TWI498391B - Coating solution for forming transparent coated film and substrate with the transparent coated film - Google Patents

Description

Coating liquid for forming a transparent coating film and a substrate having a transparent coating film

The present invention relates to a coating liquid for forming a transparent coating film having high flatness, whitening resistance, water resistance, chemical resistance, and the like, and a substrate having the transparent coating film.

In order to improve the scratch resistance of a substrate surface such as a glass, a plastic sheet or a plastic lens, or a display device, it is known to form a transparent coating film having a hard coat function on the surface of the substrate. Specifically, an organic resin film or an inorganic film having transparency is formed on the surface of a glass, a plastic, or a display device substrate. In this case, when inorganic particles such as resin particles or cerium oxide are blended in the organic resin film or the inorganic film, adhesion to the substrate, scratch resistance, and the like are further enhanced.

However, the transparent coating film is required to have chemical resistance, water resistance, water repellency, fingerprint adhesion resistance, and the like in addition to transparency, adhesion to a substrate, film strength, and scratch resistance. For example, when water droplets are attached, there is no trace of water droplets (water resistance), and it is difficult to graffiti with a water-based pen or an oil-based pen. Even if it is graffiti, it can be easily wiped (water resistance, water repellency, oil repellency), and further, touch with a finger. It is also difficult to attach fingerprints, and it is easy to wipe even if fingerprints are attached (fingerprint adhesion resistance).

In order to impart water repellency, oil repellency, water resistance, fingerprint adhesion resistance, and the like, a fluorene resin having a hydrophobic group, a fluorine resin, or the like is used as a leveling agent (Patent Document 1: Japanese Patent Laid-Open No. 10) -40834, etc.).

In addition, the applicant of the present invention has disclosed that a monofunctional oxime resin monomer and other polyfunctional oxime resins are used in combination to obtain a transparent coating film which is excellent in bleed out and water repellency (Patent Document 2: JP-A-2010- Bulletin No. 126675).

[references]

(Patent Literature)

Patent Document 1: Japanese Patent Laid-Open No. 10-40834

Patent Document 2: Japanese Laid-Open Patent Publication No. 2010-126675

(The subject to be solved by the invention)

However, the conventional method can improve the water repellency, the oil repellency, and the fingerprint adhesion resistance to some extent, but the adhesion to the substrate and the film strength are insufficient, and the water repellency is insufficient.

Further, even if a part of a resin having a hydrophobic group (for example, a fluorine-containing resin) is used, the resins are detached from the transparent coating film (also referred to as precipitation), and sufficient chemical resistance and water resistance cannot be obtained. Properties, water repellency, oil repellency, fingerprint adhesion resistance, etc., even if the above properties are obtained, the situation will be lowered over time.

Further, when the transparent coating film is formed on the TAC substrate, the base material with the transparent coating film is immersed in the alkalizing bath and the alkalizing treatment is performed on the surface of the TAC substrate in order to adhere the paste to the substrate. However, if a part of the conventional polyoxyloxy resin is used as a leveling agent, the leveling agent dissolves and the transparent coating film is whitened, the haze is deteriorated, and the contact angle of the transparent coating film is lowered. And the problem of poor scratch resistance.

Further, when a vinyl resin, an acrylic resin or the fluorine-based resin is used as a leveling agent, compatibility with other matrix forming components may occur, and the obtained transparent coating film may have insufficient hardness.

Further, in Patent Document 2, although the transparency and the haze are improved, the whitening is insufficiently suppressed, and the surface flatness of the transparent coating film is not completely satisfactory.

The present inventors have made an intensive review in view of these problems, and as a result, it has been found that when the modified polyoxynoxy resin matrix component having a molecular weight adjusted to a specific range is used as a leveling agent, it is possible to solve all of the above problems. The transparent coating film was completed, and thus the present invention was completed.

In other words, the object of the present invention is to provide excellent adhesion to a substrate, scratch resistance, film strength, transparency, and the like, and is excellent in chemical resistance and water resistance, and is not whitened and has excellent haze. A coating material for forming a transparent coating film of a transparent coating film and a substrate having a transparent coating film.

[1] A coating liquid for forming a transparent coating film comprising a matrix-forming component, metal oxide fine particles and a solvent, which comprises a fluorene-based resin having an average molecular weight of 5,000 to 30,000 as a leveling agent. And the leveling agent content is in the range of 0.001 to 7.2% by weight in terms of solid content.

[2] The coating liquid for forming a transparent coating film according to [1], wherein the concentration of the matrix-forming component is in the range of 1 to 59.9% by weight in terms of solid content, and the content of the metal oxide fine particles is as described above. The solid content ranges from 0.025 to 48% by weight, and the total solids concentration ranges from 5 to 60% by weight.

[3] The coating liquid for forming a transparent coating film according to the above [1], wherein the metal oxide fine particles are made of cerium oxide, aluminum oxide, titanium oxide, zirconium oxide, or tin oxide. At least one of the formed fine particles is selected from ruthenium pentoxide, indium oxide, and the composite oxide, the metal oxide containing a doping agent, and the composite oxide.

[4] The coating liquid for forming a transparent coating film according to the above [3], wherein the metal oxide fine particles are cerium oxide-based fine particles.

The coating liquid for forming a transparent coating film according to any one of the above aspects, wherein the metal oxide fine particles are surface-treated with an organic cerium compound.

The coating liquid for forming a transparent coating film according to any one of the above aspects, wherein the metal oxide fine particles have an average particle diameter of 5 to 300 nm.

[7] A substrate with a transparent coating film formed by a substrate and a transparent coating film formed on a substrate, the transparent coating film being composed of a matrix component and a metal oxide microparticle. The cerium-based acrylate resin having an average molecular weight of 5,000 to 30,000 is contained as a leveling agent, and the content of the matrix component is in the range of 20 to 99.5% by weight in terms of solid content, and the content of the metal oxide fine particles is in a solid form. It is in the range of 0.5 to 80% by weight.

[8] The substrate with a transparent coating film as described in [7], wherein the leveling agent content in the transparent coating film is in the range of 0.02 to 12% by weight in terms of solid content.

[9] The substrate coated with a transparent coating film according to [7] or [8], wherein the metal oxide fine particles are made of cerium oxide, aluminum oxide, titanium oxide, zirconium oxide, tin oxide, At least one selected from the group consisting of ruthenium pentoxide, indium oxide, and a composite oxide thereof, an oxide containing a dopant, and a composite oxide.

[10] The substrate having a transparent coating film according to any one of [7] to [9] wherein the metal oxide fine particles are cerium oxide-based fine particles.

[11] The substrate having a transparent coating film according to any one of [7] to [10] wherein the metal oxide fine particles are surface-treated with an organic cerium compound.

[12] The substrate with a transparent coating film according to any one of [7] to [11] wherein the metal oxide fine particles have an average particle diameter of 5 to 300 nm.

