in the same manner except that 8.94g of a surfactant was added.

Hard coat film Preparation of forming coating liquid (3)

In Example 1, a coating solution (3) for forming a hard coat film having a solid content of 37.74% by weight was prepared in the same manner except that metal oxide fine particles (A-3) made of silica having a solid content of 40.0% by weight were used. The average particle diameter of clusters (CL _P ) was measured for the coating liquid for hard coat film formation (3), and the results are shown in the table.

Hard coat shogunate Preparation of base (3)

In the same manner as in Example 1 except that the coating liquid for hard coat film formation (3) was used, the hard coat film portion base material (3) was formed. The average thickness of the hard coat film was 4 µm. In addition, the height of the protrusion (H 凸) was 100 nm. The total light transmittance, haze, curling property, anti-blocking property, adhesion, pencil hardness, and scratch resistance of the obtained base material 3 with a hard coat film were measured, and the results are shown in the table.

(Example 4)

Preparation of metal oxide fine particles (A-4) dispersion

To 1000 g of silica dispersion (manufactured by Nikki Shokubai Chemical Co., Ltd.; SI-550; average particle diameter 5 nm, SiO ₂ concentration 40.5 wt%) was added 6000 g of ion-exchanged water, followed by a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: SK- 1BH) 800g was added, and the mixture was stirred for 1 hour to be deallocated.

Subsequently, after separation with a cation exchange resin, 400 g of an anion exchange resin (manufactured by Mitsubishi Chemical Co., Ltd.: SANUPC) was added and stirred for 1 hour to deanionic treatment. Then, 400 g of a cation exchange resin (manufactured by Mitsubishi Chemical Co., Ltd.: SK-1BH) was added again, followed by stirring for 1 hour to deal with alkalizing treatment to prepare a silica particle (A) dispersion having a SiO ₂ concentration of 5% by weight.

This dispersion was solvent-substituted with methanol using an ultrafiltration membrane to obtain a methanol dispersion having a solid content concentration of 40% by weight. Then, 5.84 g of γ-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd.: KBM-503, SiO ₂ component 81.2% by weight) was mixed with 100 g of the methanol dispersion, and then 4.2 g of ultrapure water was added thereto. The mixture was stirred at °C for 6 hours to obtain a surface-treated silica fine particle dispersion having a solid content of 40.5% by weight.

Then, the solvent was replaced with methyl isobutyl ketone (MIBK) in a rotary evaporator to obtain a surface-treated silica fine particle MIBK dispersion having a solid content of 40.5% by weight. In Example 1, a dispersion of metal oxide fine particles (A-4) made of silica having a solid content concentration of 40.0% by weight was prepared in the same manner except that 100 g of the silica MIBK dispersion was used.

Hard coat film Preparation of forming coating liquid (4)

In Example 1, a coating solution (4) for forming a hard coat film having a solid content of 37.74% by weight was prepared in the same manner except that metal oxide particles (A-4) made of silica having a solid content of 40.0% by weight were used. The average particle diameter of clusters (CL _P ) was measured for the coating liquid for hard coat film formation (4), and the results are shown in the table.

Hard coat shogunate Preparation of base (4)

A hard coat film part substrate 4 was formed in the same manner as in Example 1 except that the hard coat film forming coating liquid 4 was used. The average thickness of the hard coat film was 4 µm. Further, the height of the protrusion (H 凸) was 18 nm. The total light transmittance, haze, curling property, anti-blocking property, adhesion, pencil hardness, and scratch resistance of the obtained hard coat film portion substrate 4 were measured, and the results are shown in the table.

(Example 5)

Preparation of metal oxide fine particles (A-5) dispersion

To 1000 g of silica dispersion (manufactured by Nikki Shokubai Chemical Co., Ltd.; SI-80P; average particle diameter 80 nm, SiO ₂ concentration 40.5 wt%) was added 6000 g of ion-exchanged water, followed by a cation exchange resin (manufactured by Mitsubishi Chemical Co., Ltd.: SK- 1BH) 800g was added, and the mixture was stirred for 1 hour to be deallocated.

Subsequently, after separation with a cation exchange resin, 400 g of an anion exchange resin (manufactured by Mitsubishi Chemical Co., Ltd.: SANUPC) was added and stirred for 1 hour to deanionic treatment. Then, 400 g of a cation exchange resin (manufactured by Mitsubishi Chemical Co., Ltd.: SK-1BH) was added again, followed by stirring for 1 hour to deal with alkalizing treatment to prepare a silica particle (A) dispersion having a SiO ₂ concentration of 5% by weight.

