TWI599484B - Substrate with hard coating film and coating solution for forming hard coating film - Google Patents

Description

Substrate with hard coating film and coating liquid for forming a hard coating film

The base material with a hard coating film and the coating liquid for forming a hard coating film which are excellent in the anti-adhesive property (the hard coating film does not adhere to each other) and have a curl suppressing effect.

In order to improve the scratch resistance of the surface of a substrate such as a glass, a plastic sheet, a plastic lens, a resin film, a front panel of a display device, etc., it is known to form a hard coating film on the surface of the substrate, and an organic resin can be formed on the surface of glass, plastic, or the like. A film or an inorganic film is used as such a hard coating film. Further, by blending inorganic particles such as resin particles or cerium oxide in the organic resin film or the inorganic film, the scratch resistance can be further improved. Such a resin substrate with a hard coating film is also used for attaching a front panel of a display device or the like.

However, in the conventional substrate having a hard coating film, when the hard coating film substrate is rolled up during the production, or when the hard coating film substrate is laminated after the production, the hard coating film substrates are adhered to each other, and after the processing, There is a problem that it becomes difficult to peel off during use, and the appearance of the film is poor.

In order to improve the anti-sticking property, it can be exemplified on the surface of the coating film. Set the bump.

In order to provide the anti-glare property of the hard coating film, the embossing is proposed in the patent document 1 (JP-A-2007-76055), the patent document 2 (JP-A-2009-169409), and the patent document 3 (JP-A-2008). In the case of the anti-glare property, there is no known knowledge of the purpose of the present invention for suppressing adhesion of a substrate having a clear coating film, and there is a case where transparency is inhibited.

In addition, Patent Document 4 (JP-A-2009-35614) discloses a curable resin composition for a hard coat layer containing reactive inorganic fine particles A and organic polyfluorinated fine particles B. In order to prevent the mirror surfaces from sticking to each other, the reactive inorganic fine particles A coated with an organic component on the surface having excellent dispersibility and adhesion to the binder component and the reactive inorganic fine particles A are contained in combination with the reactive inorganic fine particles A. By separating the organic-based organic polysiloxane fine particles B which are inclined, the organic polysulfide fine particles B are distributed on the surface of the hard coat layer by the volume exclusion effect of the reactive inorganic fine particles A, and irregularities are formed on the surface.

However, in Citation 4, the adhesion to the substrate is low, and the scratch resistance is insufficient.

The present inventors have disclosed that when a metal oxide particle having a spherical coefficient of a specific range is dispersed in a hydrophobic organic resin in a coating liquid for forming a hard coating film, the metal oxide particles are convex on the surface of the hard coating film. In the presence of the part, the adhesion is lowered to obtain the anti-adhesive property. (Patent Document 5: Japanese Laid-Open Patent Publication No. 2011-68087)

Furthermore, the inventors have revealed that by virtue of being hydrophobic The organic resin matrix component contains a metal oxide fine particle having no compatibility with the matrix component and having a refractive index adjusted, and can form a convex portion of a specific height on the surface of the hard coating film without the visibility of the particle. And improve the anti-adhesion. (Patent Document 6: JP-A-2011-136490)

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-76055

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2009-169409

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2008-163205

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2009-35614

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2011-68087

[Patent Document 6] Japanese Laid-Open Patent Publication No. 2011-136490

In Patent Documents 5 and 6, when the particles are unevenly distributed and the convex portions are formed, although the anti-adhesive property can be obtained, the metal oxide particles aggregate, and even if the surface is still agglomerated, the anti-adhesive property cannot be effectively improved. At this time, there is a case where the scratch resistance, the pencil hardness, and the like become insufficient. Further, the transparency of the hard coating film is lowered, and the haze is deteriorated.

Further, in the conventional hard coat film, there is a problem that the base material with the transparent film is curled (bent) depending on the thickness of the transparent film or the type and thickness of the base material. Moreover, in recent years, in order to improve weight reduction and transparency, it is aimed at a substrate having a small thickness.

Therefore, it is desired to have a transparent film-attached substrate which has the above-mentioned anti-adhesive property and can suppress curling and peeling even when a substrate having a small thickness is used.

In this case, it has been found that not only the use of fine particles as irregularities but also the formation of irregularities by the formation of clusters can solve the conventional problems, and it has been found that a substrate having a hard coating film having anti-stick properties and suppressing curl can be obtained. The present invention has been completed.

A substrate coated with a hard coating film according to the present invention, comprising: a substrate and a hard coating film formed on the substrate, the hard coating film comprising (i) metal oxide microparticles (A) cluster (cluster) (CL), (ii) a matrix component, and (iii) a cluster forming agent, at least a part of the cluster (CL) is present on the surface of the hard coating film to form a convex portion, and has a height of 15 to 200 nm (H convex ) the convexity of the range.

Further, the coating liquid for forming a hard coating film according to the present invention is characterized by comprising metal oxide fine particles (A), a matrix forming component, a cluster forming agent, and a dispersing medium, and the metal is used as a solid component. The concentration (C _A ) of the oxide fine particles (A) is in the range of 0.025 to 48% by weight, and the concentration (C _M ) of the matrix-forming component is in the range of 1 to 59.7% by weight, based on the solid content, as a solid component. The concentration of the cluster forming agent (C _CL ) is in the range of 0.0005 to 6% by weight, the total solid content is in the range of 1 to 60% by weight, and the metal oxide fine particles (A) form a group. Cluster (CL _P ).

The present invention can provide a substrate coated with a hard coating film excellent in adhesion to a substrate, transparency, scratch resistance, scoring strength, pencil hardness, etc., and excellent in suppression of sticking resistance and curling, and the hard coating film A coating liquid for formation.

Hereinafter, a substrate to which the hard coat film of the present invention is attached will be described first.

[Substrate with hard coating]

The substrate coated with a hard coating film of the present invention comprises a substrate and a hard coating film having irregularities on the surface formed on the substrate.

Substrate

The substrate used in the present invention may be a conventionally used glass sheet, polycarbonate, acrylic resin, PET, TAC, or the like, a plastic film, or the like, a plastic plate, etc., wherein a low refractive index and an alkali resistance are required. A triethylene sulfonated cellulose (TAC) substrate, a polyolefin resin substrate such as PET, a polyvinyl alcohol resin substrate, a polyether fluorene resin substrate, or 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, even The thin substrate still suppresses curl and exhibits anti-stick properties.

Hard coating

The hard coating film contains metal oxide fine particles (A) clusters (CL), a matrix component, and a cluster forming agent. A part of the cluster (CL) is present on the surface of the hard coating film to form a convex portion.

(i) Metal oxide microparticles (A) clusters (CL)

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

When the average particle diameter (D _A ) of the metal oxide fine particles (A) is too small as compared with the above range, fine particles may be aggregated, and the haze of the hard coating film may be deteriorated, and the transparency may be lowered.

When the average particle diameter (D _A ) of the metal oxide fine particles ( _A ) is too large, the haze of the obtained hard coating film may be deteriorated, and the transparency may be lowered, and the hard coating film may be damaged by friction or the like.

The metal oxide fine particles (A) are preferably cerium oxide, aluminum oxide, zirconium dioxide, titanium dioxide, antimony pentoxide, boron oxide, tin oxide doped with antimony, tin oxide doped with phosphorus, or doped Indium oxide of hetero-tin and fine particles of composite oxides and mixtures thereof.

The cluster (CL) of the present invention is in a coating liquid, and the metal oxide fine particles (A) are weakly aggregated clusters (CL _p ) (described later) due to the presence of the cluster forming agent, and are attached to the hard coating film. When it is formed, let it dry. Particles that are gathered together with shrinkage during hardening.

Although it is not possible to directly measure the size of the cluster (CL) in the hard coating film, it is estimated from the size of the convex portion of the uneven surface of the surface that it is a metal oxide fine particle (A) in the coating liquid for forming a hard coating film to be described later. The average particle size (D _CLP ) of the clusters (CL _P ) is about the same, or about 50 to 2,000 nm after a slight shrinkage. (Also, general particles do not form bumps in the general method.)

(ii) cluster forming agent

The cluster forming agent is preferably at least one surfactant selected from the group consisting of a polyfluorene-based surfactant, a polyacrylic acid-based surfactant, an acrylic surfactant, a phosphate-based surfactant, and a polyoxygen. Ethyl alkylamine ether surfactant is extended.