[13] The substrate with a transparent coating film according to any one of [7] to [12] wherein the contact angle (CA ₁ ) of the transparent coating film is in the range of 60° to 110° The contact angle difference with the contact angle (CA ₂ ) of the surface of the transparent coating film after alkalization is 10° or less.

[14] The substrate having a transparent coating film according to any one of [7] to [13] wherein the transparent coating film has a haze of 1.0% or less.

[15] The substrate having a transparent coating film according to any one of [7], wherein the transparent coating film has a surface roughness (Ra) of 20 nm or less.

(Effect of the invention)

In the present invention, a small amount of a specific range of the molecular weight of the fluorene-based resin matrix component is used in the matrix-forming component, thereby providing adhesion to the substrate, scratch resistance, film strength, transparency, and the like. A coating liquid for forming a transparent coating film and a substrate having a transparent coating film, which are excellent in chemical resistance and water resistance, and which have a flat surface, are smooth, and are not whitened and have excellent haze.

The coating liquid for forming a transparent coating film of the present invention will be described below.

[Coating liquid for forming a transparent coating film]

The coating liquid for forming a transparent coating film of the present invention is composed of a leveling agent, a matrix forming component, metal oxide fine particles, and a solvent.

(leveling agent)

Acrylic resin is used as a leveling agent, and has a function as a leveling agent, and has adhesion to a transparent coating film and a substrate, scratch resistance, film strength, transparency, chemical resistance, water resistance, and dialing. Waterborne, fingerprint-resistant, flat/smooth.

The acrylic ruthenium resin (A) is a polymer of a bifunctional polysiloxane resin represented by the following formula (1), and a monofunctional polyoxane represented by the following (2). The polyoxyalkylene polymer of the polymer is used as a main chain, and two acryloyl or methacrylinyl groups are bonded to the terminal at the terminal via a polyester group.

(Provided that R ₁ to R ₄ represents a hydroxyl group, a substituted or unsubstituted alkyl group of from 1 to 6 carbon atoms, the alkyl group (oxyalkyl), a polyether group (-OR), poly alkyl group ((- (OR n)), alkoxycarbonyl, polyester, polyalkoxycarbonyl, urethane (-CONH-R), polyurethane ((-CONH-R)n-CONH -R), aralkyl; Y, Y ₁ , Y ₂ represents -O-CO-R"-, -CO-OR"-, -(O-CO-R")n-, -(CO-OR" n) (R" is a divalent hydrocarbon group or a direct bond) structure, a polyester group; X, X ₁ , X ₂ represents an acryl fluorenyl group, a methacryl fluorenyl group, and the like may be the same or different. Specific examples of the positive number of 1 to 50 include diacrylate modified polyoxyalkylene, di(methacrylic acid) modified polyoxyalkylene, and the like, and mixtures thereof.

Further, in the present invention, an acrylic fluorene-based resin (B) having a acrylate polymer represented by the following formula (3) as a main chain and a side chain-bonded fluorene oxygen can be used.

(R ₁ or R ₂ is H or CH ₃ ; R ₃ is alkyl, polyester, polyether, polyurethane, aralkyl or a salt; R ₄ is Si-OR', - (Si-O) _n' R' (R is an alkyl group or a hydroxyl group); and is a copolymer of two or more.)

In the present invention, the yttrium acrylate has a weight average molecular weight of 5,000 to 30,000, and a suitable range of 6,000 to 20,000. These molecular weighters have higher leveling agents.

In addition, those having a low molecular weight are not separated (segregated) and are compatible in the coating material, and are dissolved and detached during alkalization treatment or the like after the formation of the coating film to cause whitening, and the contact angle is lowered, and the contact angle is lowered. Obtain sufficient water and water resistance. Even if the average molecular weight is too high, it is substantially incompatible with the coating material, so that the function of the aforementioned leveling agent cannot be obtained. The weight average molecular weight of the matrix-forming components can be determined by a colloidal permeation chromatography (GPC) method using a tetrahydrofuran (THF) solvent, and the molecular weight in terms of polystyrene is determined.

(matrix forming component)

In the present invention, an organic resin matrix is used to form a component as a matrix forming component. Specifically, a conventionally known coating resin may be mentioned, and specific examples thereof include a polyester resin, a polycarbonate resin, a polyamide resin, a polyphenylene oxide resin, a thermoplastic acrylic resin, and a vinyl chloride resin. , thermoplastic resin such as fluororesin, vinyl acetate resin, polyoxyxene rubber; urethane resin, melamine resin, enamel resin, butyral resin, phenol resin, epoxy resin, unsaturated polyester resin A thermosetting acrylic resin, an ultraviolet curable acrylic resin, or the like.

The organic resin matrix forming component specifically includes pentaerythritol triacrylate, trimethylolpropane tri (meth) acrylate, neopentyl alcohol tetraacrylate, and bis (trishydroxyl). In addition to tetrapropyl (meth) acrylate, dipentaerythritol hexaacrylate, etc., diethylaminomethyl methacrylate, dimethylaminomethyl methacrylate, methyl may also be used. Dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxy propyl acrylate Ester, 2-hydroxybutyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-propenyl propyl acrylate, methoxy triethylene glycol bis (methacrylic acid) Methoxytriethylene glycol dimethacryl, butoxydiethylene glycol methacrylate, triethylene glycol diacrylate, 1,6-hexanediol diacrylate, 2-methylpropenyloxy succinate Ester, 2-propenyloxyethyl succinate, 2-propenyloxyethyl butyrate, hexahydrophthalic acid 2-methacryloyloxyethyl acid phosphate, 2-propenyloxyethyl-2-hydroxyethyl phthalate, 2-methacryloyloxyethyl acid phosphate , 2-methylpropenyloxyethyl acid phosphate, 2-propenyloxyethyl acid phosphate, and a mixture thereof, or a hydrophilic organic compound such as a copolymer or a modified product of two or more of these resins a resin-based matrix-forming component; or a polyfunctional (meth)acrylic acid having a hydrophobic functional group such as a vinyl group, a urethane group, an epoxy group, a (meth) acryl fluorenyl group, or a CF ₂ group; Ester resin, specifically, neopentyl alcohol triacrylate, neopentyl alcohol tetraacrylate, trimethylolpropane tri (meth) acrylate, neopentyl alcohol tetraacrylate, bis (trishydroxyl) Propane) tetra(meth)acrylate, dipentaerythritol hexaacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, methacrylic acid 2- Ethylhexyl ester, isodecyl methacrylate, n-dodecyl acrylate, n-octadecyl acrylate, 1,6-hexanediol A hydrophobic organic resin matrix forming component such as a acrylate, perfluorooctyl methacrylate, trifluoroethyl methacrylate, urethane acrylate, or the like, and the like.

In the present invention, an ultraviolet curable resin or an electron beam curable resin is preferred. In the present invention, it is particularly preferred to use an ultraviolet curable resin.

