JP5554904B2 - Paint for forming transparent film and substrate with transparent film - Google Patents

Description

  The present invention relates to a coating material for forming a transparent film and a substrate with a transparent film, which are excellent in adhesion to a substrate, scratch resistance, film hardness, etc., and excellent in antistatic performance, transparency, haze and the like.

  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. Furthermore, it is practiced to add resin particles or inorganic particles such as silica in an organic resin film or inorganic film to further improve the adhesion to the 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: Japanese Patent Laid-Open No. 2003-105268). At this time, tin oxide, tin oxide doped with F, Sb or P, indium oxide, indium oxide doped with Sn or F, antimony pentoxide, low-order titanium oxide, or the like is used as the conductive oxide fine particles. It is disclosed.

  The present inventors have disclosed a hard coat film in which antimony pentoxide fine particles are blended in order to impart antistatic performance to the hard coat film itself (Patent Document 2: Japanese Patent Application Laid-Open No. 2004-50810). Furthermore, it has also been proposed to impart antistatic performance to the transparent film by blending the chain antimony pentoxide fine particles into the transparent film (Patent Document 3: Japanese Patent Application Laid-Open No. 2005-139026).

In the transparent film such as the above-described conventional conductive film or hard coat film, as a binder or matrix component of the conductive fine particles, a silicone matrix component which is a hydrolyzed polycondensate of an organosilicon compound, or an organic resin type As the matrix component, for example, paint resins such as polyester resin, polycarbonate resin, polyamide resin, urethane resin, phenol resin, epoxy resin, unsaturated polyester resin, and acrylic resin are used.
JP 2003-105268 A JP 2004-50810 A JP 2005-139026 A

However, when metal particles having high conductivity are used for the transparent film, there is a problem that coloring becomes remarkable particularly in the case of a film thickness.
In addition, when the conductive oxide fine particles are used, in order to improve the antistatic performance, for example, if the content of the conductive oxide fine particles in the coating is increased, the strength of the film and the adhesion to the substrate are increased. Etc. may be insufficient, and in this case, there is a problem of coloring when the film thickness is increased depending on the application. Further, when 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, and thus the antistatic performance is insufficient, and therefore the conductive When a high Sb-doped tin oxide (ATO) or Sn-doped indium oxide (ITO) is used in combination, a transparent film having a film thickness of 0.5 μm or more has a problem of coloring, and is colored. In a display device using a substrate with a transparent coating, for example, the appearance is a problem, and there is a new problem that reading and writing are hindered.

Under such circumstances, as a result of intensive studies to solve the problems that occur when using conductive oxide fine particles, as a matrix component, glycol-based acrylate resin (A) and non-glycol-based acrylate resin (B). It has been found that the transparency and the conductivity are remarkably improved when mixed at a predetermined ratio, and the present invention has been completed.

The configuration of the present invention is as follows.
[1] A transparent film-forming paint comprising conductive oxide fine particles, a matrix-forming component, and a solvent,
The matrix forming component consists of a glycol acrylate resin (A) and a non-glycol acrylate resin (B),
A transparent film-forming paint in which the content of the glycol-based acrylate resin (A) in the matrix-forming component is in the range of 10 to 80% by weight as a solid content.
[2] The non-glycol acrylate resin (B)
Non-glycol-based bifunctional acrylate resin (B1) and one or more non-glycol-based acrylate resins selected from non-glycol-based trifunctional acrylate resins, non-glycol-based tetrafunctional acrylate resins and non-glycol-based hexafunctional acrylate resins (B2) A mixture of
Non-glycolic bifunctional acrylate resin (B1) in non-glycolic acrylate resin (B)
[1] transparent film-forming paint with a solid content of 5 to 50% by weight
[3] The conductive oxide fine particles are selected from tin oxide, tin oxide doped with Sb or P, indium oxide, indium oxide doped with Sn or F, antimony pentoxide, and low-order titanium oxide. The transparent film-forming paint according to [1] or [2] as described above.
[4] The transparent film-forming paint according to [1] to [3], wherein the conductive oxide fine particles have an average particle diameter in the range of 5 to 200 nm.

[5] The solid content concentration of the conductive oxide fine particles in the paint is in the range of 0.5 to 40% by weight,
The solid content concentration of the matrix-forming component is in the range of 1 to 45% by weight,
The transparent film-forming paint according to [1] to [4], wherein the total solid content in the paint is in the range of 5 to 50% by weight.
[6] comprising a base material and a transparent film formed on the base material,
The transparent coating contains conductive oxide fine particles and a matrix component,
The matrix component consists of glycol acrylate resin (A) and non-glycol acrylate resin (B),
The content of glycol acrylate resin (A) in the matrix component is 10 as the solid content.
A substrate with a transparent coating in a range of ˜80% by weight.
[7] The non-glycol acrylate resin (B) is composed of a non-glycol bifunctional acrylate resin (B1), a non-glycol trifunctional acrylate resin, a non-glycol tetrafunctional acrylate resin, and a non-glycol hexafunctional acrylate resin. It consists of a mixture with one or more selected non-glycol acrylate resins (B2),
Non-glycolic bifunctional acrylate resin (B1) in non-glycolic acrylate resin (B)
[6] The substrate with a transparent coating, wherein the solid content is in the range of 5 to 50% by weight.
[8] The conductive oxide fine particles are one or more selected from tin oxide, tin oxide doped with Sb or P, indium oxide, indium oxide doped with Sn or F, antimony pentoxide, and low-order titanium oxide. [6] or [7] is a substrate with a transparent coating.
[9] The substrate with a transparent coating according to [6] to [8], wherein the conductive oxide fine particles have an average particle diameter in the range of 5 to 200 nm.
[10] The substrate with a transparent coating according to [6] to [9], wherein the content of the conductive oxide fine particles in the transparent coating is in the range of 10 to 80% by weight as a solid content.
[11] The substrate with a transparent film according to [6] to [10], wherein the film thickness of the transparent film is in the range of 30 nm to 20 μm.

According to the present invention, regardless of the film thickness of the transparent film, it is possible to form a transparent film that is excellent in adhesion to the substrate, scratch resistance, hardness, transparency and the like, as well as antistatic performance and economy. Can do.
For example, when the film thickness of the transparent coating is approximately 30 to 300 nm, it is possible to provide a substrate with a transparent coating that is excellent in antistatic performance, economy and the like useful for a display device or the like. Moreover, even if the film thickness of a transparent film becomes 0.3-20 micrometers, the base material with a hard-coat film excellent in abrasion resistance and antistatic performance can be provided, without coloring. In addition, since a specific matrix and conductive oxide fine particles are combined, transparency and conductivity are improved, and when used in a display device, etc., it is colored in addition to scratch resistance and antistatic performance. In addition, it is possible to provide a display device having high transparency and excellent readability and writeability.

First, the transparent film-forming paint according to the present invention will be described.
[Paint for forming transparent film]
The paint for forming a transparent film according to the present invention comprises conductive oxide fine particles, a matrix forming component, and a solvent.
Conductive oxide fine particles As the conductive oxide fine particles, conventionally known conductive oxide fine particles can be used. For example, tin oxide, tin oxide doped with Sb or P, indium oxide, Sn or F doped oxide One or more selected from conductive oxide fine particles such as indium, antimony oxide, and low-order titanium oxide can be suitably used.

These conductive oxide fine particles have high conductivity, and when blended in a transparent film, antistatic performance can be imparted to the transparent film.
The average particle diameter of the conductive oxide fine particles is preferably in the range of 5 to 200 nm, more preferably 10 to 100 nm.

