JP6360660B2 - Base material with antireflection film and method for producing the same - Google Patents

Description

  The present invention relates to a substrate with an antireflection film that has excellent water repellency and excellent antireflection performance and antiglare performance, and a method for producing the same. More specifically, since the refractive index gradually decreases from the bottom to the top of the film, the present invention relates to a substrate with an antireflection film that has excellent water repellency and excellent antireflection performance and antiglare performance, and a method for producing the same. .

  Conventionally, it has been known to form an antireflection film on the surface of a substrate in order to prevent reflection on the surface of the substrate such as glass, plastic sheet, and plastic lens. For example, a coating method, a vapor deposition method, a CVD method, etc. To form a film of a low refractive index substance such as fluororesin or magnesium fluoride on the surface of a glass or plastic substrate, or apply a coating solution containing low refractive index fine particles such as silica fine particles to the substrate surface. Thus, a method of forming an antireflection coating is known (for example, see Patent Document 1: Japanese Patent Laid-Open No. 7-133105). At this time, in order to improve the antireflection performance, it is also known to form a high refractive index film containing fine particles of high refractive index under the antireflection coating.

Furthermore, in the display device or the like, it is also known to form irregularities on the surface in order to provide string-proofing properties (sometimes referred to as anti-glare properties). (Patent Literature 2: JP 2002-169001, JP-Patent Document 3: JP 2002-71904, JP-Patent Document 4: JP 2001-281411, JP-Patent Document 5: JP 2001-34350 3 JP)

  On the other hand, in general, when the solid surface has a fractal structure, when the solid surface is hydrophilic, the hydrophilicity is improved and super hydrophilicity is exhibited. Conversely, when the solid surface is hydrophobic, the water repellency is improved. It is known to improve and exhibit super water repellency.

  In Patent Document 6 (Japanese Patent Laid-Open No. 2005-343016), in a super water-repellent coating-coated article in which the surface of a base material is coated with a super-water-repellent coating, a protrusion and a water-repellent film in which the super-water-repellent coating is a fine particle aggregate A super-water-repellent coating in which in the coating area of the coating, there are a portion where the protrusion is present and a portion where the protrusion is not present, and the surface of the coating where the protrusion is present is uneven A coated article is disclosed.

  Specifically, colloidal silica bonded in three dimensions, alkylalkoxysilane, and alkylalkoxysilane containing fluorine are mixed to prepare a cohydrolyzed / condensed polymer of water repellent material and silicon oxide fine particles. Is used as a dispersion for water repellent treatment, applied by a flow coat method, and naturally dried to prepare a super water repellent treated glass substrate.

  Patent Document 7 (WO2003 / 039856) discloses a superstructure including a base, a base film having micro unevenness formed on the surface of the base, and a water-repellent film formed on the micro unevenness of the base film. A super-water-repellent substrate comprising a water-repellent substrate, wherein the surface shape of the water-repellent coating is composed of particulate protrusions and columnar protrusions having a height measured from the surface of the substrate higher than the particulate protrusions. It is disclosed.

  Patent Document 8 (Japanese Patent Application Laid-Open No. 2004-137137) discloses an article coated with a film mainly composed of silicon oxide having fine irregularities on the surface, and the fine irregularities are formed by minute protrusions and columnar protrusions. A film-coated article characterized by being configured is disclosed. As its production method, it is disclosed that a film having such a structure can be formed by applying a coating solution in which a chlorosilyl group-containing compound is dissolved in a solvent mainly composed of silicon oil.

Patent Document 9 (JP-A-8-40748) discloses at least one of a glass substrate and a micropit-like surface layer, an uneven surface layer, and a convex surface layer in a state where the film is formed on the surface of the substrate without performing surface treatment. An underlayer composed of an oxide thin film or mixed oxide thin film having a surface layer shape of more than one species, tin oxide particles containing at least fluoroalkylsilane and antimony oxide as a dopant on the underlayer, and a silicone compound Then, a water / oil repellent liquid in which an acid is added to 5 × 10 ⁻⁴ mol to 2 × 10 ⁻² mol with respect to 1 mol of fluoroalkylsilane was applied to a mixed solution composed of water and an organic solvent. A water repellent glass comprising a water repellent layer that is a thin film is disclosed.

JP 7-133105 A JP 2002-169001 A JP 2002-71904 A JP 2001-281411 A JP 2001-343503 A JP 2005-343016 A WO2003 / 039856 JP 2004-137137 A JP-A-8-40748

  However, in recent years, there has been a demand for an antireflection film that not only has antireflection performance and antiglare performance, but also has suppressed water adhesion and water repellency, as well as suppressed adhesion of fingerprints. . Conventionally, an antireflection film having both of these performances has not been obtained.

