JP5686942B2 - Hard coat film-forming coating material and substrate with hard coat film - Google Patents

Description

  The present invention is excellent in adhesion to a base material, scratch resistance, film hardness, etc., and has excellent antistatic performance, transparency / colorlessness, haze, etc. Regarding materials.

  It is known to form a hard coat film on the surface of the base material in order to improve the scratch resistance of the base material surface such as glass, plastic sheet, plastic lens, etc. As such hard coat film, an organic resin film or inorganic A film is formed on the surface of glass or plastic. In addition, resin particles or inorganic oxide particles such as silica are blended in an organic resin film or an inorganic film to further improve adhesion to a substrate, scratch resistance, and the like.

  In addition, in order to impart antistatic performance and electromagnetic wave shielding performance to a substrate such as a display device, a conductive film containing metal fine particles and conductive oxide fine particles is also formed on the surface of the substrate (patent) Document 1, JP-A-2003-105268). At this time, it is disclosed that tin oxide, tin oxide doped with F, Sb or P, indium oxide, indium oxide doped with Sn or F, antimony oxide, low-order titanium oxide or the like is used as the conductive oxide fine particles. Has been.

In addition, the present inventors have proposed a hard coat film in which antimony pentoxide fine particles are blended in order to impart antistatic performance to the hard coat film itself (Japanese Patent Application Laid-Open No. 2004-50810). Furthermore, a transparent coating containing chain antimony pentoxide fine particles has been proposed (Patent Document 3, JP-A-2005-139026).
JP 2003-105268 A JP 2004-50810 A JP 2005-139026 A

However, when conventional antimony pentoxide fine particles or tin oxide fine particles are used, the surface resistance value of the obtained hard coat film and transparent film is relatively high, so that the antistatic performance is insufficient. Further, instead of these, highly conductive metal fine particles, tin oxide fine particles (ATO) doped with Sb or indium oxide fine particles (ITO) doped with Sn are used as a hard coat film forming component, In a hard coat film having a thickness of 0.5 μm or more, there is a problem of coloring. In a display device using a colored base material with a hard coat film, for example, the appearance is a problem, and a recording device such as a CD or a DVD It has also been found that reading and writing are hindered when used for various purposes.

Under these circumstances, the present inventors have intensively studied to solve the above problems. As a result, when tin oxide fine particles doped with P as metal oxide fine particles are blended into the hard coat film forming component, the color does not color over a long period of time. In addition, the inventors have found that the antistatic performance is also high and have completed the present invention.
[1] A hard coat film-forming paint comprising P-doped tin oxide fine particles, a matrix-forming component, and a solvent,
The P content of the P-doped tin oxide fine particles is in the range of 0.5 to 10% by weight as an oxide,
The concentration of P-doped tin oxide fine particles as a solid content is in the range of 0.5 to 40% by weight,
The concentration of the matrix-forming component as a solid content is in the range of 1 to 45% by weight,
A paint for forming a hard coat film, wherein the total solid concentration is in the range of 5 to 50% by weight.
[2] The coating material for forming a hard coat film according to [1], wherein the P-doped tin oxide fine particles have an average particle diameter in the range of 5 to 30 nm.
[3] The paint for forming a hard coat film according to [1] or [2], wherein the P-doped tin oxide fine particles are surface-treated with an organosilicon compound represented by the following formula (1).
_{R n -SiX 4-n (1} )
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms or a silanol group) , Halogen, hydrogen, n: an integer of 0 to 3)
[4] The hard coat film forming paint according to [1] or [2], wherein the P-doped tin oxide fine particles are surface-treated with an anionic surfactant and / or a nonionic surfactant.
[5] The hard coat film forming paint according to [1] to [4], wherein the matrix forming component is an organic resin.
[6] The hard coat film forming paint according to [1] to [5], wherein the organic resin is an ultraviolet curable resin.
[7] A substrate and a hard coat film having an average film thickness of 0.5 to 20 μm formed on the substrate, the hard coat film including a matrix component and P-doped tin oxide fine particles, The content of P in the tin oxide fine particles is in the range of 0.5 to 10% by weight as an oxide, and the content of the P-doped tin oxide fine particles in the hard coat film is in the range of 5 to 80% by weight as the solid content. Base material with hard coat film.
[8] The substrate with a hard coat film according to [7], wherein the P-doped tin oxide fine particles have an average particle diameter in the range of 5 to 30 nm.
[9] The substrate with a hard coat film according to [7] or [8], wherein the P-doped tin oxide fine particles are surface-treated with an organosilicon compound represented by the following formula (1).
R _n -SiX _4-n (1)
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms or a silanol group) , Halogen, hydrogen, n: an integer of 0 to 3)
[10] The substrate with a hard coat film according to [7] or [8], wherein the P-doped tin oxide fine particles are surface-treated with an anionic surfactant and / or a nonionic surfactant.
[11] The substrate with a hard coat film according to [7] to [10], wherein the matrix component is an organic resin.
[12] The substrate with a hard coat film according to [7] to [11], wherein the organic resin is an ultraviolet curable resin.
[13] The substrate with a hard coat film according to [7] to [12], wherein the surface resistance value is in the range of 10 ⁵ to 10 ¹² Ω / □.

  In the present invention, a paint for forming a hard coat film for forming a hard coat film excellent in transparency without coloring, excellent in adhesion to a substrate, scratch resistance, hardness and the like and having excellent antistatic performance and The object is to provide a substrate with a hard coat film.

  In the present invention, since the hard coat film provided on the surface of the base material contains tin oxide fine particles doped with P, there is no coloring even if the film thickness is 0.5 to 20 μm. It is transparent, so when it is installed in a display device etc., the appearance or haze does not become a problem, and reading and writing are not hindered. In addition, adhesion to the substrate, scratch resistance Further, it is possible to provide a hard coat film-forming coating material and a hard coat film-coated substrate that can be used for a hard coat film-coated substrate having excellent film hardness and the like and having antistatic performance.

Hereinafter, the hard coat film-forming paint according to the present invention will be described first.
Hard coat film forming paint The hard coat film forming paint according to the present invention comprises tin oxide fine particles doped with P, a matrix forming component, and a solvent.
[P-doped tin oxide fine particles]
P-doped tin oxide is obtained by doping tin oxide with phosphorus. P-doped tin oxide has the same level of conductivity as ITO, ATO, and FTO (F-doped tin oxide) and high transparency.

  The doping amount of P in the P-doped tin oxide fine particles is preferably in the range of 0.5 to 10% by weight, more preferably 1.0 to 7% by weight as an oxide. If the amount of P-doping is small, the conductivity may be insufficient, and the antistatic performance of the resulting hard coat film may be insufficient. Even if the amount of P doping is too large, the conductivity is not further improved, it becomes difficult to dope uniformly, and P may be unevenly distributed on the surface of the particle, resulting in a decrease in conductivity.