Examples of the polyoxo-based surfactants include DISPARLON LS-220, LS-240, LS-260, LS-280, LS-460, LS-480, and 1711EF manufactured by Nanben Chemical Co., Ltd.

Examples of the polyacrylic acid-based surfactants include DISPARLON LHP-810, NSH-8430HF, UVX-270, UVX-271, UVX-272, UVX-2280, UVX-2285, and the like manufactured by Nanben Chemical Co., Ltd.

Examples of the acrylic surfactant include DISPARLON UVX-3750, UVX-35, UVX-36, UVX-39, and the like manufactured by Nanben Chemical Co., Ltd.

Examples of the phosphate ester surfactant include PLYSURF A-212E, AL, and the like manufactured by Dai-ichi Kogyo Co., Ltd.

Examples of the polyoxyalkylene ether alkyl ether surfactants include Amirajin C-1802 manufactured by Dai-ichi Kogyo Co., Ltd., and the like.

By such a cluster forming agent, the metal oxide fine particles (A) are condensed into an appropriate size to form a cluster (CL). Furthermore, by using a cluster forming agent, The clusters on the surface of the transparent coating are unevenly distributed, and the desired convex portions are formed on the surface to form a transparent coating excellent in adhesion resistance.

. Metal oxide microparticles (B)

In the present invention, in addition to the metal oxide fine particles (A), the metal oxide fine particles (B) treated with the surfactant may be contained. When the hard coating film contains the metal oxide fine particles (B), a substrate coated with a hard coating film which is more excellent in anti-sticking property and scratch resistance can be obtained. Although the reason is not completely clear, it is considered that the metal oxide fine particles (B) are more likely to form fine clusters than the metal oxide fine particles (A) clusters (CL), but are present in the metal oxide fine particles (A) cluster. The clusters (CL) are buried in the cluster (CL) gap and have a function as an adhesive material.

The average particle diameter of the metal oxide fine particles (B) is in the range of 5 to 300 nm, and more preferably in the range of 5 to 150 nm.

When the average particle diameter of the metal oxide fine particles (B) is less than the above range, the surface treatment may be different depending on the surface treatment to be described later. However, when the fine particles are aggregated, the haze of the hard coating film may be deteriorated, and the transparency may be lowered.

When the average particle diameter of the metal oxide fine particles (B) is too large, the content of the metal oxide fine particles (B) varies depending on the content of the metal oxide fine particles (B), but the obtained hard coating film may have a deteriorated haze and a decrease in transparency. There is a case where the hard coating film is damaged by friction or the like.

As the metal oxide fine particles (B), the same fine particles as the metal oxide fine particles (A) described above can be used.

The metal oxide fine particles (B) are preferably surface-treated with a surfactant.

The surfactant for surface treatment of the metal oxide fine particles (B) may be at least one selected from the group consisting of a cationic surfactant, an anionic surfactant, a zwitterionic surfactant, and a nonionic surfactant. .

Specific examples of the cationic surfactant include lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, and ethyl octyl dimethyl ethyl sulfate. Ammonium, ethyl sulfate, lauryl dimethyl ethyl ammonium, ethyl sulphate, palm dimethyl dimethyl ammonium, dimercapto dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl Methylbenzyl ammonium chloride, p-toluenesulfonic acid stearyl dimethyl hydroxyethyl ammonium, stearyl dimethyl amino propyl decylamine, tributyl benzyl ammonium chloride, 1, 4 - Sodium bis(2-ethylhexyl) sulfosuccinate dioctyl sulfosuccinate or the like. Examples of the anionic surfactant include polyoxyethylene ethyl ether phosphate, polyoxyalkylene alkyl phosphate, polyoxyalkylene alkyl phenyl ether phosphate, and polyoxyethylene ethyltridecyl. Ether phosphate, polyoxyethylene ethyl ether phosphate, polyoxyethylene ethyl ether phosphate monoethanolamine salt, polyoxyethylene ethyl lauryl ether phosphate, polyoxyethylene ethyl lauryl ether phosphate Ester monoethanolamine salt, polyoxyethylene ethyl styrenated phenyl ether phosphate, sodium alkyl phosphate, alkyl phosphate monoethanolamine salt, polyoxyethylene ethyl lauryl ether acetate, lauryl sulfosuccinic acid Disodium, polyoxyethylene ethyl sulfosuccinate, lauryl disodium, polyoxyethylene ethyl sulfosuccinate disodium, polyoxystyrene phenyl ether ammonium sulfate, polyoxyalkylene alkyl sulfhydryl Sodium ether sulfate, polyoxyethylene ethyl isodecyl ether sulfate, sodium polysulfate ethyltridecyl ether sulfate, polyoxyethylene ethyl lauryl ether sulfate, polyoxyethylene ethyl lauryl ether sulfate, Polyoxyethylene ethyl ether sulfate, polyoxygen Base oil based cetyl ether ammonium sulfate, polyoxyethyl ether ethyl oleyl cetyl ether sodium sulfate, sodium alkylbenzene sulfonate, alkyl benzene sulfonic acid, sodium α-olefin sulfonate, phenol sulfonic acid , sodium dioctylsulfosuccinate, sodium lauryl sulfate, and the like.

Examples of the zwitterionic surfactant include lauryl dimethylaminoacetate betaine, decyl propyl citrate laurate, decyl propyl citrate, and lauryl dimethylamine oxide.

Examples of the nonionic surfactant include polyoxyalkylene alkyl ether, polyoxyethylene ethyltridecyl ether, polyoxyalkylene tridecyl ether, polyoxyalkylene alkyl ether, polyoxyethylene Isodecyl ether, polyoxyalkylene lauryl ether, polyoxyethylidene styrenated phenyl ether, polyoxyethylene ethyl naphthyl ether, phenoxyethanol, polyoxyethylene ethyl phenyl ether, Polyoxyethylene ethyl polyoxypropyl propylene glycol, polyoxyethylene ethyl lauryl ether, polyoxyethyl ether methyl cetyl ether, polyoxyethylene ethyl oleate, polyoxyethylene ethyl stearate Acid ester, polyoxyethylene ethyl sorbitan monococoate, polyoxyethylene ethyl sorbitan monostearate, polyoxyethylene ethyl sorbitan monooleate, isostearyl Acid polyoxyethylene ethyl glyceride, polyoxyethylene ethylamine, octyl polyglycoside, butyl polyglycoside and the like.

Among them, a cationic surfactant, an anionic surfactant, and a nonionic surfactant are preferred.

Specific examples of the cationic surfactant include octyldimethylethylammonium ethyl sulfate, lauryl dimethylethylammonium ethyl sulfate, palmitoyldimethylethylammonium ethyl sulfate, p-toluenesulfonate. Acid stearyl dimethyl hydroxyethyl ammonium and the like.

Polyanthracene Ether ether phosphate, polyoxyalkylene alkyl ether phosphate, polyoxyalkylene alkylphenyl ether phosphate, polyoxyethylidene tridecyl ether phosphate, polyoxyethylene ethyl ether phosphate Ester, polyoxyethylene ethyl ether phosphate monoethanolamine salt, polyoxyethylene ethyl lauryl ether phosphate, polyoxyethylene ethyl lauryl ether phosphate monoethanolamine salt, polyoxyethylene ethyl styrene Phenyl ether phosphate, polyoxyethylene ethyl lauryl ether acetate, polyoxyethylene ethyl sulfosuccinate disodium lauryl, polyoxyethylene ethyl sulfosuccinate disodium, polyoxystyrene Amide phenyl ether sulfate, polyoxyalkylene alkyl branched decyl ether sulfate, polyoxyethylene ethyl isodecyl ether sulfate, polyoxyethylene ethyl tridecyl ether sulfate, polyoxyethylene ethyl lauryl ether Sodium sulphate, polyoxy-extension ethyl ammonium lauryl ether sulfate, polyoxyethylene ethyl ether alkyl sulfate, polyoxy-extended ethyl oleyl cetyl ether ammonium sulfate, polyoxyethyl ether ethyl cetyl ether Sodium sulfate, etc.

