JP2012140533A - Coating liquid for forming transparent film and base material with transparent film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating liquid for forming a transparent film having high flatness and excellent whitening, water, and chemical resistances etc., and to provide a base material with the transparent film.SOLUTION: There is provided the coating liquid for forming the transparent film including a matrix-forming component; metal oxide fine particles; and a solvent. The coating liquid contains an acrylic silicone-based resin having an average molecular weight within the range of 5,000-30,000 as a leveling agent, and the content of the leveling agent is within the range of 0.001-7.2 wt.% in terms of solids. The base material with the transparent film includes the base material and transparent film formed on the base material. The transparent film includes the matrix component and metal oxide fine particles, and further contains the acrylic silicone-based resin having an average molecular weight within the range of 5,000-30,000 as the leveling agent. The content of the matrix component is within the range of 20-99.5 wt.% in terms of the solids, and the content of the metal oxide fine particles is within the range of 0.5-80 wt.% in terms of the solids.

Description

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

  It is known to form a transparent film having a hard coat function on the surface of a substrate in order to improve the scratch resistance of a substrate surface such as glass, a plastic sheet, or a plastic lens, or a display device. Specifically, an organic resin film or an inorganic film having transparency is formed on the surface of glass, plastic, a display device substrate or the like. At this time, inorganic particles such as resin particles or silica are blended in the organic resin film or inorganic film to further improve the adhesion to the substrate, scratch resistance, and the like.

  However, the transparent coating is required to have chemical resistance, water resistance, water repellency, fingerprint resistance and the like in addition to transparency, adhesion to a substrate, film strength, scratch resistance, and the like. For example, when water droplets adhere, there are no traces of water droplets (water resistance), water pens, oil pens, etc. are difficult to scribble, and even if scribbled, they can be easily wiped off (water resistance, water repellency, water repellency) Furthermore, there is a demand for fingerprints that are difficult to adhere to even when touched by a finger, and that they can be easily wiped off (fingerprint resistance).

  In order to impart such water repellency, oil repellency, water resistance, fingerprint resistance, etc., use of a silicon-based resin having a hydrophobic group, a fluorine-containing resin, etc. as a leveling agent has been carried out (patents). Document 1: Japanese Patent Laid-Open No. 10-40834).

  Further, the applicant of the present application discloses that when a one-functional silicone resin monomer is used in combination with another polyfunctional silicone resin, a transparent coating excellent in water repellency and the like can be obtained without the above-mentioned bleed-out. (Patent Document 2: JP 2010-126675 A)

Japanese Patent Laid-Open No. 10-40834 JP 2010-126675 A

  However, although the conventional methods can improve the water repellency, oil repellency and fingerprint resistance to some extent, the adhesion to the substrate, the film strength may be insufficient, or the water repellency may be insufficient. It was.

  In addition, even if a resin having a hydrophobic group, for example, a fluorine-containing resin is used in combination, these resins are detached from the transparent film (called bleed out), and have sufficient chemical resistance and water resistance. In some cases, water repellency, oil repellency, fingerprint adhesion resistance, etc. could not be obtained, or even if obtained, performance deteriorated over time.

  Further, when a transparent film is formed on the TAC substrate, the surface of the TAC substrate is saponified by immersing the substrate with the transparent film in a saponification bath in order to adhere the adhesive paste. Problems such as when the silicone resin is partially blended and used as a leveling agent, the leveling agent dissolves, the transparent coating whitens and haze deteriorates, or the contact angle of the transparent coating decreases and scratch resistance deteriorates. was there.

  In addition, when a vinyl resin, an acrylic resin, or the fluororesin is used as a leveling agent, there may be a problem in compatibility with other matrix forming components, or the resulting transparent film may have insufficient hardness. It was.

  In Patent Document 2, although transparency and haze are improved, whitening is not sufficiently suppressed, and the flatness of the surface of the transparent film is not always satisfactory.

  As a result of intensive studies in view of such problems, the present inventors have used a modified silicone resin matrix component whose molecular weight has been adjusted to a predetermined range as a leveling agent, and used it as a leveling agent. As a result, the present invention has been completed.

That is, in the present invention, a transparent film having excellent adhesion to the substrate, scratch resistance, film strength, transparency and the like, as well as excellent chemical resistance and water resistance, and excellent haze without whitening is formed. An object of the present invention is to provide a coating material for forming a transparent film and a substrate with a transparent film.
[1] A coating solution for forming a transparent film comprising a matrix-forming component, metal oxide fine particles, and a solvent,
Transparent, characterized in that it contains an acrylic silicone resin having an average molecular weight in the range of 5,000 to 30,000 as the leveling agent, and the content of the leveling agent in the range of 0.001 to 7.2% by weight as a solid content Coating liquid for film formation.
[2] The concentration of the matrix-forming component is in the range of 1 to 59.9% by weight as the solid content, and the content of the metal oxide fine particles is in the range of 0.025 to 48% by weight as the solid content. The coating solution for forming a transparent film according to [1], wherein the concentration of is in the range of 5 to 60% by weight.
[3] The metal oxide fine particles include silica, alumina, titanium oxide, zirconium oxide, tin oxide, antimony pentoxide, indium oxide and a composite oxide thereof, and the metal oxide and a composite oxide thereof containing a doping agent. The coating liquid for forming a transparent film according to [1] or [2], which is fine particles comprising at least one selected from
[4] The coating liquid for forming a transparent film according to [3], wherein the metal oxide fine particles are silica-based fine particles.

[5] The coating solution for forming a transparent film according to [1] to [4], wherein the metal oxide fine particles are surface-treated with an organosilicon compound.
[6] The coating liquid for forming a transparent film according to [1] to [5], wherein the metal oxide fine particles have an average particle diameter in the range of 5 to 300 nm.
[7] Consists of a base material and a transparent film formed on the base material, the transparent film is composed of a matrix component and metal oxide fine particles, and has an average molecular weight in the range of 5,000 to 30,000. An acrylic silicon resin is included as a leveling agent, the content of the matrix component is in the range of 20 to 99.5% by weight as the solid content, and the content of the metal oxide fine particles is 0.5 to 5% as the solid content. A substrate with a transparent coating in the range of 80% by weight.
[8] The substrate with a transparent coating according to [7], wherein the leveling agent content in the transparent coating is in the range of 0.02 to 12% by weight as a solid content.