  If the conductive oxide fine particles are too small, the particles are likely to aggregate in the coating for forming a transparent coating, and the grain boundary resistance is increased, so the antistatic performance of the resulting transparent coating is insufficient. There is a case. If the conductive oxide fine particles are too large, the transparency of the resulting transparent film may decrease or haze may increase, and furthermore, it is difficult to form a conductive path in the transparent film, and the antistatic performance is insufficient. It may become.

The conductive oxide fine particles used in the present invention may have been surface-treated with a hydrolyzable organosilicon compound and / or a surfactant.
As the hydrolyzable organosilicon compound, an organosilicon compound represented by the following formula (1) is used. Such hydrolyzable organosilicon compounds also include silane coupling agents.
^{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)
Specifically, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, Phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3 , 3,3-trifluoropropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltriethylene Silane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxy Silane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ- (meth) acrylooxymethyltrimethoxysilane, 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, hexyltriethoxy Silane, octyltriethoxysilane, decyltriethoxysilane, 3-ureidoisopropylpropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriisopropoxysilane, trifluoropropyltri Methoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimeth Shishiran, N- phenyl--γ- aminopropyltrimethoxysilane, .gamma.-mercaptopropyltrimethoxysilane, trimethylsilanol,
And methyltrichlorosilane.

  Among these, tetrafunctional organosilicon compounds such as tetramethoxysilane and tetraethoxysilane tend to have higher antistatic performance than when other organosilicon compounds are used, and can be suitably used. The reason for this is not clear, but it is thought to be because it does not inhibit the conductivity of the conductive oxide fine particles because there is no hydrocarbon group directly bonded to silicon.

  The surface treatment amount of the conductive oxide fine particles by the organosilicon compound varies depending on the average particle diameter of the conductive oxide fine particles, but the weight ratio between the organosilicon compound and the conductive oxide fine particles (solid weight of the organosilicon compound) / Solid weight of conductive oxide fine particles) is 0.2 or less, preferably 0.1 or less. The lower limit is not particularly limited, but when the surface treatment is performed, the lower limit of the weight ratio is 0.01 or more, preferably 0.02 or more.

The surface treatment amount is preferably as small as possible within a range where uniform dispersibility in the matrix-forming component and the solvent can be obtained.
If the weight ratio is too large, the surface of the conductive oxide fine particles will be thickly coated with the organosilicon compound, the conductivity of the conductive oxide fine particles themselves will be lowered, and the antistatic performance will be insufficient. There is.

  In the surface treatment, for example, a predetermined amount of the above-mentioned organosilicon compound is added to an alcohol dispersion of conductive 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.

  In addition, the conductive oxide fine particles described above may be surface-treated with an anionic surfactant and / or a nonionic surfactant in place of the organosilicon compound or together with the organosilicon compound.

Surfactants include propylene glycol stearate, polyoxyethylene alkyl ether, polyoxyethylene alkylene alkyl ether, isostearyl glyceryl ether, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, ethylene distearate Glycol, polyoxyethylene tridecyl ether, polyoxyalkylene tridecyl ether, polyoxyalkylene alkyl ether, polyoxyethylene lauryl ether, polyoxyalkylene lauryl ether, polyoxyethylene isodecyl ether, polyoxyalkylene alkyl ether phosphate ester, Polyoxyethylene norylphenol phosphate, polyoxy Nonionic surfactants such as tylene nolyl phenol ether and polyoxyethylene octyl phenyl ether, sodium polyoxyethylene lauryl ether sulfate, ammonium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkyl Anionic surfactants such as sodium diphenyl ether disulfonate, sodium dioctylsulfosuccinate, and the like, and mixtures thereof.

The surface treatment with a surfactant can be prepared, for example, by adding the surfactant to a conductive oxide fine particle dispersion and adsorbing or binding a desired amount.
At this time, the surface treatment amount of the conductive oxide fine particles by the surfactant varies depending on the average particle diameter of the conductive oxide fine particles, but the weight ratio of the surfactant to the conductive oxide fine particles (surfactant). Weight / weight as the solid content of the conductive oxide fine particles) is preferably in the range of 0.01 to 0.2, more preferably 0.02 to 0.1.

If the weight ratio is too large, the surface of the conductive oxide fine particles will be thickly coated with the surfactant, the conductivity of the conductive oxide fine particles themselves will be lowered, and the antistatic performance will be insufficient. There is.
Matrix-forming component The matrix-forming component used in the present invention comprises a glycol-based acrylate resin (A) and a non-glycol-based acrylate resin (B). What are the matrix-forming ingredients? It is an uncured product of the above acrylate resins (A) and (B), and is before the polymerization reaction.
Glycol-based acrylate resin (A)
As glycol-based acrylate resin (A), polyethylene glycol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, tripropylene glycol dimethacrylate, Examples include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, and the like, and mixtures thereof. By blending glycol acrylate resin (A),
Although the reason is not clear, there is an effect of improving conductivity.

The content of the glycol acrylate resin (A) in the matrix-forming component is preferably in the range of 10 to 80% by weight, more preferably 20 to 60% by weight in terms of solid content. If the content of the glycol acrylate resin (A) in the matrix-forming component is small, the effect of improving the conductivity may be insufficient, and the antistatic performance of the resulting transparent film may be insufficient. If the content of glycol acrylate resin (A) in the matrix-forming component is too large, the film may have insufficient adhesion to the substrate and scratch resistance.
Non-glycol acrylate resin (B)
As the non-glycol acrylate resin (B), 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, Glycerin dimethacrylate, 2hydroxy-3-acryloyloxypropyl methacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, dimethylol-tricyclodecane diacrylate, 2-hydroxy-3-acryloyloxy Non-glycol type 2 such as propyl methacrylate
Functional acrylate resins, pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trifunctional (urethane) acrylate resins such as pentaerythritol hexamethylene diisocyanate urethane prepolymer, and tetrafunctional acrylate resins such as pentaerythritol tetraacrylate And hexafunctional acrylate resins such as dipentaerythritol hexaacrylate and mixtures thereof.

By blending the non-glycol acrylate resin (B), the reason is not clear, but it has the effect of improving curling prevention, adhesion, and scratch resistance.
On the other hand, the content of the non-glycol acrylate resin (B) in the matrix-forming component is preferably in the range of 20 to 90% by weight, more preferably 40 to 80% by weight as the solid content. If the content of the non-glycol acrylate resin (B) in the matrix-forming component is small, adhesion to a substrate or the like, scratch resistance, etc. may be insufficient.

If the content of the non-glycol acrylate resin (B) in the matrix-forming component is too large, the glycol acrylate resin (A) will decrease, resulting in insufficient conductivity improvement effect, and the resulting transparent coating has an antistatic performance. In the present invention, the non-glycol acrylate resin (B) comprises a non-glycol bifunctional acrylate resin (B1), a non-glycol trifunctional acrylate resin, a non-glycol tetrafunctional acrylate resin, and It consists of a mixture with at least one non-glycol polyfunctional acrylate resin (B2) selected from non-glycol hexafunctional acrylate resins.

  By including the non-glycol-based bifunctional acrylate resin (B1), the shrinkage of the film can be suppressed, and curling of the substrate with a transparent film and a decrease in adhesion with the substrate can be suppressed. In addition, by including the non-glycol polyfunctional acrylate resin (B2), it is possible to improve adhesion to the substrate, scratch resistance, and the like.