Examples of the nonionic surfactant include polyoxyalkylene alkyl ether, polyoxyethylene ethyltridecyl ether, polyoxyalkylene tridecyl ether, polyoxyalkylene alkyl ether, polyoxyethylene Isodecyl ether, polyoxyalkylene lauryl ether, polyoxyethylidene styrenated phenyl ether, polyoxyethylene ethyl naphthyl ether, polyoxyethylidene ether, polyoxyethylene Polyoxypropylene propylene glycol, polyoxyethylene ethyl lauryl ether, polyoxyethylene ethyl ketone cetyl ether, polyoxyethylene ethyl oleate, polyoxyethylene ethyl stearate, polyoxygen Ethyl sorbitan monococoate, polyoxyethylene ethyl sorbitan monostearate, polyoxyethylene ethyl sorbitan monooleate, isostearic acid polyoxyethylene Glyceryl ester, polyoxyethylene ethylamine, and the like.

Particularly preferred is a surfactant having an ethylene oxide modified skeleton. Specifically, the cationic surfactant may be exemplified by ethyl sulfoethyl sulfate. Dimethylammonium (CATIOGEN ES-O manufactured by Daiichi Kogyo Co., Ltd.), stearyl dimethyl hydroxyethylammonium p-toluenesulfonate (CATIOGEN D2 manufactured by Daiichi Kogyo Co., Ltd.), and the like. Further, examples of the anionic surfactant include polyoxyalkylene alkylphenyl ether phosphate (PLYSURF A-212E manufactured by Daiichi Kogyo Co., Ltd.) and polyoxydissoethyl tridecyl ether sulfate ( HITENOL 330T manufactured by Daiichi Kogyo Co., Ltd., polyoxyethylene ethyl (C8) ether phosphate (PLYSURF A-208F manufactured by Daiichi Kogyo Co., Ltd.), polyoxyalkylene styrenated Phenyl ether phosphate (PLYSURF AL, manufactured by Daiichi Kogyo Co., Ltd.) and the like. Examples of the nonionic surfactant include polyoxyethylene ethyltridecyl ether (NOIGEN TDS-80 manufactured by Daiichi Kogyo Co., Ltd.), and polyoxyethyl sorbitan monostearate (first). SORGEN TW-60, manufactured by Industrial Pharmaceutical Co., Ltd., etc.

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

When the content of the surfactant is small, the dispersibility of the matrix-forming component and the dispersion medium to be described later is insufficient, and it is aggregated in the coating liquid, and the aggregated particles form convex portions on the surface of the film, and are scratch-resistant and transparent. The sex is reduced and the case where sufficient anti-adhesion is not obtained. When the content of the surfactant is too large, the surfactant which is free from particles in the coating liquid increases, and the obtained hard coating film is atomized, and the hardness, scratch resistance, and the like are insufficient.

Surfactant-treated metal oxide microparticles (B) The metal oxide fine particles (B) can be prepared by dispersing the metal oxide fine particles (B) in a solvent, adding a predetermined amount of a surfactant, and adsorbing the surfactant to the metal oxide fine particles (B). Further, a surfactant which is previously dissolved in a solvent can be used.

(iii) matrix components

As the matrix component, an organic resin can be suitably used.

As the organic resin matrix component, specifically, any of a well-known thermosetting resin or a thermoplastic resin which is a resin for coating can be used. For example, thermoplasticity such as a polyester resin, a polycarbonate resin, a polyamide resin, a polyphenylene ether resin, a thermoplastic acrylic resin, a vinyl chloride resin, a fluororesin, a vinyl acetate resin, or a ruthenium rubber which can be used in the past can be mentioned. Resin; thermosetting resin such as urethane resin, melamine resin, oxime resin, butyral resin, reactive polyoxyl resin, phenol resin, epoxy resin, unsaturated polyester resin, thermosetting acrylic resin, etc. . Further, a copolymer or a modified body of two or more of these resins may be used.

These resins may also be emulsion resins, water-soluble resins, and hydrophilic resins. 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 contained.

Among them, one or more kinds of polyfunctional (meth) acrylate resins selected from functional groups having a vinyl group, a urethane group, an epoxy group, a (meth) acryl fluorenyl group, and a CF ₂ group are preferable. More specifically, neopentyl alcohol triacrylate, neopentyl alcohol tetraacrylate, trimethylolpropane tri (meth) acrylate, neopentyl alcohol tetraacrylate, di-trihydroxyl can be suitably used. Propane tetra(meth)acrylate, dipentaerythritol hexaacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethyl methacrylate Hexyl hexyl ester, isodecyl methacrylate, n-lauryl acrylate, n-stearyl acrylate, 1,6-hexanediol dimethacrylate, perfluorooctyl methacrylate, trifluoromethane methacrylate Ethyl ester, ethyl urethane acrylate, etc. and mixtures thereof.

Among them, the urethane urethane oligomer-based resin can be suitably used because it can obtain a hard coating film which is excellent in anti-stick property, has appropriate hardness, and has excellent curl suppressing effect.

Composition of hard coating

The content (W _A ) of the metal oxide fine particles (A) in the hard coating film is in the range of 0.5 to 80% by weight, and more preferably 1 to 70% by weight, based on the solid content.

When the content (W _A ) of the metal oxide fine particles (A) in the hard coating film is small, the anti-adhesive property may be insufficient due to the film thickness, and the curl suppressing effect may be insufficient. When the content (W _A ) is too large, the haze of the hard coating film may be deteriorated, and the transparency may be lowered, and the scratch resistance may be insufficient and the adhesion to the substrate may be insufficient.

The content of the matrix component (W _M ) in the hard coating film is in the range of 20 to 99.5% by weight, and more preferably 30 to 99% by weight, based on the solid content.

When the content (W _M ) of the matrix component is small, the haze of the hard coating film is deteriorated, the transparency is lowered, and the scratch resistance and the adhesion to the substrate are insufficient. When the content (W _M ) is too large, the anti-adhesive property may be insufficient due to the film thickness, and the curl suppressing effect may be insufficient.

The content of the cluster forming agent (W _CL ) in the hard coating film is from 0.01 to 10% by weight, and more preferably from 0.02 to 5% by weight, based on the solid content. When the content (W _CL ) of the cluster forming agent in the hard coating film is small, the anti-adhesive property may be insufficient due to the film thickness. When the content (W _CL ) is too large, the haze of the hard coating film may be deteriorated, and the transparency may be lowered, and the scratch resistance and the adhesion to the substrate may be insufficient.

(W _CL )/(W _A ) is in the range of 0.0005 to 1, and more preferably in the range of 0.0001 to 0.5. In this range, the microparticles (A) can form clusters of a desired size. Further, when the size of the cluster is adjusted, if the above (W _CL )/(W _A ) is increased, the size becomes large, and when (W _CL )/(W _A ) is small, the size becomes small.

When the metal oxide fine particles (B) surface-treated with a surfactant are optionally contained, the content (W _B ) of the surface-treated metal oxide fine particles (B) in the hard coating film is based on the solid content, and is 30 The % by weight or less, more preferably, is in the range of 1 to 20% by weight.

When the content (W _B ) of the metal oxide fine particles (B) in the hard coating film is within the above range, a substrate coated with a hard coating film which is more excellent in anti-sticking property and scratch resistance can be obtained.

The hard coating film of the present invention is partially formed by forming a convex portion on the surface of the hard coating film, and the height (H convex) of the convex portion is 10 to 200 nm, and preferably 15 to 150 nm. range.

When the height of the convex portion (H convex) is small, the anti-adhesion property may be insufficient.

When the height of the convex portion (H convex) is too large, the haze of the hard coating film is deteriorated, When the transparency is lowered, the scratch resistance and the adhesion to the substrate may be insufficient.

The height (H convex) of the convex portion can be adjusted by dissolving or dispersing a polymerization initiator or the like described later.

The average film thickness of the hard coating film can be appropriately selected in the range of 0.5 to 20 μm, and more preferably in the range of 1 to 10 μm, depending on the purpose.

When the average film thickness of the hard coating film is within this range, the stress can be sufficiently absorbed, so that the scratch resistance is high and the curl during drying is also reduced.

In the present invention, the average film thickness of the hard coat film is measured by a transmission electron micrograph (TEM) photograph of a longitudinal section of a probe type surface profilometer or a hard coat film.

Further, the height (H-convex) (Rmax) of the convex portion was measured by an atomic force microscope (AFM) (Dimension 3100 manufactured by Bruker Co., Ltd.).

Further, the thickness of the hard coat film in the present invention is not considered in consideration of the thickness of the convex portion height (H convex) (Rmax).

