JP2009035573A - Surface treatment method for metal oxide particle, dispersion liquid containing the surface treated metal oxide particle, coating liquid for forming transparent coating film, and substrate with transparent coating film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an efficient surface treatment method for metal oxide particles excellent in dispersibility and dispersion stability. <P>SOLUTION: An organic silicon compound expressed by general formula (1) is added to hydrolyze in a dispersion liquid of metal oxide particles in water and/or an organic solvent, to which, subsequently, an organic silicon compound expressed by formula (2) is added to hydrolyze. The formulae are: (1):(NH<SB>2</SB>-C<SB>n</SB>H<SB>2n</SB>-Z-C<SB>m</SB>H<SB>2m</SB>)<SB>L</SB>-Si-Y<SB>4-L</SB>, wherein Z represents -NH or -CH<SB>2</SB>, Y represents a 1-4C alkoxy group, a hydroxyl group, halogen or hydrogen, L represents an integer of 1 to 3, n represents an integer of 0 to 10 and m represents an integer of 0 to 10; and (2):R<SB>p</SB>-SiX<SB>4-p</SB>, wherein R represents a 1-10C substituted or unsubstituted hydrocarbon group and may be identical or different from each other, X represents a 1-4C alkoxy group, a hydroxyl group, halogen or hydrogen, and p represents an integer of 1 to 3, however, the formula excludes an amino group-substituted hydrocarbon group. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  According to the present invention, the metal oxide particles are first surface-treated with an organosilicon compound having an amino group, and then surface-treated with an organosilicon compound not containing an amino group. The present invention relates to a method, a coating solution containing surface-treated metal oxide particles, and a substrate with a transparent coating.

  It is known that a hard coat film is formed on the surface of the base material in order to improve the scratch resistance of the surface of the base material such as glass, plastic sheet, plastic lens, resin film, and display device front plate. An organic resin film or an inorganic film is formed as a coat film on the surface of glass, plastic or the like. Furthermore, it is practiced to further improve the scratch resistance by blending resin particles or inorganic particles such as silica in an organic resin film or an inorganic film.

In addition, a substrate with a transparent coating having antistatic performance, electromagnetic shielding performance and the like by blending conductive particles in the transparent coating is also known. Furthermore, a high refractive index transparent film in which high refractive index particles are blended in a transparent film, a low refractive index transparent film having antireflection performance in which low refractive index particles are blended in a transparent film, and a transparent film in which colored pigment particles are blended Etc. are known.
When, for example, metal oxide fine particles are blended in the transparent film, the dispersibility may be poor depending on the matrix components constituting the transparent film, and the stability of the coating liquid for forming the transparent film becomes insufficient. Adhesion with the material, strength, scratch resistance, etc. may be insufficient. For this reason, the metal oxide fine particles are previously treated with a silane coupling agent to improve the dispersibility in the matrix component.

  However, even if treated with a silane coupling agent, the dispersibility, dispersion stability, etc. are improved to some extent, but unreacted silane coupling agent remains in the resulting transparent film, and thus the smoothness of the film is reduced. In some cases, the temperature may be lowered, or curing may be insufficient or non-uniform. For this reason, cracks may be generated, or moisture resistance may be insufficient due to cracks. For this reason, a desired reflectance may not be obtained, and in addition, sufficient adhesion to the substrate, scratching properties, and the like may not be obtained.

The applicant of the present application treats the metal oxide particles with the silane coupling agent on the surface of the metal oxide particles by treating the metal oxide particles with a tetrafunctional alkoxysilane in advance before treating the metal oxide particles with the silane coupling agent. A high-functional hydroxyl group (silanol group) is formed. For this reason, the silane coupling agent is firmly bonded to the surface of the metal oxide particles at high density, and the dispersibility and dispersion stability are improved. Has been found to improve.
However, even if this method is used, the smoothness and curability of the film are improved to some extent, but the unreacted silane coupling agent in the transparent film may remain, and sufficient adhesion to the substrate or In some cases, scratch resistance or the like could not be obtained.

  Under such circumstances, as a result of intensive studies to solve the above-mentioned problems, the present inventors first treated the metal oxide particles with an organosilicon compound having an amino group, and then contained an amino group. It has been found that when metal oxide particles surface-treated with no organosilicon compound are used, cracks are not generated in the resulting transparent film, and the moisture resistance, adhesion to the substrate, scratch resistance, etc. are greatly improved. The present invention has been completed.

  The present invention relates to an efficient surface treatment method for metal oxide particles having excellent dispersibility and dispersion stability, and a dispersion containing the obtained surface-treated metal oxide particles, a coating liquid for forming a transparent film, and a base with a transparent film The purpose is to provide materials.

In the surface treatment method for metal oxide particles of the present invention, an organic silicon compound represented by the following (1) is added to water and / or an organic solvent dispersion of the metal oxide particles for hydrolysis, and then the following formula: Hydrolysis is performed by adding an organosilicon compound represented by (2).
_{(NH 2 -C n H 2n -Z} -C m H 2m) L -Si-Y 4-L (1)
(Wherein, Z: —NH, —CH ₂ , Y: C 1-4 alkoxy group, hydroxyl group, halogen, hydrogen. L: integer of 1 to 3, n: integer of 0 to 10, m: An integer from 0 to 10.)
R _p -Si x _4-p (2)
(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, a hydroxyl group, Halogen, hydrogen, p: an integer of 1 to 3, with the exception of an amino group-substituted hydrocarbon group in the substituted hydrocarbon group.

The content of the organosilicon compound represented by the formula (1) in the surface-treated metal oxide particles is [(NH ₂ —C _n H _2n —Z—C _m H _2m ) _L —SiO _{4 -L / 2} ] in the range of 0.001 to 20 wt%, and the content of the organosilicon compound represented by the formula (2) is in the range of 1 to 60 wt% as R _p —Si—O _{4−p / 2} It is preferable that it exists in.
The metal oxide particles are silica, alumina, zirconia, titanium oxide, tin oxide, zinc oxide, antimony pentoxide, indium oxide, low-order titanium oxide and complex oxides thereof, or Sb-doped tin oxide (ATO), F-doped One or more selected from tin oxide, P-doped tin oxide, Sn-doped indium oxide (ITO), and F-doped indium oxide, and preferably having an average particle diameter in the range of 3 to 300 nm.
The average particle diameter of the surface-treated metal oxide particles is preferably in the range of 3 to 300 nm.

  The surface-treated metal oxide particle dispersion of the present invention comprises the surface-treated metal oxide particles obtained by the surface treatment method and a dispersion medium, and the concentration of the surface-treated metal oxide particles is in the range of 1 to 50% by weight. It is characterized by that.

The coating liquid for forming a transparent film of the present invention comprises the surface-treated metal oxide particles obtained by the surface treatment method, a matrix-forming component, and a dispersion medium.
The concentration (C _P ) of the surface-treated metal oxide particles is in the range of 0.1 to 40% by weight as the solid content, and the concentration (C _M ) of the matrix-forming component is 1.9 to 49.9 as the solid content. The total concentration (C _P ) + (C _M ) is preferably in the range of 2 to 50% by weight as the solid content.