Specific examples of the 6-functional ultraviolet curable resin include dipentaerythritol hexaacrylate; the 4-functional ultraviolet curable resin may be neopentyl alcohol tetraacrylate; and the trifunctional ultraviolet curable resin may be neopentyl alcohol triacrylate. Ester, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, isocyanuric acid acrylate, neopentyl alcohol hexamethylene diisocyanate urethane Ethylene prepolymer (prepolymer); bifunctional ultraviolet curable resin can be exemplified by ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 1,4-butanediol Dimethacrylate, 1,4-hexanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-fluorene Glycol dimethacrylate, glycerin dimethacrylate, 2-hydroxy-3-propenyl propyl methacrylate, triethylene glycol dimethacrylate, neopentyl Alcohol dimethacrylate, 2-methylpropenyloxyethyl acid phosphate, acid 2-phosphate Ethyloxyethyl ester, polypropylene glycol diacrylate, tripropylene glycol diacrylate, tetraethyl stilbene diacrylate, triethylene glycol diacrylate, neopentyl glycol diacrylate, 3-methyl-1,5 - pentanediol diacrylate, 3-methyl-1,7-octanediol diacrylate, 1,6-hexanediol diacrylate, 2-butyl-2-ethyl-1,3-propanediol Diacrylate, 1,9-nonanediol diacrylate, 1,10-nonanediol diacrylate, 2,4-diethyl-1,5-pentanediol diacrylate, dimethylol three Dimethyloltricyclo-decane diacrylate, 2-hydroxy-3-propenyl propyl methacrylate, bisphenol A diacrylate, perfluorooctyl methacrylate, methacrylic acid Fluoroethyl ester and the like and mixtures thereof.

A monomer may be used as the organic resin matrix-forming component, but an oligomer or a polymer of a dimer or more may also be used.

When such an ultraviolet curable resin is used, a transparent coating film excellent in scratch resistance and hardness can be produced in a short period of time.

(metal oxide microparticles)

As the metal oxide fine particles used in the present invention, conventionally known metal oxide fine particles used for the transparent coating film can be used. In the present invention, preferred are cerium oxide, aluminum oxide, titanium oxide, zirconium oxide, tin oxide, antimony pentoxide, indium oxide, and composite oxides thereof, oxides containing dopants, and composite oxides. Select at least one or more.

These particles can be used in consideration of appropriate selection such as refractive index, transparency, and antistatic property of the transparent coating film.

In the present invention, the metal oxide fine particles are preferably cerium oxide fine particles.

The cerium oxide-based fine particles represent particles containing cerium oxide as a main component, and may contain components other than cerium oxide, aluminum oxide, titanium oxide, or the like, without impairing transparency. Further, in the present invention, monodispersed spherical cerium oxide fine particles are preferred. When these particles are used, a transparent coating film excellent in scratch resistance, transparency, haze, and the like can be obtained.

The metal oxide fine particles are preferably surface-treated by an organic cerium compound (also referred to as a decane coupling agent), and the surface treatment method is not particularly limited, and a conventionally known method such as an alcohol dispersion of metal oxide fine particles can be employed. The organic hydrazine compound is added, and if necessary, an organic hydrazine compound such as an acid or a base is hydrolyzed by a catalyst to be hydrolyzed, thereby performing surface treatment.

The metal oxide fine particles surface-treated in this manner are highly dispersed in the organic solvent and the organic resin matrix forming component, and a stable coating liquid can be obtained, and the resulting transparent coating film is resistant to scratches, transparency, haze, and the like. Excellent.

The metal oxide fine particles have an average particle diameter of 5 to 300 nm, preferably more preferably 8 to 200 nm.

When the average particle diameter of the metal oxide fine particles is too low, the particles tend to aggregate and the aggregated particles are less likely to be highly dispersed, and the haze of the obtained transparent coating film may be deteriorated. Even if the average particle diameter of the metal oxide fine particles is too large, the transparency of the transparent coating film may be lowered and the haze may be deteriorated.

(polymerization initiator)

The coating liquid of the present invention may contain a polymerization initiator depending on the matrix forming component used. The polymerization initiator is not particularly limited, and a known one can be used, and examples thereof include bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide and bis(2,6-dimethoxybenzene). 2-Hydroxymethyl-2-methyl-phenyl-2-phenyl-phenyl-2-methyl-phenyl-2-yl-methyl-2-methyl-phenyl -propane-1-ketone), 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-1-[4 -(methylthio)phenyl]-2-(N-morpholinino)-1-one (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one), etc. .

Further, a known component such as a sensitizer or a hardening aid may be contained as necessary.

(solvent)

In the present invention, the above-mentioned matrix-forming component is used as a solvent, and a conventionally known solvent which can dissolve or disperse the polymerization initiator which is used as necessary, and uniformly disperse the aforementioned metal oxide fine particles can be used.

Specific examples thereof include: water; methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofuran methanol, and the like; methyl acetate, ethyl acetate , isopropyl acetate, propyl acetate, isobutyl acetate, butyl acetate, isoamyl acetate, amyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, cyclohexyl acetate, Ethylene glycol monoacetate and other esters; containing glycols such as ethylene glycol and hexanediol; containing diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene a hydrophilic solvent for ethers such as alcohol isopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether; propyl acetate, isobutyl acetate, butyl acetate, acetic acid Isovaleryl ester, amyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, cyclohexyl acetate, ethylene glycol monoacetate, etc.; acetone, methyl ethyl ketone, A Ketones such as isobutyl ketone, butyl methyl ketone, cyclohexanone, methylcyclohexanone, dipropyl ketone, methyl amyl ketone, diisobutyl ketone; non-polar such as toluene Solvent. These may be used alone or in combination of two or more.

(Composition of coating liquid for forming a transparent coating film)

In the coating liquid for forming a transparent coating film, the concentration of the matrix-forming component containing the leveling agent is from 1 to 59.9% by weight, preferably from 2 to 59.4% by weight, based on the solid content. When the matrix forming component in the coating liquid for forming a transparent coating film is small, the amount of the matrix component in the obtained transparent coating film is small, and the content of the metal oxide fine particles is too large, and the scratch resistance may be insufficient. Further, in the case of one application, a transparent film of a thick film may not be formed, and there is a problem that productivity is lowered due to repeated application and drying.

In the coating liquid for forming a transparent coating film, when the matrix forming component is too large, the content of the metal oxide fine particles in the obtained transparent coating film is small, and the adhesion to the substrate is not obtained, and the scratch resistance and strength are sufficiently obtained. Waiting for the situation.

In the coating liquid for forming a transparent coating film, the concentration of the polyacrylic acid of the leveling agent is from 0.001 to 7.2% by weight, preferably from 0.002 to 6% by weight, based on the solid content.

When the concentration of the leveling agent is small, the surface tension of the surface of the coating film cannot be maintained at a low value (high surface tension), surface smoothness is deteriorated, and appearance such as orange peel is poor in the drying step after coating. The situation. Further, the contact angle of the transparent coating film is also lowered, and there is a case where water resistance and water repellency are insufficient. If the leveling agent is too much, the transparent coating film may have insufficient hardness and strength.