[9] The metal oxide fine particles are at least one selected from silica, alumina, titania, zirconia, tin oxide, antimony pentoxide, indium oxide and complex oxides thereof, oxides containing doping agents, and complex oxides. [7] or [8] is a substrate with a transparent coating.
[10] The transparent film-coated substrate according to [7] to [9], wherein the metal oxide fine particles are silica-based fine particles.
[11] The substrate with a transparent coating according to [7] to [10], wherein the metal oxide fine particles are surface-treated with an organosilicon compound.
[12] The substrate with a transparent coating according to [7] to [11], wherein the metal oxide fine particles have an average particle diameter in the range of 5 to 300 nm.
[13] The contact angle (CA ₁ ) of the transparent coating is in the range of 60 to 110 °, and the contact angle difference from the contact angle (CA ₂ ) after saponifying the surface of the transparent coating is 10 ° or less. A base material with a transparent coating film according to any one of [7] to [12].
[14] The substrate with a transparent coating according to [7] to [13], wherein the haze of the transparent coating is 1.0% or less.
[15] The substrate with a transparent coating according to [7] to [14], wherein the transparent coating has a surface roughness (Ra) of 20 nm or less.

  In the present invention, a small amount of an acrylic silicon-based resin matrix component having a molecular weight within a predetermined range is used in the matrix-forming component, thereby providing excellent adhesion to the substrate, scratch resistance, film strength, transparency, and chemical resistance. It is possible to provide a coating liquid for forming a transparent film and a substrate with a transparent film for forming a transparent film excellent in heat resistance and water resistance, having a flat, smooth surface and having no haze.

Hereinafter, first, the coating liquid for forming a transparent film according to the present invention will be described.
[Transparent coating solution]
The coating liquid for forming a transparent film according to the present invention comprises a leveling agent, a matrix forming component, metal oxide fine particles, and a solvent.

Leveling agent Acrylic silicon resin is used as a leveling agent and functions as such leveling agent. Adhesion with substrate, scratch resistance, film strength, transparency, chemical resistance, water resistance, water repellency, fingerprint resistance And has a function of imparting flatness and smoothness to the transparent film.

  Acrylic silicon is composed of a bifunctional silicone resin polymer represented by the following formula (1), a silicone polymer that is a monofunctional silicone resin polymer represented by the following formula (2) as a main chain, and a polyester group in the side chain. An acrylic silicon resin (A) in which two acrylic groups or methacrylic groups are bonded to the terminal via the terminal.

（但し、Ｒ₁〜Ｒ₄は、水酸基、置換、非置換の炭素数１〜６のアルキル基、オキシアルキル基、ポリエーテル基(-O-R)、ポリオキシアルキル基（(-(O-R)n)、アルキルオキシカルボニル基、ポリエステル基、ポリアルキルオキシカルボニル基、ウレタン基（-CONH-R）、ポリウレタン基（(-CONH-R)n-CONH-R）、アラルキル基、Ｙ、Ｙ₁、Ｙ₂は、-O-CO-R"-、-CO-O-R"-、-(O-CO-R")n-、-(CO-O-R")n-（R"は２価の炭化水素基、または直接結合）であらわされる構造、ポリエステル基、Ｘ、Ｘ₁、Ｘ₂はアクリル基、メタクリル基を表し、同じであってもよく、異なっていてもよい。ｎは１〜５０の正数）

(However, R _{1 to} R ₄ are a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, an oxyalkyl group, a polyether group (—OR), a polyoxyalkyl group ((— (OR) n) , Alkyloxycarbonyl group, polyester group, polyalkyloxycarbonyl group, urethane group (-CONH-R), polyurethane group ((-CONH-R) n-CONH-R), aralkyl group, Y, Y ₁ , Y ₂ -O-CO-R "-, -CO-OR"-,-(O-CO-R ") n-,-(CO-OR") n- (R "is a divalent hydrocarbon group, Or a structure represented by a direct bond), a polyester group, X, X ₁ and X ₂ represent an acryl group and a methacryl group, and may be the same or different. N is a positive number of 1 to 50)

Specific examples include diacrylate-modified polysiloxane, dimethacryl-modified polysiloxane, and the like, and mixtures thereof.
In the present invention, an acrylic silicon resin (B) in which an acrylic polymer represented by the following formula (3) is a main chain and silicone is bonded to a side chain can also be used.

（但し、Ｒ₁又はＲ₂はＨまたはＣＨ₃、Ｒ₃はアルキル基、ポリエステル基、ポリエーテル基、ポリウレタン基、アラルキル基、または塩、Ｒ₄はＳｉ−ＯＲ'、−(Ｓｉ−Ｏ)_n'Ｒ'（Ｒはアルキル基ないし水酸基）であり、２つ以上のコポリマーである。）

(However, R ₁ or R ₂ is H or CH ₃ , R ₃ is an alkyl group, polyester group, polyether group, polyurethane group, aralkyl group, or 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, it is preferable that such acrylic silicon has a weight average molecular weight in the range of 5,000 to 30,000, more preferably 6,000 to 20,000. Such molecular weight has a high function as a leveling agent.

  Those with low molecular weights are not separated (unevenly distributed) in the paint and are compatible, and when the film is formed and then saponified, it dissolves and desorbs, whitens, and the contact angle decreases. In some cases, sufficient water repellency and water resistance cannot be obtained. Even if the average molecular weight is too high, the function as the leveling agent may not be obtained because it is not substantially compatible in the paint. The weight average molecular weight of such a matrix-forming component can be measured by a gel permeation (GPC) method using a tetrahydrofuran (THF) solvent and can be obtained as a polystyrene-converted molecular weight.