The substrate with a transparent coating of the present invention comprises a substrate and a transparent coating provided on the substrate, and the transparent coating comprises a matrix component and the surface-treated metal oxide particles obtained by the production method. The content of the surface-treated metal oxide particles in the transparent film is in the range of 0.2 to 80% by weight as the solid content.
It is preferable that the film thickness of the transparent coating is in the range of 30 nm to 50 μm.

In the method of the present invention, since the metal oxide particles are surface-treated with an organosilicon compound having an amino group in advance, the organosilicon compound not containing an amino group, which is the main surface treatment agent, is then uniformly distributed on the surface of the metal oxide particles. Surface treatment can be performed without unevenness.
For this reason, the metal oxide particles are uniformly and stably dispersed in the matrix component, and have excellent binding properties with the matrix, excellent denseness, film strength, chemical resistance and the like, and also have excellent moisture resistance. A surface treatment method of metal oxide particles that can be suitably used for forming a coating, and a dispersion containing the surface-treated metal oxide particles, a coating solution for forming a transparent coating, and a substrate with a transparent coating can be provided. .

  Hereinafter, the surface treatment method for metal oxide particles according to the present invention will be described first.

[Surface Treatment Method for Metal Oxide Particles]
In the surface treatment method for metal oxide particles according to the present invention, an organic silicon compound represented by the following formula (1) is added to water and / or an organic solvent dispersion of the metal oxide particles, and then hydrolyzed. It is characterized by adding an organosilicon compound represented by the following formula (2) for hydrolysis.
_{(NH 2 -C n H 2n -Z-} C m H 2m) L -Si-Y 4-L (1)
(Wherein, Z: —NH, —CH ₂ , Y: C 1-4 alkoxy group, hydroxyl group, halogen, hydrogen. L: integer of 1 to 3, n: integer of 0 to 10, m: An integer from 0 to 10.)
R _p -Si x _4-p (2)
(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, a hydroxyl group, Halogen, hydrogen, p: an integer of 1 to 3, except for an amino group-substituted hydrocarbon group.

As the metal oxide particles used in the metal oxide particles present invention may be a conventionally known metal oxide particles used in the various transparent film.
Specifically, in addition to silica, alumina, zirconia, titanium oxide, tin oxide, zinc oxide, antimony pentoxide, indium oxide, low-order titanium oxide, magnesium oxide, boria, niobium oxide, etc., these composite oxides, or Examples thereof include Sb-doped tin oxide (ATO), F-doped tin oxide, P-doped tin oxide, Sn-doped indium oxide (ITO), and F-doped indium oxide.

Among these, silica, alumina, zirconia, titanium oxide, tin oxide, zinc oxide, antimony pentoxide, indium oxide, low-order titanium oxide and complex oxides thereof or Sb-doped tin oxide (ATO), F-doped tin oxide, P Doped tin oxide, Sn-doped indium oxide (ITO), F-doped indium oxide, and the like can be suitably used.
Composite oxides include silica / alumina, silica / zirconia, silica / titania, alumina / titania, titania / zirconia, titania / tin oxide / zirconia / silica, zirconia / antimony oxide / silica, zirconia / antimony oxide, titania / zirconia Silica, titania / zirconia / antimony oxide / silica / tin oxide, titania / zirconia / antimony oxide / silica, zirconia / silica / antimony oxide, antimony oxide / silica, and the like.

Further, the composite oxide includes particles having a core-shell structure in which the surface of the metal oxide particles is coated with another metal oxide or composite oxide. Further, silica-based particles mainly composed of silica having voids therein disclosed in Japanese Patent Application Laid-Open Nos. 2001-167737 and 2001-233611 filed by the applicant of the present application have a low refractive index and an antireflection film. It can be suitably used for a transparent film.
Furthermore, porous silica-based fine particles whose surface is coated with antimony oxide or silica-based fine particles having cavities inside as disclosed in JP-A-2005-119909 can be suitably used as an antireflection / antistatic film. Moreover, the particle | grains which each said particle | grain connected in the chain form may be sufficient.

The average particle diameter of the metal oxide particles is preferably in the range of 3 to 300 nm, more preferably 5 to 200 nm.
When the average particle diameter of the metal oxide particles is less than 3 nm, it is difficult to obtain, and even if obtained, there is a tendency to aggregate in the dispersion, and it is difficult to uniformly treat the surface. Even if particles are used, the effects of the present application, i.e., improvement in dispersibility in matrix components, improvement in binding properties with the matrix, denseness, film strength, chemical resistance, film smoothness, etc. may not be obtained. .
When the average particle diameter of the metal oxide particles exceeds 300 nm, the smoothness of the obtained transparent film is deteriorated, the denseness, the film strength and the chemical resistance are insufficient, and the haze tends to be further deteriorated.

Water and / or an organic solvent is used as a dispersion medium for the metal oxide particles when the dispersion medium is surface treated.
Examples of the organic solvent include hydrophilic solvents including alcohols such as methanol, ethanol, propanol and 2-propanol (IPA), esters such as methyl acetate, ethyl acetate and isopropyl acetate, ketones such as acetone and methyl ethyl ketone, and toluene. And other hydrophobic solvents. These may be used singly or in combination of two or more.

In addition, alcohols such as butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol; glycols such as ethylene glycol and hexylene glycol; diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether , Hydrophilic solvents including ethers such as ethylene glycol isopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propyl acetate, isobutyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, succinate Esters such as hexyl and ethylene glycol monoacetate; and hydrophobic solvents such as methyl ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methyl cyclohexanone, dipropyl ketone, methyl pentyl ketone, and diisobutyl ketone . These may be used singly or in combination of two or more.
Of these, monoalcohols such as methanol, ethanol, propanol and butanol are common.

The concentration of the metal oxide particles in water and / or the organic solvent dispersion is preferably in the range of 1 to 50% by weight, more preferably 3 to 40% by weight as the solid content.
When the concentration of the dispersion is less than 1% by weight, the particles do not aggregate, but the productivity is low and impractical.
When the concentration of the dispersion exceeds 50% by weight, the interaction between the particles is strong and the viscosity may increase or in some cases, the particles may aggregate.

Organosilicon compound represented by formula (1) In the present invention, an organosilicon compound having an amino group represented by the following formula (1) is used.
_{(NH 2 -C n H 2n -Z-} C m H 2m) L -Si-Y 4-L (1)
(Wherein, Z: —NH, —CH ₂ , Y: C 1-4 alkoxy group, hydroxyl group, halogen, hydrogen. L: integer of 1 to 3, n: integer of 0 to 10, m: An integer from 0 to 10.)

  Examples of such organosilicon compounds include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, and γ-aminopropylmethyldiethoxysilane. , Γ-aminopropylmethyldiisopropoxysilane, γ-aminopropyldimethylmonomethoxysilane, γ-aminopropyldimethylmonoethoxysilane, γ-aminopropyldimethylmonoisopropoxysilane, N-β (aminoethyl) γ-aminopropyl Trimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltriisopropoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysila N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiisopropoxysilane, N-β (aminoethyl) γ-aminopropyldimethylmonomethoxysilane One or more organic silicon compounds selected from N-β (aminoethyl) γ-aminopropyldimethylmonoethoxysilane and N-β (aminoethyl) γ-aminopropyldimethylmonoisopropoxysilane are preferably used. It is done.