  The present inventors have formed an antireflection film comprising an inorganic oxide fine particle layer composed of particles of a specific shape on the surface of a flexible resin film substrate, whereby the film exhibits super water repellency and is based on The present invention has been completed by finding that it has excellent adhesion to materials, abrasion resistance, scratch resistance, etc., and excellent antireflection performance.

The substrate with antireflection film according to the present invention comprises a resin substrate and an antireflection film formed on the substrate,
The contact angle of the antireflection film with water is 130 to 180 °, the reflectance (Rf) is 2% or less, and the haze is 10% or less.

The antireflection film comprises an inorganic oxide fine particle layer containing surface-treated inorganic oxide fine particles, the antireflection film surface has an uneven structure, and the average height (T _F ) of the convex portions is 30 to 500 nm. The average inter-convex distance (pitch width) (W _F ) is in the range of 50 to 1000 nm.
The antireflection film has an overcoat layer on the inorganic oxide fine particle layer.

The ratio (T _F ) / (W _F ) between the average height (T _F ) and the average inter-convex distance (W _F ) is in the range of 0.1-10.
The surface of the convex part of the concavo-convex structure further has fine irregularities, the average height (T _FF ) of the fine convex part is in the range of 3 to 50 nm, and the average distance between convex parts (W _FF ) is It is smaller than the average inter-convex distance (W _F ) of the part and is in the range of 3 to 50 nm.

The surface-treated inorganic oxide fine particles are surface-treated with a hydrolyzable organosilicon compound represented by the following formula (1) and / or (2) or a hydrolyzate of the hydrolyzable organosilicon compound: R _n − SiX _4-n (1)
(In the formula, R is a fluorine-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, a halogen, Hydrogen, n: an integer of 1 to 3)
R _n -SiX _4-n (2)
(In the formula, R is a hydrocarbon group (excluding fluorine substitution) which may be substituted with a (meth) acryloyl group having 1 to 10 carbon atoms, an amino group, or a mercapto group, and is the same as each other. X: an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, halogen, hydrogen, n: an integer of 0 to 3)
The inorganic oxide fine particle layer contains a binder.

  ADVANTAGE OF THE INVENTION According to this invention, the base material with an anti-reflective film which was excellent in water repellency while being excellent in anti-reflective performance and anti-glare performance using a resin base material, and its manufacturing method can be provided.

It is a schematic sectional drawing which shows the one aspect | mode of the base material with an antireflection film concerning this invention. The scanning electron micrograph (SEM) of the alumina hydrate microparticles prepared in Example 1 is shown.

[Base material with antireflection film]
The base material with an antireflection film according to the present invention comprises a resin base material and an antireflection film formed on the base material, and the contact angle of the antireflection film with water is in the range of 130 to 180 °. It is characterized by that.

Resin Substrate As the resin substrate used in the present invention, conventionally known ones can be used without particular limitation, and polycarbonate, acrylic resin, polyethylene terephthalate (PET), triacetyl cellulose (TAC), cyclohexane Examples thereof include plastic sheets such as polyolefin and norbornene, plastic films, and plastic panels.

Antireflection film The antireflection film includes an inorganic oxide fine particle layer containing surface-treated inorganic oxide fine particles.
(i) Inorganic oxide fine particle layer The inorganic oxide fine particles used in the present invention preferably have a plate shape, a fiber shape, or a chain shape.

Examples of the plate-like inorganic oxide fine particles include plate-like alumina fine particles, plate-like alumina hydrate fine particles, and plate-like alumina / silica fine particles.
In the case of plate-like alumina hydrate fine particles, pseudo boehmite alumina hydrate fine particles (Al ₂ O ₃ .nH ₂ O, n = 0.5 to 2.5) are often used, which is crystalline alumina water. It is a kind of Japanese fine particles, and primary particles are usually arranged in a plate shape to form secondary particles.

When the shape of the inorganic oxide fine particles is plate-like, the inorganic oxide fine particle layer is formed on the base material in such a manner that the particle group formed by laminating the plate-like inorganic oxide fine particles in contact with the surface forms irregularities. The average particle diameter (D _P ) of the plate-like inorganic oxide fine particles is in the range of 10 to 300 nm, the average thickness (T _P ) is in the range of 1 to 60 nm, and the average particle diameter (D _P ) and the average thickness (T it is preferred _{to P)} and the ratio of (D _P) / (T _P) is in the range of 1.5 to 30.

The average particle diameter (D _P ) of the plate-like alumina fine particles is preferably in the range of 10 to 300 nm, more preferably 30 to 250 nm. It is difficult to obtain a particle having an average particle size (D _P ) exceeding the lower limit of the above range, and even if it is obtained, it does not have the plate shape described above, and the desired unevenness cannot be formed. In some cases, the water repellency of the antireflective film is insufficient, and the refractive index of the antireflective film gradually decreases from the bottom to the top. The dazzling performance may be insufficient.