This dispersion was solvent-substituted with methanol using an ultrafiltration membrane to obtain a methanol dispersion having a solid content concentration of 40% by weight. 5.84 g of γ-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd.: KBM-503, SiO ₂ component 81.2% by weight) was mixed with 100 g of methanol dispersion, and 4.2 g of ultrapure water was added thereto at 50°C. The mixture was stirred for 6 hours to obtain a surface-treated silica fine particle dispersion having a solid content of 40.5% by weight.

Thereafter, the solvent is substituted with methyl isobutyl ketone (MIBK) in a rotary evaporator to obtain a surface-treated silica fine particle MIBK dispersion having a solid content of 40.5% by weight. In the same manner as in Example 1 except that 100 g of the silica MIBK dispersion was used, a dispersion of metal oxide fine particles (A-5) made of silica having a solid content of 40.0% by weight was prepared.

Hard coat film Preparation of forming coating liquid (5)

In Example 1, a coating solution (5) for forming a hard coat film having a solid content of 37.74% by weight was prepared in the same manner except that the metal oxide particles (A-5) made of silica having a solid content of 40.0% by weight were used. In the coating liquid for hard coat film formation (5), the average particle diameter of the clusters (CL _P ) was measured, and the results are shown in the table.

Hard coat shogunate Preparation of base (5)

In Example 1, except for using the coating liquid for hard coat film formation (5), a hard coat film portion substrate (5) was formed in the same manner. The average thickness of the hard coat film was 4 µm. Further, the height of the protrusion (H 凸) was 80 nm. The total light transmittance, haze, curling property, anti-blocking property, adhesion, pencil hardness, and scratch resistance of the obtained hard coat film portion substrate (5) were measured, and the results are shown in the table.

(Example 6)

Preparation of metal oxide fine particles (A-6) dispersion

In Example 1, except for adding 1.61 g of a silicone surfactant (manufactured by Kusumoto Chemical Co., Ltd.: Days Faron LS-260, solid content concentration 20%) as a cluster forming agent in Example 1, it was made of silica having a solid content concentration of 40.0% by weight. A dispersion of metal oxide fine particles (A-6) was prepared.

Hard coat film Preparation of forming coating liquid (6)

In Example 1, a coating solution (6) for forming a hard coat film having a solid content of 37.74% by weight was prepared in the same manner except that metal oxide particles (A-6) made of silica having a solid content of 40.0% by weight were used. In the coating liquid for hard coat film formation (6), the average particle diameter of the clusters (CL _P ) was measured, and the results are shown in the table.

Hard coat shogunate Preparation of base (6)

In Example 1, except for using the coating liquid for hard coat film formation (6), a hard coat film portion substrate (6) was formed in the same manner. The average thickness of the hard coat film was 4 µm. In addition, the height of the protrusion (H凸) was 50 nm. The total light transmittance, haze, curling property, anti-blocking property, adhesion, pencil hardness, and scratch resistance of the obtained hard coat film portion substrate 6 were measured, and the results are shown in the table.

(Example 7)

Hard coat film Preparation of forming coating liquid (7)

In Example 1, a urethane acrylate oligomer resin having 8 functional groups instead of an acrylate resin (urethane acrylate oligomer resin) having 9 functional groups (manufactured by Shinnakamura Chemical Co., Ltd.: NK oligo UA-8LR, average molecular weight = 3,000) Except for using 19.41 g and adding 11.04 g of PGME, a coating solution (7) for forming a hard coat film having a solid content concentration of 37.74% by weight was prepared. In the coating liquid for hard coat film formation (7), the average particle diameter of the clusters (CL _P ) was measured, and the results are shown in the table.

Hard coat film Preparation of attachment base (7)

In the same manner as in Example 1, except that the coating liquid for hard coat film formation (7) was used, the hard coat film portion substrate (7) was formed. The average thickness of the hard coat film was 4 µm. Further, the height of the protrusion (H凸) was 30 nm. The total light transmittance, haze, curling property, anti-blocking property, adhesion, pencil hardness, and scratch resistance of the obtained hard coat film portion substrate 7 were measured, and the results are shown in the table.