In the coating liquid for forming a transparent coating film, the concentration of the metal oxide fine particles is from 0.025 to 48% by weight, preferably from 0.1 to 40% by weight, based on the solid content.

When the amount of the metal oxide fine particles is small, the content of the metal oxide fine particles in the obtained transparent coating film is lowered, and the adhesion to the substrate, the scratch resistance, the film hardness, the film strength, and the like may be insufficient. When the amount of the metal oxide fine particles is too large, the content of the matrix component in the obtained transparent coating film is small, and the adhesion to the substrate and the scratch resistance may be insufficient.

The total solid content of the coating liquid for forming a transparent coating film is from 5 to 60% by mass, preferably from 10 to 50% by weight. When the concentration of the total solid content is small, it is difficult to obtain a transparent coating film having a film thickness of 0.5 μm or more in one application, and if the coating or drying is repeated, the hardness and scratch resistance of the obtained transparent coating film may be obtained. Problems such as insufficientness, haze or appearance deterioration, and productivity. When the concentration of the total solid content is too large, the viscosity of the coating liquid becomes high, and the coating property is lowered, the haze of the obtained transparent coating film is increased, the surface roughness is increased, and the scratch resistance is insufficient.

A method of forming a transparent coating film using the coating liquid for forming a transparent coating film by a dipping method, a spray method, a spinner method, a roll coating method, a bar coating method, a gravure printing method, or a micro gravure printing method It is applied to a substrate and dried by a known method such as a method, and then cured by a usual method such as ultraviolet irradiation or heat treatment to form a transparent coating film.

The film thickness of the transparent coating film to which the transparent coating film is obtained is 0.5 to 20 μm, and the adhesion to the substrate, scratch resistance, film hardness, film strength, transparency, and haze. It is excellent, and the surface is flat and does not whiten even if it is alkalized, and is excellent in water resistance and chemical resistance.

Next, a substrate to which the transparent coating film of the present invention is attached will be described.

[Substrate with transparent coating]

The substrate with a transparent coating film of the present invention is formed of a substrate and a transparent coating film formed on the substrate, and the transparent coating film is formed of a matrix component and metal oxide fine particles.

(substrate)

The substrate to be used in the present invention can be used without any particular limitation, and examples thereof include glass, polycarbonate, acrylic resin, plastic sheets such as PET and TAC, plastic films, and the like, and plastic panels. Among them, a substrate such as polycarbonate, acrylic resin, PET, or TAC, particularly a TAC substrate, dissolves and swells a part of the substrate and enters the transparent coating film to make the interface of the boundary unclear. Therefore, interference fringe can be suppressed, and from this viewpoint, a TAC substrate can be suitably used.

(transparent coating)

The transparent coating film is composed of a matrix component and metal oxide microparticles, and contains a matrix component and a leveling agent.

(matrix composition)

The matrix component corresponds to a hardened substance of the aforementioned matrix forming component. The content of the matrix component in the transparent coating film is from 20 to 99.5% by weight, preferably from 40 to 99% by weight. When the amount of the matrix component is small, the content of the matrix component in the obtained transparent coating film is small, and the scratch resistance is insufficient. When the amount of the matrix component is too large, the content of the metal oxide fine particles in the obtained transparent coating film is small, and the scratch resistance may be insufficient.

(leveling agent)

The leveling agent becomes a cured product in the coating film, and its content is 0.02 to 12% by weight in terms of solid content, and preferably in the range of 0.04 to 10% by weight. When the leveling agent is small, as described above, the surface tension of the surface of the coating film cannot be maintained at a low value (high surface tension), surface smoothness is deteriorated, and appearance of orange peel is generated in the drying step after coating. Bad situation. Further, the contact angle of the transparent coating film is also lowered, and the water resistance is insufficient. If the leveling agent is too much, the transparent coating film may have insufficient hardness and strength.

Further, in the transparent coating film, the cured product of the yttrium yttrium used as the leveling agent is relatively concentrated on at least the upper surface of the transparent coating film, and when the proportion of the cured yttrium resin polymer in the matrix component is large In the transparent coating film, it exists in the form of fine particles, and the hardness and strength of the transparent coating film are insufficient.

When the leveling agent is concentrated on the upper portion, the surface tension of the surface of the coating film can be lowered, so that the surface smoothness is good and uneven appearance is not caused, and the contact angle is increased to obtain a transparent coating film excellent in water resistance.

Further, since the leveling agent has a affinity with the substrate when it is concentrated in the lower portion, it has a function as a wetting agent. Therefore, even if a foreign matter is present on the substrate, it can be covered, and a transparent one which is free from defects such as foreign matter can be obtained. Laminating.

(metal oxide microparticles)

The transparent coating film of the present invention uses the metal oxide fine particles as the metal oxide fine particles.

The content of the metal oxide fine particles in the transparent coating film is from 0.5 to 80% by weight, preferably from 1 to 60% by weight, based on the solid content. When the amount of the metal oxide fine particles is small, the content of the metal oxide fine particles in the transparent coating film is small, so that a remarkable effect of using the metal oxide fine particles cannot be obtained, for example, the transparent coating film is adhered to the substrate. Insufficient circumstances such as sex and film strength.

When the amount of the metal oxide fine particles is too large, the haze and the transparency of the transparent coating film are deteriorated. Further, since the matrix component is small, the adhesion to the substrate, the scratch resistance, and the film strength are insufficient.

The film thickness of the transparent coating film is usually from 0.5 to 30 μm, preferably from 1 to 20 μm. When the thickness of the transparent coating film is small, the scratch resistance is insufficient, and when it is thick, curling occurs due to shrinkage of the film, and the adhesion to the substrate is insufficient.

Since the transparent coating film formed by the present invention is composed of the above-described constituent components, the surface is flat and the surface roughness (Ra) is 20 nm or less. In particular, it is desirable that the Ra of the transparent coating film be 15 nm or less. When the surface roughness (Ra) is within this range, the surface smoothness of the coating film is improved, and the water resistance and water repellency are excellent due to an increase in the contact angle. In addition, the scratch resistance and film hardness are high. The surface roughness (Ra) can be measured by a laser microscope.

Further, the contact angle (CA ₁ ) of the transparent coating film formed by the present invention is in the range of 60 to 110°. The transparent coating film is preferably in the range of 70 to 100°. When the contact angle (CA ₁ ) of the transparent coating film is in this range, the water resistance is high, and if necessary, another transparent coating film can be laminated on the transparent coating film of the present invention, for example, the laminated antireflection film can maintain each other. Adhesion, and scratch resistance, film strength, etc. do not decrease. Further, when the contact angle is outside the above range, the transparent coating film is whitened and the haze is deteriorated, and the scratch resistance is deteriorated.