Even if the average particle diameter (D _P ) is too large, the strength and hardness of the finally obtained antireflection film and the adhesion to the substrate may be insufficient.
Further, the average thickness (T _P) of the plate-like alumina fine particles 1 nm to 60 nm, more preferably in the range of 3 to 50 nm. It is difficult to obtain a film having an average thickness (T _P ) that is too thin, and even if it is obtained, the desired unevenness cannot be formed, so that the finally obtained antireflection film may have insufficient water repellency. In addition, the refractive index of the antireflection film gradually decreases as it goes from the lower part to the upper part, so that the refractive index is not sufficiently lowered, and the antireflection performance and the antiglare performance may be insufficient.

If the average thickness (T _P ) is too thick, it is difficult to take a plate-like structure, it becomes close to a cube, and since sufficient unevenness cannot be formed, the water repellency, strength, Adhesion, antireflection performance, antiglare performance, etc. may be insufficient.

The ratio (D _P ) / (T _P ) between the average particle diameter (D _P ) and the average thickness (T _P ) is preferably in the range of 1.5 to 50, more preferably 4 to 40. The ratio between the average particle diameter (D _P) and the average thickness _{(T P) (D P)} / (T P) is in the range, it is possible to form a desired uneven, finally water repellency, strength An antireflection film excellent in adhesion to the substrate, antireflection performance, antiglare performance and the like can be obtained.

  Examples of the fibrous inorganic oxide fine particles include fibrous alumina fine particles, fibrous alumina hydrate fine particles, fibrous alumina / silica fine particles, fibrous silica fine particles, and fibrous titanium oxide fine particles.

Also in the case of fibrous alumina hydrate fine particles, it is preferable to use pseudo boehmite alumina hydrate fine particles (Al ₂ O ₃ .nH ₂ O, n = 0.5 to 2.5). In the case where the shape of the inorganic oxide fine particles is fibrous, the inorganic oxide fine particle layer is formed on the base material in such a manner that the particle group entangled with the fibrous inorganic oxide fine particles forms irregularities. These fine particle layers form desired irregularities on the surface of the finally obtained water-repellent coating.

When the shape of the inorganic oxide fine particles is fibrous, the average length (L _F ) of the fibrous inorganic oxide fine particles is in the range of 10 to 500 nm, and the average particle width (W _FF ) is in the range of 1 to 100 nm. And the ratio (L _F ) / (W _FF ) of the average length (L _F ) to the average particle width (W _PF ) is preferably in the range of 1.5-50. The average length (L _F ) of the fibrous inorganic oxide fine particles is preferably in the range of 30 to 400 nm.

When the average length (L _F ) is short, the particles may not be prepared stably and with good reproducibility. The water repellency of the resulting water repellent coating may be insufficient, and the antireflection performance and antiglare performance may be insufficient.

If the average length (L _F ) is too long, the particles may not be prepared stably and with good reproducibility. In some cases, the water repellency of the finally obtained water repellent film may be insufficient, and the antireflection performance and antiglare performance may be insufficient.

The average particle width (W _F ) is further preferably in the range of 3-80.
When the average particle width (W _F ) is small, it is difficult to stably prepare particles with good reproducibility. In some cases, the water repellency of the resulting water repellent film may be insufficient, and the refractive index of the antireflective film gradually decreases from the lower part to the upper part. Performance may be insufficient. If the average particle width (W _F ) is too large, it will not be fibrous and will not form irregularities, resulting in insufficient water repellency of the resulting water-repellent coating, resulting in strength, adhesion to the substrate, and reflection. The prevention performance and antiglare performance may be insufficient.

The ratio (L _F ) / (W _PF ) between the average length (L _F ) and the average particle width (W _PF ) is preferably in the range of 4 to 40. If the average length (L _F) the ratio of the average particle width _{(W PF) (L F)} / (W PF) is in the range, for a predetermined fibrous form, to form a desired uneven Finally, an antireflection film excellent in water repellency, strength, adhesion to a substrate, antireflection performance, antiglare performance and the like can be obtained.

  Examples of the chain inorganic oxide fine particles include chain silica fine particles, chain zirconia fine particles, and chain antimony pentoxide fine particles. When the shape of the inorganic oxide fine particles is a chain shape, as in the case of the fibrous inorganic oxide fine particles described above, the particle group in which the chain inorganic oxide fine particles are entangled forms an irregularity on the base material. An oxide fine particle layer is formed. These fine particle layers form desired irregularities on the surface of the finally obtained water-repellent coating.