Non-glycolic bifunctional acrylate resin (B1) in non-glycolic acrylate resin (B)
Is preferably in the range of 5 to 50% by weight, more preferably 10 to 40% by weight as the solid content. If the content of the non-glycol bifunctional acrylate resin (B1) is small, the substrate with a transparent coating that can provide large film shrinkage may curl or may have insufficient adhesion to the substrate. If the content of the non-glycol bifunctional acrylate resin (B1) is too large, the coating may be insufficiently cured, and the adhesion to the substrate, scratch resistance, etc. may be insufficient.

The content of the non-glycol polyfunctional acrylate resin (B2) in the non-glycol acrylate resin (B) is preferably in the range of 50 to 95% by weight, more preferably 60 to 90% by weight as the solid content.

Non-glycol polyfunctional acrylate resin (B2) in non-glycol acrylate resin (B)
If the content of is small, scratch resistance and the like may be insufficient. If the content of the non-glycol polyfunctional acrylate resin (B2) is too large, the substrate with a transparent film that can provide large film shrinkage may curl or may have insufficient adhesion to the substrate.
Polymerization initiator In the present invention, a polymerization initiator may be included together with the conductive oxide fine particles and the matrix-forming component. As the polymerization initiator, known ones can be used without any particular limitation, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,4-trimethyl-pentylphosphine oxide, 2-hydroxy-methyl-2-methyl-phenyl-propane-1-ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc. It is done. Further, a photosensitizer, a stabilizer, an auxiliary agent and the like may be contained.
Solvent As the solvent used in the present invention, a conventionally known solvent that can dissolve or disperse the matrix-forming component, a polymerization initiator added if necessary, and can uniformly disperse the P-doped tin oxide fine particles is used. Can do.

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.
Coating Composition The solid content concentration of the conductive oxide fine particles in the transparent film forming coating according to the present invention is preferably in the range of 0.5 to 40% by weight, more preferably 1 to 30% by weight. If the solid content concentration of the conductive oxide fine particles is too low, the content of the conductive oxide fine particles in the transparent film is reduced, and sufficient antistatic performance may not be obtained. Moreover, even if the solid content concentration of the conductive oxide fine particles is too high, the content of the conductive oxide fine particles in the transparent film increases, and the scratch resistance may be insufficient due to a small amount of matrix components.

  It is preferable that the density | concentration of the matrix formation component in the coating material for transparent film formation exists in the range of 1-45 weight% as solid content, Furthermore, it is 2-30 weight%. If the concentration of the matrix-forming component is too low, the content of the conductive oxide fine particles in the transparent film becomes too large, and adhesion to the substrate, scratch resistance, etc. may be insufficient. If the concentration of the matrix forming component is too high, the content of the conductive oxide fine particles in the transparent film is reduced, and sufficient antistatic performance may not be obtained.

  The weight ratio of the conductive oxide fine particles to the matrix forming component in the coating is appropriately selected in view of conductivity, adhesion, transparency, etc., but the normal (fine particle: matrix forming component) weight ratio is 10:90 to It is desirable to be in the range of 80:20, preferably 20:80 to 70:30.

The total solid content concentration (conductive oxide fine particles, matrix forming components, other components) of the coating for forming a transparent film is preferably in the range of 5 to 50% by weight, more preferably 10 to 45% by weight.

If the total solid concentration of the coating material for forming a transparent film is small, it may be difficult to obtain a transparent film having a desired film thickness by a single application. There are problems such as insufficient hardness and scratch resistance of the coating, haze or appearance deterioration, and reduced productivity. If the total solid content concentration of the coating material for forming a transparent film is too high, the viscosity of the coating material will increase, the coating property will decrease, the haze of the resulting transparent film will increase, the surface roughness will increase, and the scratch resistance will be increased. It may be insufficient.

  The transparent film-forming method using such a transparent film-forming coating is a known method such as dipping, spraying, spinner, roll coating, bar coating, gravure printing, or micro gravure printing. A transparent coating film can be formed by applying to a substrate, drying, and curing by an ordinary method such as ultraviolet irradiation or heat treatment.

The film thickness of the transparent coating of the obtained substrate with a transparent coating is preferably in the range of 30 nm to 20 μm. The surface resistance value is preferably in the range of 10 ⁵ to 10 ¹² Ω / □. The surface resistance value can be appropriately adjusted by adjusting the amount of conductive oxide fine particles.

Below, the base material with a transparent film which concerns on this invention is demonstrated.
[Base material with transparent coating]
The substrate with a transparent coating according to the present invention comprises a substrate and a transparent coating formed on the substrate.
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 these, a resin-based substrate can be preferably used.
The transparent coating transparent coating contains conductive oxide fine particles and a matrix component, and the matrix component is composed of a glycol acrylate resin (A) and a non-glycol acrylate resin (B). The content of A) is 10 to 80 as solid content
It is in the range of weight percent.
(i) Conductive oxide fine particles The conductive oxide fine particles are as described above. The content of the conductive oxide fine particles in the transparent coating is preferably in the range of 10 to 80% by weight, more preferably 20 to 70% by weight as the solid content.

If the content of the conductive oxide fine particles in the transparent film is small, sufficient antistatic performance may not be obtained. If the content of the conductive oxide fine particles is too large, the haze and transparency of the transparent film may be deteriorated, and the scratch resistance may be sufficient due to a small amount of matrix components.
(ii) Matrix component The matrix component used in the present invention comprises a glycol acrylate resin (A) and a non-glycol acrylate resin (B). The matrix component is 20 to 90% by weight in the transparent coating,
Furthermore, it is contained in the range of 30 to 80% by weight. Such a matrix component is derived from the matrix-forming component described above, and is usually a cured product or polymer of the matrix-forming component.

  If the content of the matrix component in the transparent film is too short, the adhesiveness with the substrate becomes insufficient, and the content of the conductive oxide fine particles is too much to reduce the scratch resistance, haze, Transparency may be insufficient. Even if the content of the matrix component in the transparent coating is too large, sufficient antistatic performance may not be obtained.

The content of glycol acrylate resin (A) in the matrix is 1 as solid content.
It is preferably 0 to 80% by weight, more preferably 20 to 60% by weight. If the content of the glycol acrylate resin (A) in the matrix component is small, the effect of improving the conductivity may be insufficient and the antistatic performance may be insufficient. Glycol-based acrylate resin (A)
If the content of is too large, adhesion to the substrate and scratch resistance may be insufficient.

On the other hand, the content of the non-glycol acrylate resin (B) in the matrix component is preferably in the range of 20 to 90% by weight, more preferably 40 to 80% by weight as the solid content. If the content of the non-glycol acrylate resin (B) in the matrix component is too small, adhesion to the substrate, scratch resistance, etc. may be insufficient. In addition, if the content of the non-glycol acrylate resin (B) is too large, the glycol acrylate resin (A) is reduced, resulting in insufficient conductivity improvement effect and insufficient antistatic performance of the resulting transparent film. There is a case.

In the present invention, the non-glycol acrylate resin (B) is composed of a non-glycol bifunctional acrylate resin (B1), a non-glycol trifunctional acrylate resin, a non-glycol tetrafunctional acrylate resin, and a non-glycol hexafunctional acrylate resin. It consists of a mixture with one or more selected non-glycol polyfunctional acrylate resins (B2), and the non-glycol bifunctional acrylate resin (B1) in the non-glycol acrylate resin (B) is 5 to 50 wt. %
Further, it is preferably in the range of 10 to 40% by weight.