Matrix-forming component In the present invention, an organic resin matrix-forming component is used as the matrix-forming component. Specific examples include conventionally known paint resins, such as polyester resins, polycarbonate resins, polyamide resins, polyphenylene oxide resins, thermoplastic acrylic resins, vinyl chloride resins, fluororesins, vinyl acetate resins, silicone rubbers, and the like. And thermoplastic resins, urethane resins, melamine resins, silicon resins, butyral resins, phenol resins, epoxy resins, unsaturated polyester resins, thermosetting acrylic resins, and ultraviolet curable acrylic resins.

Specific examples of organic resin-based matrix forming components include pentaerythritol triacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexaacrylate, and the like. Methyl methacrylate, dimethylaminomethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-acryl Iroxypropyl acrylate, methoxytriethylene glycol dimethacrylate, butoxydiethylene glycol methacrylate, triethylene glycol diacrylate, 1.6-hexanediol diacrylate, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl succinic acid, 2 -Acryloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid, 2-methacryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate , 2-Acroyloxyethyl acid phosphate, and mixtures thereof, or formation of hydrophilic organic resin matrix such as two or more copolymers or modified products of these resins Min, or a vinyl group, a urethane group, an epoxy group, (meth) acryloyl group, a polyfunctional (meth) acrylic acid ester resins. Having a hydrophobic functional group such as CF ₂ group, specifically pentaerythritol triacrylate , Pentaerythritol tetraacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexaacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl Metecrylate, isodecyl metecrylate, n-lauryl acrylate, n-stearyl acrylate, 1,6-hexanediol dimethacrylate, par Hydrophobic organic resin matrix forming components such as fluorooctylethyl methacrylate, trifluoroethyl methacrylate, urethane acrylate, and the like, and mixtures thereof can also be used.

In the present invention, among them, an ultraviolet curable resin or an electron beam curable resin is preferable.
In particular, it is preferable to use an ultraviolet curable resin in the present invention.
Specifically, as hexafunctional ultraviolet curable resin, dipentaerythritol hexaacrylate, as tetrafunctional ultraviolet curable resin, pentaerythritol tetraacrylate, as trifunctional ultraviolet curable resin, pentaerythritol triacrylate, trimethylolpropane trimethacrylate, trimethylol. Propane triacrylate, isocyanuric acid triacrylate, pentaerythritol hexamethylene diisocyanate urethane prepolymer, bifunctional UV curable resin, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 1,4 butanediol dimethacrylate Crate, 1,4 hexanediol dimethacrylate, 1,6 hexanediol dimethacrylate, 1,9 nonanediol Methacrylate, 1,10 decanediol dimethacrylate, glycerin dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate, polypropylene glycol diacrylate, tripropylene glycol diacrylate, tetraethylene 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-2ethyl-1,3-propane All diacrylate, 1,9 nonanediol diacrylate, 1,10 decanediol diacrylate, 2,4-diethyl-15-pentanediol diacrylate, dimethylol-tricyclodecane diacrylate, 2-hydroxy-3 acryloyloxypropyl Examples include methacrylate, bisphenol A diacrylate, perfluorooctylethyl methacrylate, trifluoroethyl methacrylate, and the like, and mixtures thereof.

A monomer can be used as the organic resin matrix-forming component, but an oligomer or polymer of a dimer or higher can also be used.
When such an ultraviolet curable resin is used, a transparent film excellent in scratch resistance, hardness, and the like can be produced in a short time.

Metal Oxide Fine Particles As the metal oxide fine particles used in the present invention, conventionally known metal oxide fine particles generally used for transparent coatings can be used. In the present invention, at least one selected from silica, alumina, titania, zirconia, tin oxide, antimony pentoxide, indium oxide and complex oxides thereof, oxides containing a doping agent, and complex oxides is preferable.

These particles can be appropriately selected and used in consideration of the refractive index, transparency, antistatic performance and the like of the transparent coating.
In the present invention, the metal oxide fine particles are preferably silica-based fine particles.

  The silica-based fine particles mean particles containing silica as a main component, and may contain components other than silica, such as alumina and titania, as long as transparency is not impaired. Furthermore, monodispersed spherical silica fine particles are preferred in the present invention. When such particles are used, a transparent film excellent in scratch resistance, transparency, haze and the like can be obtained.

  The metal oxide fine particles are preferably surface-treated with an organosilicon compound (sometimes referred to as a silane coupling agent), and the surface treatment method is not particularly limited, and a conventionally known method can be employed. Surface treatment can be performed by adding an organosilicon compound to an alcohol dispersion of fine oxide particles, and adding and hydrolyzing an organosilicon compound hydrolysis catalyst such as acid or alkali as necessary.

  The surface-treated metal oxide fine particles are highly dispersed in an organic solvent and an organic resin matrix-forming component, and a stable coating solution can be obtained. The resulting transparent coating has excellent scratch resistance, transparency, haze, etc. Are better.

The average particle diameter of the metal oxide fine particles is preferably in the range of 5 to 300 nm, more preferably 8 to 200 nm.
If the average particle size of the metal oxide fine particles is too low, the particles are likely to aggregate, and it becomes difficult to highly disperse the aggregated particles, and the haze of the obtained transparent film may be deteriorated. Even if the average particle diameter of the metal oxide fine particles is too large, the transparency of the transparent film may be lowered and 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. As the polymerization initiator, known ones can be used without particular limitation. For example, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) 2, 4,4-trimethyl-pentylphosphine oxide, 2-hydroxy-methyl-2-methyl-phenyl-propane-1-ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy- Examples include cyclohexyl-phenyl-ketone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one.
Moreover, well-known components, such as a sensitizer and a hardening adjuvant, may be contained as needed.

Solvent As the solvent used in the present invention, a conventionally known solvent that can dissolve or disperse the matrix-forming component and, if necessary, the polymerization initiator and can uniformly disperse the metal oxide fine particles can be used.