The amount of the organosilicon compound represented by the formula (1) is such that the content of the organosilicon compound in the obtained surface-treated metal oxide particles is [(NH ₂ —C _n H _2n —Z—C _m H _{2m) L -SiO 4-L /} 2] as 0.001 to 20 wt%, more used to be in the range of 0.01 to 15 wt%.
When the amount of the organosilicon compound represented by the formula (1) is less than 0.001% by weight as [(NH ₂ —C _n H _2n —Z—C _m H _2m ) _L —SiO _{4 -L / 2} ] Since the introduction amount of the organosilicon compound represented by formula (1) having an amino group is small, the organosilicon compound represented by formula (2) and the hydrolyzate of the organosilicon compound are represented by formula (1). There is a tendency that unbonded organosilicon compound represented by formula (2) and hydrolyzate of organosilicon compound remain on the surface of the metal oxide particles surface-treated with the organosilicon compound to be formed. .
Furthermore even exceed 20% by weight The amount of the organic silicon compound _{[(NH 2 -C n H 2n} -Z-C m H 2m) L -SiO 4-L / 2] represented by the formula (1) The ratio of the metal oxide fine particles is reduced because the surface is excessively treated without reducing the unbonded organosilicon compound represented by the formula (2), and the characteristics of the particles, for example, conductivity, In some cases, the refractive index or the like is not sufficiently expressed.

Organosilicon compound represented by formula (2) In the present invention, an organosilicon compound containing no amino group represented by formula (2) below is then used.
R _p -Si x _4-p (2)
(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, a hydroxyl group, Halogen, hydrogen, p: an integer of 1 to 3, with the exception of an amino group-substituted hydrocarbon group in the substituted hydrocarbon group.

  Such organosilicon compounds include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxy. Silane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltriethoxysilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyl Triethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycyl Sidoxyethoxy) propyltrimethoxysilane, γ- (meth) acrylooxymethyltrimethoxysilane, γ- (meth) acrylooxymethyltriethoxysilane, γ- (meth) acrylooxyethyltrimethoxysilane, γ- (Meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acrylooxypropyltriethoxysilane, butyltrimeth Xysilane, isobutyltriethoxysilane, hexyltriethoxysilaoctyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, 3-ureidoisopropyl Propyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriisopropoxysilane, trifluoropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylsilanol, methyltri A chlorosilane etc., and these mixtures are mentioned.

The amount of the organosilicon compound represented by the formula (2) is such that the content of the organosilicon compound in the obtained surface-treated metal oxide particles is 1 to 60 as R _p —Si—O _{4-p / 2.} It is preferable to be in the range of wt%, more preferably 2 to 50 wt%.
When the amount of the organosilicon compound represented by the formula (2) is less than 1% by weight as R _p —Si—O _{4 -p / 2} , the effect of improving the dispersibility and the matrix bondability is insufficient. The resulting transparent film may be insufficient in denseness, film strength, chemical resistance, film smoothness, and the like.
When the amount of the organosilicon compound represented by the formula (2) exceeds 60% by weight as R _p —Si—O _{4−p / 2} , the ratio of the metal oxide fine particles in the surface-treated metal oxide particles In some cases, the particle characteristics such as conductivity and refractive index are not sufficiently exhibited.

The surface treatment method surface treatment method, it is possible to employ the same method as the surface treatment by a conventionally known silane coupling agents.
For example, first, an organosilicon compound represented by the above formula (1) or an organic solvent solution of an organosilicon compound is added to a metal oxide particle dispersion to cause hydrolysis. At this time, if necessary, an acid or an alkali can be added as a hydrolysis catalyst.
The temperature for hydrolysis varies depending on the boiling point of the dispersion medium to be used, but is generally in the range of 30 to 80 ° C.

Subsequently, the organic silicon compound represented by the above formula (2) or an organic solvent solution of the organic silicon compound is added for hydrolysis. At this time, if necessary, an acid or an alkali can be added as a hydrolysis catalyst.
Moreover, although it depends on the value of P of the organosilicon compound represented by the formula (2), the number of moles of water (M _H2O ) and the number of moles of hydrolyzable functional groups of the organosilicon compound (M _OS2 ) It is preferable to use water having a molar ratio (M _H2O ) / (M _OS2 ) of 1 to 1000, more preferably 2 to 500.
When the molar ratio (M _H2O ) / (M _OS2 ) is less than 1, the amount of water used for hydrolysis is too small, resulting in insufficient hydrolysis and the addition of unbonded organosilicon compound or organosilicon compound. Decomposition products tend to remain.
When the molar ratio (M _H2O ) / (M _OS2 ) exceeds 1000, although depending on the type of the organosilicon compound represented by the formula (2), the hydrolysis rate is fast and precipitates on the surface of the metal oxide fine particles. In some cases, a sol / gel or particle that is a hydrolyzate of an organosilicon compound in a dispersion medium may not be obtained, and the surface treatment effect by the organosilicon compound represented by the formula (2) may not be sufficiently obtained. is there.

The temperature at the time of hydrolysis varies depending on the boiling point of the dispersion medium used, but is generally in the range of 30 to 100 ° C.
The dispersion of the surface-treated metal oxide particles obtained in this way can be heated and aged as necessary. Further, impurity ions can be removed with an ion exchange resin, or an ultrafiltration membrane or the like. It can be used after washing, concentration, solvent substitution and the like.

[Surface-treated metal oxide particle dispersion]
The resulting dispersion of the surface-treated metal oxide particles preferably has a concentration of the surface-treated metal oxide particles in the range of 1 to 50% by weight, more preferably 1 to 40% by weight as the solid content.
When the concentration of the surface-treated metal oxide particle dispersion of the surface-treated metal oxide particle dispersion is less than 1% by weight as the solid content, the concentration is low, so it is unsuitable for use in the coating liquid for forming a transparent film of the present invention, The film thickness of the resulting transparent coating may be too thin, and thus may require repeated, coating, drying, and the like.

When the concentration of the surface-treated metal oxide particles in the surface-treated metal oxide particle dispersion exceeds 50% by weight as the solid content, the viscosity may increase and the stability may be insufficient. It is unsuitable for use as a coating solution.
The dispersion medium for the surface-treated metal oxide particle dispersion can be the same as that used for the surface treatment, but is preferably the same as the dispersion medium used for the transparent film-forming coating liquid described later. .

[Transparent coating solution]
The coating liquid for forming a transparent film of the present invention comprises the surface-treated metal oxide particles obtained by the above method, a matrix-forming component, and a dispersion medium.
Surface-treated metal oxide particles As the surface-treated metal oxide particles, the surface-treated metal oxide particles obtained above or a dispersion of surface-treated metal oxide particles is used.

Matrix-forming component As the matrix-forming component, a silicone-based (sol-gel) matrix-forming component, an organic resin-based matrix-forming component, or the like is used.
As the silicone-based matrix forming component, an organosilicon compound represented by the following formula (3), a hydrolyzate thereof, and a hydrolyzed polycondensate are preferably used.
R _q -SiX _4-q (3)
(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, a hydroxyl group, Halogen, hydrogen, q: an integer from 0 to 3.)