When the shape of the inorganic oxide fine particles is a chain shape, the chain inorganic oxide fine particles are fine particles in which 2 to 100 primary fine particles having an average particle diameter (D _C ) in the range of 3 to 50 nm are connected in a chain shape. Yes, the average length (L _C ) is in the range of 6 to 500 nm, and the ratio of the average length (L _C ) to the average particle diameter (D _C ) (L _C ) / (D _C ) is 2 to 50 It is preferable to be in the range.

The average particle size (D _C ) of the primary particles constituting the chain inorganic oxide fine particles is preferably in the range of 3 to 100 nm, more preferably 5 to 80 nm. When the average particle diameter (D _C ) of the primary particles is less than the lower limit of the above range, chain particles may not be easily aggregated, and if they are too large, the primary particles are difficult to connect to obtain chain particles. It may not be possible.

The average length (L _C ) of the chain inorganic oxide fine particles is preferably in the range of 10 to 500 nm, more preferably 30 to 400 nm.
When the average length (L _C ) is short, the particle group in which the chain-like inorganic oxide fine particles are entangled is small, and the desired anti-reflection cannot be formed, so that the finally obtained antireflection film has insufficient water repellency. In some cases, the refractive index gradually decreases as the refractive index of the antireflection film increases from the lower part to the upper part, and the antireflective performance and antiglare performance may be insufficient.

Even if the average length (L _C ) is too long, it is impossible to form the predetermined unevenness, so that the final antireflection film may have insufficient water repellency, strength, adhesion to the substrate, and reflection. The prevention performance and antiglare performance may be insufficient.

The ratio (L _C ) / (D _C ) between the average length (L _C ) and the average primary particle size (D _C ) is preferably in the range of 1.5 to 50, more preferably 4 to 40.
When the ratio (L _C ) / (D _C ) between the average length (L _C ) and the average primary particle diameter (D _C ) is within the above range, a predetermined chain shape is formed, and thus desired irregularities are formed. Finally, an antireflection film excellent in water repellency, strength, adhesion to a substrate, antireflection performance, antiglare performance and the like can be obtained.

  In the present invention, the particle shape and size are important. The particles used in the present invention can form unevenness as described later, and because fine unevenness is formed on the surface of the unevenness, the refractive index of the antireflection film gradually decreases from the bottom to the top, and further the surface layer The refractive index of a part becomes low, and while being excellent in water repellency, the antireflection film excellent in antireflection performance and antiglare performance can be obtained.

In the present invention, the average particle diameter (D _P ), the average thickness (T _P ), the average length (L _F ), and the average particle width (W _F ) of the fibrous inorganic oxide fine particles. The average length (L _C ) and average primary particle diameter (D _C ) of the chain inorganic oxide fine particles correspond to the numerical values of the plate-like, fiber-like, and chain-like inorganic oxide fine particles used in the raw material. .

Such inorganic oxide fine particles are surface-treated with an organosilicon compound represented by the formula (1) and / or an organosilicon compound represented by the formula (2) or a hydrolyzate thereof.
_{R n -SiX 4-n (1} )
(In the formula, R is a fluorine-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, a halogen, Hydrogen, n: an integer of 1 to 3)
R _n -SiX _4-n (2)
(In the formula, R is a hydrocarbon group (excluding fluorine substitution) which may be substituted with a (meth) acryloyl group having 1 to 10 carbon atoms, an amino group, or a mercapto group, and is the same as each other. X: an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, halogen, hydrogen, n: an integer of 0 to 3)

  Examples of the hydrolyzable organosilicon compound represented by the formula (1) include perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriisopropoxysilane, and trifluoropropyltrimethoxy. Examples include silane, tridecafluorooctyltrimethoxysilane, heptadecatrifluorodecyltrimethoxysilane, dimethoxymethyltrifluoropropylsilane, pentadecatrifluorodecyltrimethoxysilane, heptadecatrifluorodecyltripropoxysilane, and the like.

  Examples of the hydrolyzable organosilicon compound represented by formula (2) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, and diphenyl. Dimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, 3,3, 3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyltrimeth Xysilane, γ-glycidoxymethyltriexisilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxy Silane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ- (meth) acrylooxymethyltrimethoxysilane, γ- (meth) acrylooxymethyltriethoxysilane, γ- (meth) acrylooxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (meth) acrylooxypropyltrimethoxy Silane, γ- (meth) acrylooxypropyltrimethoxysilane, γ- (meta ) Acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, butyltrimethoxysilane, isobutyltriethoxysilane, hexyltriethoxysiloctyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane , Isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, 3-ureidoisopropylpropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylsilanol, methyltrichlorosila , Dimethyldiethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyl Examples include methyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and the like, and mixtures thereof.

  In the present invention, when the hydrolyzable organosilicon compound represented by the formula (1) is used for the surface treatment, it is not necessary to use a binder and it is not always necessary to form an overcoat layer. Further, the organosilicon compound represented by the formula (1) and the organosilicon compound represented by the formula (2) may be used in combination.