Specifically, water; methanol, ethanol, propanol, 2-propanol (IPA),
Alcohols such as butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol; methyl acetate, ethyl acetate, isopropyl, acetate, isobutyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, 3-methoxybutyl acetate, acetic acid Esters such as 2-ethylbutyl, cyclohexyl acetate, ethylene glycol monoacetate, glycols such as ethylene glycol, hexylene glycol; diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol isoprene Pill ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol Hydrophilic solvents including ethers such as rumonomethyl ether and purpylene glycol ethyl ether, propyl acetate, isobutyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, cyclohexyl acetate, ethylene Esters such as glycol acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methyl cyclohexanone, dipropyl ketone, methyl pentyl ketone, and diisobutyl ketone; polar solvents such as toluene. These may be used singly or in combination of two or more.

Composition of the coating solution for forming a transparent coating The concentration of the matrix-forming component containing the leveling agent in the coating solution for forming the transparent coating is in the range of 1 to 59.9% by weight, more preferably 2 to 59.4% by weight, as a solid content. It is preferable. When there are few matrix formation components in the coating liquid for transparent film formation, there are few matrix components in the obtained transparent film, content of metal oxide microparticles will increase too much, and scratch resistance may become inadequate. In addition, there is a case where a thick transparent film cannot be formed by a single application, and there is a problem that productivity is lowered because it requires repeated application and drying.

  Even if there are too many matrix forming components in the coating liquid for forming a transparent film, the content of the metal oxide fine particles in the resulting transparent film is reduced, and adhesion to the substrate, sufficient scratch resistance, strength, etc. It may not be obtained.

The concentration of the acrylic silicone as the leveling agent in the coating solution for forming a transparent coating is preferably in the range of 0.001 to 7.2% by weight, more preferably 0.002 to 6% by weight as the solid content.
If the concentration of the leveling agent is low, the surface tension of the coating film surface cannot be kept low in the drying process after coating (surface tension becomes high), the surface smoothness is poor, and the appearance failure such as orange peel is poor. May occur. In addition, the contact angle of the transparent coating may be lowered, resulting in insufficient water resistance and water repellency. Even if there are too many leveling agents, the hardness and strength of the transparent film may be insufficient.

The concentration of the metal oxide fine particles in the coating solution for forming a transparent film is preferably in the range of 0.025 to 48% by weight, more preferably 0.1 to 40% by weight as the solid content.
If the amount of metal oxide fine particles is small, the content of metal oxide fine particles in the resulting transparent film is reduced, and adhesion to the substrate, scratch resistance, film hardness, film strength, etc. may be insufficient. . Even if there are too many metal oxide fine particles, the content of the matrix component in the resulting transparent film is reduced, and adhesion to the substrate and scratch resistance may be insufficient.

  The total solid concentration of the coating solution for forming a transparent film is preferably in the range of 5 to 60% by weight, more preferably 10 to 50% by weight. If the total solid content is low, it may be difficult to obtain a transparent film having a film thickness of 0.5 μm or more by a single application, and if repeated application and drying are repeated, the hardness and scratch resistance of the resulting transparent film May be insufficient, haze or appearance may deteriorate, and productivity may be a problem. Even if the total solid content is too high, the viscosity of the coating solution increases, the coating property decreases, the haze of the resulting transparent film increases, the surface roughness increases, and the scratch resistance becomes insufficient. There is a case.

  The method for forming a transparent film using such a coating solution for forming a transparent film is a known method such as 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. A transparent film can be formed by applying to a substrate, drying, and then curing by an ordinary method such as ultraviolet irradiation or heat treatment.

The film thickness of the transparent film of the obtained substrate with a transparent film is in the range of 0.5 to 20 μm and is excellent in adhesion to the substrate, scratch resistance, film hardness, film strength, transparency, haze and the like. It has a flat surface, does not whiten even after saponification, and has excellent water resistance and chemical resistance.
Below, the base material with a transparent film which concerns on this invention is demonstrated.

[Base material with transparent film]
The substrate with a transparent coating according to the present invention comprises a substrate and a transparent coating formed on the substrate, and the transparent coating comprises a matrix component and metal oxide fine particles.

Substrate As the substrate used in the present invention, known materials can be used without particular limitation, and examples thereof include glass, polycarbonate, acrylic resin, plastic sheets such as PET and TAC, plastic films, and plastic panels. It is done. Among them, substrates such as polycarbonate, acrylic, PET, and TAC, especially TAC substrates, partially dissolve or swell the substrate, the transparent coating components enter each other, and the interface at the boundary becomes unclear. It can be suitably used in that it can be suppressed.

Transparent coating The transparent coating consists of a matrix component and metal oxide fine particles, and contains a matrix component and a leveling agent.

Matrix component The matrix component corresponds to the cured product of the matrix-forming component described above. The content of the matrix component in the transparent coating is preferably in the range of 20 to 99.5% by weight, more preferably 40 to 99% by weight. When the amount of the matrix component is small, the content of the matrix component in the obtained transparent film is decreased, and the scratch resistance may be insufficient. Even if there are too many matrix components, the content of the metal oxide fine particles in the resulting transparent film is reduced, and the scratch resistance may be insufficient.

Leveling agent The leveling agent is a cured product in the film, and the content thereof is preferably in the range of 0.02 to 12% by weight, more preferably 0.04 to 10% by weight as the solid content. If the leveling agent is small, as described above, the surface tension of the coating film cannot be kept low in the drying process after coating (the surface tension becomes high), the surface smoothness is poor, and the appearance such as orange peel is poor. May occur. In addition, the contact angle of the transparent coating may be lowered and water resistance may be insufficient. Even if there are too many leveling agents, the hardness and strength of the transparent coating may be insufficient.

  In the transparent film, the cured product of acrylic silicon used as a leveling agent is relatively unevenly distributed at least on the upper surface of the transparent film, and there is a large proportion of the cured product of the acrylic silicon resin polymer in the matrix component. It may exist in a fine particle state in the transparent film, and the hardness and strength of the transparent film may be insufficient.