  If the amount of the non-glycolic bifunctional acrylate resin (B1) is small, the substrate with a transparent film that can obtain a large film shrinkage may curl or the adhesion to the substrate may be insufficient. If the amount of the non-glycol bifunctional acrylate resin (B1) is too large, the coating may be insufficiently cured, and the adhesion to the substrate, scratch resistance, etc. may be insufficient.

The content of the non-glycol polyfunctional acrylate resin (B2) in the non-glycol acrylate resin (B) is preferably in the range of 50 to 95% by weight, more preferably 60 to 90% by weight as the solid content. If the amount of the non-glycol polyfunctional acrylate resin (B2) is small, the scratch resistance and the like may be insufficient. Even if the amount of the non-glycol polyfunctional acrylate resin (B2) is too large, the substrate with a transparent film that can provide large film shrinkage may curl or may have insufficient adhesion to the substrate.

In addition to the above components, the transparent film may contain a polymerization initiator, a stabilizer, and the like used during polymerization, such as a low refractive material (silica or magnesium fluoride).
The film thickness of the transparent film formed on the substrate is preferably in the range of 30 nm to 20 μm.

  In the case of a transparent film having a thickness in the range of 30 nm to 300 nm, the conductive oxide fine particles are tin oxide, tin oxide doped with Sb or P, indium oxide, indium oxide doped with Sn or F, oxide One or more selected from antimony and low-order titanium oxide are preferred. In this case, when the film thickness of the transparent coating is less than 30 nm, sufficient scratch resistance and antistatic performance may not be obtained. When the film thickness of the transparent coating exceeds 300 nm, the conductive property of the particles is high when tin oxide (ATO) doped with Sb or indium oxide (ITO) doped with Sn is used as the conductive oxide fine particles. Although the prevention performance is excellent, there is a problem of coloring, and when used in a display device, reading and writing may be defective. In this case, the more preferable film thickness of the transparent coating is in the range of 50 to 200 nm.

  In the case of a transparent film having a thickness in the range of 0.3 to 20 μm, tin oxide, tin oxide doped with Sb or P, indium oxide, indium oxide doped with Sn or F, oxidation One or more kinds of conductive oxide fine particles selected from antimony and low-order titanium oxide can be used. In particular, when using tin oxide doped with Sb (ATO) or indium oxide doped with Sn (ITO), the conductive oxide in the transparent film is sufficiently colored so that sufficient antistatic performance can be obtained. It is preferable to use a small amount of fine particles, specifically 1 to 30% by weight, more preferably 2 to 20% by weight.

In the present invention, glycol-based acrylate resin (A) whose conductivity is improved in the matrix component
Therefore, even if the content of conductive oxide fine particles such as colored ATO and ITO particles is reduced, a transparent film excellent in transparency, antistatic performance, scratch resistance and the like can be obtained. . Specifically, even in the range of 10 to 30% by weight, and further 15 to 25% by weight, it is possible to form a transparent film having excellent conductivity, scratch resistance, and high transparency (low coloration). The amount used can also be reduced.

  If the film thickness of the transparent film is too thin, there is no problem of coloring, but the antistatic performance is insufficient due to insufficient conductivity of the particles. If the film thickness of the transparent film is too thick, curling occurs due to film shrinkage. May occur or the adhesion to the substrate may be insufficient. A more preferable film thickness in this case is in the range of 0.5 to 10 μm.

The surface resistance value of the transparent film according to the present invention is preferably in the range of 10 ⁵ to 10 ¹² Ω / □, more preferably 10 ⁵ to 10 ¹⁰ Ω / □.
The surface resistance of the transparent film is difficult to obtain the 10 ⁵ Ω / □ of less than one, 10 ¹² Ω /
If it exceeds □, the antistatic performance becomes insufficient.

Such a transparent film can be produced by applying the above-described transparent film-forming coating solution to the substrate surface, heating (drying), and curing the resin.
The base material with a transparent coating of the present invention may be provided with an antireflection film on the transparent coating.

Antireflection Film The antireflection film used in the present invention is not particularly limited as long as it has antireflection performance, and a conventionally known antireflection film can be used. Specifically, if the refractive index is lower than that of the transparent coating, antireflection performance is provided.

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 that of the transparent film can be used.

It is also possible to use a hydrolyzate of an organosilicon compound as a matrix component.
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 organic silicon compound 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, Alternatively, alkoxysilane represented by 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 the content of the low refractive index component is too large, the strength and / or the strength of the coating may be reduced, or the adhesiveness with the transparent coating may be insufficient.

  The thickness of the antireflection film is preferably 50 to 300 nm, more preferably 80 to 200 nm. Within this range, an antireflection film having high film strength and excellent antireflection performance can be formed.

  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. If 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 method for forming the antireflection film is not particularly limited, and it 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 transparent film. In particular, when the forming component is a thermosetting resin, curing of the antireflection film may be promoted by heat treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, etc. When a functional organosilicon compound is contained, hydrolysis and polycondensation of the hydrolyzable organosilicon compound may be promoted.

As described above, the present invention has high conductivity because the conductive oxide fine particles and the matrix-forming component are composed of the glycol acrylate resin (A) and the non-glycol acrylate resin (B). The coating for forming a transparent film and the coating for forming a transparent film can be suitably used for the formation of a transparent film having excellent antistatic properties, scratch resistance, film hardness, transparency and the like, as well as excellent antistatic performance and economy. Thus, a substrate with a transparent coating formed can be provided.
[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by these Examples.
[Example 1]
Preparation of paint for transparent film formation (1)
(i) Preparation of P-doped tin oxide fine particles To 8060 g of pure water, 13 g of ammonium nitrate and 20 g of 15% ammonia water were added and stirred, 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 completion of the addition, the temperature was kept at 50 ° C. for 1 hour, and 10% by weight of 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 obtained P-doped tin oxide fine particles (1) have an average particle diameter of 15 nm and a volume resistance of 5000Ω.
-It was cm.
(ii) 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, quartz beads (0. 15 mm) 1000 g was added, and the mixture was sufficiently stirred and pulverized and dispersed in a bead mill. Then, the quartz beads and the dispersion were separated with a 325 mesh (mesh opening 44 microns) stainless steel wire mesh, and the quartz beads remaining on the wire mesh were further separated. The solution washed with 1560 g of ion-exchanged water was thoroughly mixed, and this solution was heat-treated at 90 ° C. for 1 hour, cooled to room temperature, and then 96 g of anion-exchange resin was added and stirred for 1 hour, followed by separation of the anion-exchange resin. Next, 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).

Next, 2 g of normal ethyl silicate (ethyl silicate 28 SiO ₂ component 28.8%, manufactured by Tama Chemical Co., Ltd.) as a coupling agent was added to 2000 g of 10 wt% P-doped tin oxide fine water spray.
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 P-doped tin oxide fine particle (1) 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.
(iii) Preparation of Transparent Film Forming Paint (1) To 50 g of the surface-treated P-doped tin oxide fine particle dispersion, polyethylene glycol diacrylate as a glycol-based acrylate resin (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Ester A-400) 12.5 g, 7.5 g of 1,6-hesandiol diacrylate (Nippon Kayaku Co., Ltd .: Kayarad KS-HDDA) as a non-glycol-based bifunctional acrylate resin and dipentaerythritol as a non-glycol-based hexafunctional acrylate resin 15 g of hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-6A) and 55 g of isopropyl alcohol
And 26.7 g of butyl cellosolve and 1.4 g of photoinitiator 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BAS Japan Co., Ltd .: Lucyrin TPO) are mixed to form a coating solution for forming a transparent film (1) Was prepared.
(iv) Production of Substrate with Transparent Film (F-1) The coating liquid (1) for forming a transparent film was obtained by using a PET film (thickness: 188 μm, refractive index: 1.65, total light transmittance: 90.0%, haze: 0) .6%) by a bar coater method (bar # 14), dried at 80 ° C. for 1 minute, and then an ultraviolet irradiation device equipped with a high-pressure mercury lamp (120 W / cm) (UV irradiation device CS30L21-3 manufactured by Nippon Batteries) Was cured by irradiation with 600 mJ / cm ² to prepare a substrate with transparent coating (F-1). At this time, the thickness of the transparent film was 4 μm. The surface resistance of the obtained transparent 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 were measured with a haze meter (manufactured by Suga Test Instruments Co., Ltd.), and the results are shown in Table 1. In addition, the colorability is visually observed and evaluated according to the following criteria, and the results are shown in the table.