The refractive index difference between the refractive index (n _B ) of the substrate and the refractive index (n _H ) of the hard coating film is 0.3 or less, and preferably 0.2 or less. When the difference between the refractive index of the hard coating film and the refractive index of the substrate exceeds 0.3, there is a problem of interference fringes.

Such a hard coating film can be formed by coating, drying, and hardening the coating liquid for forming a hard coating film of the present invention as shown below.

Next, the coating liquid for forming a hard coating film of the present invention will be described.

[Coating liquid for forming a hard coating film]

The coating liquid for forming a hard coating film of the present invention contains the aforementioned metal oxide The fine particles (A), the matrix forming component (hardening/polymerization of the matrix component of the hard coating film), the cluster forming agent and the dispersion medium. Further, the metal oxide fine particles (B) described above may be contained as needed.

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

Dispersing medium

The dispersing medium to be used in the present invention is such that the metal oxide fine particles (A), the matrix forming component, and the cluster forming agent can be dissolved or dispersed, and the metal oxide fine particles (B) which can be used as needed, and polymerization The initiator is not particularly limited, and a conventionally known solvent can be used.

Specific examples thereof include alcohols such as methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, furan methanol, tetrahydrofuran methanol, ethylene glycol, hexanediol, and isopropyl glycol; Ester, ethyl acetate, butyl acetate and other esters; diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol isopropyl ether, Ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, butyl methyl Ketones such as ketone, cyclohexanone, methylcyclohexanone, dipropyl ketone, methyl amyl ketone, diisobutyl ketone, isophorone, acetoacetone, acetamidine acetate; Toluene, xylene, and the like. These may be used alone or in combination of two or more.

The concentration of the coating liquid for forming a hard coating film is from 1 to 60% by weight, and more preferably from 2 to 50% by weight, based on the total solid content. Wai.

When the total solid content concentration is low, the desired size cluster (CL _P ) may not be formed. Therefore, even if a hard coating film is formed, the desired unevenness cannot be formed, and the anti-stick property may not be obtained, and When the secondary coating is difficult to obtain a hard coating film having a desired film thickness, when the coating is repeated and repeated drying, a predetermined convex portion may not be formed.

When the total solid content concentration is too high, the cluster (CL _P ) may become too large. Therefore, the surface unevenness may become too large, the haze of the hard coating film may be deteriorated, the transparency may be lowered, and scratch resistance may be caused. The adhesion to the substrate may be insufficient. Further, the viscosity of the coating liquid is high, and the coating property is lowered, and the haze of the obtained hard coating film is increased, and the scratch resistance is insufficient.

In the coating liquid for forming a hard coating film, the concentration (C _A ) of the metal oxide fine particles (A) is preferably from 0.025 to 48% by weight, and more preferably from 0.05 to 42% by weight, based on the solid content. When the concentration (C _A ) of the metal oxide fine particles (A) is low, the anti-sticking property may be insufficient, and the curl suppressing effect may be insufficient. When the concentration (C _A ) of the metal oxide fine particles (A) is too high, the haze of the obtained hard coating film is deteriorated, the transparency is lowered, and the scratch resistance and the adhesion to the substrate are not improved. Full case.

In the coating liquid for forming a hard coating film, the concentration (C _B ) of the metal oxide fine particles (B) or the metal oxide fine particles (B) surface-treated by the surfactant, if necessary, is 18 in terms of solid content. The amount by weight or less may be 0.05 to 18% by weight, and more preferably 0.1 to 12% by weight.

When the concentration (C _B ) is in the above range, a substrate coated with a hard coating film which is more excellent in anti-sticking property and scratch resistance can be obtained.

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

In the coating liquid for forming a hard coating film, the concentration (C _M ) of the matrix-forming component is in the range of 0.1 to 59.7% by weight, and more preferably 1 to 54% by weight, based on the solid content.

When the concentration (C _M ) of the matrix-forming component is too low, the haze of the obtained hard coating film may be deteriorated, and the transparency may be lowered, and the scratch resistance and the adhesion to the substrate may be insufficient. When the concentration (C _M ) of the matrix-forming component is too high, the anti-adhesive property may be insufficient due to the film thickness, and the curl suppressing effect may be insufficient.

Polymerization initiator

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

The polymerization initiator can be used without any particular limitation, and examples thereof include bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide and bis(2,6-dimethoxy). Benzomethane) 2,4,4-trimethyl-pentylphosphine oxide, 2-hydroxy-methyl-2-methyl-phenyl-propan-1-one, 2,2-dimethoxy 1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-one, 2-methyl-1-[4-(methylthio)phenyl]-2- N-morpholinylpropan-1-one and the like.

Further, the concentration (C _CL ) of the cluster forming agent is in the range of 0.0005 to 6% by weight, and more preferably 0.001 to 3% by weight, based on the solid content.

When the concentration (C _CL ) of the cluster forming agent is less than 0.0005 wt% based on the solid content, the anti-adhesive property may be insufficient due to the film thickness.

When the concentration (C _CL ) of the cluster forming agent exceeds 6% by weight based on the solid content, the haze of the obtained hard coating film is deteriorated, the transparency is lowered, and the scratch resistance and adhesion to the substrate are obtained. It is not enough.

The ratio (C _CL ) of the aforementioned cluster forming agent based on the solid content to the concentration (C _A ) of the metal oxide fine particles (A) in terms of solid content (C _CL )/(C _A ) is 0.0005. Further, it is preferably in the range of 0.0001 to 0.5.

The concentration ratio (C _CL )/(C _A ) does not form a cluster, and the anti-adhesive property may be insufficient due to the film thickness. When the concentration ratio (C _CL )/(C _A ) is large, the haze of the obtained hard coating film is deteriorated, and the transparency is lowered, and the scratch resistance and the adhesion to the substrate are insufficient.

In the above, the average particle diameter (D _CLP ) of the cluster (CL _P ) in the coating liquid for forming a hard coating film is in the range of 50 to 2,000 nm, and more preferably in the range of 50 to 1,500 nm.

When the average particle diameter (D _CLP ) of the cluster (CL _P ) in the coating liquid for forming a hard coating film is too small, the anti-adhesive property may be insufficient due to the film thickness. When the average particle diameter (D _CLP ) of the cluster (CL _P ) in the coating liquid for forming a hard coating film is too large, the haze of the obtained hard coating film may be deteriorated, the transparency may be lowered, and scratch resistance may be caused. The adhesion to the substrate may be insufficient.

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

Further, predetermined irregularities cannot be formed by a general monodisperse particle system. Although the cluster of the present invention is one type of aggregated particles, it is not possible to exhibit hard coatability in the case of irregular or unspecific aggregated particles.

The coating liquid is applied to the substrate by a known method such as a dipping method, a spray method, a spin coating method, or a bar coating method, and is dried by heat treatment, ultraviolet irradiation or the like to be hardened to form a hard coating film. .

Example

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples.

[Example 1] Modulation of metal oxide microparticles (A-1) dispersion

In the cerium oxide organosol (CATALOID SI-30 manufactured by Nippon Chemical Co., Ltd.; average particle diameter: 12 nm, SiO ₂ concentration: 40.5 wt%, dispersion medium: water, particle refractive index: 1.46), 1000 g, 6000 g of water was exchanged, and then 800 g of a cation exchange resin (Mitsubishi Chemical Co., Ltd.: SK-1BH) was added, and the mixture was stirred for 1 hour and subjected to alkali removal treatment.

Then, after separating the cation exchange resin, 400 g of an anion exchange resin (Mitsubishi Chemical Co., Ltd.: SANUPC) was added, and the mixture was stirred for 1 hour to carry out deanionization treatment. Then, 400 g of a cation exchange resin (Mitsubishi Chemical Co., Ltd.: SK-1BH) was further added, and the mixture was stirred for 1 hour and subjected to a dealkalization treatment to prepare a cerium oxide particle (A) dispersion having a SiO ₂ concentration of 5% by weight.

Using an ultrafiltration membrane, This dispersion was subjected to solvent replacement in methanol to obtain a methanol dispersion having a solid concentration of 40% by weight.

Then, gamma-methacryloxypropyltrimethoxydecane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd., SiO ₂ component: 81.2% by weight) was mixed with 5.84 g of 100 g of the methanol dispersion, followed by addition of super 4.2 g of pure water was stirred at 50 ° C for 6 hours to obtain a surface-treated cerium oxide fine particle dispersion having a solid concentration of 40.5 % by weight.