  If the leveling agent is unevenly distributed at the top, the surface tension of the coating film surface can be reduced, so that the surface smoothness is good and the appearance unevenness does not occur, and the contact angle is also high and the water resistance is excellent. A transparent film can be obtained.

  Also, if the leveling agent is unevenly distributed in the lower part, it acts as a wetting agent because it has an affinity with the base material, so that it can cover even if there is a foreign substance on the base material. It is possible to obtain a transparent film free from defects due to the above.

Metal oxide fine particles The metal oxide fine particles described above are used as the metal oxide fine particles used in the transparent film of the present invention.

  The content of the metal oxide fine particles in the transparent coating is preferably in the range of 0.5 to 80% by weight, more preferably 1 to 60% by weight as the solid content. When the metal oxide fine particles are small and the content of the metal oxide fine particles in the transparent film is small, the remarkable effect of using the metal oxide fine particles cannot be obtained. Properties and film strength may be insufficient.

  Even if there are too many metal oxide fine particles, the haze and transparency of the transparent coating may be deteriorated, and the adhesion to the substrate, scratch resistance, and film strength are insufficient due to the small amount of matrix components. There is.

  Usually, it is preferable that the film thickness of a transparent film exists in the range of 0.5-30 micrometers, and also 1-20 micrometers. If the film thickness of the transparent coating is thin, the scratch resistance may be insufficient, and if it is too thick, curling may occur due to film shrinkage or adhesion to the substrate may be insufficient.

  Since the transparent film formed in 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, as a transparent film, Ra is desirably 15 nm or less. When the surface roughness (Ra) is in this range, the surface smoothness of the coating film is high and the contact angle is high, so that the water resistance and water repellency are excellent. In addition, scratch resistance and film hardness are high. Such surface roughness (Ra) can be measured by a laser microscope.

Further, the contact angle (CA ₁ ) of the transparent film formed in the present invention is in the range of 60 to 110 °.
The transparent film is preferably in the range of 70 to 100 °. If the contact angle (CA ₁ ) of the transparent film is within this range, the water resistance is high, and when necessary, when another transparent film, for example, an antireflection film is laminated on the transparent film of the present invention, The adhesiveness of the film can be maintained, and the scratch resistance, film strength, etc. are not lowered. On the other hand, if the contact angle is out of the above range, the transparent film may be whitened and haze may be deteriorated or scratch resistance may be deteriorated.

In the transparent coating of the present invention, the contact angle difference between the contact angle (CA ₁ ) and the contact angle (CA ₂ ) after the transparent coating is saponified is 10 ° or less. In particular, when the difference is 8 ° or less, the effect becomes more remarkable. In addition, if the contact angle difference is large before and after the saponification treatment, if the refractive index difference is small in this way, whitening of the transparent coating proceeds, and transparency, haze, and the like may be insufficient.

The contact angle can be measured with a fully automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd .: DM700).
The haze of the transparent film is 1.0% or less, and particularly preferably 0.8% or less.

  If the haze of the transparent coating is in this range, the transparency is high, and when used as an optical thin film, for example, a display screen such as a liquid crystal display device, the display performance such as contrast, brightness, and definition is excellent. .

  In order to adjust the surface roughness, the surface roughness is adjusted by using the acrylic silicon leveling agent used in the present invention and changing the amount thereof. In order to adjust the haze, in addition to the particle diameter and content of the metal oxide fine particles to be used, the haze is adjusted by changing the amount and use of the acrylic silicon leveling agent used in the present invention. To adjust the contact angle: Use the acrylic silicon leveling agent used in the present invention and adjust the amount used. In order to adjust the contact angle difference, an acrylic silicon leveling agent in the range of a predetermined average molecular weight that is difficult to dissolve in alkali is used. In addition, these are not adjusted uniquely and are adjusted mutually.

As described above, in the present invention, since acrylic silicon having a predetermined average molecular weight is used as a leveling agent together with a matrix component, it has excellent adhesion to a substrate, scratch resistance, film strength, transparency, and chemical resistance, It is possible to provide a substrate with a transparent coating that is excellent in water resistance, water repellency, and fingerprint resistance, has a flat surface, is smooth and has no haze, and has excellent haze.
Such a transparent film can be produced by applying the above-described coating solution and curing it.

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by these Examples.

[Example 1]
Preparation of coating liquid (1) for forming transparent film Silica fine particle dispersion (manufactured by JGC Catalysts & Chemicals Co., Ltd .; OSCAL1432; average particle diameter 12 nm, SiO ₂ concentration 30.5% by weight, dispersion medium: isopropanol, particle refractive index 1.46) 100 g is mixed with 4.50 g of γ-methacrylooxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicon Co., Ltd .: KBM-503, SiO ₂ component 81.2%) and 3.1 g of ultrapure water is added. The mixture was stirred at 50 ° C. for 20 hours to obtain a surface-treated silica fine particle dispersion (1) having a solid concentration of 30.5% by weight.

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

  Next, 51.85 g of a silica fine particle PGME dispersion (1) having a solid content concentration of 40.5% by weight, 18.80 g of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: DPE-6A), and 1.6- 4.20 g of hexanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate SR-238F), 0.20 g of acrylic silicon leveling agent (manufactured by Enomoto Kasei Co., Ltd .: Disparon NSH-8430HF) and photopolymerization initiator (Ciba Japan Co., Ltd .: Irgacure 184, dissolved in PGME to a solid content concentration of 10%) 12.60 g, 4.35 g of PGME and 10.0 g of acetone were thoroughly mixed to form a transparent film with a solid content concentration of 42.0 wt% A coating solution (1) was prepared. At this time, as a result of measuring the molecular weight of the leveling agent, the average molecular weight was 11,000.

Production of substrate with transparent film (1) The coating liquid for forming a transparent film (1) was placed on a TAC film (manufactured by Panac Corporation: FT-PB80UL-M, thickness: 80 μm, refractive index: 1.51). After coating by the coater method (# 14) and drying at 80 ° C. for 120 seconds, a substrate with a transparent coating (1) was produced by irradiating with 300 mJ / cm ² of ultraviolet rays and curing. The film thickness of the transparent coating was 6 μm.