  Examples of such organosilicon compounds include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyl Diethoxysilane, 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-glycyl Sidoxymethyltriexylsilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycyl Sidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ- (meth) acrylooxymethyltrimethoxysilane, γ- (meth) Acryloxymethyltriexylsilane, γ- (meth) acrylooxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- ( (Meth) acryloxypropyltrimethoxysilane, γ- (meth) acrylooxyp Propyltriethoxysilane, γ- (meth) acrylooxypropyltriethoxysilane, butyltrimethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilaoctyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane, isobutyltri Ethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, 3-ureidoisopropylpropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriisopropoxy Silane, trifluoropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylsilanol, methyltrichlorosila Etc., and mixtures thereof.

Examples of the organic resin matrix forming component include known thermosetting resins, thermoplastic resins, electron beam curable resins, and the like as coating resins.
Examples of such resins include conventionally used thermoplastic resins such as polyester resins, polycarbonate resins, polyamide resins, polyphenylene oxide resins, thermoplastic acrylic resins, vinyl chloride resins, fluororesins, vinyl acetate resins, and silicone rubbers. , 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, etc., UV curable type An acrylic resin etc. are mentioned.

Specifically, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexaacrylate, methyl methacrylate, ethyl methacrylate, butyl Methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl acrylate, n-stearyl acrylate, 1,6-hexanediol dimethacrylate, perfluorooctylethyl methacrylate, trifluoroethyl methacrylate, urethane acrylate and the like A mixture is mentioned.
Further, it may be a copolymer or modified body of two or more of these resins. These resins may be emulsion resins, water-soluble resins, and hydrophilic resins. Further, in the case of a thermosetting resin, it may be an ultraviolet curable type or an electron beam curable type, and in the case of a thermosetting resin, a curing catalyst may be included.

Dispersion medium The dispersion medium used in the present invention is not particularly limited as long as it can dissolve or disperse the matrix-forming component and, if necessary, the polymerization initiator and uniformly disperse the surface-treated metal oxide particles. A dispersion medium can be used.

  Specifically, alcohols such as water, methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, hexylene glycol, isopropyl glycol; acetic acid Esters such as methyl ester, ethyl acetate, butyl acetate; ethers such as diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetate Ketones such as acetate, methyl cellosolve, ethylcellosolve, butyl cellosolve, toluene, cyclohexanone, isophorone and the like.

The total concentration of the concentration (C _P ) as the solid content of the surface-treated metal oxide particles in the coating solution for forming a transparent film and the concentration (C _M ) as the solid content of the matrix forming component is 2 to 50% by weight, Is preferably in the range of 3 to 40% by weight.
If the total solid concentration in the coating solution for forming a transparent film is less than 2% by weight, the film thickness of the transparent film may be thin, and the performance of the transparent film, for example, hard coat performance and antireflection performance is sufficient. It may not be. For this reason, although application | coating, drying, etc. can be repeated and a film thickness can be thickened, economical efficiency falls.
If the total solid content in the coating liquid for forming a transparent film exceeds 50% by weight, the viscosity of the coating liquid increases, so that the coating property may be deteriorated or the stability of the coating liquid may be insufficient. In some cases, the adhesiveness, strength, and the like of the resulting transparent film may be reduced.

The concentration (C _P ) as the solid content of the surface-treated metal oxide particles in the coating solution for forming a transparent film is preferably in the range of 0.1 to 40% by weight, more preferably 0.2 to 30% by weight.
When the concentration (C _P ) as the solid content of the surface-treated metal oxide particles in the coating liquid for forming a transparent film is less than 0.1% by weight, the content of the metal oxide particles in the obtained transparent film is small. Therefore, the characteristics of the metal oxide fine particles, such as conductivity and refractive index, may not be sufficiently expressed.
When the concentration (C _P ) of the surface-treated metal oxide particles in the coating solution for forming a transparent coating exceeds 40% by weight, the interaction between the particles is high, the viscosity of the paint is increased, and the stability over time is not good. May be sufficient.

Further, the concentration (C _M ) of the matrix forming component in the coating solution for forming a transparent film is preferably in the range of 1.9 to 49.9% by weight, more preferably 2.8 to 40% by weight as the solid content.
When the concentration (C _M ) of the matrix-forming component in the coating liquid for forming a transparent film is less than 1.9% by weight as a solid content, the film thickness of the obtained transparent film is too thin, the performance of the transparent film, for example, Hard coat performance and antireflection performance may be insufficient, or the ratio of particles may be too high, resulting in insufficient adhesion.
If the concentration (C _M ) of the matrix-forming component in the coating solution for forming the transparent film exceeds 49.9% by weight as the solid content, the content of the matrix of the resulting transparent film is large, and conversely the content of the metal oxide particles Since the amount is small, the characteristics of the metal oxide fine particles, such as conductivity and refractive index, may not be sufficiently exhibited.

Further, the concentration (C _P ) as the solid content of the surface-treated metal oxide particles in the coating solution for forming the transparent coating and the concentration (C _M ) as the solid content of the matrix-forming component are determined by the surface treatment in the obtained transparent coating. It is used by adjusting so that the content of the metal oxide particles is in the range of 0.2 to 80% by weight, and further 0.5 to 78% by weight.
When the content of the surface-treated metal oxide particles in the obtained transparent film is less than 0.2% by weight, the content of the metal oxide particles is reduced, so the characteristics of the metal oxide fine particles, for example, conductivity, In some cases, the refractive index or the like is not sufficiently expressed.
If the content of the surface-treated metal oxide particles in the resulting transparent coating exceeds 80% by weight, the proportion of the particles may be too high, resulting in insufficient adhesion and film strength.

A conventionally well-known method can be employ | adopted as a method of forming a transparent film using the coating liquid for transparent film formation concerning this invention.
Specifically, the transparent film-forming paint is applied to the substrate by a known method such as dipping, spraying, spinner, roll coating, bar coating, slit coater printing, gravure printing, or micro gravure printing. A transparent film can be formed by applying, drying, and curing by an ordinary method such as ultraviolet irradiation or heat treatment.

[Base material with transparent film]
The base material with a transparent film according to the present invention includes a base material and a transparent film provided on the base material.

As the base material , a conventionally known base material can be used. In addition to glass, cellulose base materials such as triacetyl cellulose film (TAC), diacetyl cellulose film, acetate butyrate cellulose film, polyethylene terephthalate (PET) ), Polyester base materials such as polyethylene naphthalate, polyolefin base materials such as polyethylene film, polypropylene film and cyclic polyolefin film, polyamide base materials such as nylon-6, nylon-66, polyacrylic film, polyurethane film , Substrates such as polycarbonate film, polyether film, polyethersulfone film, polystyrene film, polymethylpentene film, polyetherketone film, acrylonitrile film And the like. Moreover, the base material with a film in which the other base film was formed on such a base material can also be used.

Transparent coating The transparent coating comprises a matrix component and surface-treated metal oxide particles.
Surface-treated metal oxide particles As the surface-treated metal oxide particles, the aforementioned surface-treated metal oxide particles are used.