(Example 8)

Preparation of metal oxide fine particles (B-1) dispersion

Anionic surfactant in methanol dispersion of silica sol (manufactured by Nikki Shokubai Chemical Co., Ltd.: ELCOM V-8901, average particle diameter 120 nm, SiO ₂ concentration 20.5 wt%) (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.: FlySafe A212E) 2.05g was mixed and stirred for 20 hours to prepare a surfactant-treated metal oxide fine particle (B-1) methanol dispersion made of silica having a solid content concentration of 22.10% by weight.

Hard coat film Preparation of forming coating liquid (8)

A dispersion of 56.85 g of metal oxide fine particles (A-1) composed of silica having a solid content concentration of 40.0% by weight prepared in the same manner as in Example 1 and a surfactant-treated metal oxide fine particles (B-1) composed of silica having a solid content concentration of 22.10% by weight (B-1) Urethane acrylate oligomer resin (manufactured by Shin-Nakamura Chemical Co., Ltd.: NK oligo UA-33H, average molecular weight = 4,000) 13.58 g and dimethylloyl-tricyclodecanediacrylic with 3.42 g of a methanol dispersion and an acrylate resin with 9 functional groups 1.51 g of late (manufactured by Gongyeongsa Chemical Co., Ltd.; Light acrylate DCP-A) and 0.91 g of a photopolymerization initiator (manufactured by Chiba Japan Co., Ltd.: Irugakyua 184), PGME 14.30g, and 9.43g of acetone were sufficiently mixed and solid content A coating solution (8) for forming a hard coat film having a concentration of 37.74% by weight was prepared. In the coating liquid for hard coat film formation (8), the average particle diameter of the clusters (CL _P ) was measured, and the results are shown in the table.

Hard coat shogunate Preparation of base (8)

In Example 1, except for using the coating liquid for hard coat film formation (8), a hard coat film portion base material (8) was formed in the same manner. The average thickness of the hard coat film was 4 µm. In addition, the height of the protrusion (H 凸) was 53 nm. The total light transmittance, haze, curling property, anti-blocking property, adhesion, pencil hardness, and scratch resistance of the obtained hard coat film portion substrate (8) were measured, and the results are shown in the table.

(Example 9)

Preparation of metal oxide fine particles (A-9) dispersion

In a solution in which 25 g of caustic potassium (manufactured by Asahi Glass Co., Ltd.: 85% purity) was dissolved in 800 g of pure water, 50 g of antimony trioxide (manufactured by Japan Concentrate Co., Ltd.; PATOX-K, purity 98.5%) was suspended. This suspension was heated to 95° C., and then an aqueous solution obtained by diluting 15 g of hydrogen peroxide (manufactured by Limsoon Pharmaceutical Co., Ltd.: 35% by weight of special grade) in 50 g of pure water was added for 9 hours to dissolve antimony trioxide and then aged for 11 hours. Subsequently, after cooling, 800 g of the obtained solution was taken, diluted with 4800 g of pure water, and deionized by treatment with a cation exchange resin (manufactured by Mitsubishi Chemical Co., Ltd.: pk-216) until the pH reached 3.5. The solution obtained by the deionization treatment was aged for 10 hours at a temperature of 70° C. and then concentrated with an ultrafiltration membrane to prepare a dispersion of inorganic oxide-based conductive particles (1) composed of antimony pentoxide having a solid content of 14%. The pH of the dispersion of the inorganic oxide-based conductive particles (1) was 4.0. The average particle diameter of the inorganic oxide-based conductive particles 1 was 20 nm.

Then, by adjusting 100 g of the dispersion of inorganic oxide-based conductive particles (1) to 25°C, 2.5 g of tetraethoxysilane (manufactured by Tama Chemical Co., Ltd.: regular acid ethyl, SiO ₂ component 28.8% by weight) was added in 3 minutes. Stirring was performed for 30 minutes. Then, 100 g of ethanol was added over 1 minute, heated at 50° C. for 30 minutes, and heated for 3 hours. At this time, the solid content concentration was 7% by weight.

Subsequently, a dispersion of inorganic oxide-based conductive particles (1), which was surface-treated with an organosilicon compound having a solid content concentration of 30% by weight, was prepared by substituting ethanol for water and ethanol as dispersion media in an ultrafiltration membrane.

Next, 5.84 g of γ-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd.: KBM-503, SiO ₂ component 81.2% by weight) was mixed with 100 g of the ethanol dispersion, and then 4.2 g of ultrapure water was added. The mixture was stirred at 50° C. for 6 hours to obtain a surface-treated silica fine particle dispersion having a solid content of 40.5% by weight.