About the obtained base material with a transparent film, the total light transmittance and haze were measured with the haze meter (made by Suga Test Instruments Co., Ltd.). The uncoated TAC film had a total light transmittance of 93.2% and a haze of 0.2%.
Further, adhesion, saponification resistance, scratch resistance, pencil hardness and surface roughness were measured and evaluated by the following methods, and the results are shown in the table.

Evaluation of saponification resistance Saponification test method: A substrate (1) with a transparent coating is immersed in a 10 wt% NaOH aqueous solution at 40 ° C. for 80 seconds. The contact angle (CA ₁ ) and (CA ₂ ) on the surface of the transparent coating before and after the saponification test was measured with a fully automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd .: DM700) to determine the contact angle difference, and the results are shown in the table. Indicated.

Measurement of Scratch Resistance Using # 0000 steel wool, sliding 10 times at a load of 2 kg / cm ² , visually observing the surface of the film, and evaluating according to the following criteria, the results are shown in Table 1.
Evaluation criteria:
No streak injury is found: ◎
Slightly scratched streak: ○
Many scratches are found in the streak: △
The surface has been cut entirely: ×

Adhesive transparent film-coated substrate (F-1) surface is made with 11 parallel scratches with a knife at intervals of 1 mm in length and width to make 100 squares, and cellophane tape (registered trademark) is adhered to it, then Adhesiveness was evaluated by classifying the number of squares remaining after the cellophane tape (registered trademark) was peeled off into the following four stages. The results are shown in Table 1.
Number of remaining cells: 95 or more: ◎
Number of remaining squares 90-94: ○
Number of remaining squares: 85-89:
Number of remaining squares: 84 or less: ×

Measurement of pencil hardness It measured with the pencil hardness tester according to JIS-K-5600.
Measurement of surface roughness Measured by laser microscopy.

[Example 2]
Preparation of coating liquid for forming transparent film (2) In Example 1, a coating liquid for forming transparent film having a solid content concentration of 42.0% by weight (2) except that 0.05 g of an acrylic silicon leveling agent was mixed. Was prepared.

Production of substrate with transparent film (2) A substrate with transparent film (2) was produced in the same manner as in Example 1 except that the coating liquid for forming a transparent film (2) was used. The film thickness of the transparent coating was 6 μm.
About the obtained base material with a transparent film, total light transmittance, haze, adhesion, saponification resistance, scratch resistance, pencil hardness and surface roughness were measured, and the results are shown in the table.

[Example 3]
Preparation of coating liquid for forming transparent film (2) In Example 1, a coating liquid for forming a transparent film having a solid content concentration of 42.0% by weight (3) except that 1.0 g of an acrylic silicon leveling agent was mixed. Was prepared.

Production of substrate with transparent film (3) A substrate with transparent film (3) was produced in the same manner as in Example 1 except that the coating liquid for forming a transparent film (3) was used. The film thickness of the transparent coating was 6 μm.
About the obtained base material with a transparent film, total light transmittance, haze, adhesion, saponification resistance, scratch resistance, pencil hardness and surface roughness were measured, and the results are shown in the table.

[Example 4]
Preparation of coating liquid for forming transparent film (4) In Example 1, the solid content concentration was 42.0% by weight, except that an acrylic silicon leveling agent (manufactured by Enomoto Kasei Co., Ltd .: Disparon NSF-8363) was mixed. A coating solution (4) for forming a transparent film was prepared. At this time, as a result of measuring the molecular weight of the leveling agent, the average molecular weight was 7,500.

Production of substrate with transparent film (4) A substrate with transparent film (4) was produced in the same manner as in Example 1, except that the coating liquid for forming a transparent film (4) was used. The film thickness of the transparent coating was 6 μm.
About the obtained base material with a transparent film, total light transmittance, haze, adhesion, saponification resistance, scratch resistance, pencil hardness and surface roughness were measured, and the results are shown in the table.

[Example 5]
Preparation of coating liquid (5) for forming transparent coating Silica fine particle dispersion (manufactured by JGC Catalysts & Chemicals Co., Ltd .: CATALOID SI-50; average particle diameter 25 nm, dispersion medium water, SiO ₂ concentration 48 wt%) 1000 g of pure water Addition of 600 g to 30% concentration, 336 g of cation exchange resin (Mitsubishi Chemical Corporation: Diaion SK1B) is used for ion exchange at 80 ° C. for 3 hours, and a silica fine particle dispersion having a solid content concentration of 30% by weight (2) was obtained.

The silica fine particle dispersion (2) having a solid content concentration of 30% by weight was subjected to solvent substitution with methanol using an ultrafiltration membrane to obtain a silica fine particle methanol dispersion (2) having a solid content concentration of 30% by weight.
Next, 100 g of this silica fine particle methanol dispersion (2) was mixed with 4.50 g of γ-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd .: KBM-503, SiO ₂ component 81.2%). 3.1 g of pure water was added and stirred at 50 ° C. for 20 hours to obtain a surface-treated silica fine particle dispersion (2) (solid content concentration 30.5% by weight).

Solvent substitution with propylene glycol monomethyl ether (PGM) was performed with a rotary evaporator to obtain a silica fine particle PGME dispersion (2) having a solid content concentration of 40% by weight.
Subsequently, in Example 1, the solid content concentration of 42.0 wt% was similarly used except that the silica fine particle PGME dispersion liquid (2) was used instead of the silica fine particle PGME dispersion liquid (1) having a solid content concentration of 40.5 wt%. % Transparent film-forming coating solution (5) was prepared.

Production of substrate with transparent film (5) A substrate with transparent film (5) was produced in the same manner as in Example 1 except that the coating liquid for forming a transparent film (5) was used. The film thickness of the transparent coating was 6 μm.
About the obtained base material with a transparent film, total light transmittance, haze, adhesion, saponification resistance, scratch resistance, pencil hardness and surface roughness were measured, and the results are shown in the table.