Thereafter, the solvent was replaced with methyl isobutyl ketone (MIBK) by a rotary evaporator to prepare a surface-treated cerium oxide microparticle MIBK dispersion having a solid content of 40.5% by weight.

Then, to the 100 g of the surface-treated cerium oxide microparticles MIBK dispersion having a solid concentration of 40.5% by weight, a polyacrylic acid-based surfactant (a DISPARLON LHP-810 manufactured by Nanben Chemical Co., Ltd.) was added as a cluster forming agent. The solid content concentration was 10% by weight of 1.61 g, and the mixture was stirred at 50 ° C for 20 hours to prepare a dispersion of metal oxide fine particles (A-1) containing cerium oxide having a solid concentration of 40.0% by weight.

Preparation of coating liquid (1) for forming a hard coating film

56.81 g of a metal oxide fine particle (A-1) dispersion containing cerium oxide having a solid concentration of 40.0% by weight, and an urethane acrylate oligomer resin having a ninth functional acrylate resin NK oligo UA-33H, manufactured by Shin-Nakamura Chemical Co., Ltd., average molecular weight = 4,000) 13.58 g, dimethylol-tricyclodecane diacrylate (photo-acrylate acrylate DCP-A manufactured by Kyoeisha Chemical Co., Ltd.) ) 1.51 g, photopolymerization initiator (IRGACURE 184, manufactured by Chiba Japan Co., Ltd.), 0.91 g, 16.86 g of PGME and 9.43 g of acetone were sufficiently mixed to prepare a coating liquid for forming a hard coating film (1) having a solid concentration of 37.74% by weight.

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

Modulation of substrate (1) with hard coating

The coating liquid for forming a hard coating film (1) was applied to a PET film (COSMOSHINE A4300, manufactured by Toyobo Co., Ltd., thickness: 188 μm) by a bar coating method (#8), dried at 80 ° C for 120 seconds, and then irradiated with 300 m J / The ultraviolet light of cm ² hardens it to form a substrate (1) with a hard coating film. The average film thickness of the hard coating film was 4 μm. Further, the height (H convex) of the convex portion was 27 nm.

The total light transmittance, haze, curling property, anti-sticking property, adhesiveness, pencil hardness, and scratch resistance of the substrate (1) with a hard coating film were measured by the following methods, and the results are shown in the table. The total light transmittance and haze were measured by a haze meter (NDH-5000, manufactured by Nippon Denshoku Co., Ltd.). Further, the coated PET film had a total light transmittance of 92.0% and a haze of 0.9%.

Curl evaluation

The coating liquid (1) for forming a hard coating film was applied onto a TAC film substrate of 14 cm × 25 cm × 40 μm (thickness) so as to form a hard coating film having a thickness of 7 μm, and allowed to stand for 20 hours, after which the film was cut. In the size of 10 cm × 10 cm, the coated side of the film was placed on the flat plate, and the height of the apex of the substrate which was curled (curved) and lifted from the flat plate was measured and evaluated by the following criteria.

<Evaluation Benchmark>

Less than 10mm: ◎

Less than 10 to 20mm: ○

Less than 20 to 30mm: △

30mm or more: ×

Anti-sticking

A part of the substrate (1) with a hard coating film is cut into two pieces, and one of the substrates (substrate + hard coating film) with a hard coating film attached thereto is attached to the other piece with a hard coating film. The substrate (substrate + hard coating film) was loaded so as to have a load of 10 kg per 1 cm ² , and the peeling ease after standing for 24 hours was evaluated by the following criteria.

Very easy to peel off: ◎

Can be easily peeled off: ○

A little difficult to peel off: △

Unable to peel or difficult to peel: ×

Pencil hardness measurement

The pencil hardness tester was used as a reference based on JIS-K-5600. Scratch resistance measurement

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

Evaluation criteria:

Can't see strips of scars: ◎

A few strips of scars can be seen: ○

Most strips of scars can be seen: △

The whole face has been removed: ×

Adhesive

On the surface of the substrate (1) with the clear coating film, 11 parallel scratches were cut at intervals of 1 mm in length with a knife to make 100 squares, and the transparent tape was bonded thereto, and then the transparent tape was peeled off. The number of squares remaining without peeling off the film was classified according to the following four stages, thereby evaluating the adhesion. The results are shown in Table 1.

Evaluation criteria:

The number of remaining squares is 100: ◎

The number of remaining squares is 90 to 99: ○

The number of remaining squares is 85 to 89: △

The number of remaining squares is 84 or less: ×

[Embodiment 2] Modulation of metal oxide microparticles (A-2) dispersion

A metal oxide fine particle (A-2) dispersion containing cerium oxide having a solid content concentration of 40.0% by weight was prepared in the same manner as in Example 1 except that 0.54 g of a surfactant was added.

Preparation of coating liquid for forming a hard coating film (2)

A coating liquid for forming a hard coating film having a solid content concentration of 37.74% by weight was prepared in the same manner as in Example 1 except that the metal oxide fine particles (A-2) containing cerium oxide having a solid concentration of 40.0% by weight were used. (2). The average particle diameter of the cluster (CL _P ) was measured for the coating liquid for forming a hard coating film (2), and the results are shown in the table.

Modulation of substrate (2) with hard coating

A substrate (2) having a hard coating film was formed in the same manner as in Example 1 except that the coating liquid (2) for forming a hard coating film was used. Hard coating The film thickness was 4 μm. Further, the height (H convex) of the convex portion was 23 nm. The obtained light-coated film substrate (2) was measured for total light transmittance, haze, curling property, anti-stick property, adhesiveness, pencil hardness, and scratch resistance, and the results are shown in the table.

[Example 3] Modulation of metal oxide microparticles (A-3) dispersion

A metal oxide fine particle (A-3) dispersion containing cerium oxide having a solid content concentration of 40.0% by weight was prepared in the same manner as in Example 1 except that the surfactant was added in an amount of 8.94 g.

Preparation of coating liquid for forming a hard coating film (3)

A coating liquid for forming a hard coating film having a solid content concentration of 37.74% by weight was prepared in the same manner as in Example 1 except that the metal oxide fine particles (A-3) containing cerium oxide having a solid concentration of 40.0% by weight were used. (3).

The average particle diameter of the cluster (CL _P ) was measured for the coating liquid for forming a hard coating film (3), and the results are shown in the table.

Modulation of a substrate (3) with a hard coating film

A substrate (3) having a hard coating film was formed in the same manner as in Example 1 except that the coating liquid (3) for forming a hard coating film was used. The average film thickness of the hard coating film was 4 μm. Furthermore, the height (H convex) of the convex portion was 100 nm.

The obtained light-coated film substrate (3) was measured for total light transmittance, haze, curling property, anti-stick property, adhesiveness, pencil hardness, and scratch resistance, and the results are shown in the table.

[Example 4] Modulation of metal oxide microparticles (A-4) dispersion

In 1000 g of yt sol dispersion (SI-550 manufactured by Nippon Chemical Co., Ltd.; average particle diameter: 5 nm, SiO ₂ concentration: 40.5 wt%), 6000 g of ion-exchanged water was added, followed by addition of cation exchange resin (Mitsubishi Chemical) Co., Ltd.: SK-1BH) 800g, stirred for 1 hour and subjected to alkali removal treatment.

Then, after separating the cation exchange resin, 400 g of an anion exchange resin (Mitsubishi Chemical Co., Ltd.: SANUPC) was added, and the mixture was stirred for 1 hour to carry out deanionization treatment. Then, 400 g of a cation exchange resin (Mitsubishi Chemical Co., Ltd.: SK-1BH) was further added, and the mixture was stirred for 1 hour and subjected to a dealkalization treatment to prepare a cerium oxide particle (A) dispersion having a SiO ₂ concentration of 5% by weight.

This dispersion was subjected to solvent replacement in methanol using an ultrafiltration membrane to obtain a methanol dispersion having a solid concentration of 40% by weight.

Then, γ-methylpropenyloxypropyltrimethoxydecane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd., SiO ₂ component: 81.2% by weight) was mixed with 5,800 g of the methanol dispersion, and then added with 5.84 g. 4.2 g of pure water was stirred at 50 ° C for 6 hours to obtain a surface-treated cerium oxide fine particle dispersion having a solid concentration of 40.5 % by weight.