Thereafter, the solvent was substituted with methyl isobutyl ketone (MIBK) in a rotary evaporator to obtain a surface-treated silica fine particle MIBK dispersion having a solid content of 40.5% by weight. In Example 1, a dispersion of surface-treated inorganic oxide-based conductive particles (A-9) having a solid content concentration of 40.0% by weight was prepared in the same manner, except that 100 g of the surface-treated inorganic oxide-based conductive particle MIBK dispersion was used.

Hard coat film Preparation of forming coating liquid (9)

In Example 1, except for using the surface-treated inorganic oxide conductive particles (A-9) having a solid content concentration of 40.0% by weight, a coating solution (9) for forming a hard coat film having a solid content concentration of 37.74% by weight was prepared in the same manner. I did. In the coating liquid for hard coat film formation (9), the average particle diameter of the clusters (CL _P ) was measured, and the results are shown in the table.

Hard coat shogunate Preparation of base (9)

In Example 1, a hard coat film portion substrate 9 was formed in the same manner, except that the hard coat film forming coating liquid 9 was used. The average thickness of the hard coat film was 4 µm. In addition, the height of the protrusion (H 凸) was 25 nm. The total light transmittance, haze, curling property, anti-blocking property, adhesion, pencil hardness, and scratch resistance of the obtained hard coat film portion substrate 9 were measured, and the results are shown in the table.

(Example 10)

Hard coat film Preparation of forming coating liquid (10)

Urethane acrylate oligomer resin (manufactured by Shinnakamura Chemical Co., Ltd.) with 47.49 g of a dispersion of metal oxide particles (A-1) consisting of silica with a solid content of 40.0% by weight and 9 functional groups. NK oligo UA-33H, average Molecular weight = 4,000) 16.98 g and dimethylloyl-tricyclodecane diacrylate (manufactured by Gongyeongsa Chemical Co., Ltd.; light acrylate DCP-A) 1.89g and a photopolymerization initiator (manufactured by Chiba Japan Co., Ltd.: Irugakyua 184) ) 1.89g, PGME 22.18g, and acetone 9.43g were sufficiently mixed to prepare a coating solution (1) for forming a hard coat film having a solid content concentration of 37.74% by weight. In the coating liquid for hard coat film formation (10), the average particle diameter of the clusters (CL _P ) was measured, and the results are shown in the table.

Hard coat shogunate Preparation of base (10)

In Example 1, a hard coat film portion substrate 10 was formed in the same manner except that the hard coat film forming coating liquid 10 was used. The average thickness of the hard coat film was 4 µm. In addition, the height of the protrusion (H 凸) was 20 nm. The total light transmittance, haze, curling property, anti-blocking property, adhesion, pencil hardness, and scratch resistance of the obtained hard coat film portion substrate 10 were measured, and the results are shown in the table.

(Example 11)

Hard coat film Preparation of forming coating liquid (11)

A urethane acrylate oligomer resin (manufactured by Shinnakamura Chemical Co., Ltd.) with 61.46 g of a dispersion of metal oxide particles (A-1) composed of silica with a solid content of 40.0% by weight and 9 functional groups. Molecular weight = 4,000) 11.89 g and dimethylloyl-tricyclodecane diacrylate (manufactured by Gongyeongsa Chemical Co., Ltd.; 1.32g of light acrylate DCP-A) and photopolymerization initiator (manufactured by Chiba Japan Co., Ltd.: Irugakyua 184) ) 0.79g, PGME 14.20g, and acetone 9.43g were sufficiently mixed to prepare a coating solution (11) for forming a hard coat film having a solid content concentration of 37.74% by weight. In the coating liquid for hard coat film formation (11), the average particle diameter of the clusters (CL _P ) was measured, and the results are shown in the table.

Hard coat shogunate Preparation of base material (11)

A hard coat film portion substrate 11 was formed in the same manner as in Example 1 except that the coating liquid 11 for hard coat film formation was used. The average thickness of the hard coat film was 4 µm. Further, the height of the protrusion (H 凸) was 80 nm. The total light transmittance, haze, curling property, anti-blocking property, adhesion, pencil hardness, and scratch resistance of the obtained hard coat film portion substrate 11 were measured, and the results are shown in the table.

(Comparative Example 1)

Metal oxide fine particles ( RA -1) Preparation of dispersion

A dispersion of metal oxide fine particles (RA-1) made of silica having a solid content of 40.0% by weight was prepared in the same manner as in Example 1 except that an acrylic-silicone-based surfactant was not used as the cluster forming agent.