  At this time, n = 0 (tetrafunctional) hydrolyzable organosilicon compound represented by formula (2) or n = 0 (tetrafunctional) hydrolyzable organosilicon compound and n = 1 (Trifunctional) mixture with a hydrolyzable organosilicon compound is excellent in adhesion to the substrate, strength, hardness, etc., and the overcoat layer described later also increases the bondability with the final, finally A base material with an antireflection film excellent in strength, hardness, water repellency, antireflection performance and antiglare performance can be obtained.

The amount of surface treatment of the inorganic oxide fine particles with the hydrolyzable organosilicon compound is such that the hydrolyzable organosilicon compound is R _n —SiO 2 _(4-n) with respect to 100 parts by weight of the inorganic oxide fine particles as the oxide (1 _{). / 2} is preferably in the range of 1 to 200 parts by weight, more preferably 5 to 100 parts by weight.

When the surface treatment amount is within the above range with a hydrolyzable organosilicon compound of inorganic oxide fine particles, the dispersibility is high and the bonding with the binder is promoted, and finally the strength, hardness, haze, antireflection performance, A substrate with an antireflection film having water repellency excellent in dazzling performance and the like can be obtained.
The surface-treated inorganic oxide fine particle layer preferably contains a binder.

(ii) Binder The antireflection film preferably contains a binder for the purpose of binding the surface-treated inorganic oxide fine particles and improving the adhesion, strength, and hardness with the substrate.

  In the case where the surface treatment is performed with the organosilicon compound represented by the formula (2), it is preferable to include a binder because the adhesion and strength can be increased. In addition, it does not exclude including a binder in what was surface-treated with the organosilicon compound of Formula (1).

As the binder, silica is desirable, and silica derived from silica sol, acidic silicic acid solution, and hydrolyzable organosilicon compound is more preferable.
Among these, a silica binder which is a hydrolyzed polycondensate of a hydrolyzable organosilicon compound represented by the following formula (3) is preferable.

_{R n -SiX 4-n (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, n: an integer of 0 to 1)

  Here, the hydrolyzed polycondensate is a hydrolyzable organosilicon compound, a partial hydrolyzate thereof, or a hydrolyzate that has been polycondensed by heat treatment in the production process described later. I mean.

  Such hydrolyzable organosilicon compounds include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxy. Silane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, 3,3,3-trifluoropropyltri Methoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysila , Γ-glycidoxymethyltriethoxysilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxy Silane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ- (meth) acrylooxymethyltrimethoxysilane, γ- (meth) acrylooxymethyltriethoxysilane, γ- (meth) acrylooxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (meth) acrylooxypropyltrimethoxy Silane, γ- (meth) acrylooxypropyltrimethoxysilane, γ- (meth) acrylic Rooxypropyltriethoxysilane, γ- (meth) acrylooxypropyltriethoxysilane, butyltrimethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilaoctyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane, isobutyl Triethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, 3-ureidoisopropylpropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriiso Propoxysilane, trifluoropropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (amino Ethyl) .gamma.-aminopropyltrimethoxysilane, N- phenyl--γ- aminopropyltrimethoxysilane, .gamma.-mercaptopropyltrimethoxysilane, trimethylsilanol, methyl trichlorosilane, and the like and mixtures thereof.

  Among them, n = 0 (tetrafunctional) hydrolyzable organosilicon compound, or n = 0 (tetrafunctional) hydrolyzable organosilicon compound and n = 1 (trifunctional) hydrolyzable organosilicon compound When the mixture is used, it has excellent adhesion to the base material, strength, hardness, etc., and also increases the bondability with the overcoat layer composed of the fluorine-containing silica-based layer described later, and finally has excellent strength, hardness, water repellency. A substrate with an antireflection film can be obtained.

  The content of the binder is 1 to 200 parts by weight, more preferably 10 to 190 parts by weight when the binder is converted to an oxide with respect to 100 parts by weight of the inorganic oxide fine particles in the inorganic oxide fine particle layer. It is preferable that it exists in the range.

  If the binder content is low, the adhesion, strength, hardness, etc. between the inorganic oxide fine particle layer and the substrate may be insufficient. Even if the content of the silica binder is too much, irregularities on the surface of the inorganic oxide fine particle layer may be reduced, and the water repellency of the finally obtained antireflection film may be insufficient, The refractive index gradually decreases as the refractive index of the prevention film decreases from the lower part to the upper part, so that the antireflection performance and the antiglare performance may be insufficient.