As the matrix component , a silicone (sol-gel) matrix component, an organic resin matrix component, or the like is used.
As the silicone matrix component, a hydrolyzed polycondensate of an organosilicon compound similar to the formula (3) is preferably used.
In addition, as the organic resin matrix component, a known thermosetting resin, thermoplastic resin, electron beam curable resin, or the like is used as the coating resin.

The content of the surface-treated metal oxide particles in the transparent film is preferably in the range of 0.2 to 80% by weight, more preferably 0.5 to 78% by weight as the solid content.
When the content of the surface-treated metal oxide particles in the transparent film is less than 0.2% by weight, the content of the metal oxide particles decreases, so the characteristics of the metal oxide fine particles, such as conductivity, refractive index, etc. May not be sufficiently expressed.
If the content of the surface-treated metal oxide particles in the transparent coating exceeds 80% by weight, the proportion of the particles may be too high, resulting in insufficient adhesion and film strength.

Moreover, although the film thickness of a transparent film changes with uses, it is preferable that it exists in the range of 30 nm-50 micrometers, Furthermore, 50 nm-30 micrometers.
When the thickness of the transparent film is less than the lower limit of the above range, the film thickness is thin and the antireflection performance is insufficient, and the stress applied to the hard coat film surface is not sufficiently absorbed because the hard coat film is thin. Therefore, the hard coat function is insufficient.

If the thickness of the transparent film exceeds the upper limit of the above range, it becomes difficult to apply the film to a uniform thickness or to dry uniformly, and further shrinkage increases. The material may be curved). Also, the film thickness may be too thick and the transparency may be insufficient.
The base material with a transparent film according to the present invention can be provided with other films having different purposes or effects.

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

Preparation of surface-treated metal oxide particles (1 ) 100 g of an aqueous dispersion of antimony pentoxide fine particles (manufactured by Catalyst Kasei Kogyo Co., Ltd .: Rsb-Ku-70, solid content concentration 14 wt%, average particle size 20 nm) Dilute with 100 g. 1.4 g of γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBE-603, concentration 81.2% by weight) was added thereto and aged at 60 ° C. for 1 hour. Thereafter, 5 g of γ-methacrylooxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical: KBM-503, concentration: 81.2 wt%), 100 g of methanol and 1 g of ammonia water having a concentration of 29.8 wt% were added, and further 60 ° C. For 5 hours. Thereafter, the solvent was replaced with 2-propanol using a ceramic limit membrane to prepare a 2-propanol dispersion of surface-treated metal oxide particles (1) having a solid content concentration of 30% by weight. The average particle diameter of the surface-treated metal oxide particles (1) is shown in the table.

Transparent film-forming coating liquid (1) Preparation of acrylic resin (Dainippon Ink Co., Ltd.: 17-824-9, resin concentration: 79.8 wt%, solvent: isopropyl alcohol) to the diluted with isopropyl alcohol A resin component (1) for forming a transparent film having a resin concentration of 30% by weight was prepared.
A coating solution (1) for forming a transparent film was prepared by mixing 10 g of the surface-treated metal oxide particle (1) dispersion with 10 g of this resin component (1) for forming a transparent film.

Evaluation of dispersion stability of coating liquid The viscosity of the coating liquid for forming a transparent film (1) was measured with a B-type viscometer, and then allowed to stand in a thermostatic bath at 50 ° C. for 24 hours. The change was confirmed. The smaller the change in viscosity at this time, the better the stability, and the larger the viscosity, the poorer the stability. The results are shown in the table.

Production of substrate with transparent coating (1) Coating solution (1) for forming transparent coating was applied to a PET film (Toyobo Cosmo Shine A4100, thickness: 188 μm, refractive index: 1.67, substrate haze 0.8%). After coating by the coater method (# 20) and drying at 80 ° C. for 120 seconds, the substrate with transparent coating (1) was produced by irradiating and curing with 600 mJ / cm ² ultraviolet rays. The thickness of the transparent film at this time was 10 μm.
The surface resistance value of the obtained transparent coating was measured with Hiresta (Mitsubishi Chemical), the total light transmittance and haze were measured with a haze meter (Suga Test Instruments Co., Ltd.), and the reflectance was measured with a reflectometer (MCPD manufactured by Otsuka Electronics). -3000) and the results are shown in the table. Furthermore, scratch resistance, alkali resistance, and moisture resistance were measured as follows.

Measurement of scratch resistance Using # 0000 steel wool, sliding 20 times at a load of 1000 g / cm ² , visually observing the surface of the film, and evaluating according to the following criteria, the results are shown in the table.
No streak injury is found: ◎
Slightly scratched streak: ○
Many scratches are found in the streak: △
The surface has been cut entirely: ×

Evaluation of alkali resistance On the transparent film of the substrate with a transparent film (1), a 0.01N NaOH aqueous solution was dropped, left to stand for 3 minutes, wiped, the surface of the film was visually observed, and evaluated according to the following criteria: The results are shown in the table.
No trace of dripping: ◎
After breathing is observed when breathing: ○
Dripping marks are observed: △
The film surface is totally peeled: ×

Moisture resistance test substrate with transparent coating (1) is left in an environmental testing machine manufactured by Tabay Espec for 60 hours at 60 ° C. and RH 95% for 1000 hours, and measurement of reflectance before and after exposure and visual confirmation of film cracks went.
Moreover, the reflectance was not evaluated about what has cracked visually.

Preparation of surface-treated metal oxide particles (2) In Example 1, a solid content concentration of 30% by weight was similarly obtained except that 0.7 g of γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical: KBE-603) was used. Surface-treated metal oxide particles (2) A 2-propanol dispersion was prepared. The average particle diameter of the surface-treated metal oxide particles (2) is shown in the table.

Preparation of coating solution for forming transparent film (2) In Example 1, the coating solution for forming transparent film (2) was prepared in the same manner except that 10 g of the surface-treated metal oxide particles (2) 2-propanol dispersion was mixed. did.
Subsequently, the dispersion stability of the coating solution was evaluated in the same manner as in Example 1, and the results are shown in the table.

In the production example 1 of the substrate with a transparent film (2), except that the transparent film-forming coating liquid (2) was prepared substrate with a transparent film (2) in the same manner. The thickness of the transparent film at this time was 10 μm.
The base material with a transparent coating (2) was evaluated in the same manner as in Example 1, and the results are shown in the table.

Preparation of surface-treated metal oxide particles (3) In Example 1, a solid content concentration of 30% by weight was used except that 5.6 g of γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical: KBE-603) was used. Surface-treated metal oxide particles (3) A 2-propanol dispersion was prepared. The average particle diameter of the surface-treated metal oxide particles (3) is shown in the table.

Preparation of transparent coating film forming coating solution (3) In Example 1, a transparent coating film forming coating solution (3) was prepared in the same manner except that 10 g of the surface-treated metal oxide particles (3) 2-propanol dispersion was mixed. did.
Subsequently, the dispersion stability of the coating solution was evaluated in the same manner as in Example 1, and the results are shown in the table.