Evaluation / Colorability The colorability was evaluated from the following viewpoints.
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.
· Using a scratch resistance of the measuring # 0000 steel wool, and slide 50 times at a load 500 g / cm ^2, the surface of the film was visually observed, and evaluated according to the following criteria, the results shown in the tables.

Evaluation criteria:
No streak injury is found: ◎
Slightly scratched streak: ○
Many scratches are found in the streak: △
The surface has been cut entirely: ×
・ Adhesiveness 11 parallel scratches are made on the surface of the substrate with transparent coating (F-1) at intervals of 1 mm in length and width with a knife 1
00 cells were made, cellophane tape (registered trademark) was adhered to this, and then the cellophane tape (registered trademark) was peeled off, and the number of cells remaining without peeling off was determined by the following four steps. The adhesion was evaluated by classifying into 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]
(iii) Preparation of Transparent Film Forming Paint (2) To 50 g of the surface-treated P-doped tin oxide fine particle dispersion prepared in the same manner as in Example 1, a glycol-based acrylate resin polyethylene glycol diacrylate (Shin Nakamura Chemical Co., Ltd.) Manufactured: NK ester A-400) 5 g, non-glycol bifunctional acrylate resin 1,6-Hesandiol diacrylate (Nippon Kayaku Co., Ltd. product: Kayarad KS-HDDA) 12.5 g and non-glycol hexafunctional acrylate Resin dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-6A), 17.5 g, isopropyl alcohol 55 g, butyl cellosolve 26.7 g, photoinitiator 2,4,6-trimethylbenzoyldiphenylphosphine oxide (BSS Japan Co., Ltd .: Lucillin TPO) 1.4 g was mixed to prepare a coating solution (2) for forming a transparent film.
(iv) Production of transparent film-coated substrate (F-2) A transparent film-coated substrate (F-2) was prepared in the same manner as in Example 1 except that the transparent film-forming coating solution (2) was used. . The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the transparent coating were evaluated, and the results are shown in the table.
[Example 3]
(iii) Preparation of Transparent Film Forming Paint (3) To 50 g of the surface-treated P-doped tin oxide fine particle dispersion prepared in the same manner as in Example 1, a glycol acrylate resin polyethylene glycol diacrylate (Shin Nakamura Chemical Co., Ltd.) Manufactured by: NK ester A-400) 17.5 g, non-glycol bifunctional acrylate resin 1,6-Hesandiol diacrylate (manufactured by Nippon Kayaku Co., Ltd .: Kayarad KS-HDDA) 2.5 g and non-glycol 6 15 g of functional acrylate resin dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-6A), 55 g of isopropyl alcohol, 26.7 g of butyl cellosolve, and photoinitiator 2.4.6-trimethylbenzoyldiphenylphosphine oxide (Bi -Made by AS Japan Co., Ltd .: Lucilin TPO) 1 4 g was mixed to prepare a coating liquid for forming a transparent film (3).
(iv) Production of substrate with transparent coating (F-3) A substrate with transparent coating (F-3) was prepared in the same manner as in Example 1, except that the coating solution for forming a transparent coating (3) was used. . The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the transparent coating were evaluated, and the results are shown in the table.
[Example 4]
(iii) Preparation of paint for forming transparent film (4) In Example 1, 50 g of the surface-treated P-doped tin oxide fine particle dispersion was mixed with polypropylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK) as a glycol-based acrylate resin. 12.5 g of ester APG-400), 7.5 g of 1,9-nonanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate 1,9ND-A) and non-glycol 4 15 g of pentaerythritol tetraacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate PE-4A) as a functional acrylate resin
A coating solution (4) for forming a transparent film was prepared in the same manner except that was mixed.
(iv) Production of substrate with transparent coating (F-4) A substrate with transparent coating (F-4) was prepared in the same manner as in Example 1, except that the coating solution for forming a transparent coating (4) was used. .

The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the transparent coating were evaluated, and the results are shown in the table.
[Example 5]
(iii) Preparation of paint for forming transparent film (5) In Example 1, 50 g of the surface-treated P-doped tin oxide fine particle dispersion was mixed with polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK) as a glycol-based acrylate resin. 12.5 g of ester A-600), 7.5 g of 3-methyl-1,5-pentanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate MPD-A) as a non-glycolic bifunctional acrylate resin 15 g of pentaerythritol triacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate PE-3A) as a trifunctional acrylate resin
A coating solution (5) for forming a transparent film was prepared in the same manner except that was mixed.
(iv) Production of transparent film-coated substrate (F-5) A transparent film-coated substrate (F-5) was prepared in the same manner as in Example 1 except that the transparent film-forming coating solution (5) was used. . The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the transparent coating were evaluated, and the results are shown in the table.
[Example 6]
(iii) Preparation of Transparent Film Forming Paint (6) In Example 1, 37.5 g of the surface-treated P-doped tin oxide fine particle dispersion was added to polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) as a glycol-based acrylate resin. : NK ester A-400) 20 g, 1,6-hesandiol diacrylate (Nippon Kayaku Co., Ltd .: Kayrad KS-HDDA) 10.5 g and non-glycol 6-functional acrylate as non-glycol bifunctional acrylate resin A coating solution (6) for forming a transparent film was prepared in the same manner except that 12 g of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-6A) was mixed as the resin.
(iv) Production of substrate with transparent coating (F-6) A substrate with transparent coating (F-6) was prepared in the same manner as in Example 1, except that the coating solution for forming a transparent coating (6) was used. . The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the transparent coating were evaluated, and the results are shown in the table.
[Example 7]
(iii) Preparation of Transparent Film Forming Paint (7) In Example 1, 100 g of the surface-treated P-doped tin oxide fine particle dispersion was added to polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK) as a glycol-based acrylate resin. 2.5 g of ester A-400), 1,6-hesandiol diacrylate (Nippon Kayaku Co., Ltd .: Kayrad KS-HDDA) as a non-glycol bifunctional acrylate resin, and non-glycol hexafunctional A coating solution (7) for forming a transparent film was prepared in the same manner except that 15 g of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-6A) was mixed as the acrylate resin.
(iv) Production of substrate with transparent coating (F-7) A substrate with transparent coating (F-7) was prepared in the same manner as in Example 1, except that the coating solution for transparent coating formation (7) was used. . The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the transparent coating were evaluated, and the results are shown in the table.
[Example 8]
(iii) Preparation of transparent film-forming coating material (8) Tin-doped indium oxide fine particles (manufactured by Catalyst Kasei Kogyo Co., Ltd .: ELCOM TL-130, SnO ₂ content 8% by weight, average particle diameter 20 nm, volume resistance value 0.05Ω・ Cm) 60g
And ethanol (140 g) were put into a 2 L glass beaker, acetylacetone (1.8 g) and 61% nitric acid solution (0.02 g) were added, and then quartz beads (0.15 mm) (1000 g) were added. After that, the quartz beads and the dispersion were separated with a 325 mesh (mesh opening 44 microns) stainless steel wire mesh, and the quartz beads remaining on the wire mesh were washed thoroughly with 100 g of ethanol to sufficiently mix the tin-doped indium oxide fine particles. A dispersion (concentration 20% by weight) was obtained.