(iii) Overcoat layer An overcoat layer is formed on the infinite oxide fine particle layer.
In particular, when the hydrolyzable organosilicon compound represented by the formula (2) is not used for the surface treatment of the inorganic oxide fine particles, the formation of an overcoat layer is essential.
Such an overcoat layer is not particularly limited as long as it can bind to the inorganic oxide fine particle layer and improve water repellency, but in the present invention, the hydrolyzable organosilicon compound represented by the following formula (4) is hydrolyzed. A fluorine-containing silica-based layer that is a decomposed polycondensate is preferred.

_{R n -SiX 4-n (4} )
(In the formula, R is a fluorine-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, a halogen, Hydrogen, n: an integer of 1 to 3)

  Here, the hydrolyzable polycondensate of a hydrolyzable organosilicon compound means a hydrolyzable organosilicon compound, a partial hydrolyzate thereof, or a hydrolyzate that has been subjected to heat treatment in the production process described later. It means that it is condensed.

Examples of such a hydrolyzable organosilicon compound include the same compounds as the hydrolyzable organosilicon compound represented by the above formula (1).
The fluorine-containing silica-based layer may further contain a hydrolysis polycondensate of a hydrolyzable organosilicon compound represented by the following formula (5).

SiX ₄ (5)
(Wherein, X: C1-C4 alkoxy group, hydroxyl group, halogen, hydrogen)
Here, the hydrolyzed polycondensate is a hydrolyzable organosilicon compound, a partial hydrolyzate thereof, or a hydrolyzate that has been polycondensed by heat treatment in the production process described later. I mean.

  Examples of the hydrolyzable organosilicon compound represented by the formula (5) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and the like, and mixtures thereof.

In addition to the above, a hydrolyzable organosilicon compound having an alkoxy group having 5 or more carbon atoms as X can also be used in combination.
When the hydrolyzable polycondensate of the hydrolyzable organosilicon compound represented by the formula (5) is mixed and contained, the hydrolyzate polycondensate of the hydrolyzable organosilicon compound represented by the formula (4) The hydrolyzable polycondensate of the hydrolyzable organosilicon compound represented by the formula (5) as SiO ₂ is less than 200 parts by weight based on 100 parts by weight of R _n —SiO 2 _{(4-n) / 2.} Is preferably contained in the range of 1 to 100 parts by weight. When the content of the hydrolyzable polycondensate of the hydrolyzable organosilicon compound represented by the formula (5) is in the above range, the antireflection excellent in strength, hardness and the like without reducing the water repellency of the antireflection film. A substrate with a film can be obtained.

The overcoat layer is 1 to 100 parts by weight in terms of oxide (R _n —SiO _{(4-n) / 2} ), more preferably ₂ to 80 parts _per 100 parts by weight of the inorganic oxide fine particles in the inorganic oxide fine particle layer. It is preferably in the range of parts by weight.

If the content of the overcoat layer is small, uneven coating may occur in some cases where the overcoat layer is not formed, and sufficient water repellency, strength, hardness, and scratch resistance may not be obtained. Even if the layer content is too large, the distance (W _F ) between the projections and depressions on the surface of the antireflection film, which will be described later, may be reduced, and the water repellency may rather decrease, and the strength and hardness of the antireflection film May become insufficient.

Hard Coat Layer In the present invention, it is desirable to have a hard coat layer between the base material and the inorganic oxide fine particle layer. As a result, the adhesion of the inorganic oxide fine particle layer can be further improved, and a substrate with an antireflection film excellent in hardness and scratch resistance can be obtained.

  The hard coat layer is not particularly limited as long as the adhesion of the inorganic oxide fine particle layer and the antireflection film can be improved and the hard coat properties (hardness and scratch resistance) can be improved. A film made of an oxide, and a film in which inorganic oxide fine particles such as silica fine particles are blended with these can be formed.

  Furthermore, the chain antimony pentoxide particles disclosed in Japanese Patent Application Laid-Open No. 2005-186435 filed by the applicant of the present application, the spherical coefficient disclosed in Japanese Patent Application Laid-Open No. 2009-83224 filed by the present applicant, and the like are specified. A hard coat layer containing metal oxide particles mainly composed of a certain silica can also be suitably employed.

  The forming method is not particularly limited as long as it can improve adhesion to the substrate, scratch resistance, etc., and a coating solution containing the organic resin component or the inorganic oxide component and the above-described particles is a bar coater method, a dip method, a spray method, It can be formed by applying on a substrate, drying by a well-known method such as spinner method, roll coating method, gravure coating method, slit coating method, and then curing by heat treatment, electron beam irradiation or the like.

The hard coat layer is preferably formed so that the thickness of the hard coat layer is in the range of 0.5 to 20 μm, more preferably 1.0 to 15 μm.
If the hard coat layer is thin, the effect of improving the hard coat property may be insufficient. Even if the hard coat layer is too thick, the hard coat properties are not further improved, cracks may be generated, and the hardness may be lowered or insufficient.