Thereafter, the solvent was replaced with methyl isobutyl ketone (MIBK) by a rotary evaporator to prepare a surface-treated cerium oxide microparticle MIBK dispersion having a solid content of 40.5% by weight. A metal oxide containing cerium oxide having a solid content concentration of 40.0% by weight was prepared in the same manner as in Example 1 except that 100 g of the above-mentioned cerium oxide MIBK dispersion was used. Particle (A-4) dispersion.

Preparation of coating liquid for forming a hard coating film (4)

A coating liquid for forming a hard coating film having a solid content concentration of 37.74% by weight was prepared in the same manner as in Example 1 except that the metal oxide fine particles (A-4) containing cerium oxide having a solid concentration of 40.0% by weight were used. (4).

The average particle diameter of the cluster (CL _P ) was measured for the coating liquid for forming a hard coating film (4), and the results are shown in the table.

Modulation of substrate (4) with hard coating

A substrate (4) having a hard coating film was formed in the same manner as in Example 1 except that the coating liquid (4) for forming a hard coating film was used. The average film thickness of the hard coating film was 4 μm. Furthermore, the height (H convex) of the convex portion was 18 nm.

The obtained light-coated film substrate (4) was measured for total light transmittance, haze, curling property, anti-stick property, adhesiveness, pencil hardness, and scratch resistance, and the results are shown in the table.

[Example 5] Modulation of metal oxide microparticles (A-5) dispersion

Addition of cation exchange water (6000 g) to 1000 g of 矽 sol dispersion (SI-80P, manufactured by Nippon Chemical Co., Ltd.; average particle diameter: 80 nm, SiO ₂ concentration: 40.5 wt%), followed by addition of cation exchange resin (Mitsubishi Chemical Co., Ltd. Ltd.: SK-1BH) 800g, stirred for 1 hour and subjected to alkali removal treatment.

Then, after separating the cation exchange resin, an anion exchange resin (Mitsubishi Chemical Co., Ltd.: SANUPC) 400 was added, and the mixture was stirred for 1 hour and subjected to deanionization treatment. Then, 400 g of a cation exchange resin (Mitsubishi Chemical Co., Ltd.: SK-1BH) was further added, and the mixture was stirred for 1 hour and subjected to a dealkalization treatment to prepare a cerium oxide particle (A) dispersion having a SiO ₂ concentration of 5% by weight.

This dispersion was subjected to solvent replacement in methanol using an ultrafiltration membrane to obtain a methanol dispersion having a solid concentration of 40% by weight. Γ-methyl propylene methoxy propyl trimethoxy decane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd., SiO ₂ component: 81.2% by weight) was mixed with 5.84 g of 100 g of the methanol dispersion, followed by the addition of ultrapure water. 4.2 g was stirred at 50 ° C for 6 hours to obtain a surface-treated cerium oxide microparticle dispersion having a solid concentration of 40.5% by weight.

Thereafter, the solvent was replaced with methyl isobutyl ketone (MIBK) by a rotary evaporator to prepare a surface-treated cerium oxide microparticle MIBK dispersion having a solid content of 40.5% by weight.

A metal oxide fine particle (A-5) dispersion containing cerium oxide having a solid content concentration of 40.0% by weight was prepared in the same manner as in Example 1 except that 100 g of the above-mentioned cerium oxide MIBK dispersion was used.

Preparation of coating liquid for forming a hard coating film (5)

A coating liquid for forming a hard coating film having a solid content concentration of 37.74% by weight was prepared in the same manner as in Example 1 except that the metal oxide fine particles (A-5) containing cerium oxide having a solid concentration of 40.0% by weight were used. (5).

The average particle diameter of the cluster (CL _P ) was measured for the coating liquid for forming a hard coating film (5), and the results are shown in the table.

Modulation of substrate (5) with hard coating

A substrate (5) having a hard coating film was formed in the same manner as in Example 1 except that the coating liquid (5) for forming a hard coating film was used. The average film thickness of the hard coating film was 4 μm. Furthermore, the height (H convex) of the convex portion was 80 nm.

The obtained light-coated film substrate (5) was measured for total light transmittance, haze, curling property, anti-stick property, adhesiveness, pencil hardness, and scratch resistance, and the results are shown in the table.

[Embodiment 6] Modulation of metal oxide microparticles (A-6) dispersion

A solid component was prepared in the same manner as in Example 1 except that 1.61 g of a polyfluorene-based surfactant (DISPARLON LS-260, manufactured by Kuamoto Kasei Co., Ltd., solid content concentration: 20%) was added as a cluster forming agent. A dispersion of metal oxide fine particles (A-6) containing cerium oxide at a concentration of 40.0% by weight.

Preparation of coating liquid for forming a hard coating film (6)

A coating liquid for forming a hard coating film having a solid content concentration of 37.74% by weight was prepared in the same manner as in Example 1 except that the metal oxide fine particles (A-6) containing cerium oxide having a solid concentration of 40.0% by weight were used. (6).

The average particle diameter of the cluster (CL _P ) was measured for the coating liquid for forming a hard coating film (6), and the results are shown in the table.

Modulation of substrate (6) with hard coating

A substrate (6) having a hard coating film was formed in the same manner as in Example 1 except that the coating liquid (6) for forming a hard coating film was used. Hard coating The film thickness was 4 μm. Furthermore, the height (H convex) of the convex portion was 50 nm.

The obtained light-coated film substrate (6) was measured for total light transmittance, haze, curling property, anti-stick property, adhesiveness, pencil hardness, and scratch resistance, and the results are shown in the table.

[Embodiment 7] Preparation of coating liquid for forming a hard coating film (7)

In addition to using an 8-functional urethane acrylate oligomer resin (NK oligo UA-8LR, manufactured by Shin-Nakamura Chemical Co., Ltd., average molecular weight = 3,000), 19.41 g of a acrylate resin (amine) having a substituted functional group of 9-functionality In the same manner as in Example 1, a coating liquid for forming a hard coating film (7) having a solid content concentration of 37.74% by weight was prepared in the same manner as in Example 1 except that the chloroform acrylate oligo resin was added.

The average particle diameter of the cluster (CL _P ) was measured for the coating liquid for forming a hard coating film (7), and the results are shown in the table.

Modulation of substrate (7) with hard coating

A substrate (7) having a hard coating film was formed in the same manner as in Example 1 except that the coating liquid (7) for forming a hard coating film was used. The average film thickness of the hard coating film was 4 μm. Furthermore, the height (H convex) of the convex portion was 30 nm.

The obtained light-coated film substrate (7) was measured for total light transmittance, haze, curling property, anti-stick property, adhesiveness, pencil hardness, and scratch resistance, and the results are shown in the table.

[Embodiment 8] Modulation of metal oxide microparticle (B-1) dispersion

Anionic surfactant was mixed in a methanol dispersion of 矽Sol (ELCOM V-8901, an average particle size of 120 nm and a SiO ₂ concentration of 20.5 wt%, manufactured by Nippon Chemical Co., Ltd.) (First Industrial Pharmaceutical Co., Ltd.) 2.05 g of PLYSURF A212E) was stirred for 20 hours to prepare a surfactant-treated metal oxide fine particle (B-1) methanol dispersion containing cerium oxide having a solid concentration of 22.10% by weight.

Preparation of coating liquid (8) for forming a hard coating film

A cerium oxide containing 56.85 g of a metal oxide fine particle (A-1) dispersion containing cerium oxide prepared in the same manner as in Example 1 and having a solid content concentration of 22.10% by weight Surfactant-treated metal oxide fine particle (B-1) methanol dispersion 3.42 g, urethane acrylate oligomer resin which is a nin-functional acrylate resin (manufactured by Shin-Nakamura Chemical Co., Ltd.) NK oligo UA-33H, average molecular weight = 4,000) 13.58g, dimethylol-tricyclodecane diacrylate (photo-acrylate acrylate DCP-A manufactured by Kyoeisha Chemical Co., Ltd.) 1.51g, photopolymerization initiation The agent (IRGACURE 184, manufactured by Chiba Japan Co., Ltd.), 0.91 g, and PGME, 14.30 g, and 9.43 g of acetone were sufficiently mixed to prepare a coating liquid for forming a hard coating film (8) having a solid concentration of 37.74% by weight.

The average particle diameter of the cluster (CL _P ) was measured for the coating liquid for forming a hard coating film (8), and the results are shown in the table.