  To this, 0.6 g of polyethylene ethylene alkyl ether phosphate (Daiichi Kogyo Seiyaku Co., Ltd .: Prisurf 217E) was added as a surfactant and stirred for 30 minutes to carry out a surface treatment with a solid concentration of 20% by weight. An alcohol dispersion of tin-doped indium oxide fine particles was prepared.

Polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Ester A-400) was added as a glycol-based acrylate resin to 37.5 g of a tin-doped indium oxide fine particle dispersion surface-treated with a surfactant of polyoxyethylene alkyl ether phosphate. ) 15 g, 1,6-Hesandiol diacrylate (Nippon Kayaku Co., Ltd .: Kayrad KS-HDDA) as a non-glycolic bifunctional acrylate resin and dipentaerythritol hexaacrylate (as non-glycolic hexafunctional acrylate resin) 17.5 g of Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-6A), 55 g of isopropyl alcohol, 30 g of butyl cellosolve and photoinitiator 2.4.6-trimethylbenzoyldiphenylphosphine oxide (BJS Japan) A coating solution for forming a transparent film (8) was prepared by mixing 1.7 g of Lucillin TPO (manufactured by Co., Ltd.).
(iv) Production of transparent film-coated substrate (F-8) A transparent film-coated substrate (F-8) was prepared in the same manner as in Example 1 except that the transparent film-forming coating solution (8) was used. . The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the transparent coating were evaluated, and the results are shown in the table.
[Example 9]
(iii) Preparation of paint for forming transparent film (9) Antimony-doped tin oxide fine particles (manufactured by Catalyst Kasei Kogyo Co., Ltd .: ELCOM TL-30HK, Sb ₂ O ₅ content 16% by weight, average particle diameter 8 nm, volume resistivity 60 g of 1.0 Ω · cm) was dispersed in 140 g of a 4.3 wt% potassium hydroxide aqueous solution, and the dispersion was pulverized with a sand mill for 3 hours while maintaining the dispersion at 30 ° C. to prepare a sol.

  The sol was subjected to dealkalization ion treatment with an ion exchange resin until the pH became 3.0, and then pure water was added to prepare a Sb-doped tin oxide fine particle dispersion having a solid content concentration of 20% by weight. The pH of this Sb-doped tin oxide fine particle dispersion was 3.3. The average particle size was 8 nm.

Next, 100 g of a 20% by weight Sb-doped tin oxide fine particle dispersion was adjusted to 25 ° C., and tetraethoxysilane (manufactured by Tama Chemical Co., Ltd .: normal ethyl silicate, SiO ₂ concentration 28.8%) 4
. After adding 0 g in 3 minutes, the mixture was stirred for 30 minutes. Thereafter, 100 g of ethanol was added over 1 minute, the temperature was raised to 50 ° C. over 30 minutes, and a heat treatment was performed for 15 hours. The solid concentration at this time was 10% by weight.

The dispersion medium water and ethanol were replaced with ethanol using an ultrafiltration membrane to prepare a surface-treated Sb-doped tin oxide fine particle dispersion having a solid content concentration of 20% by weight.
50 g of the surface-treated Sb-doped tin oxide fine particle dispersion, 15 g of polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Ester A-400) as a glycol acrylate resin, and 1 as a non-glycol bifunctional acrylate resin 7.5 g of 6-Hesanediol diacrylate (Nippon Kayaku Co., Ltd .: Kayarad KS-HDDA) and dipentaerythritol hexaacrylate (non-glycolic 6-functional acrylate resin: Kyoeisha Chemical Co., Ltd .: Light Acrylate DPE-6A) 17.5g and isopropyl alcohol 45
g, 30 g of butyl cellosolve and 1.6 g of photoinitiator 2.4.6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BAES Japan Co., Ltd .: Lucyrin TPO) Prepared.
(iv) Production of Substrate with Transparent Film (F-9) A coating liquid for forming a transparent film (9) was obtained by using a PET film (thickness: 188 μm, refractive index: 1.65, total light transmittance: 90.0%, haze: 0) .6%) by a bar coater method (bar # 14), dried at 80 ° C. for 1 minute, and then an ultraviolet irradiation device equipped with a high-pressure mercury lamp (120 W / cm) (UV irradiation device CS30L21-3 manufactured by Nippon Batteries) Was cured by irradiation with 600 mJ / cm ² to prepare a substrate with transparent coating (F-9). At this time, the thickness of the transparent film was 4 μm.

The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the transparent coating were evaluated, and the results are shown in the table.
[Example 10]
(iii) Preparation of Transparent Film Forming Paint (10) Antimony trioxide (Nippon Seiko Co., Ltd .; Patex M) in a solution of 250 g of caustic potash (Asahi Glass Co., Ltd .: 85% purity) dissolved in 8000 g of pure water ) 500 g was suspended. This suspension was heated to 95 ° C., and an aqueous solution obtained by diluting 150 g of hydrogen peroxide water (produced by Hayashi Junyaku Co., Ltd .: special grade, concentration 35% by weight) with 500 g of pure water was added in 9 hours, and antimony trioxide was added. And then aged for 11 hours. Next, after cooling, 8000 g is taken from the resulting solution, this solution is diluted with 48 kg of pure water, and treated with a cation exchange resin (Mitsubishi Chemical Corporation: pk-216) until the pH becomes 3.5. And deionized. The solution obtained by deionization was aged at a temperature of 70 ° C. for 10 hours, and then concentrated with an ultra-fine film to prepare a conductive fine particle dispersion composed of antimony pentoxide having a solid concentration of 14%. The pH of this conductive fine particle dispersion was 4.0. The average particle size of the conductive fine particles was 20 nm.

1000 g of the obtained conductive fine particle dispersion was adjusted to 25 ° C., and 25 g of tetraethoxysilane (manufactured by Tama Chemical Co., Ltd .: normal ethyl silicate, SiO ₂ concentration 28.8%) was added in 3 minutes.
Stirring was performed for 0 minutes. Thereafter, 1000 g of methanol was added over 1 minute, the temperature was raised to 50 ° C. over 30 minutes, and a heat treatment was performed for 19 hours. The solid concentration at this time was 7% by weight.

  An antimony pentoxide fine particle dispersion coated with silica having a solid content of 20% by weight was prepared by replacing water and methanol as a dispersion medium with an ultrafiltration membrane. 4 g of γ-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503) was added as a silane coupling agent to 400 g of this antimony pentoxide fine particle dispersion (average particle diameter 20 nm, volume resistivity 500 Ω · cm). Then, heat treatment was performed at 50 ° C. Subsequently, 400 g of a surface-treated antimony pentoxide fine particle dispersion having a solid content concentration of 20 wt% was prepared by substituting the solvent (isopropyl alcohol / methanol weight ratio = 90/10).