Hard coat film Forming coating liquid ( R1 ) Of

In Example 1, a coating solution for forming a hard coat film (R1) having a solid content of 37.74% by weight was prepared in the same manner as in Example 1 except that the dispersion of metal oxide fine particles (RA-1) made of silica having a solid content of 40.0% by weight was used. In the coating liquid for hard coat film formation (R1), the average particle diameter of the clusters (CL _P ) was measured, and the results are shown in the table.

Hard coat shogunate Materials ( R1 ) Of

In Example 1, except that the coating liquid for hard coat film formation (R1) was used, a hard coat film portion base material (R1) was formed in the same manner. The average thickness of the hard coat film was 4 µm. In addition, the height of the protrusion (H 凸) was 10 nm. The total light transmittance, haze, curling property, anti-blocking property, adhesion, pencil hardness, and scratch resistance of the obtained hard coat film part substrate (R1) were measured, and the results are shown in the table.

(Comparative Example 2)

Metal oxide fine particles ( RA -2) Preparation of dispersion

In Example 1, 100.0 g of an acrylic-silicone-based surfactant (manufactured by Kusumoto Chemical Co., Ltd.: Days Faron LHP-810, solid content 10% by weight) was added and stirred at 50° C. for 20 hours to 40.0 weight of solid content A dispersion of metal oxide fine particles (RA-2) consisting of% silica was prepared.

Hard coat film Forming coating liquid ( R2 ) Of

A coating solution (R2) for forming a hard coat film having a solid content of 37.74% by weight was prepared in the same manner as in Example 1 except that the dispersion of metal oxide fine particles (RA-2) made of silica having a solid content of 40.0% by weight was used. In the coating liquid for hard coat film formation (R2), the average particle diameter of the clusters (CL _P ) was measured, and the results are shown in the table.

Hard coat shogunate Materials ( R2 ) Of

A hard coat film part base material (R2) was formed in the same manner as in Example 1 except that the hard coat film forming coating liquid (R2) was used. The average thickness of the hard coat film was 4 µm. In addition, the height of the protrusion (H 凸) was 1000 nm. The total light transmittance, haze, curling property, anti-blocking property, adhesion, pencil hardness, and scratch resistance were measured for the obtained hard coat film part substrate (R2), and the results are shown in the table.

(Comparative Example 3)

Hard coat film Forming coating liquid ( R3 ) Of

Urethane acrylate oligomer resin with 0.47 g of a dispersion of metal oxide particles (A-1) consisting of silica with a solid content of 40.0% by weight and an acrylate resin with 9 functional groups (manufactured by Shinnakamura Chemical Co., Ltd.: NK oligo UA-33H average molecular weight =4,000) 33.80g and dimethylloyl-tricyclodecanediacrylate (manufactured by Gongyeongsa Chemical Co., Ltd.; light acrylate DCP-A) 3.76g and photopolymerization initiator (manufactured by Chiba Japan Co., Ltd.: Irugakyua 184) 2.25g, PGME50.28g, and 9.43g of acetone were sufficiently mixed to prepare a coating solution (R3) for forming a hard coat film having a solid content of 37.74% by weight. The average particle diameter of clusters (CL _P ) was measured for the coating liquid for hard coat film formation (R3), and the results are shown in the table.

Hard coat shogunate Materials ( R3 ) Of

A hard coat film portion base material (R3) was formed in the same manner as in Example 1 except that the hard coat film forming coating liquid (R3) was used. The average thickness of the hard coat film was 4 µm. In addition, the height of the protrusion (H 凸) was 12 nm. The total light transmittance, haze, curling property, anti-blocking property, adhesion, pencil hardness, and abrasion resistance of the obtained hard coat film portion substrate (R3) were measured, and the results are shown in the table.

(Comparative Example 4)

Hard coat film Forming coating liquid ( R4 ) Of

Urethane acrylate oligomer resin (manufactured by Shinnakamura Chemical Co., Ltd.) with 80.11 g of a dispersion of metal oxide particles (A-1) consisting of silica with a solid content of 40.0% by weight and 9 functional groups. =4,000) 15.09g and dimethylloyl-tricyclodecane diacrylate (manufactured by Gongyeongsa Chemical Co., Ltd.; 0.57g of light acrylate DCP-A) and photopolymerization initiator (manufactured by Chiba Japan Co., Ltd.: Irugakyua 184) 0.34g, PGME3.56g, and 9.43g of acetone were sufficiently mixed to prepare a coating solution (R4) for forming a hard coat film having a solid content of 37.74% by weight. The average particle diameter of clusters (CL _P ) was measured for the coating liquid for hard coat film formation (R4), and the results are shown in the table.