[Example 6]
Preparation of coating liquid for forming transparent film (6) Silica fine particle dispersion (manufactured by JGC Catalysts & Chemicals Co., Ltd .: CATALOID SI-80P; average particle diameter 80 nm, SiO ₂ concentration 40 wt%, dispersion medium: water) Was added to adjust the solid content concentration to 30% by weight, and then cation exchange resin (Mitsubishi Chemical Corporation: Diaion SK1B) 336 g was used for ion exchange at 80 ° C. for 3 hours for washing. A silica fine particle dispersion (3) having a solid content concentration of 30% by weight was obtained. The dispersion was subjected to solvent substitution with methanol using an ultrafiltration membrane to obtain a silica fine particle methanol dispersion (3) having a solid concentration of 30% by weight.

Ultrafine water is prepared by mixing 4.50 g of γ-methacrylooxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd .: KBM-503, SiO ₂ component 81.2%) into 100 g of silica fine particle methanol dispersion (3). 3.1 g was added and stirred at 50 ° C. for 20 hours to obtain a surface-treated silica fine particle methanol dispersion (3) having a solid content concentration of 30.5% by weight.

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

  Next, in Example 1, the solid content concentration of 42.0 wt% was the same as in Example 1 except that the silica fine particle PGME dispersion (3) was used instead of the silica fine particle PGME dispersion (1). % Transparent film-forming coating solution (6) was prepared.

Production of substrate with transparent film (6) A substrate with transparent film (6) was produced in the same manner as in Example 1 except that the coating liquid for forming a transparent film (6) was used. The film thickness of the transparent coating was 6 μm.
About the obtained base material with a transparent film, total light transmittance, haze, adhesion, saponification resistance, scratch resistance, pencil hardness and surface roughness were measured, and the results are shown in the table.

[Example 7]
Preparation of coating solution (7) for transparent film formation
Preparation of P-doped tin oxide fine particles 80 g of pure water was charged with 13 g of ammonium nitrate and 20 g of 15% aqueous ammonia, and the temperature was raised to 50 ° C. A solution obtained by dissolving 1519 g of potassium stannate in 4290 g of pure water was added with a roller pump over 10 hours. At this time, nitric acid having a concentration of 10% by weight was added and adjusted so as to maintain the pH at 8.8 with a pH controller. After the addition was completed, the temperature was kept at 50 ° C. for 1 hour, and then 10% by weight nitric acid was added to lower the pH to 3.0. Next, it was washed with pure water until the filtered water conductivity reached 10 μS / cm with an ultrafiltration membrane, and then concentrated with an ultrafiltration membrane. The amount of liquid taken out at this time was 6000 g, and the solid content (SnO ₂ ) concentration was 12% by weight. To this slurry, 264 g of a phosphoric acid aqueous solution having a concentration of 16% by weight was added and stirred for 0.5 hour. This was dried and fired at 700 ° C. for 2 hours to prepare P-doped tin oxide fine particles.
The average particle diameter of the obtained P-doped tin oxide fine particles was 15 nm.

Preparation of 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 after adding 50 g of 20 wt% KOH aqueous solution, 1000 g of quartz beads (0.15 mm) , Pulverize and disperse thoroughly with a bead mill, then separate the quartz beads and the dispersion with a 325 mesh (44 micron mesh) stainless steel wire mesh, and ion exchange the quartz beads remaining on the wire mesh. The liquid washed with 1560 g of water was mixed well, this liquid was heat-treated at 90 ° C. for 1 hour, cooled to room temperature, 96 g of anion exchange resin was added and stirred for 1 hour, and then the anion exchange resin was separated. After adding 96 g of cation exchange resin and stirring for 1 hour, the cation resin was separated to obtain a P-doped tin oxide fine particle aqueous dispersion (concentration: 10% by weight).

20.8 g of ethyl silicate (ethyl silicate 28 SiO ₂ component 28.8%, manufactured by Tama Chemicals) as a coupling agent in 2000 g of 10 wt% P-doped tin oxide fine water spray Ratio = 100/3) and 2000 g of methanol were added and stirred at 50 ° C. for 18 hours for surface treatment. Thereafter, an ethanol dispersion of fine P-doped tin oxide particles that was solvent-substituted with ethanol and surface-treated with a silane coupling material having a concentration of 30% by weight was prepared.

  Thereafter, the solvent was replaced 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% by weight.

  Subsequently, in Example 1, the solid content concentration was 42.0% by weight except that the P-doped tin oxide fine particle PGME dispersion was used instead of the silica fine particle PGME dispersion (1) having a solid content concentration of 40.5% by weight. A coating solution (7) for forming a transparent film was prepared.

Production of transparent film-coated substrate (7) In Example 1, the transparent film-coated substrate (7) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (7) was used and coated using a bar coater # 20. Manufactured. The film thickness of the transparent coating was 6 μm.
About the obtained base material with a transparent film, total light transmittance, haze, adhesion, saponification resistance, scratch resistance, pencil hardness and surface roughness were measured, and the results are shown in the table.

[Comparative Example 1]
Preparation of coating liquid for transparent film formation (R1) In Example 1, the solid content concentration was 42.0 except that an acrylic silicon leveling agent (manufactured by Enomoto Kasei Co., Ltd .; Disparon NSH-8430HF) was not mixed. A coating solution (R1) for forming a transparent coating film with a weight% was prepared.

Production of substrate with transparent coating (R1) A substrate with transparent coating (R1) was produced in the same manner as in Example 1 except that the coating solution for forming a transparent coating (R1) was used. The film thickness of the transparent coating was 6 μm.
About the obtained base material with a transparent film, total light transmittance, haze, adhesion, saponification resistance, scratch resistance, pencil hardness and surface roughness were measured, and the results are shown in the table.