Moreover, it is preferable that the average particle diameter of P dope tin oxide fine particle exists in the range of 5-30 nm, Furthermore, 5-20 nm.
If the average particle size of the P-doped tin oxide fine particles is too small, the particles are likely to aggregate, making it difficult to highly disperse the aggregated particles, and the resulting hard coat film may have high haze. Even if the dispersion is high, the grain boundary resistance increases and the conductivity decreases, so that the antistatic performance may be insufficient. If the average particle size of the P-doped tin oxide fine particles is too large, the transparency is lowered and the haze is also increased. In addition, it is difficult to form a conductive path (for example, particles can be linked in a chain form or the like in the hard coat film) and the conductivity is lowered, so that the antistatic performance may be insufficient.

  The volume resistivity of the P-doped tin oxide fine particles used in the present invention is preferably in the range of 100 to 100,000 Ω · cm, more preferably 100 to 50,000 Ω · cm. If it exists in this range, electroconductivity is high and can demonstrate high antistatic performance. As described above, the volume resistance value is affected by the P doping amount, and the resistance value decreases as the doping amount relatively increases.

  The P-doped tin oxide fine particles are not particularly limited as long as the P doping amount, the average particle diameter, and the volume resistance are within the above ranges, and conventionally known P-doped tin oxide fine particles can be used. For example, it can be produced by a method according to the method for producing conductive fine particles disclosed in Japanese Patent Application Laid-Open No. 63-11519 filed by the applicant of the present application.

The P-doped tin oxide fine particles used in the present invention are preferably surface-treated with an organosilicon compound represented by the following formula (1).
_{R n -SiX 4-n (1} )
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms or a silanol group) , Halogen, hydrogen, n: an integer of 0 to 3)
As such an organosilicon compound,
Specifically, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, Phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3, 3,3-trifluoropropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltrioxy Silane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxy Silane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ- (meth) acryloxymethyltrimethoxysilane, γ- (meth) acrylooxymethyltri Excisilane, γ- (meth) acrylooxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acrylooxy Propyltrimethoxysilane, γ- (meth) acrylooxypropyltriethoxysilane Γ- (Meth) acrylooxypropyltriethoxysilane, butyltrimethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilaoctyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, hexyltri Ethoxysilane, octyltriethoxysilane, decyltriethoxysilane, 3-ureidoisopropylpropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriisopropoxysilane, trifluoropropyl Trimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimeth Shishiran, N- phenyl--γ- aminopropyltrimethoxysilane, .gamma.-mercaptopropyltrimethoxysilane, trimethylsilanol, and the like methyltrichlorosilane.

  In addition, when the matrix forming component is a hydrophilic resin, it is not necessary to perform surface treatment, but an organic silicon compound with n = 0 is used as necessary. When the matrix forming component is a hydrophobic resin, it is desirable to use an organosilicon compound with n = 1 to 3, preferably n = 1, as necessary.

  In the surface treatment, for example, a predetermined amount of the above-mentioned organosilicon compound is added to an alcohol dispersion of P-doped tin oxide fine particles, water is added thereto, and an acid or alkali is added as a catalyst for hydrolysis of the organosilicon compound as necessary. A conventionally known method such as hydrolyzing an organosilicon compound can be employed.

  The surface treatment amount is preferably as small as possible within a range in which uniform dispersibility in the matrix-forming component and the solvent is obtained. If the amount is too large, the conductivity of the P-doped tin oxide fine particles may be impaired, and the resulting anti-static performance of the hard coat film may be insufficient.

  The surface treatment amount of the P-doped tin oxide fine particles by the organosilicon compound varies depending on the average particle diameter of the P-doped tin oxide fine particles, but the weight ratio of the organosilicon compound to the P-doped tin oxide fine particles (as the solid content of the organosilicon compound) Weight / weight as the solid content of P-doped tin oxide fine particles) is preferably 0.2 or less, more preferably 0.1 or less.

If the weight ratio is too large, the surface of the P-doped tin oxide fine particles may be thickly coated with the organosilicon compound, the conductivity may be lowered, and the antistatic performance may be insufficient.
The lower limit of the surface treatment amount is not particularly limited, but if the weight ratio is too small, the effect of surface treatment with an organosilicon compound is thin, and in some cases, dispersibility in the paint may be insufficient. In addition, the transparent conductive film formed using this paint has a high haze and may have insufficient antistatic performance. For this reason, as a lower limit of the surface treatment amount, the weight ratio is preferably 0.01 or more, and more preferably 0.02 or more.

  The P-doped tin oxide fine particles used in the present invention are surface-treated with an anionic surfactant and / or a nonionic surfactant in place of or together with the surface treatment of the organosilicon compound. It may be.

  Surfactants include polyoxyethylene alkyl ethers such as propylene glycol stearate ester and propylene glycol monomethyl ether, polyoxyethylene alkylene alkyl ether, isostearyl glyceryl ether, polyethylene glycol monolaurate, polyethylene glycol monostearate, distearic acid Polyethylene glycol, ethylene glycol distearate, polyoxyethylene tridecyl ether, polyoxyalkylene tridecyl ether, polyoxyalkylene alkyl ether, polyoxyethylene lauryl ether, polyoxyalkylene lauryl ether, polyoxyethylene isodecyl ether, polyethylene alkyl ether Polyoxyalkylenes such as phosphate esters Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene norylphenol phosphate, polyoxyethylene norylphenol ether, polyoxyethylene octylphenyl ether, polyoxyethylene lauryl ether sodium sulfate, polyoxyethylene lauryl ether ammonium sulfate, Examples include anionic surfactants such as sodium polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, sodium alkyldiphenyl ether disulfonate, sodium dioctylsulfosuccinate, and the like, and mixtures thereof.

  The surface treatment with a surfactant is, for example, by firing particles impregnated with P in tin oxide to form P-doped tin oxide, and then pulverizing the particles in the presence of the surfactant when pulverizing the particles. The surface active agent is adsorbed or bound to the pulverized particle surface. P-doped tin oxide fine particles that can be highly dispersed can be obtained by surface treatment with such a surfactant.

  The surface treatment amount of the P-doped tin oxide fine particles by the surfactant at this time varies depending on the average particle diameter of the P-doped tin oxide fine particles, but the weight ratio of the surfactant to the P-doped tin oxide fine particles (surfactant) (Weight / solid weight of P-doped tin oxide fine particles) is preferably 0.2 or less, more preferably 0.1 or less. If the weight ratio is too large, the surface of the P-doped tin oxide fine particles may be coated with an excessive surfactant, resulting in reduced electrical conductivity and insufficient antistatic performance.

  Note that the lower limit of the surface treatment amount of the surfactant is not particularly limited, but if the weight ratio is too small, the effect of surface treatment with the surfactant is weak, and in some cases, the dispersibility in the paint is low. In some cases, the transparent conductive film formed using this paint has a high haze, and the antistatic performance may be insufficient. For this reason, as a lower limit of the surface treatment amount, the weight ratio is preferably 0.01 or more, and more preferably 0.02 or more.