Further, in the transparent coating film of the present invention, the contact angle difference between the contact angle (CA ₁ ) and the contact angle (CA ₂ ) of the transparent coating film after the alkalizing treatment is 10° or less. In particular, if the difference is below 8°, the effect becomes more remarkable. Further, if the difference in contact angle between the alkalinization treatment is large, the difference in refractive index is small, so that the transparent coating film is whitened, and there are cases where transparency or haze is insufficient.

The contact angle can be determined by a fully automatic contact angle meter (Concord Interface Science: DM700).

Further, the haze of the transparent coating film is 1.0% or less, and particularly preferably 0.8% or less.

When the haze of the transparent coating film is in this range, the transparency is high, and it is excellent in display performance such as contrast, brightness, and fineness when used in a display screen such as a liquid crystal display device.

The adjustment of the surface roughness is adjusted by using the lanthanum-based leveling agent used in the present invention or by changing the amount thereof. The haze can be adjusted by using the lanthanum-based leveling agent used in the present invention or by changing the amount thereof in addition to the particle size and content of the metal oxide fine particles used. The adjustment of the contact angle is adjusted by using the lanthanum-based leveling agent used in the present invention or by changing the amount thereof. The contact angle difference is adjusted by using a lanthanum-based leveling agent which is hardly soluble in a base and is in a range of a specific average molecular weight. In addition, these are not unilaterally adjusted, but are adjusted for each other.

In the present invention as described above, since the matrix component and the leveling agent are made of cerium acrylate having a specific average molecular weight, it is excellent in adhesion to the substrate, scratch resistance, film strength, transparency, etc.; and chemical resistance and water resistance. A substrate with a transparent coating film which is excellent in properties, water repellency, and fingerprint-resistant adhesion, and which has a flat surface, is smooth, and is not whitened and has excellent haze.

The transparent coating film can be produced by applying the coating liquid and curing it.

(Example)

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

[Example 1]

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

The γ-methyl group was mixed with 100 g of a cerium oxide microparticle dispersion (manufactured by Nisko Catalyst Co., Ltd.; OSCAL1432; average particle diameter: 12 nm, SiO ₂ concentration: 30.5 wt%, dispersing medium: isopropyl alcohol, particle refractive index: 1.46). Propylene methoxypropyltrimethoxydecane 4.50 g (manufactured by Shin-Etsu SILICONE Co., Ltd.: KBM-503, SiO ₂ component: 81.2%) and added 3.1 g of ultrapure water, followed by stirring at 50 ° C for 20 hours to obtain a solid fraction A surface-treated cerium oxide microparticle dispersion (1) having a concentration of 30.5% by weight.

Thereafter, the solvent was substituted with propylene glycol monopropyl ether (PGME) by a rotary evaporator to obtain a cerium oxide fine particle PGME dispersion (1) having a solid concentration of 40.5% by weight.

Next, a solid content of 40.5 wt% of cerium oxide microparticles PGME dispersion (1) 51.85 g, dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd.: DPE-6A) 16.80 g, 1,6 - hexanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.: LIGHT ACRYLATE SR-238F) 4.20g, lanthanum acrylate leveling agent (manufactured by Nanben Chemical Co., Ltd.: DISPARLON NSH-8430HF) 0.20g, photopolymerization The starter (manufactured by Ciba Japan Co., Ltd.: Irgacure 184, dissolved in PGME to a solid content of 10%) 12.60 g, PGME 4.35 g, and acetone 10.0 g were mixed well to prepare a transparent coating film having a solid concentration of 42.0% by weight. The coating liquid (1) for formation. At this time, the molecular weight of the leveling agent was measured, and as a result, the average molecular weight was 11,000.

(Manufacture of substrate with transparent coating (1))

The coating liquid for forming a transparent coating film (1) was applied to a TAC film by a bar coating method (#14) (manufactured by PANAC Co., Ltd.: FT-PB80UL-M, thickness: 80 μm, refractive index: 1.51) Then, after drying at 80 ° C for 120 seconds, it was hardened by irradiation with ultraviolet rays of 300 mJ/cm ² to produce a substrate (1) with a transparent coating film. The film thickness of the transparent coating film was 6 μm.

The total light transmittance and haze of the obtained substrate with a transparent coating film were measured by a haze meter (manufactured by Suga Test Instruments Co., Ltd.). Further, the uncoated TAC film had a total light transmittance of 93.2% and a haze of 0.2%.

Further, the adhesion, the alkali resistance, the scratch resistance, the pencil hardness, and the surface roughness were measured and evaluated by the following methods, and the results are shown in the table.

(Evalation of alkali resistance)

Alkalinization test method: The substrate (1) with a transparent coating film was immersed in a 10 wt% aqueous NaOH solution at 40 ° C for 80 seconds. The contact angles (CA ₁ ) and (CA ₂ ) of the surface of the transparent coating film before and after the alkalization test were measured by a fully automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.: DM700), and the contact angle difference was obtained. In the table.

(Measurement of scratch resistance)

Using #0000 steel wool and sliding 10 times at a load of 2 kg/cm ² , the surface of the film was visually observed and evaluated on the following basis. The results are shown in Table 1.

Evaluation criteria:

No strips were confirmed: ◎

A small number of strips were confirmed: ○

A large number of strips were confirmed: △

The whole surface is cut: ╳

(adhesiveness)

On the surface of the substrate (F-1) with the transparent coating film, 11 parallel scratches were cut by a knife at intervals of 1 mm in length and width to make 100 checkerboards, which were then attached to a cellophane tape (registered trademark). Then, the cellophane tape (registered trademark) was peeled off, and the number of cells remaining without being peeled off at this time was classified into the following four stages, thereby evaluating the adhesion. The results are shown in Table 1.

The number of residual cells is 95 or more: ◎

The number of residual cells is 90 to 94: ○

The number of residual cells is 85 to 89: △

The number of residual cells is 84 or less: ╳

(Measurement of pencil hardness)

It was measured by a pencil hardness tester based on JIS-K-5600.

(Measurement of surface roughness)

Determined by laser microscopy

[Embodiment 2]

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

In the first embodiment, a coating liquid (2) for forming a transparent coating film having a solid content concentration of 42.0% by weight was prepared in the same manner except that 0.05 g of a lanthanum-based leveling agent was mixed.

(Manufacture of substrate with transparent coating (2))

In the first embodiment, a substrate (2) having a transparent coating film was produced in the same manner except that the coating liquid (2) for forming a transparent coating film was used. The film thickness of the transparent coating film was 6 μm.

The total light transmittance, haze, adhesion, alkali resistance, scratch resistance, pencil hardness, and surface roughness of the obtained base material with a transparent coating film were measured, and the results are shown in the table.

[Example 3]

(Modulation coating liquid for forming a transparent coating film (3))

In the first embodiment, a coating liquid (3) for forming a transparent coating film having a solid content concentration of 42.0% by weight was prepared in the same manner except that 1.0 g of a lanthanum-based leveling agent was mixed.