50 g of the surface-treated antimony pentoxide fine particle dispersion, 15 g of polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .: NK Ester A-400) as a glycol acrylate resin, and 1, 6 as a non-glycol bifunctional acrylate resin -Hesandiol diacrylate (Nippon Kayaku Co., Ltd .: Kayrad KS-HDDA) 7.5 g and dipentaerythritol hexaacrylate as a non-glycol 6-functional acrylate resin (Kyoeisha Chemical Co., Ltd .: Light Acrylate DPE-6A) 17.5g and isopropyl alcohol 18
g, 15 g of butyl cellosolve and 1.6 g of photoinitiator 2.4.6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BIAS JAPAN KK: Lucyrin TPO) are mixed to form a coating solution for forming a transparent film (10) Was prepared.
(iv) Production of substrate with transparent coating (F-10) The coating for transparent coating (10) was applied to a PET film (thickness: 188 μm, refractive index: 1.65) by the bar coater method (# 20). After drying at 80 ° C. for 1 minute, a high pressure mercury lamp (80 W / cm) was irradiated for 1 minute to cure, thereby preparing a substrate with transparent coating (F-10). The thickness of the transparent film at this time was 12 μm. The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the transparent coating were evaluated, and the results are shown in the table.
[Example 11]
(iii) Preparation of Transparent Film Forming Paint (11) 100 g of the surface-treated tin-doped indium oxide fine particle dispersion prepared in the same manner as in Example 8 was added with polyethylene glycol diacrylate as a glycol-based acrylate resin (Shin Nakamura Chemical Co., Ltd.) Manufactured by: NK Ester A-400), 3 g of 1,6-hesandiol diacrylate (Nippon Kayaku Co., Ltd .: Kayalad KS-HDDA) and non-glycol 6-functional acrylate resin 14 g of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-6A)
And 100 g of isopropyl alcohol, 200 g of butyl cellosolve, and 0.8 g of photoinitiator 2.4.6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BIAS JAPAN KK: Lucyrin TPO) are mixed to form a coating solution for forming a transparent film (11) was prepared.
(iv) Production of substrate with transparent coating (F-11) A coating solution (11) for forming a transparent coating was prepared by using an acrylic substrate (thickness: 3 mm, refractive index: 1.52), total light transmittance 92.0%, After coating with haze 0.1% by the bar coater method (bar # 4), drying at 80 ° C. for 1 minute, an ultraviolet irradiation device equipped with a high-pressure mercury lamp (120 W / cm) (UV irradiation device CS30L21-3 manufactured by Nippon Batteries) ) Was cured by irradiation with 600 mJ / cm ² to prepare a substrate with transparent coating (F-11). The thickness of the transparent film at this time was 120 nm.

The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the transparent coating were evaluated, and the results are shown in the table.
[Example 12]
(iii) Preparation of Transparent Film Forming Paint (12) 100 g of the surface-treated antimony-doped tin oxide fine particle dispersion prepared in the same manner as in Example 9 was added to polyethylene glycol diacrylate (Shin Nakamura Chemical Co., Ltd.) as a glycol-based acrylate resin. ): NK ester A-400) 1.5 g, 1,6-hesandiol diacrylate (Nippon Kayaku Co., Ltd .: Kayrad KS-HDDA) 1.5 g and non-glycol as a non-glycol bifunctional acrylate resin Dipentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer (manufactured by Kyoeisha Chemical Co., Ltd .: urethane acrylate UA-306H), 10.3 g of isopropyl alcohol, 200 g of butyl cellosolve, and photoinitiator 2.4. .6-Trimethylbenzo Le diphenylphosphine oxide (bi - Eesu Japan Ltd.: Lucirin TPO) was transparent film-forming coating liquid was mixed with 0.6g (12) was prepared.
(iv) Production of substrate with transparent coating (F-12) Transparent coating-forming coating solution (12) was prepared using an acrylic substrate (thickness: 3 mm, refractive index: 1.52), total light transmittance of 92.0%, After coating with haze 0.1% by the bar coater method (bar # 4), drying at 80 ° C. for 1 minute, an ultraviolet irradiation device equipped with a high-pressure mercury lamp (120 W / cm) (UV irradiation device CS30L21-3 manufactured by Nippon Batteries) ) Was cured by irradiation with 600 mJ / cm ² to prepare a substrate with transparent coating (F-12). The thickness of the transparent film at this time was 100 nm.

The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the transparent coating were evaluated, and the results are shown in the table.
[Example 13 (reference example) ]
(iii) Preparation of Transparent Film Forming Paint (13) In Example 1, as the non-glycol acrylate resin, non-glycol hexafunctional acrylate resin, dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-6A ) A coating solution (13) for forming a transparent film was prepared in the same manner except that 22.5 g was used.
(iv) Production of substrate with transparent coating (F-13) A substrate with transparent coating (F-13) was prepared in the same manner as in Example 1, except that the coating solution for transparent coating formation (13) was used. did.

The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the transparent coating were evaluated, and the results are shown in the table.
[Comparative Example 1]
(iii) Preparation of Transparent Film Forming Paint (R-1) In Example 1, 50 g of the surface-treated P-doped tin oxide fine particle (1) dispersion was mixed with polyethylene glycol diacrylate (Shin Nakamura Chemical Co., Ltd.) as a glycol-based acrylate resin. Co., Ltd .: NK Ester A-400) was mixed with 35 g, and a coating solution for forming a transparent film (R-) was used except that a non-glycolic bifunctional acrylate resin and a nonglycolic hexafunctional acrylate resin were not added. 1) was prepared.
(iv) Production of substrate with transparent coating (RF-1) A substrate with transparent coating (RF-1) was prepared in the same manner as in Example 1 except that the coating solution for transparent coating formation (R-1) was used. Prepared.

The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the transparent coating were evaluated, and the results are shown in the table.
[Comparative Example 2]
(iii) Preparation of Transparent Film Forming Paint (R-2) In Example 1, 50 g of the surface-treated P-doped tin oxide fine particle (1) dispersion was added to 1,6-hesandiol as a non-glycol bifunctional acrylate resin. 20 g of diacrylate (manufactured by Nippon Kayaku Co., Ltd .: Kayrad KS-HDDA) and 15 g of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate DPE-6A) as a non-glycol-based hexafunctional acrylate resin were mixed. A coating solution (R-2) for forming a transparent film was prepared in the same manner except that.
(iv) Production of substrate with transparent coating (RF-2) A substrate with transparent coating (RF-2) was prepared in the same manner as in Example 1, except that the coating solution for transparent coating formation (R-2) was used. Prepared.

The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the transparent coating were evaluated, and the results are shown in the table.
[Comparative Example 3]
(iii) Preparation of Transparent Film Forming Paint (R-3) In Example 1, 50 g of the surface-treated P-doped tin oxide fine particle (1) dispersion was mixed with polyethylene glycol diacrylate (Shin Nakamura Chemical ( Co., Ltd .: NK Ester A-400) 31.5 g, 1,6-hesandiol diacrylate (Nippon Kayaku Co., Ltd .: Kayrad KS-HDDA) 1 g and non-glycolic bifunctional acrylate resin A coating solution for forming a transparent film (R-3) was prepared in the same manner except that 2.5 g of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-6A) was mixed as a hexafunctional acrylate resin. .
(iv) Production of substrate with transparent coating (RF-3) A substrate with transparent coating (RF-3) was prepared in the same manner as in Example 1 except that the coating solution for transparent coating formation (R-3) was used. Prepared.