[Matrix forming component]
As the matrix forming component, an organic resin matrix forming component is preferably used.
Examples of the organic resin matrix forming component include conventionally known paint resins, specifically polyester resins, polycarbonate resins, polyamide resins, polyphenylene oxide resins, thermoplastic acrylic resins, vinyl chloride resins, fluorine resins, vinyl acetate resins, Thermoplastic resins such as silicone rubber, urethane resin, melamine resin, silicon resin, butyral resin, reactive silicone resin, phenol resin, epoxy resin, unsaturated polyester resin, thermosetting acrylic resin, UV curable acrylic resin, electron beam Examples thereof include curable resins. In the case of a thermoplastic resin, the matrix forming component becomes the matrix component as it is. In the case of a curable resin, the matrix-forming component is the resin component before curing (before reaction or polymerization) (before reaction or polymerization)
Monomer / oligomer and reaction component), and the matrix component is a cured product, which is a polymer.

Specific examples of the organic resin-based matrix-forming component include a hydrophilic matrix-forming component and a hydrophobic matrix-forming component.
As a hydrophilic matrix forming component, diethylaminomethyl 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-acryloyloxypropyl acrylate, methoxytriethylene glycol dimethacrylate, butoxydiethylene glycol methacrylate, triethylene glycol diacrylate, 1.6-hexane Diol diacrylate, 2-methacryloyloxyethyl succinic acid, -Acryloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid, 2-methacryloyloxyethyl acid phosphate , 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate, a mixture thereof, or a copolymer or modified body of two or more of these resins.

Examples of the hydrophobic matrix-forming component include polyfunctional (meth) acrylate resins having hydrophobic functional groups such as vinyl groups, urethane groups, epoxy groups, (meth) acryloyl groups, CF ₂ groups, and the like. Is pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane tri (meth) acrylate, 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, perfluorooctyl Chill methacrylate, trifluoroethyl Mete chestnut rate, urethane acrylate and may be used a hydrophobic organic resin based matrix forming components, such as mixtures thereof.

In the present invention, among them, an ultraviolet curable resin or an electron beam curable resin is preferable, and an ultraviolet curable resin is particularly preferable.
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.

When such an ultraviolet curable resin is used, a hard coat film excellent in scratch resistance, hardness, etc. can be produced in a short time.
In the present invention, when using such an ultraviolet curable resin, if necessary, ethyl-4-
Sensitizers such as dimethylaminobenzoate, 2-ethylhexyl-4-dimethylaminobenzoate, (2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone mixture, polymerization initiators such as 2-hydroxy-1-phenyl-propan-1-one, stabilizers, etc. These contents are not particularly limited as long as they do not impair the performance of the hard coat film, and may be in a range usually added.
[solvent]
As the solvent used in the present invention, a conventionally known solvent capable of dissolving or dispersing the matrix forming component and the polymerization initiator and uniformly dispersing the P-doped tin oxide fine particles can be used.

Specifically, water; alcohols such as methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol; methyl acetate, ethyl acetate, isopropyl acetate, and propyl acetate , Esters such as isobutyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, cyclohexyl acetate, ethylene glycol monoacetate, glycols such as ethylene glycol and hexylene glycol; diethyl ether, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol isopropyl ether, diethylene glycol Hydrophilic solvents including ethers such as rumonomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether and purpylene glycol ethyl ether, propyl acetate, isobutyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, 3-methoxybutyl acetate Esters such as 2-ethylbutyl acetate, cyclohexyl acetate, and ethylene 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; Examples include polar solvents such as toluene. These may be used singly or in combination of two or more.
[composition]
The concentration of the P-doped tin oxide fine particles or the surface-treated P-doped tin oxide fine particles in the hard coat film forming coating as a solid content is preferably in the range of 0.5 to 40% by weight, more preferably 1 to 30% by weight. . When the solid content concentration is low, the content of the P-doped tin oxide fine particles in the hard coat film decreases, and sufficient antistatic performance may not be obtained. If the solid content concentration is too high, the content of the P-doped tin oxide fine particles in the hard coat film increases, and on the other hand, the matrix component decreases, so that the scratch resistance may be insufficient.

The solid content concentration of the matrix-forming component in the hard coat film-forming coating material is preferably in the range of 1 to 45% by weight, more preferably 2 to 40% by weight. If the solid content concentration of the matrix-forming component is too low, the matrix component in the resulting hard coat film is small, the content of P-doped tin oxide fine particles is excessive, and the scratch resistance may be insufficient. In addition, there is a case where a thick hard coat film cannot be formed by a single application, which requires repeated application and drying, resulting in a decrease in productivity. If the solid content concentration of the matrix-forming component is too high, the content of P-doped tin oxide fine particles in the resulting hard coat film decreases, and sufficient antistatic performance may not be obtained.

The coating material for forming a hard coat film preferably has a total solid concentration of the P-doped tin oxide fine particles and the matrix forming component in the range of 5 to 50% by weight, more preferably 10 to 40% by weight.
If the total solid content is low, it may be difficult to obtain a hard coat film having a film thickness of 0.5 μm or more by a single application. If repeated application and drying are repeated, the hardness of the hard coat film obtained is repeated. In addition, there are problems such as insufficient scratch resistance, haze or poor appearance, and reduced productivity. If the total solid content is too high, the viscosity of the paint will increase, the coating properties will decrease, the haze of the resulting hard coat film will increase, the surface roughness will increase, and the scratch resistance will be insufficient. There is.

  In addition, the hard coat film-forming paint of the present invention includes a conventionally known leveling agent (for example, used for the purpose of flattening the film by reducing the viscosity of the paint), an antifoaming agent, a repellent, if necessary. A liquid preparation may be included.

Such a hard coat film-forming coating is applied to a substrate by a known method such as dipping, spraying, spinner, roll coating, bar coating, gravure printing, or micro gravure printing, and then dried. The hard coat film can be formed by curing by an ordinary method such as ultraviolet irradiation or heat treatment.
The base material with a hard coat film The base material with a hard coat film according to the present invention comprises a base material and a hard coat film having an average film thickness of 0.5 to 20 μm formed on the base material. Consists of a matrix component and P-doped tin oxide fine particles.
[Base material]
As the base material 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. Among these, a resin-based substrate can be preferably used.
[Hard coat film]
The hard coat film is composed of a matrix component and the doped tin oxide fine particles.

As described above, the matrix component is composed of a matrix-forming component or derived from a matrix-forming component.
The content of the P-doped tin oxide fine particles in the hard coat film is preferably in the range of 5 to 80% by weight, more preferably 20 to 70% by weight as the solid content. If the content of the P-doped tin oxide fine particles is small, sufficient antistatic performance may not be obtained. If the content of the P-doped tin oxide fine particles is too large, adhesion to the substrate, scratch resistance, strength, transparency, haze, etc. may be insufficient.