(Manufacture of substrate with transparent coating (3))

In the first embodiment, a substrate (3) having a transparent coating film was produced in the same manner except that the coating liquid (3) for forming a transparent coating film was used. The film thickness of the transparent coating film was 6 μm.

The total light transmittance, haze, adhesion, alkali resistance, scratch resistance, pencil hardness, and surface roughness of the obtained base material with a transparent coating film were measured, and the results are shown in the table.

[Example 4]

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

In the same manner as in the first embodiment, a coating liquid for forming a transparent coating film having a solid content concentration of 42.0% by weight was prepared in the same manner except that a fluorene-based leveling agent (DISPARLON NSF-8363, manufactured by Kumoto Chemical Co., Ltd.) was mixed. ). The molecular weight of the leveling agent was measured at this time, and the average molecular weight was 7,500.

(Manufacture of substrate with transparent coating (4))

In the first embodiment, a substrate (4) having a transparent coating film was produced in the same manner except that the coating liquid (4) for forming a transparent coating film was used. The film thickness of the transparent coating film was 6 μm.

The total light transmittance, haze, adhesion, alkali resistance, scratch resistance, pencil hardness, and surface roughness of the obtained base material with a transparent coating film were measured, and the results are shown in the table.

[Example 5] (Preparation of coating liquid for forming a transparent coating film (5))

600 g of pure water was added to 1000 g of cerium oxide microparticle dispersion (manufactured by Nippon Chemical Co., Ltd.: CATALOID SI-50; average particle diameter: 25 nm, dispersion medium: water, SiO ₂ concentration: 48% by weight) The concentration was 336 g of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: DIAION SK1B), and ion exchange was carried out at 80 ° C for 3 hours to obtain a cerium oxide fine particle dispersion (2) having a solid content concentration of 30% by weight.

The cerium oxide microparticle dispersion (2) having a solid concentration of 30% by weight was subjected to solvent substitution by methanol through an ultrafiltration membrane to obtain a cerium oxide microparticle methanol dispersion having a solid concentration of 30% by weight. (2).

Next, γ-methylpropenyloxypropyltrimethoxydecane 4.50g (manufactured by Shin-Etsu SILICONE Co., Ltd.: KBM-503, SiO ₂ component 81.2%) was mixed with 100 g of the cerium oxide microparticle-methanol dispersion (2). Further, 3.1 g of ultrapure water was added, followed by stirring at 50 ° C for 20 hours to obtain a surface-treated cerium oxide fine particle dispersion (2) (solid content concentration: 30.5 wt%).

Thereafter, the solvent was substituted with propylene glycol monomethyl ether (PGM) by a rotary evaporator to obtain a cerium oxide fine particle PGME dispersion (2) having a solid concentration of 40.5% by weight.

Next, in Example 1, a solid content concentration of 42.0% by weight was prepared in the same manner except that the cerium oxide fine particle PGME dispersion (1) having a solid content concentration of 40.5% by weight was replaced by the cerium oxide fine particle PGME dispersion (2). A coating liquid (5) for forming a transparent coating film.

(Manufacture of substrate with transparent coating (5))

In the first embodiment, a substrate (5) having a transparent coating film was produced in the same manner except that the coating liquid (5) for forming a transparent coating film was used. The film thickness of the transparent coating film was 6 μm.

The total light transmittance, haze, adhesion, alkali resistance, scratch resistance, pencil hardness, and surface roughness of the obtained base material with a transparent coating film were measured, and the results are shown in the table.

[Embodiment 6]

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

Adding 333 g of pure water to 1000 g of cerium oxide microparticle dispersion (manufactured by Nippon Chemical Co., Ltd.: CATALOID SI-80P; average particle diameter 80 nm, Sio ₂ concentration: 40% by weight, dispersion medium: water) to adjust the solid content concentration 30% by weight, followed by 336 g of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: DIAION SK1B), ion-exchanged at 80 ° C for 3 hours, and washed to obtain a cerium oxide fine particle dispersion having a solid content concentration of 30% by weight. (3). This dispersion liquid was subjected to solvent replacement with methanol using an ultrafiltration membrane to obtain a cerium oxide microparticle methanol dispersion (3) having a solid concentration of 30% by weight.

Γ-methylpropenyloxypropyltrimethoxydecane 4.50g (manufactured by Shin-Etsu SILICONE Co., Ltd.: KBM-503, SiO ₂ component 81.2%) was added to 100 g of the cerium oxide microparticles methanol dispersion (3) and added. After 3.1 g of ultrapure water, the mixture was stirred at 50 ° C for 20 hours to obtain a surface-treated cerium oxide microparticle-methanol dispersion (3) having a solid concentration of 30.5 wt%.

Thereafter, the solvent was substituted with propylene glycol monopropyl ether (PGME) by a rotary evaporator to obtain a cerium oxide fine particle PGME dispersion (3) having a solid concentration of 40.5% by weight.

Next, in Example 1, a solid content concentration of 42.0% by weight was prepared in the same manner except that the cerium oxide fine particle PGME dispersion liquid (1) having a solid content concentration of 40.5% by weight was replaced by the cerium oxide fine particle PGME dispersion liquid (3). A coating liquid (6) for forming a transparent coating film.

(Manufacture of substrate with transparent coating (6))

In the first embodiment, a substrate (6) having a transparent coating film was produced in the same manner except that the coating liquid for forming a transparent coating film (6) was used. The film thickness of the transparent coating film was 6 μm.

The total light transmittance, haze, adhesion, alkali resistance, scratch resistance, pencil hardness, and surface roughness of the obtained base material with a transparent coating film were measured, and the results are shown in the table.

[Embodiment 7]

(Preparation of coating liquid for forming a transparent coating film (7))

(Modulating P-doped Tin Oxide Particles)

To 8060 g of pure water, 13 g of ammonium nitrate and 20 g of 15% aqueous ammonia were added and stirred, and then the temperature was raised to 50 °C. A liquid in which 1519 g of potassium stannate was dissolved in 4,290 g of pure water was added for 10 hours in a roller pump. At this time, the pH controller was used to adjust the concentration of 10% by weight of nitric acid so that the pH was maintained at 8.8. After the end of the addition, it was maintained at 50 ° C for 1 hour, after which a concentration of 10% by weight of nitric acid was added to lower the pH to 3.0. Subsequently, the membrane was filtered through ultrafiltration, and washed with pure water until the conductivity of the filtered water became 10 μS/cm, and then concentrated by an ultrafiltration membrane and taken out. The amount of liquid taken out at this time was 6000 g and the solid content (SnO ₂ ) concentration was 12% by weight. To the slurry, 264 g of a 16% by weight aqueous phosphoric acid solution was added and stirred for 0.5 hour. It was dried and fired at 700 ° C for 2 hours to prepare P-doped tin oxide fine particles.

The obtained P-doped tin oxide fine particles had an average particle diameter of 15 nm.