Hard coat film Attachment base ( R4 ) Of

A hard coat film part base material (R4) was formed in the same manner as in Example 1 except that the hard coat film forming coating liquid (R4) was used. The average thickness of the hard coat film was 4 µm. In addition, the height of the protrusion (H 凸) was 900 nm. The total light transmittance, haze, curling property, anti-blocking property, adhesion, pencil hardness, and scratch resistance were measured for the obtained hard coat film part substrate (R4), and the results are shown in the table.

Claims (17)

Consisting of a substrate and a hard coat film formed on the substrate,
The hard coat film is made of a cluster (CL) of metal oxide fine particles (A), a matrix component, and a cluster forming agent,
The average particle diameter (D _A ) of the metal oxide fine particles ( _A ) is 5 to 200 nm,
The cluster forming agent is at least one surfactant selected from a silicone-based surfactant, an acrylic silicone-based surfactant, an acrylic surfactant, a phosphate ester-based surfactant, or a polyoxyethylenealkylamine ether-based surfactant,
The cluster (CL) forms a protrusion having a height of 15 to 200 nm on the surface of the hard coat film,
In the hard coat film portion substrate, characterized in that the average particle diameter of the cluster is 50 to 2,000 nm,
In addition to the metal oxide fine particles (A), the hard coat film portion substrate, characterized in that it further comprises metal oxide fine particles (B) having an average particle diameter in the range of 5 to 300 nm treated with a surfactant.
delete The method according to claim 1, wherein the content (W _A ) of the metal oxide fine particles (A) in the hard coat film is in the range of 0.5 to 70% by weight as a solid content, and the content (W _M ) of the matrix component is 20 to 99 as a solid content. It is in the range of weight %, and the content of the cluster forming agent (W _CL ) is in the range of 0.01 to 10% by weight as a solid content.
The method of claim 1, wherein the metal oxide fine particles (A) are silica, alumina, zirconia, titanium oxide, antimony pentoxide, boria, antimony-doped tin oxide, indoping tin oxide, tin-doped indium oxide, or a composite oxide thereof or a mixture thereof. Hard coat film substrate, characterized in that selected from.
delete delete delete ◈ Claim 8 was abandoned upon payment of the set registration fee. The hard coat layer substrate according to claim 1, wherein the average thickness of the hard coat layer is in the range of 0.5 to 20 μm.
◈ Claim 9 was abandoned upon payment of the set registration fee. The hard coat layer substrate according to claim 1, wherein the difference in refractive index between the refractive index of the substrate and the refractive index of the hard coat layer is 0.3 or less.
Including metal oxide fine particles (A) having an average particle diameter of 5 to 200 nm, a matrix forming component, a cluster forming agent and a dispersion medium,
The concentration (C _A ) of the metal oxide fine particles (A) is in the range of 0.025 to 48% by weight as a solid content, and the concentration (C _M ) of the matrix forming component is in the range of 1 to 59.7% by weight as a solid content, The concentration (C _CL ) is in the range of 0.0005 to 6% by weight as a solid content,
The total solid content concentration is in the range of 1 to 60% by weight,
The cluster forming agent is at least one surfactant selected from a silicone-based surfactant, an acrylic silicone-based surfactant, an acrylic surfactant, a phosphate ester-based surfactant, or a polyoxyethylenealkylamine ether-based surfactant,
Metal oxide fine particles (A) form a cluster,
In the coating liquid for forming a hard coat film, characterized in that the average particle diameter of the cluster is 50 to 2,000 nm,
In addition to the metal oxide fine particles (A), the coating liquid for forming a hard coat film further comprises metal oxide fine particles (B) having an average particle diameter in the range of 5 to 300 nm treated with a surfactant.
delete delete delete The method of claim 10, wherein the ratio (C _CL )/(C _A ) between the concentration of the cluster forming agent (C _CL ) and the concentration (C _A ) of the metal oxide fine particles ( _A ) is in the range of 0.0005 to 1. Coating liquid for forming a hard coat film.
delete The hard coat film part base material according to claim 1, wherein the matrix component comprises a urethane acrylate resin.
The coating liquid for forming a hard coat film according to claim 10, wherein the matrix component has a urethane group and a (meth)acryloyl group.