The content of the matrix component in the hard coat film is preferably in the range of 95 to 20% by weight, more preferably 80 to 30% by weight as a solid content (note that the total amount with the fine particles is 100).
Not exceed% by weight). If the amount of the matrix component is small, the adhesion to the substrate is insufficient, and if the content of the P-doped tin oxide fine particles is too high, the scratch resistance is lowered, the coloring becomes strong, or the haze increases. However, transparency may be reduced. If the amount of the matrix component is too large, the content of the P-doped tin oxide fine particles in the hard coat film decreases, and sufficient antistatic performance may not be obtained.

The thickness of the hard coat film is preferably in the range of 0.5 to 20 μm, more preferably 1 to 15 μm. When the thickness of the hard coat film is less than the lower limit of the above range, the hard coat film is thin, so that the stress applied to the film surface cannot be sufficiently absorbed, and scratch resistance, pencil hardness, etc. are insufficient, In some cases, the conductivity decreases and sufficient antistatic performance cannot be obtained. Even if the hard coat film is made too thick, it becomes difficult to apply the film so that the thickness of the film becomes uniform or to dry uniformly, which may cause cracks and voids. Strength and transparency may be insufficient. Furthermore, curling (warping) may occur depending on the substrate.

If the composition of the present invention is used, the surface resistance of the hard coat film is 10 ⁵ to 10 ¹² Ω /
It is in the range of □. In particular, the hard coat film preferably has a surface resistance in the range of 10 ⁵ to 10 ¹⁰ Ω / □.

When the surface resistance value of the hard coat film is within this range, a film having high antistatic performance can be obtained.
In the base material with a hard coat film of the present invention, an antireflection film may be provided on the hard coat film.
[Antireflection film]
The antireflection film is not particularly limited as long as it has antireflection performance, and a conventionally known antireflection film is usually formed. Specifically, an antireflection performance is provided if the refractive index is lower than that of the hard coat film.

Such an antireflection film comprises an antireflection film forming matrix and, if necessary, a low refractive index component.
The matrix for forming an antireflection film is a component that can form an antireflection film, and can be selected and used from the viewpoints of adhesion to a substrate, hardness, coatability, and the like.

Specifically, the same matrix component as the hard coat film forming component can be used.
It is also possible to use a hydrolyzable organosilicon compound as the matrix. Specifically, for example, a partial hydrolyzate of alkoxysilane is suitably used by adding water and an acid or alkali as a catalyst to a mixture of alkoxysilane and alcohol.

The hydrolyzable organic silicon compounds of the general formula _{R n Si (OR ') 4} -n [R, R': an alkyl group, an aryl group, a vinyl group, an acrylic group, a hydrocarbon group such as, n = 0, 1 , 2, or 3] can be used. In particular, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

The low refractive index component which may be optionally contained includes low refractive index substances such as CaF ₂ , NaF, NaAlF ₆ and MgF, as well as silica-based particles (silica particles, silica hollow particles, silica / alumina composite oxides). Particles), porous silica-based particles, and the like.

  For example, when composite oxide fine particles in which the surface of porous inorganic oxide fine particles disclosed in JP-A-7-133105 filed by the applicant of the present application is coated with silica are used, the refractive index is low and the reflection is excellent in antireflection performance. A prevention film can be obtained.

  The content of the low refractive index component in the antireflection film is preferably 90% by weight or less, more preferably 50% by weight or less. If it is included in this range, the adhesiveness with a substrate such as a hard coat film can be maintained high without deteriorating the strength of the film.

The thickness of the antireflection film is preferably 50 to 300 nm, more preferably 80 to 200 nm.
When the thickness of the antireflection film is less than the above range, the film strength, antireflection performance, and the like may be inferior. If the thickness of the antireflection film exceeds the above range, cracks may occur in the film, which may increase the strength of the film, and the film may be too thick, resulting in insufficient antireflection performance.

  The refractive index of such an antireflection film varies depending on the mixing ratio of the low refractive index component and the matrix such as resin and the refractive index of the resin used, but is usually in the range of 1.28 to 1.50. preferable. When the refractive index of the antireflection film exceeds 1.50, although depending on the refractive index of the substrate, the antireflection performance may be insufficient, and it is difficult to obtain a film having a refractive index of less than 1.28. is there.

  The antireflection film is formed by applying an antireflection film forming coating liquid containing the above-described antireflection film forming matrix and, if necessary, a low refractive index component and a solvent. Any solvent can be used as long as it easily evaporates and does not adversely affect the resulting antireflection film.

  The coating solution for forming the antireflection film is not particularly limited, and is applied to the substrate by a known method such as a dipping method, a spray method, a spinner method, or a roll coating method, as in the case of forming the hard coat film. It may be applied and dried. In particular, when the forming component is a thermosetting resin, curing of the hard coat film may be promoted by heat treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, etc. When a decomposable organosilicon compound is contained, hydrolysis and polycondensation of the hydrolyzable organosilicon compound may be promoted.

The base material with a hard coat film according to the present invention as described above is colored even though the film thickness is as thick as 0.5 to 20 μm because the hard coat film contains P-doped tin oxide fine particles. No transparency and excellent transparency and haze. For this reason, when reading or writing is performed in a display device or the like, no error occurs and reading and writing are not hindered. In addition, as with other conductive fine particles, the generated static electricity Is removed by the P-doped tin oxide fine particles, and as a result, adhesion of dust and the like is suppressed, and the formed hard coat film is excellent in adhesion to the substrate, scratch resistance, film hardness, and the like.
[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by these Examples.
[Example 1]
Preparation of P-doped tin oxide fine particles (1) To 806 g of pure water, 1.3 g of ammonium nitrate and 2.0 g of 15 wt% aqueous ammonia were added and stirred, and the temperature was raised to 50 ° C. A solution obtained by dissolving 151.9 g of potassium stannate in 429 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 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 600 g, and the solid content (SnO ₂ ) concentration was 12% by weight. To this slurry, 26.4 g of a 16% by weight aqueous phosphoric acid solution 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 (1).

The composition, average particle diameter, and volume resistance of the obtained P-doped tin oxide fine particles (1) were measured, and the results are shown in Table 1.
The volume resistance value was measured by the following method.

Using a volume resistivity ceramic cell (with a cylindrical hollow (with a cross-sectional area of 0.5 cm ² ) inside), the cell was first placed on the gantry electrode, and P-doped tin oxide fine particles (1 ) 0.6
Insert the protrusion of the upper electrode with a cylindrical protrusion, pressurize the upper and lower electrodes with a hydraulic machine, and the resistance value (Ω) and the height of the sample when 100 kg / cm ² (9.80 MPa) is applied (cm) was measured, and the volume resistance value (Ω · cm) was determined from the resistance value and the height.

Preparation of surface-treated P-doped tin oxide fine particles (1) dispersion P-doped tin oxide fine particles (1) 193.3 g and propylene glycol monomethyl ether 3
75.2 g, 14.9 g of polyethylene alkyl ether phosphate ester (Price Surf A-217E, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as a surfactant (weight ratio with P-doped tin oxide fine particles (1)) = 0.077 ), 998.6 g of glass beads (0.3 to 0.5 mmφ) are put in a 2 L glass beaker, and are sufficiently stirred and dispersed by a bead mill, and then glass beads are collected with a stainless steel wire mesh of 325 mesh (aperture 44 microns). Then, the concentration was adjusted with propylene glycol monomethyl ether to prepare a dispersion of P-doped tin oxide fine particles (1) which was surface-treated with a surfactant having a solid concentration of 30% by weight.