[Comparative Example 2]
Preparation of coating solution for forming transparent film (R2) In Example 1, the solid content concentration was 42.0% by weight except that an acrylic silicon leveling agent (manufactured by Enomoto Kasei Co., Ltd .; Disparon UVX-271) was mixed. A coating solution (R2) for forming a transparent film was prepared. At this time, as a result of measuring the molecular weight of the leveling agent, the average molecular weight was 4,000.

Production of substrate with transparent film (R2) A substrate with transparent film (R2) was produced in the same manner as in Example 1, except that the coating liquid for forming a transparent film (R2) was used. The film thickness of the transparent coating was 6 μm.
About the obtained base material with a transparent film, total light transmittance, haze, adhesion, saponification resistance, scratch resistance, pencil hardness and surface roughness were measured, and the results are shown in the table.

[Comparative Example 3]
Preparation of coating solution for forming transparent film (R3) In Example 1, the solid content concentration was 42.0% by weight except that an acrylic silicon leveling agent (manufactured by Enomoto Kasei Co., Ltd .; Disparon UVX-2280) was mixed. A coating solution for forming a transparent film (R3) was prepared. At this time, as a result of measuring the molecular weight of the leveling agent, the average molecular weight was 35,000.

Production of substrate with transparent coating (R3) A substrate with transparent coating (R3) was produced in the same manner as in Example 1 except that the coating solution for forming a transparent coating (R3) was used. The film thickness of the transparent coating was 6 μm.
About the obtained base material with a transparent film, total light transmittance, haze, adhesion, saponification resistance, scratch resistance, pencil hardness and surface roughness were measured, and the results are shown in the table.

[Comparative Example 4]
Preparation of coating liquid for forming transparent film (R4) In Example 1, 37.04 g of a propylene glycol monopropyl ether dispersion of silica sol having a solid content concentration of 40.5% by weight and dipentaerythritol hexaacrylate (Kyoeisha Chemical Co., Ltd.) Product: DPE-6A) 12.00 g, dimethylol-tricyclodecane diacrylate 1.6-hexanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .; light acrylate SR-238F) 3.00 g and an acrylic silicon leveling agent ( Enomoto Kasei Co., Ltd .; Disparon NSH-8430HF (30 g) and photopolymerization initiator (Ciba Japan Co., Ltd.): Irgacure 184, PGME dissolved in 20% solid content) 4.50 g, PGME 3.46 g and acetone 10 0.0 g of the mixture is mixed thoroughly to obtain a transparent coating with a solid content of 30% by weight. Forming coating liquid (R4) was prepared.

Production of substrate with transparent film (R4) In Example 1, the substrate with transparent film (R4) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (R4) was used and coated with bar coater # 20. Manufactured. The film thickness of the transparent coating was 6 μm.
About the obtained base material with a transparent film, total light transmittance, haze, adhesion, saponification resistance, scratch resistance, pencil hardness and surface roughness were measured, and the results are shown in the table.

Claims (15)

A coating liquid for forming a transparent film comprising a matrix-forming component, metal oxide fine particles, and a solvent,
Transparent, characterized in that it contains an acrylic silicone resin having an average molecular weight in the range of 5,000 to 30,000 as the leveling agent, and the content of the leveling agent in the range of 0.001 to 7.2% by weight as a solid content Coating liquid for film formation.   The concentration of the matrix-forming component is in the range of 1 to 59.9% by weight as the solid content, the content of the metal oxide fine particles is in the range of 0.025 to 48% by weight as the solid content, and the concentration of the total solid content is 2. The coating liquid for forming a transparent film according to claim 1, wherein the coating liquid is in the range of 5 to 60% by weight.   The metal oxide fine particles are selected from silica, alumina, titanium oxide, zirconium oxide, tin oxide, antimony pentoxide, indium oxide and composite oxides thereof, metal oxides containing a doping agent, and composite oxides thereof. The coating liquid for forming a transparent film according to claim 1 or 2, wherein the coating liquid is a fine particle comprising at least one kind.   The coating liquid for forming a transparent film according to claim 3, wherein the metal oxide fine particles are silica-based fine particles.   5. The coating liquid for forming a transparent film according to claim 1, wherein the metal oxide fine particles are surface-treated with an organosilicon compound.   6. The coating liquid for forming a transparent film according to claim 1, wherein the average particle diameter of the metal oxide fine particles is in the range of 5 to 300 nm.   Acrylic silicon type comprising a base material and a transparent film formed on the base material, the transparent film comprising a matrix component and metal oxide fine particles, and an average molecular weight in the range of 5,000 to 30,000 Resin is included as a leveling agent, the content of the matrix component is in the range of 20 to 99.5% by weight as the solid content, and the content of the metal oxide fine particles is 0.5 to 80% by weight as the solid content The base material with a transparent film characterized by existing in the range.   The leveling agent content in the said transparent film exists in the range of 0.02 to 12 weight% as solid content, The base material with a transparent film of Claim 7 characterized by the above-mentioned.   The metal oxide fine particles are at least one selected from silica, alumina, titania, zirconia, tin oxide, antimony pentoxide, indium oxide and complex oxides thereof, oxides containing doping agents, and complex oxides. The substrate with a transparent coating according to claim 7 or 8, wherein   The substrate with a transparent coating according to any one of claims 7 to 9, wherein the metal oxide fine particles are silica-based fine particles.   The substrate with a transparent coating according to any one of claims 7 to 10, wherein the metal oxide fine particles are surface-treated with an organosilicon compound.   The substrate with a transparent coating according to any one of claims 7 to 11, wherein the average particle diameter of the metal oxide fine particles is in the range of 5 to 300 nm. The contact angle (CA ₁ ) of the transparent coating is in the range of 60 to 110 °, and the contact angle difference from the contact angle (CA ₂ ) after saponifying the surface of the transparent coating is 10 ° or less. The base material with a transparent film in any one of Claims 7-12 characterized by these.   The substrate with a transparent film according to any one of claims 7 to 13, wherein the haze of the transparent film is 1.0% or less.   The surface roughness (Ra) of the said transparent film is 20 nm or less, The base material with a transparent film in any one of Claims 7-14 characterized by the above-mentioned.