Intermediate Film In the present invention, it is desirable to have an intermediate film containing high refractive index fine particles and / or conductive fine particles between the base material or the hard coat layer on the base material and the inorganic oxide fine particle layer. Thereby, the antireflection performance of the antireflection film can be further increased, or the antistatic performance can be imparted.

Examples of the high refractive index fine particles include TiO ₂ , ZrO ₂ , ZnO, Sb ₂ O ₅ , ZnO ₂ , SnO ₂ , In ₂ O _{3 and the} like, and composite oxide fine particles, mixtures thereof, and the like.
Further, as the conductive fine particles, antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), F-doped tin oxide (FTO), such as Sb ₂ O ₅ , ZnO ₂ , SnO ₂ , In ₂ O _3, etc. Examples thereof include conductive fine particles having a high refractive index such as phosphorus-doped tin oxide (PTO) and aluminum-doped zinc oxide (AZO).

The refractive index (n _M ) of the intermediate film is higher than the refractive index (n _R ) of the antireflection film, the refractive index difference (n _M ) −refractive index (n _R ) is 0.01 to 0.5, and further It is preferable to be in the range of 02 to 0.3.
The thickness of the intermediate film is preferably in the range of 10 to 300 nm, more preferably 30 to 200 nm.

Irregular structure The surface of the substrate with an antireflection film according to the present invention has an uneven structure.
The concavo-convex structure is defined by the average height (T _F ) of the convex portions, the distance between the average convex portions (pitch width), and the contact angle with water.

It is preferable that the average height (T _F ) of the projections of the concavo-convex structure is in the range of 30 to 500 nm, more preferably 50 to 400 nm. When the average height (T _F ) of the convex portion is small, the water repellency of the antireflection film may be insufficient, and the decrease in the refractive index described above is also small, resulting in insufficient antireflection performance. There is.

If the average height (T _F ) of the convex portions is too large, the strength of the antireflection film may be insufficient.
Moreover, it is preferable that the distance between average convex parts (it may be called pitch width) (W _F ) is in the range of 50 to 1000 nm, more preferably 70 to 800 nm. If the average distance between convex portions (W _F ) is short, the water repellency of the antireflection film may be insufficient. Even if the average inter-convex distance (W _F ) is too large, the water repellency of the antireflection film may be insufficient.

A ratio (T _F ) / (W _F ) (sometimes referred to as an aspect ratio) between the average height (T _F ) and the average distance between the convex portions (W _F ) is 0.1 to 10, more preferably 0. It is preferable that it exists in the range of 2-5. When (T _F ) / (W _F ) is small, the height of the convex portion of the concavo-convex structure on the surface is insufficient, and thus the water repellency of the antireflection film may be insufficient.
When (T _F ) / (W _F ) is too large, it is difficult to arrange the inorganic oxide fine particles, and even if the inorganic oxide fine particles can be arranged, the strength and hardness of the antireflection film are insufficient. There is.

In the present invention, the average height (T _F ) of the protrusions and the average distance (W _F ) between the protrusions are obtained by taking a transmission electron micrograph (TEM) of the cross section of the antireflection film. The height and the distance between pitches were measured, and the average value was obtained.

The average height (T _F ) of the protrusions and the average distance (W _F ) between the protrusions are the size and shape of the inorganic oxide fine particles, that is, the average particle diameter (D _P ) for the plate-like inorganic oxide fine particles, Average thickness (T _P ), average length (L _F ), average particle width (W _PF ) for fibrous inorganic oxide fine particles, average length (L _C ), average primary particle diameter ( _C ) for chain inorganic oxide fine particles D _C ) is selected and adjusted to the concentration of the inorganic oxide fine particle dispersion, the coating method, and the like in the method for producing a transparent film-coated substrate described later. Specifically, when the average particle diameter (D _P ), average length (L _F ), and average length (L _C ) are large, the average height (T _F ) and the average inter-convex distance (W _F ) are When the concentration of the inorganic oxide fine particle dispersion is high, the average height (T _F ) tends to be high. When the concentration is low, the average distance between the convex portions (W _F ) tends to be large. It is in.

The convex portion on the surface of the antireflection film of the present invention has finer irregularities on the convex portion surface.
This is shown in a model diagram in FIG.
It is preferable that the average height (T _FF ) of the convex portions of the fine irregularities is in the range of 3 to 50 nm, more preferably 3 to 45 nm.

In the present invention, the average height (T _F ) and the average distance (W _F ) between the convex portions were measured by an atomic force microscope (AFM) (manufactured by Bruker Co., Ltd .: Dimension 3100).
When the average height (T _FF ) of the convex portions of the fine irregularities is in the above range, the water repellency is more excellent, the refractive index of the antireflection film gradually decreases from the bottom to the top, and the surface layer is more A base material with an antireflection film having a reduced refractive index and excellent antireflection performance and antiglare performance is obtained.