The average particle diameter and specific surface area of the surface-treated P-doped tin oxide fine particles (1) were measured, and the results are shown in Table 1.
It was shown to.
Preparation of Hard Coat Film Forming Paint (H-1) Surface Treatment P-doped Tin Oxide Fine Particles (1) Ultraviolet curable resin (Dai Nippon Ink Co., Ltd .: Unidec 17-824-9 (urethane acrylate)) 40%, a mixture of 40% polyester acrylate and 20% butyl acetate), solids concentration 78.9% by weight) 14.2
6 g, UV curable resin 1,6-hexanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate 1.6HX-A, solid content concentration 100%) 1.25 g, propylene glycol monomethyl ether 42.32 g, photoinitiated A coating agent (H-1) for forming a hard coat film was prepared by mixing 0.5 g of the agent 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BAES Japan KK: Lucillin TPO).
Production of Substrate with Hard Coat Film (F-1) A paint (H-1) for forming a hard coat film was formed from a PET film (thickness: 188 μm, refractive index: 1.
65, total light transmittance 90.0%, haze 0.6%) by bar coater method (bar # 14), dried at 80 ° C. for 1 minute, and then mounted with high pressure mercury lamp (120 W / cm) irradiation device to cure 600 mJ / cm ² irradiated to at (Japan Storage battery Ltd. UV irradiation apparatus CS30L21-3), a hard coat film with the base material (F-1) was prepared. The thickness of the hard coat film at this time is 4 μm
Met.

The surface resistance of the obtained hard coat film was measured with a surface resistance meter (manufactured by Mitsubishi Chemical Corporation: Hiresta), and the results are shown in Table 1.
Further, the total light transmittance and haze including the base material and the PET film were measured with a haze meter (manufactured by Suga Test Instruments Co., Ltd.), and the results are shown in Table 1.

Further, the colorability is visually observed and evaluated according to the following criteria, and the results are shown in Table 1.
Colorable hard coat film is transparent and no coloration is observed: ◎
Hard coat film is transparent and slightly colored: ○
Although the hard coat film is transparent, coloring is observed: Δ
Hard coat film is opaque and colored: x
Further, pencil hardness, scratch resistance and adhesion were evaluated by the following methods and evaluation criteria, and the results are shown in Table 1.
Measurement of pencil hardness It measured with the pencil hardness tester according to JIS-K-5400.
Measurement of Scratch Resistance Using # 0000 steel wool, sliding 50 times at a load of 500 g / 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 antireflection film-coated substrate (F-1) surface is made of 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. Next, the adhesion was evaluated by classifying the number of cells that were not peeled off when the cellophane tape (registered trademark) was peeled 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: ×
[Example 2]
Preparation of P-doped tin oxide fine particles (2) In Example 1, P-doped tin oxide fine particles were prepared in the same manner as in Example 1 except that 5.3 g of 16% by weight aqueous phosphoric acid solution was added and stirred for 0.5 hour. (2) was prepared.

The composition, average particle diameter, and volume resistance of the obtained P-doped tin oxide fine particles (2) were measured, and the results are shown in Table 1.
Preparation of surface-treated P-doped tin oxide fine particles (2) dispersion In Example 1, P-doped tin oxide fine particles (2) were used, and a polyethylene alkyl ether phosphate ester (Daiichi Kogyo Seiyaku Co., Ltd .: A surface-treated P-doped tin oxide fine particle (2) dispersion was prepared in the same manner except that 13.5 g (Plysurf A-217E) (weight ratio to P-doped tin oxide fine particle (2) = 0.070) was added. . The average particle diameter and specific surface area of the surface-treated P-doped tin oxide fine particles (2) were measured, and the results are shown in Table 1.
Preparation of Hard Coat Film Forming Paint (H-2) A hard coat film forming paint (H-2) was prepared in the same manner as in Example 1 except that the surface-treated P-doped tin oxide fine particles (2) were used. .
Production of base material with hard coat film (F-2) In Example 1, the base material with hard coat film (F-2) was prepared in the same manner except that the hard coat film forming paint (H-2) was used. did. The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the hard coat film were evaluated, and the results are shown in Table 1.
[Example 3]
Preparation of P-doped tin oxide fine particles (3) P-doped tin oxide fine particles (3) were prepared in the same manner as in Example 1 except that 53.0 g of a 16% by weight aqueous phosphoric acid solution was added and stirred for 0.5 hour. 3) was prepared.

The composition, average particle diameter, and volume resistance of the obtained P-doped tin oxide fine particles (3) were measured, and the results are shown in Table 1.
Preparation of surface-treated P-doped tin oxide microparticles (3) dispersion In Example 1, P-doped tin oxide microparticles (3) were used, and a polyethylene alkyl ether phosphate ester (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Plysurf A-217E) A surface-treated P-doped tin oxide fine particle (3) dispersion was prepared in the same manner except that 15.9 g (weight ratio with P-doped tin oxide fine particle (3) = 0.082) was added. . The average particle diameter and specific surface area of the surface-treated P-doped tin oxide fine particles (3) were measured, and the results are shown in Table 1.
Preparation of Hard Coat Film Forming Paint (H-3) A hard coat film forming paint (H-3) was prepared in the same manner as in Example 1 except that the surface-treated P-doped tin oxide fine particles (3) were used. .
Preparation of base material with hard coat film (F-3) In Example 1, the base material with hard coat film (F-3) was prepared in the same manner except that the coating material for forming a hard coat film (H-3) was used. did. The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the hard coat film were evaluated, and the results are shown in Table 1.
[Example 4]
Preparation of P-doped tin oxide fine particles (4) In Example 1, P-doped tin oxide fine particles (4) were added in the same manner as in Example 1 except that nitric acid having a concentration of 10% by weight was added so as to keep the pH at 9.8 with a pH controller. 4) was prepared.

The composition, average particle diameter, and volume resistance of the obtained P-doped tin oxide fine particles (4) were measured, and the results are shown in Table 1.
Preparation of surface-treated P-doped tin oxide fine particles (4) dispersion In Example 1, P-doped tin oxide fine particles (4) were used, and a polyethylene alkyl ether phosphate ester (Daiichi Kogyo Seiyaku Co., Ltd .: Plysurf A-217E) 17.8 g (weight ratio with P-doped tin oxide fine particles (4) = 0.092) was added in the same manner, and a surface-treated P-doped tin oxide fine particle (4) dispersion was prepared. .