In the production example 1 of the substrate with a transparent film (3), except that the transparent film-forming coating liquid (3) was prepared substrate with a transparent film (3) in the same manner. The thickness of the transparent film at this time was 10 μm.
The substrate with transparent film (3) was evaluated in the same manner as in Example 1, and the results are shown in the table.

Preparation of surface-treated metal oxide particles (4) In Example 1, the solid content concentration was 30 except that 1.0 g of γ-methacrylooxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical: KBM-503) was used. Weight% surface-treated metal oxide particles (4) A 2-propanol dispersion was prepared. The average particle diameter of the surface-treated metal oxide particles (4) is shown in the table.

Preparation of coating liquid for forming transparent film (4) In Example 1, a coating liquid for forming transparent film (4) was prepared in the same manner except that 10 g of the surface-treated metal oxide particles (4) 2-propanol dispersion was mixed. did.
Subsequently, the dispersion stability of the coating solution was evaluated in the same manner as in Example 1, and the results are shown in the table.

Production of substrate with transparent film (4) A substrate with transparent film (4) was produced in the same manner as in Example 1, except that the coating liquid for forming a transparent film (4) was used. The thickness of the transparent film at this time was 10 μm.
The base material with transparent film (4) was evaluated in the same manner as in Example 1, and the results are shown in the table.

Preparation of surface-treated metal oxide particles (5) A solid content concentration of 30% by weight was obtained in the same manner as in Example 1, except that 15 g of γ-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical: KBM-503) was used. Surface treated metal oxide particles (5) A 2-propanol dispersion was prepared. The average particle diameter of the surface-treated metal oxide particles (5) is shown in the table.

Preparation of coating solution for forming transparent film (5) In Example 1, a coating solution for forming transparent film (5) was prepared in the same manner except that 10 g of the surface-treated metal oxide particles (5) 2-propanol dispersion was mixed. did.
Subsequently, the dispersion stability of the coating solution was evaluated in the same manner as in Example 1, and the results are shown in the table.

Production of substrate with transparent film (5) A substrate with transparent film (5) was produced in the same manner as in Example 1 except that the coating liquid for forming a transparent film (5) was used. The thickness of the transparent film at this time was 10 μm.
The substrate with transparent film (5) was evaluated in the same manner as in Example 1, and the results are shown in the table.

Preparation of surface-treated metal oxide particles (6 ) 100 g of methanol dispersion of titanium oxide, zirconia, and silica-based fine particles (manufactured by Catalyst Kasei Kogyo Co., Ltd .: Optlake 1130ZS7A8, solid content concentration 20 wt%, average particle diameter 20 nm) Diluted with 100 g of pure water. Subsequently, 2 g of γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical: KBM-603, concentration 81.2 wt%) was added and aged at 60 ° C. for 1 hour. Thereafter, 10 g of γ-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-5103, concentration 81.2 wt%), 100 g of methanol and 1 g of ammonia water having a concentration of 29.8 wt% were added. Aged for hours. Thereafter, the solvent was replaced with 2-propanol using a ceramic outer membrane to prepare a surface-treated metal oxide particle (6) 2-propanol dispersion having a solid concentration of 30% by weight. The average particle diameter of the surface-treated metal oxide particles (6) is shown in the table.

Preparation of coating liquid for forming transparent film (6) In Example 1, the coating liquid for forming transparent film (6) was prepared in the same manner as in Example 1, except that 10 g of the surface-treated metal oxide particles (6) 2-propanol dispersion was mixed. did.
Subsequently, the dispersion stability of the coating solution was evaluated in the same manner as in Example 1, and the results are shown in the table.

Production of substrate with transparent film (6) A substrate with transparent film (6) was produced in the same manner as in Example 1, except that the coating liquid for forming a transparent film (6) was used. The thickness of the transparent film at this time was 10 μm.
The substrate with transparent film (6) was evaluated in the same manner as in Example 1, and the results are shown in the table.

Surface-treated metal oxide particles (7) Water dispersion of Preparation zirconia silica-based fine particles (Catalysts & Chemicals Industries Co., Ltd. having a solid part concentration of 5% by weight, average particle diameter 20 nm) in 100 g N-beta (aminoethyl) 1 g of γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-903, concentration 81.2 wt%) was added and aged at 60 ° C. for 1 hour. Thereafter, 0.5 g of γ-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical: KBM-5103, concentration 81.2 wt%), 100 g of methanol and 0.1 g of aqueous ammonia having a concentration of 29.8 wt% were added, Further, it was aged at 60 ° C. for 5 hours. Thereafter, the solvent was replaced with 2-propanol using a ceramic outer membrane to prepare a surface-treated metal oxide particle (7) 2-propanol dispersion having a solid content concentration of 30% by weight. The average particle diameter of the surface-treated metal oxide particles (7) is shown in the table.

Preparation of coating liquid for forming transparent film (7) A coating liquid for forming transparent film (7) was prepared in the same manner as in Example 1 except that 10 g of the surface-treated metal oxide particles (7) 2-propanol dispersion was mixed. did.
Subsequently, the dispersion stability of the coating solution was evaluated in the same manner as in Example 1, and the results are shown in the table.

Production of substrate with transparent film (7) A substrate with transparent film (7) was produced in the same manner as in Example 1 except that the coating liquid for forming a transparent film (7) was used. The thickness of the transparent film at this time was 10 μm.
The substrate with transparent film (7) was evaluated in the same manner as in Example 1, and the results are shown in the table.

Surface-treated metal oxide particles (8) Preparation of antimony-doped tin oxide (ATO) aqueous dispersion of fine particles (Catalysts & Chemicals Industries Co., Ltd.: TL-98-FDAR: solid content concentration of 20 wt%, average particle size 8 nm) 100 g was diluted with 100 g of pure water, then 10 g of N-β (aminoethyl) γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical: KBM-903, concentration 81.2 wt%) was added, and the mixture was heated at 60 ° C. for 1 hour. Aged. Thereafter, 20 g of γ-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-5103, concentration 81.2 wt%), 100 g of methanol, and 0.1 g of ammonia water having a concentration of 29.8 wt% were added, and further 60 Aging was carried out at 5 ° C. for 5 hours. Thereafter, the solvent was replaced with 2-propanol using a ceramic outer membrane to prepare a surface-treated metal oxide particle (8) 2-propanol dispersion having a solid content concentration of 30% by weight. The average particle diameter of the surface-treated metal oxide particles (8) is shown in the table.

Prepared in Preparation Example 1 of the transparent film-forming coating liquid (8), a surface treated metal oxide particles (8) 2-propanol dispersion except that a mixture of 10g in the same manner transparent film-forming coating liquid (8) did.
Subsequently, the dispersion stability of the coating solution was evaluated in the same manner as in Example 1, and the results are shown in the table.

Production of substrate with transparent film (8) A substrate with transparent film (8) was produced in the same manner as in Example 1 except that the coating liquid for forming a transparent film (8) was used. The thickness of the transparent film at this time was 10 μm.
The substrate with transparent coating (8) was evaluated in the same manner as in Example 1, and the results are shown in the table.