(Modifying surface treated P-doped tin oxide fine particle dispersion)

217 g of P-doped tin oxide fine particles and 335 g of ion-exchanged water were placed in a 2 L glass beaker, and 50 g of a 20 wt% aqueous KOH solution was added thereto, and then 1000 g of quartz beads (0.15 mm) was added thereto, and the mixture was thoroughly stirred by a bead mill. After pulverization and dispersion, the quartz beads and the dispersion were separated by a stainless steel metal mesh of 325 mesh (a pore size of 44 μm), and the quartz beads remaining on the metal mesh were washed with 1,560 g of ion-exchanged water and the washed liquid was sufficiently After mixing, the liquid was heat-treated at 90 ° C for 1 hour, and then cooled to room temperature, after which 96 g of an anion exchange resin was added and stirred for 1 hour, after which an anion exchange resin was separated, followed by addition of 96 g of a cation exchange resin and stirring for 1 hour, after which The cationic resin was separated to obtain a P-doped tin oxide fine particle aqueous dispersion (concentration: 10% by weight).

20.8 g of ruthenium ruthenate (ETHYL SILICATE 28, SiO ₂ composition 28.8%) as a coupling agent was added to 2000 g of a P-doped tin oxide fine particle aqueous dispersion having a concentration of 10% by weight (with P-doped tin oxide). The weight ratio of the fine particles = 100 / 3) and 2000 g of methanol, followed by stirring at 50 ° C for 18 hours to carry out surface treatment. Thereafter, the solvent was substituted with ethanol, and a P-doped tin oxide fine particle ethanol dispersion liquid which was surface-treated with a decane coupling material at a concentration of 30% by weight was prepared.

Thereafter, the solvent was substituted with propylene glycol monopropyl ether (PGME) by a rotary evaporator to obtain a P-doped tin oxide fine particle PGME dispersion having a solid concentration of 40.5 wt%.

Next, in Example 1, except that the cerium oxide fine particle PGME dispersion (1) having a solid content concentration of 40.5% by weight was replaced with a P-doped tin oxide fine particle PGME dispersion, a transparent solid concentration of 42.0% by weight was prepared in the same manner. Coating liquid (7) for coating film formation.

(Manufacture of substrate with transparent coating (7))

In the first embodiment, a substrate (7) having a transparent coating film was produced in the same manner except that the coating liquid for forming a transparent coating film (7) was used and coating was carried out using a bar coater #20. The film thickness of the transparent coating film was 6 μm.

The total light transmittance, haze, adhesion, alkali resistance, scratch resistance, pencil hardness, and surface roughness of the obtained base material with a transparent coating film were measured, and the results are shown in the table.

[Comparative Example 1]

(Preparation of coating liquid (R1) for forming a transparent coating film)

In the same manner as in the first embodiment, a coating liquid for forming a transparent coating film having a solid content concentration of 42.0% by weight was prepared in the same manner except that the yttrium-based leveling agent (DISPARLON NSH-8430HF, manufactured by Kumoto Chemical Co., Ltd.) was not mixed. R1).

(Manufacture of substrate (R1) with transparent coating film)

In the first embodiment, a substrate (R1) having a transparent coating film was produced in the same manner except that the coating liquid for forming a transparent coating film (R1) was used. The film thickness of the transparent coating film was 6 μm.

The total light transmittance, haze, adhesion, alkali resistance, scratch resistance, pencil hardness, and surface roughness of the obtained base material with a transparent coating film were measured, and the results are shown in the table.

[Comparative Example 2]

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

In the same manner, a coating liquid for forming a transparent coating film (R2) having a solid content concentration of 42.0% by weight was prepared in the same manner as in Example 1 except that a fluorene-based leveling agent (DISPARLON UVX-271, manufactured by Kumoto Chemical Co., Ltd.) was mixed. ). At this time, the molecular weight of the leveling agent was measured, and as a result, the average molecular weight was 4,000.

(Manufacture of substrate (R2) with transparent coating)

In the first embodiment, a substrate (R2) having a transparent coating film was produced in the same manner except that the coating liquid for forming a transparent coating film (R2) was used. The film thickness of the transparent coating film was 6 μm.

The total light transmittance, haze, adhesion, alkali resistance, scratch resistance, pencil hardness, and surface roughness of the obtained base material with a transparent coating film were measured, and the results are shown in the table.

[Comparative Example 3]

(Preparation of coating liquid (R3) for forming a transparent coating film)

In the same manner, a coating liquid for forming a transparent coating film having a solid content concentration of 42.0% by weight (R3) was prepared in the same manner as in Example 1 except that a fluorene-based leveling agent (DISPARLON UVX-2280, manufactured by Kumoto Chemical Co., Ltd.) was mixed. ). At this time, the molecular weight of the leveling agent was measured, and as a result, the average molecular weight was 35,000.

(Manufacture of substrate (R3) with transparent coating)

In the first embodiment, a substrate (R3) having a transparent coating film was produced in the same manner except that the coating liquid for forming a transparent coating film (R3) was used. The film thickness of the transparent coating film was 6 μm.

The total light transmittance, haze, adhesion, alkali resistance, scratch resistance, pencil hardness, and surface roughness of the obtained base material with a transparent coating film were measured, and the results are shown in the table.

[Comparative Example 4]

(Preparation of coating liquid for forming a transparent coating film (R4))

In Example 1, 37.04 g of a propylene glycol monopropyl ether dispersion of silica sol having a solid content of 40.5 wt% and dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd.: DPE) -6A) 12.00g, dimethylol tricyclodecane diacrylate, 1,6-hexanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.: LIGHT ACRYLATE SR-238F) 3.00g, lanthanum acrylate Leveling agent (manufactured by Kumoto Chemical Co., Ltd.: DISPARLON NSH-8430HF) 30 g, photopolymerization initiator (Irgacure 184, manufactured by Ciba Japan Co., Ltd., dissolved in PGME to a solid concentration of 20%) 4.50 g, PGME 3.46 g In addition, the coating liquid (R4) for forming a transparent coating film having a solid content concentration of 30% by weight was prepared by thoroughly mixing 10.0 g of acetone.

(Manufacture of substrate (R4) with transparent coating)

In the first embodiment, a substrate (R4) having a transparent coating film was produced in the same manner except that the coating liquid for forming a transparent coating film (R4) was used and coating was carried out using a bar coater #20. The film thickness of the transparent coating film was 6 μm.

The total light transmittance, haze, adhesion, alkali resistance, scratch resistance, pencil hardness, and surface roughness of the obtained base material with a transparent coating film were measured, and the results are shown in the table.