Modulation of substrate (8) with hard coating

A substrate (8) having a hard coating film was formed in the same manner as in Example 1 except that the coating liquid (8) for forming a hard coating film was used. The average film thickness of the hard coating film was 4 μm. Furthermore, the height (H convex) of the convex portion was 53 nm.

The obtained light-coated film substrate (8) was measured for total light transmittance, haze, curling property, anti-stick property, adhesiveness, pencil hardness, and scratch resistance, and the results are shown in the table.

[Embodiment 9] Modulation of metal oxide microparticles (A-9) dispersion

25 g of a caustic potash (purity of 85% by Asahi Glass Co., Ltd.) was dissolved in a solution of 800 g of pure water, and 50 g of antimony trioxide (PATOX-K manufactured by Nippon Concentrate Co., Ltd., purity: 98.5%) was suspended. The suspension was heated at 95 ° C, and then 15 g of an aqueous solution diluted with 50 g of pure water was added to dissolve the trioxide in hydrogen peroxide (manufactured by Lin Chun Pharmaceutical Co., Ltd., special grade, concentration: 35 wt%) over 9 hours. Hey, after that, mature for 11 hours. Then, after cooling, 800 g of the obtained solution was taken, and the solution was diluted with 4800 g of pure water, and then treated with a cation exchange resin (pk-216 manufactured by Mitsubishi Chemical Corporation) to a pH of 3.5 to carry out deionization. The solution obtained by deionization was aged at a temperature of 70 ° C for 10 hours, and then concentrated by an ultrafiltration membrane to prepare a dispersion of the inorganic oxide-based conductive particles (1) containing cerium oxide having a solid concentration of 14%. The pH of the dispersion of the inorganic oxide-based conductive particles (1) was 4.0. The inorganic oxide-based conductive particles (1) had an average particle diameter of 20 nm.

Then, 100 g of the dispersion liquid of the inorganic oxide-based conductive particles (1) was adjusted to 25 ° C, and tetraethoxy decane (ethyl ortho-ruthenium acetate manufactured by Tama Chemical Co., Ltd.) was added in 3 minutes, and the SiO ₂ component was 28.8. After weight %) 2.5 g, it was stirred for 30 minutes. Thereafter, 100 g of ethanol was added over 1 minute, and the temperature was raised to 50 ° C over 30 minutes, and the heat treatment was performed for 3 hours. The solid content concentration at this time was 7% by weight.

Then, water and ethanol of the dispersion medium were replaced with ethanol through an ultrafiltration membrane to prepare a dispersion of the inorganic oxide-based conductive particles (1) which was subjected to surface treatment with an organic cerium compound having a solid concentration of 30% by weight.

Then, γ-methyl propylene methoxy propyl trimethoxy decane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd., SiO ₂ component: 81.2% by weight) of 5.84 g was mixed in 100 g of the ethanol dispersion, and then super was added. 4.2 g of pure water was stirred at 50 ° C for 6 hours to obtain a surface-treated cerium oxide fine particle dispersion having a solid concentration of 40.5 % by weight.

Thereafter, the solvent was replaced with methyl isobutyl ketone (MIBK) by a rotary evaporator to prepare a surface-treated cerium oxide microparticle MIBK dispersion having a solid content of 40.5% by weight.

A surface-treated inorganic oxide-based conductive particle (A) having a solid content concentration of 40.0% by weight was prepared in the same manner as in Example 1 except that 100 g of the surface-treated inorganic oxide-based conductive particle MIBK dispersion was used. -9) Dispersion.

Preparation of coating liquid for forming a hard coating film (9)

A hard coating film having a solid content concentration of 37.74% by weight was prepared in the same manner as in Example 1 except that the surface-treated inorganic oxide-based conductive particles (A-9) having a solid concentration of 40.0% by weight were used. Coating liquid (9).

The average particle diameter of the cluster (CL _P ) was measured for the coating liquid for forming a hard coating film (9), and the results are shown in the table.

Modulation of substrate (9) with hard coating

A substrate (9) having a hard coating film was formed in the same manner as in Example 1 except that the coating liquid (9) for forming a hard coating film was used. The average film thickness of the hard coating film was 4 μm. Furthermore, the height (H convex) of the convex portion was 25 nm.

The obtained light-coated film substrate (9) was measured for total light transmittance, haze, curling property, anti-stick property, adhesiveness, pencil hardness, and scratch resistance, and the results are shown in the table.

[Embodiment 10] Preparation of coating liquid (10) for forming a hard coating film

47.49 g of a dispersion of metal oxide fine particles (A-1) containing cerium oxide having a solid concentration of 40.0% by weight, and an urethane resin urethane acrylate oligomer resin having a functional group of 9 functions (new NK oligo UA-33H, Nakamura Chemical Co., Ltd., average molecular weight = 4,000) 16.98g, dimethylol-tricyclodecane diacrylate (photo-acrylate acrylate DCP-A manufactured by Kyoeisha Chemical Co., Ltd.) 1.89 g, a photopolymerization initiator (IRGACURE 184, manufactured by Chiba Japan Co., Ltd.), 1.89 g, PGME, 22.18 g, and 9.43 g of acetone were sufficiently mixed to prepare a coating liquid for forming a hard coating film having a solid concentration of 37.74% by weight. 1).

The average particle diameter of the cluster (CL _P ) was measured for the coating liquid for forming a hard coating film (10), and the results are shown in the table.

Modulation of substrate (10) with hard coating

A substrate (10) having a hard coating film was formed in the same manner as in Example 1 except that the coating liquid (10) for forming a hard coating film was used. The average film thickness of the hard coating film was 4 μm. Furthermore, the height (H convex) of the convex portion was 20 nm.

Measuring the total light transmission through the obtained substrate (10) with a hard coating film Rate, haze, curling, anti-sticking, adhesion, pencil hardness, and scratch resistance, the results are shown in the table.

[Example 11] Preparation of coating liquid (11) for forming a hard coating film

61.46 g of a dispersion of metal oxide fine particles (A-1) containing cerium oxide having a solid concentration of 40.0% by weight, and an urethane acrylate oligomer resin having an acrylate resin having a functional group of 9 (a functional group) NK oligo UA-33H, manufactured by Shin-Nakamura Chemical Co., Ltd., average molecular weight = 4,000) 11.89 g, dimethylol-tricyclodecane diacrylate (photo-acrylate acrylate DCP-A manufactured by Kyoeisha Chemical Co., Ltd.) 1.32 g, a photopolymerization initiator (IRGACURE 184, manufactured by Chiba Japan Co., Ltd.), 0.79 g, PGME, 14.20 g, and 9.43 g of acetone were sufficiently mixed to prepare a coating liquid for forming a hard coating film having a solid concentration of 37.74% by weight. (11).

The average particle diameter of the cluster (CL _P ) was measured for the coating liquid for forming a hard coating film (11), and the results are shown in the table.

Modulation of a substrate (11) with a hard coating film

A substrate (11) having a hard coating film was formed in the same manner as in Example 1 except that the coating liquid for forming a hard coating film (11) was used. The average film thickness of the hard coating film was 4 μm. Furthermore, the height (H convex) of the convex portion was 80 nm.

The obtained light-coated film substrate (11) was measured for total light transmittance, haze, curling property, anti-stick property, adhesiveness, pencil hardness, and scratch resistance, and the results are shown in the table.

[Comparative Example 1] Modulation of metal oxide microparticles (RA-1) dispersion

A metal oxide fine particle (RA-1) containing cerium oxide having a solid content concentration of 40.0% by weight was prepared in the same manner as in Example 1 except that the polyacrylic acid-based surfactant as a cluster forming agent was not used. Dispersions.

Modification of coating liquid (R1) for forming a hard coating film

A hard coating film having a solid content concentration of 37.74% by weight was prepared in the same manner as in Example 1 except that a metal oxide fine particle (RA-1) dispersion containing cerium oxide having a solid concentration of 40.0% by weight was used. Coating liquid (R1).

The average particle diameter of the cluster (CL _P ) was measured for the coating liquid for forming a hard coating film (R1), and the results are shown in the table.

Modulation of a substrate (R1) with a hard coating

A substrate (R1) having a hard coating film was formed in the same manner as in Example 1 except that the coating liquid for forming a hard coating film (R1) was used. The average film thickness of the hard coating film was 4 μm. Furthermore, the height (H convex) of the convex portion was 10 nm.