The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the transparent coating were evaluated, and the results are shown in the table.
[Comparative Example 4]
(iii) Preparation of Transparent Film Forming Paint (R-4) In Example 1, 50 g of the surface-treated P-doped tin oxide fine particle (1) dispersion was mixed with polyethylene glycol diacrylate (Shin Nakamura Chemical) as a glycol-based acrylate resin. Co., Ltd .: NK Ester A-400) 2 g, non-glycol bifunctional acrylate resin 1,6-Hesandiol diacrylate (Nippon Kayaku Co., Ltd .: Kayrad KS-HDDA) 7.5 g and non-glycol A coating solution (R-4) for forming a transparent film was prepared in the same manner except that 25.5 g of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light Acrylate DPE-6A) was mixed as a hexafunctional acrylate resin. did.
(iv) Production of substrate with transparent coating (RF-4) A substrate with transparent coating (RF-4) was prepared in the same manner as in Example 1 except that the coating solution for transparent coating formation (R-4) was used. Prepared.

The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the transparent coating were evaluated, and the results are shown in the table.
[Comparative Example 5]
(iii) Preparation of paint for forming transparent film (R-5) In Example 8, 37.5 g of the surface-treated tin-doped indium oxide fine particle dispersion was added to polyethylene glycol diacrylate (Shin Nakamura Chemical Co., Ltd.) as a glycol-based acrylate resin. Manufactured: NK ester A-400) 38 g, 1,6-Hesandiol diacrylate (Nippon Kayaku Co., Ltd .: Kayrad KS-HDDA) 0.6 g and non-glycol hexafunctional 1.3 g of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-6A) as the acrylate resin
A coating solution for forming a transparent film (R-5) was prepared in the same manner except that was mixed.
(iv) Production of substrate with transparent coating (RF-5) A substrate with transparent coating (RF-5) was prepared in the same manner as in Example 1, except that the coating solution for transparent coating formation (R-5) was used. Prepared.

The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the transparent coating were evaluated, and the results are shown in the table.
[Comparative Example 6]
(iii) Preparation of Transparent Film Forming Paint (R-6) In Example 8, 37.5 g of the surface-treated tin-doped indium oxide fine particle dispersion was added with polyethylene glycol diacrylate (Shin Nakamura Chemical Co., Ltd.) as a glycol acrylate resin. Manufactured by: NK ester A-400) 2.1 g, and non-glycolic bifunctional acrylate resin 1,6-hesandiol diacrylate (Nippon Kayaku Co., Ltd .: Kayrad KS-HDDA) 8.5 g and non-glycolic Dipentaerythritol hexaacrylate (produced by Kyoeisha Chemical Co., Ltd .: Light acrylate DPE-6A) as a hexafunctional acrylate resin 31.9 g
A coating solution for forming a transparent film (R-6) was prepared in the same manner except that was mixed.
(iv) Production of substrate with transparent coating (RF-6) A substrate with transparent coating (RF-6) was prepared in the same manner as in Example 1, except that the coating solution for transparent coating formation (R-6) was used. Prepared.

The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the transparent coating were evaluated, and the results are shown in the table.
[Reference Example 1]
(iv) Production of Substrate with Transparent Film (SF-1) A coating liquid for forming a transparent film (11) prepared in the same manner as in Example 11 was prepared from a PET film (thickness: 188 μm, refractive index: 1.65, all A UV coater (120 W / cm) mounted with a high-pressure mercury lamp (120 W / cm) after being applied to a light transmittance of 90.0% and a haze of 0.6% by a bar coater method (bar # 30) and dried at 80 ° C. for 1 minute. A base material with a transparent coating (SF-1) was prepared by curing with irradiation of 600 mJ / cm ² with a UV irradiation device CS30L21-3) manufactured by Nippon Batteries. The thickness of the transparent film at this time was 2 μm.

The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the transparent coating were evaluated, and the results are shown in the table.
[Reference Example 2]
(iv) Production of Substrate with Transparent Film (SF-2) A transparent film-forming coating material (12) prepared in the same manner as in Example 12 was placed on a PET film (thickness: 188 μm, refractive index: 1.65). After applying by the coater method (# 30) and drying at 80 ° C. for 1 minute, the substrate was irradiated with a high-pressure mercury lamp (80 W / cm) for 1 minute to be cured to prepare a substrate with a transparent coating (RF-8). The thickness of the transparent film at this time was 2 μm.

  The thickness, surface resistance, total light transmittance, haze, colorability, pencil hardness, scratch resistance and adhesion of the transparent coating were evaluated, and the results are shown in the table.

Claims (9)

A transparent film-forming paint comprising conductive oxide fine particles, a matrix-forming component, and a solvent,
The matrix-forming component comprises a glycol-based acrylate resin (A) and a non-glycol-based acrylate resin (B), and the content of the glycol-based acrylate resin (A) in the matrix-forming component is 10 to 80% by weight as a solid content. In range
The non-glycol acrylate resin (B) is
Non-glycol-based bifunctional acrylate resin (B1) and one or more non-glycol-based acrylate resins selected from non-glycol-based trifunctional acrylate resins, non-glycol-based tetrafunctional acrylate resins and non-glycol-based hexafunctional acrylate resins (B2) The non-glycolic bifunctional acrylate resin (B1) in the non-glycolic acrylate resin (B) is in the range of 5 to 50% by weight as a solid content (however, any acrylate in the matrix-forming component) Uncured resin)
Glycol-based acrylate resin (A) is polyethylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, polyethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polypropylene glycol diacrylate. A transparent film-forming paint characterized in that it is at least one selected from methacrylates .   The conductive oxide fine particles are at least one selected from tin oxide, tin oxide doped with Sb or P, indium oxide, indium oxide doped with Sn or F, antimony pentoxide, and low-order titanium oxide. The transparent film-forming paint according to claim 1.   The transparent film-forming paint according to claim 1 or 2, wherein the conductive oxide fine particles have an average particle diameter in the range of 5 to 200 nm. The solid content concentration of the conductive oxide fine particles in the paint is in the range of 0.5 to 40% by weight, the solid content concentration of the matrix-forming component is in the range of 1 to 45% by weight,
The transparent film-forming paint according to any one of claims 1 to 3, wherein the total solid concentration in the paint is in the range of 5 to 50% by weight. A substrate and a transparent film formed on the substrate;
The transparent coating contains conductive oxide fine particles and a matrix component,
The matrix component consists of glycol acrylate resin (A) and non-glycol acrylate resin (B),
The non-glycol acrylate resin (B) is selected from non-glycol bifunctional acrylate resin (B1), non-glycol trifunctional acrylate resin, non-glycol tetrafunctional acrylate resin, and non-glycol hexafunctional acrylate resin 1 It consists of a mixture with more than one kind of non-glycol acrylate resin (B2),
The content of the glycol acrylate resin (A) in the matrix component in which the non-glycol bifunctional acrylate resin (B1) in the non-glycol acrylate resin (B) is in the range of 5 to 50% by weight as the solid content is the solid content. In the range of 10 to 80% by weight,
Glycol-based acrylate resin (A) is polyethylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, polyethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polypropylene glycol diacrylate. A substrate with a transparent coating, which is at least one selected from methacrylates .   The conductive oxide fine particles are at least one selected from tin oxide, tin oxide doped with Sb or P, indium oxide, indium oxide doped with Sn or F, antimony pentoxide, and low-order titanium oxide. The base material with a transparent coating film of Claim 5 characterized by these.   The substrate with a transparent coating according to claim 5 or 6, wherein the conductive oxide fine particles have an average particle diameter in the range of 5 to 200 nm.   8. The substrate with a transparent coating according to claim 5, wherein the content of the conductive oxide fine particles in the transparent coating is in the range of 10 to 80 wt% as a solid content.   The substrate with a transparent coating according to any one of claims 5 to 8, wherein the thickness of the transparent coating is in the range of 30 nm to 20 µm.