Preparation of coating liquid for forming transparent film (9) Acrylic-urethane resin (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate UA-306H, resin concentration 100% by weight, solvent: isopropyl alcohol) and Irgacure 184 (Ciba Specialty Co., Ltd.) Manufactured at a weight ratio of 97: 3 and diluted with methyl isobutyl ketone (MIBK) to prepare a resin component (2) for forming a transparent film having a resin concentration of 30% by weight.
10 g of the surface-treated metal oxide particle (1) dispersion prepared in the same manner as in Example 1 was mixed with 10 g of this transparent film-forming resin component (2) to prepare a coating liquid (9) for forming a transparent film. Subsequently, the dispersion stability of the coating solution was evaluated in the same manner as in Example 1.

In the production example 1 of the substrate with a transparent film (9), except that the transparent film-forming coating liquid (9) was prepared substrate with a transparent film (9) in a similar manner. The thickness of the transparent film at this time was 10 μm.
The base material with a transparent film (9) was evaluated in the same manner as in Example 1, and the results are shown in the table.

Preparation of coating liquid for forming transparent film (10) 10 g of methyl silicate (manufactured by Tama Chemical Co., Ltd .: MS-51, concentration SiO ₂ conversion: 51% by weight), 40 g of isopropyl alcohol, 1 g of water and 0% nitric acid with a concentration of 63% by weight 0.1 g was mixed and stirred at 50 ° C. for 1 hour. Then, the resin component for transparent film formation (3) was prepared by diluting with a isopropyl alcohol / butyl cellosolve = 9/1 mixture to a concentration of 3% by weight.
7 g of this transparent film-forming resin component (3) was mixed with 3 g of 10 g of the surface-treated metal oxide particle (1) dispersion prepared in the same manner as in Example 1 and diluted to 3% by weight with isopropyl alcohol. Thus, a coating liquid (10) for forming a transparent film was prepared. Subsequently, the dispersion stability of the coating solution was evaluated in the same manner as in Example 1.

Production of substrate with transparent film (10) A substrate with transparent film (10) was produced in the same manner as in Example 1, except that the coating liquid for forming a transparent film (10) was used. The thickness of the transparent film at this time was 10 μm.
About the base material (10) with a transparent film, evaluation similar to Example 1 was performed and the result was shown to the table | surface.

Production of transparent coated substrate (11) Transparent coated substrate (11) prepared in the same manner as in Example 1 except that the coating solution (1) for forming a transparent coating was applied by the bar coater method (# 3). 11) was produced. The thickness of the transparent film at this time was 500 nm.
The substrate with transparent coating (11) was evaluated in the same manner as in Example 1, and the results are shown in the table.

Preparation of substrate with transparent coating (12) Transparent coating-coated substrate (12) prepared in the same manner as in Example 1 except that the coating solution (1) for transparent coating formation was applied by the bar coater method (# 50). 12) was manufactured. The thickness of the transparent film at this time was 30 μm.
About the base material (12) with a transparent film, evaluation similar to Example 1 was performed and the result was shown in the table | surface.

Comparative Example 1

Preparation of surface-treated metal oxide particles (R1 ) 100 g of an aqueous dispersion of antimony pentoxide fine particles (manufactured by Catalyst Kasei Kogyo Co., Ltd .: Rsb-Ku-70, solid content concentration 14 wt%, average particle size 20 nm) Dilute with 100 g. Thereafter, 5 g of γ-methacrylooxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503, concentration 81.2 wt%), 100 g of methanol and 1 g of ammonia water having a concentration of 29.8 wt% were added, and further 60 ° C. For 5 hours. Thereafter, the solvent was replaced with 2-propanol using a ceramic limit membrane. The dispersion increased in viscosity and gelled, and a dispersion could not be obtained.

Comparative Example 2

Preparation of surface-treated metal oxide particles (R2 ) 100 g of an aqueous dispersion of antimony pentoxide fine particles (manufactured by Catalyst Kasei Kogyo Co., Ltd .: Rsb-Ku-70, solid content concentration 14 wt%, average particle size 20 nm) Dilute with 100 g. Subsequently, 1.4 g of γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBE-603, concentration 81.2% by weight) was added and aged at 60 ° C. for 1 hour. Thereafter, the solvent was replaced with 2-propanol using a ceramic outer membrane, and a surface-treated metal oxide particle (R2) 2-propanol dispersion having a solid content concentration of 30% by weight was prepared. The average particle diameter of the surface-treated metal oxide particles (R2) is shown in the table.

Preparation of coating liquid for forming transparent film (R2) In Example 1, the coating liquid for forming transparent film (R2) was prepared in the same manner except that 10 g of the surface-treated metal oxide particles (R2) 2-propanol dispersion was mixed. did.
Subsequently, the dispersion stability of the coating solution was evaluated in the same manner as in Example 1, and the results are shown in the table.

In the production example 1 of the substrate with a transparent film (R2), except that the transparent film-forming coating liquid (R2) was prepared substrate with a transparent film (R2) in a similar manner. The thickness of the transparent film at this time was 10 μm.
The substrate with a transparent coating (R2) was evaluated in the same manner as in Example 1, and the results are shown in the table.

Comparative Example 3

Preparation of surface-treated metal oxide particles (R3 ) 100 g of an aqueous dispersion of antimony pentoxide fine particles (manufactured by Catalyst Kasei Kogyo Co., Ltd .: Rsb-Ku-70, solid content concentration 14 wt%, average particle size 20 nm) Dilute with 100 g. Subsequently, 3.6 g of normal ethyl silicate (manufactured by Tama Chemicals: ES-28, concentration 28.8 wt%) was added, and the mixture was aged at 60 ° C. for 1 hour. Thereafter, 5 g of γ-methacrylooxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503, concentration 81.2 wt%), 100 g of methanol and 1 g of ammonia water having a concentration of 29.8 wt% were added, and further 60 ° C. For 5 hours. Thereafter, the solvent was replaced with 2-propanol using a ceramic outer membrane to prepare a surface-treated metal oxide particle (R3) 2-propanol dispersion having a solid content concentration of 30% by weight. The average particle diameter of the surface-treated metal oxide particles (R3) is shown in the table.

Preparation of coating liquid for forming transparent film (R3) In Example 1, the coating liquid for forming transparent film (R3) was prepared in the same manner except that 10 g of the surface-treated metal oxide particles (R3) 2-propanol dispersion was mixed. did.
Subsequently, the dispersion stability of the coating solution was evaluated in the same manner as in Example 1, and the results are shown in the table.

Production of substrate with transparent coating (R3) A substrate with transparent coating (R3) was produced in the same manner as in Example 1, except that the coating solution for forming a transparent coating (R3) was used. The thickness of the transparent film at this time was 10 μm.
About the base material with a transparent film (R3), evaluation similar to Example 1 was performed and the result was shown in the table | surface.

Comparative Example 4

Preparation of coating liquid for forming transparent film (R4) Surface-treated metal oxide particles (R3) prepared in the same manner as in Comparative Example 3 were added to 10 g of the transparent film forming resin component (2) prepared in the same manner as in Example 9. A coating solution (R4) for forming a transparent film was prepared by mixing 10 g of 2-propanol dispersion. Subsequently, the dispersion stability of the coating solution was evaluated in the same manner as in Example 1, and the results are shown in the table.