The obtained light-coated film substrate (R1) was measured for total light transmittance, haze, curling property, anti-stick property, adhesiveness, pencil hardness, and scratch resistance, and the results are shown in the table.

[Comparative Example 2] Modulation of metal oxide microparticles (RA-2) dispersion

In Example 1, 100.0 g of a polyacrylic acid-based surfactant (DISPARLON LHP-810, manufactured by Nanben Chemical Co., Ltd., solid content concentration: 10% by weight) as a cluster forming agent was added, and the mixture was stirred at 50 ° C. In hours, a solid concentration of 40.0% by weight of cerium oxide is prepared. Metal oxide fine particle (RA-2) dispersion.

Preparation of coating liquid (R2) for forming a hard coating film

A hard coating film having a solid content concentration of 37.74% by weight was prepared in the same manner as in Example 1 except that a metal oxide fine particle (RA-2) dispersion containing cerium oxide having a solid concentration of 40.0% by weight was used. Coating liquid (R2).

The average particle diameter of the cluster (CL _P ) was measured for the coating liquid for forming a hard coating film (R2), and the results are shown in the table.

Modulation of a substrate (R2) with a hard coating

A substrate (R2) having a hard coating film was formed in the same manner as in Example 1 except that the coating liquid for forming a hard coating film (R2) was used. The average film thickness of the hard coating film was 4 μm. Furthermore, the height (H convex) of the convex portion was 1000 nm.

The obtained light-coated film substrate (R2) was measured for total light transmittance, haze, curling property, anti-stick property, adhesiveness, pencil hardness, and scratch resistance, and the results are shown in the table.

[Comparative Example 3] Preparation of coating liquid (R3) for forming a hard coating film

0.47 g of a metal oxide fine particle (A-1) dispersion containing cerium oxide having a solid concentration of 40.0% by weight, and an urethane acrylate oligomer resin having a ninth functional acrylate resin as a functional group ( NK oligo UA-33H, manufactured by Shin-Nakamura Chemical Co., Ltd., average molecular weight = 4,000) 33.80 g, dimethylol-tricyclodecane diacrylate (photo-acrylate acrylate DCP-A manufactured by Kyoeisha Chemical Co., Ltd.) 3.76 g, photopolymerization initiator (IRGACURE 184, manufactured by Chiba Japan Co., Ltd.) 2.25 g, 50.28 g of PGME and 94.34 g of acetone were sufficiently mixed to prepare a coating liquid for forming a hard coating film (R3) having a solid concentration of 37.74% by weight.

The average particle diameter of the cluster (CL _P ) was measured for the coating liquid for forming a hard coating film (R3), and the results are shown in the table.

Modulation of a substrate (R3) with a hard coating

A substrate (R3) having a hard coating film was formed in the same manner as in Example 1 except that the coating liquid for forming a hard coating film (R3) was used. The average film thickness of the hard coating film was 4 μm. Furthermore, the height (H convex) of the convex portion was 12 nm.

The obtained light-coated film substrate (R3) was measured for total light transmittance, haze, curling property, anti-stick property, adhesiveness, pencil hardness, and scratch resistance, and the results are shown in the table.

[Comparative Example 4] Preparation of coating liquid for forming a hard coating film (R4)

80.11 g of a dispersion of metal oxide fine particles (A-1) containing cerium oxide having a solid concentration of 40.0% by weight, and an urethane acrylate oligomer resin having an acrylate resin having a functional group of 9 (a functional group) NK oligo UA-33H, average molecular weight = 4,000) 15.09g, dimethylol-tricyclodecane diacrylate (light acrylate DCP-A manufactured by Kyoeisha Chemical Co., Ltd.) 0.57 g, 0.34 g of a photopolymerization initiator (IRGACURE 184, manufactured by Chiba Japan Co., Ltd.), and 3.56 g of PGME and 9.43 g of acetone were sufficiently mixed to prepare a coating liquid for forming a hard coating film having a solid concentration of 37.74% by weight (R4) ).

The average particle diameter of the cluster (CL _P ) was measured for the coating liquid for forming a hard coating film (R4), and the results are shown in the table.

Modulation of a substrate (R4) with a hard coating

A substrate (R4) having a hard coating film was formed in the same manner as in Example 1 except that the coating liquid for forming a hard coating film (R4) was used. The average film thickness of the hard coating film was 4 μm. Furthermore, the height (H convex) of the convex portion was 900 nm.

The obtained light-coated film substrate (R4) was measured for total light transmittance, haze, curling property, anti-stick property, adhesiveness, pencil hardness, and scratch resistance, and the results are shown in the table.

Claims (11)

A substrate coated with a hard coating film, comprising: a substrate and a hard coating film formed on the substrate, the hard coating film comprising (i) a cluster of metal oxide microparticles (A) (CL) And (ii) a matrix component and (iii) a cluster forming agent, wherein the cluster forming agent is at least one surfactant selected from the group consisting of a polyfluorene-based surfactant, and a polyacrylic acid-based surfactant. An acrylic surfactant, a phosphate ester surfactant, a polyoxyethylidene ether alkyl surfactant, and a content (W _A ) of the metal oxide fine particles (A) in the hard coating film based solid content from 0.5 to 80 wt%, the content of the matrix component (W _M) solid content train 20 to 99.5% by weight, the amount of forming agent comprising clusters (W _CL) based solid content to 0.01 10% by weight, the ratio (W _CL ) / (W _A ) is 0.0005 to 1, and the cluster (CL) is present on the surface of the hard coating film to form a convex portion, and has 15 to 200 nm on the surface of the hard coating film. Height (H convex) convex. The substrate coated with a hard coating film according to the first aspect of the invention, wherein the metal oxide fine particles (A) constituting the cluster (CL) have an average particle diameter (D _A ) of 5 to 200 nm. The substrate coated with a hard coating film according to the first aspect of the invention, wherein the metal oxide fine particles (A) comprise cerium oxide, aluminum oxide, zirconium dioxide, titanium dioxide, antimony pentoxide or boron oxide. Mixed A tin oxide of a cerium, a tin oxide doped with phosphorus, an indium oxide doped with tin, a composite oxide of these, and a mixture thereof. The substrate coated with a hard coating film according to claim 1, wherein the matrix component is an organic resin. The substrate coated with a hard coating film according to the first aspect of the invention, wherein, in addition to the metal oxide fine particles (A), the average particle diameter obtained by treating with a surfactant is 5 to 100 nm. Metal oxide microparticles (B). The substrate coated with a hard coating film according to the first aspect of the invention, wherein the hard coating film has an average film thickness of 0.5 to 20 μm. The substrate coated with a hard coating film according to the first aspect of the invention, wherein a refractive index difference between a refractive index (n _B ) of the substrate and a refractive index (n _H ) of the hard coating film is 0.3 or less. A coating liquid for forming a hard coating film, comprising: metal oxide fine particles (A), a matrix forming component, a cluster forming agent, and a dispersion medium, wherein the cluster forming agent is at least one selected from the group consisting of: Agent: a polyfluorene-based surfactant, a polyacrylic acid-based surfactant, an acrylic surfactant, a phosphate-based surfactant, a polyoxyethylidene ether-based surfactant, and the metal The concentration (C _A ) of the oxide fine particles (A) is 0.025 to 48% by weight based on the solid content, and the concentration (C _M ) of the matrix forming component is 1 to 59.7% by weight based on the solid content, and the cluster forming agent is The concentration (C _CL ) is 0.0005 to 6% by weight based on the solid content, the ratio (C _CL )/(C _A ) is 0.0005 to 1, and the total solid content is 1 to 60% by weight, and the metal oxide fine particles (A) ) forms a cluster (CL _P ). The coating liquid for forming a hard coating film according to the invention of claim 8, wherein the average particle diameter (D _CLP ) of the cluster (CL _P ) is 50 to 2,000 nm. The coating liquid for forming a hard coating film according to the eighth aspect of the invention, wherein the metal oxide fine particles (A) constituting the cluster (CL _P ) have an average particle diameter (D _A ) of 5 to 200 nm. The coating liquid for forming a hard coating film according to the eighth aspect of the invention, which further comprises a metal having an average particle diameter of 5 to 100 nm obtained by treatment with a surfactant in addition to the metal oxide fine particles (A). Oxide fine particles (B).