The average particle diameter and specific surface area of the surface-treated P-doped tin oxide fine particles (4) were measured, and the results are shown in Table 1.
It was shown to.
Preparation of Hard Coat Film Forming Paint (H-4) A hard coat film forming paint (H-4) was prepared in the same manner as in Example 1 except that the surface-treated P-doped tin oxide fine particles (4) were used. .
Production of base material with hard coat film (F-4) In Example 1, the base material with hard coat film (F-4) was prepared in the same manner except that the paint for forming hard coat film (H-4) was used. did. The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the hard coat film were evaluated, and the results are shown in Table 1.
[Example 5]
Preparation of P-doped tin oxide fine particles (5)
In Example 1, P-doped tin oxide fine particles (5) were prepared in the same manner as in Example 1 except that nitric acid having a concentration of 10% by weight was added so as to keep the pH at 8.2 with a pH controller.

The composition, average particle diameter, and volume resistance of the obtained P-doped tin oxide fine particles (5) were measured, and the results are shown in Table 1.
Preparation of surface-treated P-doped tin oxide fine particles (5) dispersion In Example 1, P-doped tin oxide fine particles (5) were used, and a polyethylene alkyl ether phosphate ester (Daiichi Kogyo Seiyaku Co., Ltd .: Plysurf A-217E) A surface-treated P-doped tin oxide fine particle (5) dispersion was prepared in the same manner except that 9.7 g (weight ratio with P-doped tin oxide fine particle (5) = 0.050) was added. . The average particle diameter and specific surface area of the surface-treated P-doped tin oxide fine particles (5) were measured, and the results are shown in Table 1.
Preparation of Hard Coat Film Forming Paint (H-5) A hard coat film forming paint (H-5) was prepared in the same manner as in Example 1 except that the surface-treated P-doped tin oxide fine particles (5) were used. .
Production of base material with hard coat film (F-5) In Example 1, the base material with hard coat film (F-5) was prepared in the same manner except that the coating material for forming a hard coat film (H-5) was used. did. The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the hard coat film were evaluated, and the results are shown in Table 1.
[Example 6]
Preparation of hard coat film-forming paint (H-6) 58.33 g of surface-treated P-doped tin oxide fine particles (1) dispersion prepared in the same manner as in Example 1.
UV curable resin (Dainippon Ink Co., Ltd .: Unidec 17-824-9, solid content concentration 78.9% by weight) 8.56 g, UV curable resin 1.6 hexanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) : Light acrylate 1.6HX-A, solid content concentration 100%) 0.75 g, propylene glycol monomethyl ether 32.06 g, photoinitiator 2.4.6-trimethylbenzoyldiphenylphosphine oxide (BAS Japan, Inc.) ): Lucilin TPO) 0.3 g was mixed to prepare a hard coat film forming paint (H-6).
Production of base material with hard coat film (F-6) In Example 1, the base material with hard coat film (F-6) was prepared in the same manner except that the paint for forming hard coat film (H-6) was used. did.

The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the hard coat film were evaluated, and the results are shown in Table 1.
[Example 7]
Preparation of Hard Coat Film Forming Coating Material (H-7) 25.0 g of the surface-treated P-doped tin oxide fine particle (1) dispersion prepared in the same manner as in Example 1, and an ultraviolet curable resin (Dainippon Ink Co., Ltd .: Unidec 17-824-9, solid content concentration 78.9%) 19.96 g, UV curable resin 1.6 hexanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate 1.6HX-A, solid content concentration 100% ) 1.75 g, propylene glycol monomethyl ether 52.59 g, photoinitiator 2.4.6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BIAS JAPAN KK: Lucillin TPO) 0.7 g A paint (H-6) for forming a hard coat film was prepared.
Production of base material with hard coat film (F-7) In Example 1, the base material with hard coat film (F-7) was prepared in the same manner except that the paint for forming hard coat film (H-7) was used. did. The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the hard coat film were evaluated, and the results are shown in Table 1.
[Example 8]
Production Example 1 of Substrate with Hard Coat Film (F-8) In Example 1 of hard coat film forming paint (H-1), PET film (thickness: 188)
After coating with a bar coater method (bar # 4) to μm, refractive index: 1.65) and drying at 80 ° C. for 1 minute, an ultraviolet irradiation device equipped with a high-pressure mercury lamp (120 W / cm) An irradiation apparatus CS30L21-3) was irradiated and cured by 600 mJ / cm ² to prepare a base material with a hard coat film (F-8). At this time, the thickness of the hard coat film was 1 μm.

The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the hard coat film were evaluated, and the results are shown in Table 1.
[Example 9]
Production Example 1 of Substrate with Hard Coat Film (F-9) In Example 1 of hard coat film forming coating solution (H-1), PET film (thickness: 18
8 μm, refractive index: 1.65), coated by a bar coater method (bar # 32), dried at 80 ° C. for 1 minute, and then an ultraviolet irradiation device equipped with a high-pressure mercury lamp (120 W / cm) The substrate (F-9) with a hard coat film was prepared by irradiating and curing 600 mJ / cm ² with an irradiation apparatus CS30L21-3). At this time, the thickness of the hard coat film was 10 μm.

The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the hard coat film were evaluated, and the results are shown in Table 1.
[Example 10]
Preparation of surface-treated P-doped tin oxide fine particles (10) dispersion 217 g of P-doped tin oxide fine particles (1) prepared in the same manner as in Example 1, ion-exchanged water 33
Place 5 g in a 2 L glass beaker, add 50 g of 20% strength by weight KOH aqueous solution, add 1000 g of quartz beads (0.15 mm), pulverize and disperse thoroughly with a bead mill, and then 325 mesh (opening) The quartz beads and the dispersion were separated with a 44-micron stainless steel mesh, and the quartz beads remaining on the mesh were washed with 1560 g of ion-exchanged water, and this solution was heat-treated at 90 ° C. for 1 hour. After cooling to room temperature, 96 g of anion exchange resin was added and stirred for 1 hour, then the anion exchange resin was separated, and then 96 g of cation exchange resin
After stirring for 1 hour, the cationic resin was separated to obtain a P-doped tin oxide fine particle aqueous dispersion (concentration: 10% by weight).

Subsequently, 2000 g of a 10 wt% P-doped tin oxide fine particle (10) water spray was used as a coupling agent and ethyl orthosilicate (ethyl silicate 28 SiO ₂ component 28.8% manufactured by Tama Chemical) 2
0.8 g (weight ratio with P-doped tin oxide fine particles (10) = 100/3) and 2000 g of methanol were added and stirred at 50 ° C. for 18 hours for surface treatment. Thereafter, a dispersion of P-doped tin oxide fine particles (10) was prepared by replacing the solvent with ethanol and treating the surface with a silane coupling material having a concentration of 30% by weight.

The average particle diameter and specific surface area of the surface-treated P-doped tin oxide fine particles (10) were measured, and the results are shown in Table 1.
Preparation of Hard Coat Film Forming Coating Liquid (H-10) Surface Treatment P-doped Tin Oxide Fine Particles (10) 59.18 g dispersion with UV curable resin (Dai Nippon Ink Co., Ltd .: Unidec 17-824-9, solid 13.5 g), UV curable resin 1.6 hexanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate 1.6HX-A, solid concentration 100%) 1.5 g, and propylene glycol 45.4 g of monomethyl ether and 2.46-trimethylbenzoyldiphenylphosphine oxide (manufactured by BIAS Japan KK: Lucyrin TPO) 0.47 g are mixed to form a hard coat film coating material (H -10) was prepared.