Claims (15)

A coating liquid for forming a transparent coating film comprising a matrix forming component, a metal oxide fine particle and a solvent, wherein the matrix forming component is selected from the group consisting of a polyester resin, a polycarbonate resin, a polyamide resin, and a poly a phenylene ether resin, a thermoplastic acrylic resin, a vinyl chloride resin, a fluororesin, a vinyl acetate resin, a thermoplastic resin of a polyoxyxene rubber, a urethane resin, a melamine resin, an anthracene resin, a butyral resin, a phenol resin, An epoxy resin, an unsaturated polyester resin, a thermosetting acrylic resin, or an ultraviolet curable acrylic resin, the coating liquid containing an acrylic resin (A) or an acrylic resin having an average molecular weight of 5,000 to 30,000. (B) The fluorene-based resin (A) is a polymer of a bifunctional polyanthracene resin represented by the following formula (1), and a monofunctional polyoxyl resin represented by the following (2). The polyoxyl polymer of the polymer is used as a main chain, and two acryl fluorenyl groups or methacryl oxime groups are bonded to the terminal at the terminal via a polyester group, and the yttrium acrylate resin (B) is represented by the following formula: (3) expressed Acid polymer as a main chain and a side chain bonded to silicon oxide are polyethylene, leveling agents and tuning range of parts in terms of solid content of 0.001 to 7.2 wt%, the R ₁ to R ₄ represent a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, an oxyalkyl group, a polyether group, a polyoxyalkyl group, an alkoxycarbonyl group, a polyester group, or a polyalkoxy group. a carbonyl group, a urethane group, a polyurethane group or an aralkyl group; Y, Y ₁ , Y ₂ represents -O-CO-R"-, -CO-OR"-, -(O- CO-R")n-, -(CO-OR")n (R" is a divalent hydrocarbon group or a direct bond) structure or a polyester group; X, X ₁ , X ₂ represents an acryloyl group or a methyl group Acryl sulfhydryl, the X, X ₁ , X ₂ may be the same or different; n is a positive number from 1 to 50, Wherein R ₁ or R ₂ is H or CH ₃ ; R ₃ is alkyl, polyester, polyether, polyurethane, aralkyl or a salt; R ₄ is Si-OR' or - (Si-O) _n' R' represents (R' is an alkyl group or a hydroxyl group; n' is a positive number of 1 to 50) and is a copolymer of 2 or more; n is a positive number of 1 to 50. The coating liquid for forming a transparent coating film according to the above aspect, wherein the concentration of the matrix-forming component is in the range of 1 to 59.9% by weight in terms of solid content, and the content of the metal oxide fine particles is solid. In parts ranging from 0.025 to 48% by weight, the total solids concentration is in the range of from 5 to 60% by weight. The coating liquid for forming a transparent coating film according to the above aspect of the invention, wherein the metal oxide fine particles are made of cerium oxide, aluminum oxide, titanium oxide, zirconium oxide, tin oxide, or the like. At least one of the formed fine particles is selected from cerium oxide, indium oxide, and the composite oxide, the metal oxide containing the dopant, and the composite oxide. The coating liquid for forming a transparent coating film according to the third aspect of the invention, wherein the metal oxide fine particles are cerium oxide-based fine particles. The coating liquid for forming a transparent coating film according to the above aspect of the invention, wherein the metal oxide fine particles are surface-treated with an organic cerium compound. The coating liquid for forming a transparent coating film according to the above aspect of the invention, wherein the metal oxide fine particles have an average particle diameter of 5 to 300 nm. A substrate with a transparent coating film formed by a substrate and a transparent coating film formed on a substrate, the transparent coating film being formed of a matrix component and metal oxide microparticles, the matrix The composition is selected from the group consisting of polyester resin, polycarbonate resin, polyamide resin, polyphenylene ether resin, thermoplastic acrylic resin, vinyl chloride resin, fluororesin, vinyl acetate resin, thermoplastic resin of polyoxyethylene rubber, amine A cured product of a urethane resin, a melamine resin, an anthraquinone resin, a butyral resin, a phenol resin, an epoxy resin, an unsaturated polyester resin, a thermosetting acrylic resin, and an ultraviolet curable acrylic resin, the transparent coating The film contains a fluorene-based resin (A) or a fluorene-based resin (B) having an average molecular weight of 5,000 to 30,000 as a leveling agent, and the yttrium-based resin (A) is represented by the following formula (1) A polymer of a bifunctional polyoxyxene resin, a polyfluorene oxide polymer of a polymer of a monofunctional polyoxynated resin represented by the following (2) as a main chain, and a terminal bond at a side chain via a polyester group. Acryl sulfhydryl or methyl In the oxime group, the acrylic fluorene-based resin (B) is an acrylic polymer represented by the following formula (3) as a main chain, and is bonded to a side chain in a side chain, and the content of the matrix component is in terms of a solid content. The content of the metal oxide fine particles in the range of from 20 to 99.5% by weight in the range of from 0.5 to 80% by weight, based on the solid content, R ₁ to R ₄ represent a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, an oxyalkyl group, a polyether group, a polyoxyalkyl group, an alkoxycarbonyl group, a polyester group, or a polyalkoxy group. a carbonyl group, a urethane group, a polyurethane group or an aralkyl group; Y, Y ₁ , Y ₂ represents -O-CO-R"-, -CO-OR"-, -(O- CO-R")n-, -(CO-OR")n (R" is a divalent hydrocarbon group or a direct bond) structure or a polyester group; X, X ₁ , X ₂ represents an acryloyl group or a methyl group Acryl sulfhydryl, the X, X ₁ , X ₂ may be the same or different; n is a positive number from 1 to 50, Wherein R ₁ or R ₂ is H or CH ₃ ; R ₃ is alkyl, polyester, polyether, polyurethane, aralkyl or a salt; R ₄ is Si-OR' or - (Si-O) _n' R' represents (R' is an alkyl group or a hydroxyl group; n' is a positive number of 1 to 50) and is a copolymer of 2 or more; n is a positive number of 1 to 50. The substrate with a transparent coating film according to claim 7, wherein the leveling agent content in the transparent coating film is in the range of 0.02 to 12% by weight in terms of solid content. The substrate with a transparent coating film according to claim 7 or 8, wherein the metal oxide fine particles are made of cerium oxide, aluminum oxide, titanium oxide, zirconium oxide, tin oxide, or the like. At least one of cerium oxide, indium oxide, and a composite oxide thereof, an oxide containing a dopant, and a composite oxide is selected. The base material with a transparent coating film as described in claim 7 or 8, wherein the metal oxide fine particles are ceria-based fine particles. The substrate with a transparent coating film according to Item 7 or Item 8, wherein the metal oxide fine particles are surface-treated with an organic cerium compound. The substrate having a transparent coating film according to Item 7 or Item 8, wherein the metal oxide fine particles have an average particle diameter of 5 to 300 nm. The substrate with a transparent coating film as described in claim 7 or 8, wherein the transparent coating film has a contact angle (CA ₁ ) in the range of 60° to 110°, and The contact angle (CA ₂ ) of the surface of the transparent coating film after alkalizing treatment has a contact angle difference of 10° or less. The substrate having a transparent coating film according to the seventh or eighth aspect of the invention, wherein the transparent coating film has a haze of 1.0% or less. The substrate having a transparent coating film according to the seventh or eighth aspect of the invention, wherein the transparent coating film has a surface roughness (Ra) of 20 nm or less.