In the production example 1 of the substrate with a transparent film (R4), except that the transparent film-forming coating liquid (R4) was prepared substrate with a transparent film (R4) in the same manner. The thickness of the transparent film at this time was 10 μm.
About the base material with a transparent film (R4), evaluation similar to Example 1 was performed and the result was shown in the table | surface.

Comparative Example 5

Preparation of surface-treated metal oxide particles (R5) Water dispersion of antimony-doped tin oxide (ATO) fine particles (manufactured by Catalyst Kasei Kogyo Co., Ltd .: TL-98-FDAR: solid content concentration 20% by weight, average particle size 8 nm) 100 g was diluted with 100 g of pure water, and then 5.6 g of normal ethyl silicate (manufactured by Tama Chemicals: ES-28, concentration 28.8 wt%) was added, followed by aging at 60 ° C. for 1 hour. Thereafter, 20 g of γ-methacrylooxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical: KBM-5103, concentration: 81.2 wt%), 100 g of methanol, and 0.1 g of ammonia water having a concentration of 29.8 wt% were added. Aging was performed at 60 ° C. for 5 hours. Thereafter, the solvent was replaced with 2-propanol using a ceramic outer membrane to prepare a surface-treated metal oxide particle (R5) 2-propanol dispersion having a solid content concentration of 30% by weight. The average particle diameter of the surface-treated metal oxide particles (R5) is shown in the table.

Preparation of coating liquid for forming transparent film (R5) In Example 1, the coating liquid for forming transparent film (R5) was prepared in the same manner except that 10 g of the surface-treated metal oxide particles (R5) 2-propanol dispersion was mixed. did.
Subsequently, the dispersion stability of the coating solution was evaluated in the same manner as in Example 1, and the results are shown in the table.

In the production example 1 of the substrate with a transparent film (R5), except that the transparent film-forming coating liquid (R5) was prepared substrate with a transparent film (R5) in the same manner. The thickness of the transparent film at this time was 10 μm.
About the base material with a transparent film (R5), evaluation similar to Example 1 was performed and the result was shown to the table | surface.

Comparative Example 6

Preparation of coating liquid for forming transparent film (R6) Surface-treated metal oxide particles (R3) prepared in the same manner as in Comparative Example 3 were added to 7 g of the resin component (3) for transparent film formation prepared in the same manner as in Example 10. ) Mix 3 g of 2-propanol dispersion 10 g diluted with isopropyl alcohol to a concentration of 3 wt%, and further dilute with isopropyl alcohol to a concentration of 0.5 wt% to obtain a coating solution (R6) for forming a transparent film. Prepared. Subsequently, the dispersion stability of the coating solution was evaluated in the same manner as in Example 1, and the results are shown in the table.

Production of substrate with transparent film (R6) A substrate with transparent film (R6) was produced in the same manner as in Example 1 except that the coating liquid for forming a transparent film (R6) was used. The thickness of the transparent film at this time was 10 μm.
The transparent film-coated substrate (R6) was evaluated in the same manner as in Example 1, and the results are shown in the table.

Claims (12)

An organic silicon compound represented by the following formula (1) is added to water and / or an organic solvent dispersion of the metal oxide particles for hydrolysis, and then an organosilicon compound represented by the following formula (2) is added. And a surface treatment method for metal oxide particles, wherein the metal oxide particles are hydrolyzed.
_{(NH 2 -C n H 2n -Z} -C m H 2m) L -Si-Y 4-L (1)
(Wherein, Z: —NH, —CH ₂ , Y: C 1-4 alkoxy group, hydroxyl group, halogen, hydrogen. L: integer of 1 to 3, n: integer of 0 to 10, m: An integer from 0 to 10.)
R _p -Si x _4-p (2)
(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, a hydroxyl group, Halogen, hydrogen, p: an integer of 1 to 3, with the exception of an amino group-substituted hydrocarbon group in the substituted hydrocarbon group. The content of the organic silicon compound represented by the formula (1) of the metal oxide particles that are the surface _{treatment, [(NH 2 -C n H} 2n -Z-C m H 2m) L -SiO 4-L _{/ 2} ] in the range of 0.001 to 20 wt%, and the content of the organosilicon compound represented by the formula (2) is in the range of 1 to 60 wt% as R _p —Si—O _{4−p / 2} The method for surface treatment of metal oxide particles according to claim 1, wherein:   The metal oxide particles are silica, alumina, zirconia, titanium oxide, tin oxide, zinc oxide, antimony pentoxide, indium oxide, low-order titanium oxide and complex oxides thereof, or Sb-doped tin oxide (ATO), F-doped It is 1 type (s) or 2 or more types chosen from a tin oxide, P dope tin oxide, Sn dope indium oxide (ITO), and F dope indium oxide, The average particle diameter exists in the range of 3-300 nm, It is characterized by the above-mentioned. 3. A method for surface treatment of metal oxide particles according to 1 or 2.   The surface treatment method for metal oxide particles according to any one of claims 1 to 3, wherein the average particle diameter of the surface-treated metal oxide particles is in the range of 3 to 300 nm.   A surface-treated metal oxide comprising the surface-treated metal oxide particles obtained by the surface treatment method according to claim 1 and a dispersion medium, wherein the concentration of the surface-treated metal oxide particles is in the range of 1 to 50% by weight. Product particle dispersion.   A coating liquid for forming a transparent film, comprising the surface-treated metal oxide particles obtained by the surface treatment method according to claim 1, a matrix-forming component, and a dispersion medium. The concentration (C _P ) of the surface-treated metal oxide particles is in the range of 0.1 to 40% by weight as the solid content, and the concentration (C _M ) of the matrix-forming component is 1.9 to 49.9 as the solid content. The coating solution for forming a transparent film according to claim 6, wherein the coating concentration is in the range of 2% by weight, and the total concentration (C _P ) + (C _M ) is in the range of 2 to 50% by weight as the solid content.   It consists of a base material and the transparent film provided on the base material, and this transparent film consists of a matrix component and the surface treatment metal oxide particle obtained by the manufacturing method of Claims 1-4, and a transparent film A substrate with a transparent coating, wherein the content of the surface-treated metal oxide particles is in the range of 0.2 to 80% by weight as a solid content. The substrate with a transparent coating according to claim 8, wherein the thickness of the transparent coating is in the range of 30 nm to 50 µm.
  It is characterized by adding an organosilicon compound having an amino group to water and / or an organic solvent dispersion of metal oxide particles, followed by hydrolysis, and then adding an organosilicon compound not containing an amino group for hydrolysis. A method for surface treatment of metal oxide particles.   Γ-aminopropyltriethoxysilane is added to the water and / or organic solvent dispersion of the antimony pentoxide particles for hydrolysis, and then γ- (meth) acryloxypropyltrimethoxysilane is added for hydrolysis. A method for surface treatment of antimony pentoxide particles characterized by the following.   N-β (aminoethyl) γ-aminopropyltrimethoxysilane is added to water and / or an organic solvent dispersion of silica / zirconia-based particles for hydrolysis, and then γ- (meth) acrylooxypropyltrimethoxy is added. A method for treating a surface of silica / zirconia particles, wherein silane is added and hydrolyzed.