Production of substrate with hard coat film (F-10) In Example 1, the substrate with hard coat film (F-10) was prepared in the same manner except that the coating liquid for forming a hard coat film (H-10) was used. Prepared.

The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the hard coat film were evaluated, and the results are shown in Table 1.
[Example 11 (reference example) ]
Preparation of dispersion of P-doped tin oxide fine particles (11) 193.3 g of P-doped tin oxide fine particles (1) prepared in the same manner as in Example 1, propylene glycol monomethyl ether 369.4, acetylacetone 5.8 g, glass beads (0 .3 to 0.5 mmφ) 998.6 g was put into a 2 L glass beaker and thoroughly stirred and dispersed with a bead mill, and then the glass beads were removed with a 325 mesh (mesh opening 44 microns) stainless steel wire mesh, and propylene glycol The concentration was adjusted with monomethyl ether to prepare a dispersion of P-doped tin oxide fine particles (11) having a solid content of 30% by weight. The average particle diameter and specific surface area of the P-doped tin oxide fine particles (11) were measured, and the results are shown in Table 1.
Preparation of Hard Coat Film Forming Paint (H-11) A hard coat film forming paint (H-11) was prepared in the same manner as in Example 1 except that the P-doped tin oxide fine particle (10) dispersion was used. .

Production of substrate with hard coat film (F-11) In Example 1, the substrate with hard coat film (F-11) was prepared in the same manner except that the coating liquid for forming a hard coat film (H-11) was used. Prepared. Hard coat film thickness, surface resistance, total light transmittance,
Haze, colorability, pencil hardness, scratch resistance and adhesion were evaluated, and the results are shown in Table 1.
[Example 12]
Preparation of Hard Coat Film Forming Coating Liquid (H-12) In Example 1, an ultraviolet curable resin (Dainippon Ink Co., Ltd .: Unidec 17-824-9, solid content concentration 78.9%) 14.26 g Instead, a hard coat film was formed in the same manner except that 11.25 g of an ultraviolet curable resin (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate DPE-6A, 1,6-hexanediol diacrylate, solid content concentration 100%) was used. Coating solution (H-12) was prepared.
Production of substrate with hard coat film (F-12) In Example 1, the substrate with hard coat film (F-12) was prepared in the same manner except that the coating liquid for forming a hard coat film (H-12) was used. Prepared. The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the hard coat film were evaluated, and the results are shown in Table 1.
[Comparative Example 1]
Preparation of surface-treated antimony-doped tin oxide fine particles (R1) dispersion Antimony-doped tin oxide fine particles (manufactured by Catalyst Kasei Kogyo Co., Ltd .: ELCOM TL-30HS, Sb ₂ O ₅ content 16% by weight, average particle diameter 10 nm, volume resistance (Value 0.3 Ω · cm) 193.3 g and propylene glycol monomethyl ether 375.2, polyethylene alkyl ether phosphate ester (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Prisurf A-217E) 17.4 g (antimony) The weight ratio of the doped tin oxide fine particles = 0.090) and 998.6 g of glass beads (0.3 to 0.5 mmφ) were placed in a 2 L glass beaker and dispersed with sufficient stirring, then 325 mesh (opening) 44 micron) After removing the glass beads with a stainless steel wire mesh, the concentration is adjusted with propylene glycol monomethyl ether to obtain a solid content concentration. An antimony-doped tin oxide fine particle (R1) dispersion surface-treated with a surfactant having a solid content concentration of 30% by weight and surface-treated with 30% by weight of a surfactant was prepared.

The average particle diameter and specific surface area of the surface-treated antimony-doped tin oxide fine particles (R1) were measured, and the results are shown in Table 1.
Preparation of Hard Coat Film Forming Coating Liquid (RH-1) In the same manner as in Example 1, except that the surface-treated antimony-doped tin oxide fine particle (R1) dispersion was used, a hard coat film forming paint (RH-1) was used. Was prepared.
Production of base material with hard coat film (RF-1) In Example 1, the base material with hard coat film (RF-1) was prepared in the same manner except that the coating liquid for forming a hard coat film (RH-1) was used. Prepared.

The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the hard coat film were evaluated, and the results are shown in Table 1.
[Comparative Example 2]
Preparation of surface-treated antimony-doped tin oxide fine particles (R2) dispersion Antimony-doped tin oxide fine particles (manufactured by Catalyst Kasei Kogyo Co., Ltd .: ELCOM TL-30HS, Sb ₂ O ₅ content 16% by weight, average particle diameter 10 nm, volume resistance (Value 0.3 Ω · cm) 217 g and ion-exchanged water 335 g were put in a 2 L glass beaker, 50 g of 20% strength by weight aqueous KOH solution was added, and then 1000 g of quartz beads (0.15 mm) were added and stirred thoroughly with a bead mill. After pulverizing and dispersing, the quartz beads and the dispersion are separated with a 325 mesh (mesh opening 44 microns) stainless steel wire mesh, and the quartz beads remaining on the wire mesh are sufficiently washed with 1560 g of ion-exchanged water. The mixture was heat-treated at 90 ° C. for 1 hour, cooled to room temperature, added with 96 g of anion exchange resin, stirred for 1 hour, separated from the anion exchange resin, and then positively charged. After adding 96 g of ion exchange resin and stirring for 1 hour, the cation resin was separated to obtain an antimony-doped tin oxide fine particle aqueous dispersion (concentration: 10% by weight).

Next, 2000 g of an antimony-doped tin oxide fine particle (R2) having a concentration of 10% by weight was added to an aqueous solution of ethyl silicate (ethyl silicate 28 SiO ₂ component 28.
8 wt%) 20.8 g (weight ratio of P-doped tin oxide fine particles (R2) = 100/3) and 2000 g of methanol were added and stirred at 50 ° C. for 18 hours for surface treatment. After that, an antimony-doped tin oxide fine particle (R2) dispersion liquid in which the solvent was replaced with ethanol and surface-treated with a silane coupling material having a concentration of 30% by weight was prepared.

The average particle diameter and specific surface area of the surface-treated antimony-doped tin oxide fine particles (R2) were measured, and the results are shown in Table 1.
Preparation of coating liquid for forming a hard coat film (RH-2) In Example 1, a coating composition for forming a hard coat film (RH-2) was used in the same manner as in Example 1, except that the surface-treated antimony-doped tin oxide fine particle (R2) dispersion was used. Was prepared.
Production of base material with hard coat film (RF-2) In Example 1, the base material with hard coat film (RF-2) was prepared in the same manner except that the coating liquid for forming a hard coat film (RH-2) was used. Prepared. The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the hard coat film were evaluated, and the results are shown in Table 1.
[Comparative Example 3]
Preparation of surface-treated tin-doped indium oxide fine particle (R3) dispersion Tin-doped indium oxide fine particles (Catalyst Chemical Industries, Ltd .: ELCOM TL-130, SnO ₂ content 8% by weight, average particle diameter 20 nm, volume resistivity 0.02Ω Cm) 193.3 g and propylene glycol monomethyl ether 375.2, and as a surfactant, polyethylene alkyl ether phosphate ester (Daiichi Kogyo Seiyaku Co., Ltd .: Prisurf A-217E) 13.5 g (tin-doped indium oxide fine particles and Weight ratio = 0.07), 998.6 g of glass beads (0.3 to 0.5 mmφ) were put into a 2 L glass beaker, and after sufficiently stirring and dispersing, 325 mesh (aperture 44 microns) stainless steel After removing the glass beads with a metal mesh, adjust the concentration with propylene glycol monomethyl ether, The surface-treated tin-doped indium oxide fine particles (R3) dispersion was prepared with 30% by weight of a surfactant. The average particle diameter and specific surface area of the surface-treated tin-doped indium oxide fine particles (R3) were measured, and the results are shown in Table 1.
Preparation of Hard Coat Film Forming Coating Liquid (RH-3) In Example 1, except that the surface-treated tin-doped indium oxide fine particle (R3) dispersion was used, a hard coat film forming paint (RH-3) was prepared. Prepared.
Production of base material with hard coat film (RF-3) In Example 1, the base material with hard coat film (RF-3) was prepared in the same manner except that the coating liquid for forming a hard coat film (RH-3) was used. Prepared.
The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the hard coat film were evaluated, and the results are shown in Table 1.
[Comparative Example 4]
Preparation of surface-treated tin-doped indium oxide fine particles (R4) dispersion Tin-doped indium oxide fine particles (Catalyst Kasei Kogyo Co., Ltd .: ELCOM TL-130, SnO ₂ content 8% by weight, average particle size 20 nm, volume resistivity 0.02Ω Cm) 193.3 g of ethanol 369.4 g and acetylacetone 5.8 g of glass beads (0.3 to 0.5 mmφ) 998.6 g were put in a 2 L glass beaker and dispersed by sufficiently stirring with a bead mill. The glass beads were removed with a mesh (opening 44 micron) stainless steel wire mesh, and the concentration was adjusted with ethanol to prepare a tin-doped indium oxide fine particle (R4) dispersion having a solid concentration of 30% by weight.

Next, 2000 g of a tin-doped indium oxide fine particle (R4) dispersion having a concentration of 10% by weight was added as a coupling agent to normal ethyl silicate (ethyl silicate 28 SiO ₂ component 28.
(8 wt%) 20.8 g (weight ratio with tin-doped indium oxide fine particles (R4) = 100/3) was added and stirred at 50 ° C. for 18 hours for surface treatment. Thereafter, a tin-doped indium oxide fine particle (R4) dispersion liquid in which the solvent was replaced with ethanol and surface-treated with a silane coupling material having a concentration of 30% by weight was prepared.
The average particle diameter and specific surface area of the surface-treated tin-doped indium oxide fine particles (R4) were measured, and the results are shown in Table 1.
Preparation of Hard Coat Film Forming Coating Liquid (RH-4) In Example 1, except that the surface-treated tin-doped indium oxide fine particle (R4) dispersion was used, a hard coat film forming paint (RH-4) was prepared. Prepared.
Production of base material with hard coat film (RF-4) In Example 1, the base material with hard coat film (RF-4) was prepared in the same manner except that the coating liquid for forming a hard coat film (RH-4) was used. Prepared. The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the hard coat film were evaluated, and the results are shown in Table 1.
[Comparative Example 5]
Manufacturing Example 1 of substrate with hard coat film (RF-5) In Example 1 of hard coat film forming coating solution (H-1), the solid content concentration was reduced to 1/2 with IPA.
After coating with PET film (thickness: 188 μm, refractive index: 1.65) by the bar coater method (bar # 3) and drying at 80 ° C. for 1 minute, a high pressure mercury lamp (120 W / cm) was applied. A hard coat film-coated substrate (F-8) was prepared by irradiating and curing 600 mJ / cm ² with a mounted UV irradiation device (UV irradiation device CS30L21-3 manufactured by Nippon Batteries). At this time, the thickness of the hard coat film was 0.3 μm.

The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the hard coat film were evaluated, and the results are shown in Table 1.
[Comparative Example 6]
Production Example 1 of Substrate with Hard Coat Film (RF-6) In Example 1 of hard coat film forming coating solution (H-1), a PET film (thickness: 18
8 μm, refractive index: 1.65), coated with a bar coater method (bar # 60), dried at 80 ° C. for 1 minute, and then irradiated with an ultraviolet irradiation device equipped with a high-pressure mercury lamp (120 W / cm) An irradiation apparatus CS30L21-3) was irradiated and cured by 600 mJ / cm ² to prepare a base material with a hard coat film (F-8). At this time, the thickness of the hard coat film was about 25 μm. However, since curling occurred, no other evaluation was performed.

Claims (8)

A hard coat film-forming paint comprising P-doped tin oxide fine particles, a matrix-forming component, and a solvent,
The P content of the P-doped tin oxide fine particles is in the range of 0.5 to 10% by weight as an oxide,
The concentration of P-doped tin oxide fine particles as a solid content is in the range of 0.5 to 40% by weight,
The concentration of the matrix-forming component as a solid content is in the range of 1 to 45% by weight,
P-doped tin oxide fine particles are surface-treated with an anionic surfactant and / or nonionic surfactant, and the surface treatment amount is 0.01 or more and 0.2 by weight ratio (surfactant / P-doped tin oxide fine particles). In the following range,
A paint for forming a hard coat film, wherein the total solid concentration is in the range of 5 to 50% by weight. 2. The coating material for forming a hard coat film according to claim 1 , wherein the P-doped tin oxide fine particles have an average particle diameter in the range of 5 to 30 nm.   3. The hard coat film forming paint according to claim 1, wherein the matrix forming component is an organic resin component. The paint for forming a hard coat film according to claim 3 , wherein the organic resin is an ultraviolet curable resin. A hard coat film having an average film thickness of 0.5 to 20 μm formed on the base material, the hard coat film including a matrix component and P-doped tin oxide fine particles, and P-doped tin oxide fine particles The content of P in the range of 0.5 to 10% by weight as an oxide, the content of P-doped tin oxide fine particles in the hard coat film is in the range of 5 to 80% by weight as a solid content,
P-doped tin oxide fine particles are surface-treated with an anionic surfactant and / or nonionic surfactant, and the surface treatment amount is 0.01 or more and 0.2 by weight ratio (surfactant / P-doped tin oxide fine particles). A base material with a hard coat film, which is in the following range. 6. The substrate with a hard coat film according to claim 5 , wherein an average particle diameter of the P-doped tin oxide fine particles is in the range of 5 to 30 nm. The base material with a hard coat film according to claim 5 or 6 , wherein the matrix component is an organic resin. The base material with a hard coat film according to claim 7 , wherein the organic resin is an ultraviolet curable resin.