Moreover, it is preferable that the average distance (W _FF ) between the convex portions of the fine irregularities is in the range of 3 to 50 nm, more preferably 3 to 45 nm.
When the average convex-to-convex distance (W _FF ) of the convexes of fine irregularities is in the above range, the water repellency and antireflection performance are more excellent as in the case where the average height (T _FF ) is in the predetermined range. A base material with an antireflection film is obtained.

The average height (T _FF ) and average distance between convex portions (W _FF ) of such fine irregularities should be measured when measuring the above average height (T _F ) and average distance between convex portions (W _F ). When an arbitrary five convex portions are designated and enlarged, the average height (T _FF ) and the average inter-convex distance (W _FF ) of the fine irregularities can be measured.

Next, the antireflection film preferably has a contact angle with water of 130 to 180 °, more preferably 145 to 180 °.
If the contact angle of the antireflection film with water is within the above range, a water-repellent antireflection film that repels water without water droplets adhering to the antireflection film can be obtained.

This is a characteristic of the concavo-convex structure formed from specific surface-treated inorganic oxide fine particles. In order to adjust the contact angle within the above range, the average height (T _F ) and the average inter-convex distance (W _F ) of the convex portions may be adjusted within a predetermined range by the method described above. It is preferable to set T _F ) / (W _F ) in a predetermined range of 0.1 to 10, particularly 1 to 5.

  Such a concavo-convex structure can be formed by surface-treating the above-described fibrous, plate-like, or chain-like particles to form a fine particle layer. Therefore, the concavo-convex structure can be adjusted by the particle shape, the surface treatment amount, and the type thereof.

  The substrate with an antireflection film according to the present invention preferably has a reflectance (Rf) of 2% or less, more preferably 1.5% or less. When the reflectance (Rf) exceeds 2%, the antireflection performance becomes insufficient, and when used in a display device, contrast may be lowered or reflection may occur.

The haze is preferably 10% or less, more preferably 7% or less, and particularly preferably 4% or less. If the haze exceeds 10%, the transparency may be insufficient, the contrast may be reduced, and the display screen may be white.
Below, the manufacturing method of the base material with an antireflection film concerning the present invention is explained.

[Method for producing base material with antireflection film]
The base material with an antireflection film of the present invention described above is produced by coating and drying the dispersion containing the inorganic oxide fine particles on the surface of the resin base material to form an antireflection film.

A hard coat layer may be formed on the surface of the resin base material in advance.
The coating liquid for forming the hard coat layer is not particularly limited as long as it can improve the adhesion and hard coat properties (hardness and scratch resistance) of the inorganic oxide fine particle layer and the antireflection film, and the hard coat layer described above is formed. The coating liquid containing the component which can be used can be used.

  The coating amount of the coating liquid for forming the hard coat layer varies depending on the concentration of the coating liquid, but as described above, coating is performed so that the film thickness of the hard coat layer is 0.5 to 20 μm, and further 1.0 to 15 μm. It is preferable to do.

  If the hard coat layer is thin, the effect of improving the hard coat property may be insufficient. Even if the hard coat layer is too thick, the hard coat properties are not further improved, cracks may be generated, and the hardness may be lowered or insufficient.

  Examples of the coating method include a bar coater method, a dip method, a spray method, a spinner method, a roll coating method, a gravure coating method, a slit coating method and the like, as in the coating method of the surface-treated inorganic oxide fine particle dispersion described later. .

  It is preferable to dry after applying the coating liquid for forming the hard coat layer, and a conventionally known method can be adopted as the drying method. For example, the drying temperature is substantially equal to the dispersion medium of the coating liquid for forming the hard coat layer. However, the temperature is generally 50 to 120 ° C.

Moreover, it is preferable to form an intermediate film on the substrate before or after the hard coat layer is formed.
The intermediate film is formed by applying a coating solution for forming an intermediate film and drying it.

As such a coating liquid for forming an intermediate film, such a coating liquid for forming an intermediate film includes a refractive index of the intermediate film as compared with the inorganic oxide fine particle layer in a matrix forming component made of an organic resin or an inorganic oxide. A coating solution in which metal oxide fine particles having a high refractive index are blended so as to increase the refractive index is used. Examples of the metal oxide fine particles having a high refractive index include TiO ₂ , ZrO ₂ , Sb ₂ O ₅ , B ₂ O ₃ , ZnO, SnO ₂ , In ₂ O _{3 and the} like, and complex oxides thereof, or antimony-doped tin oxide ( Examples thereof include high refractive index particles having conductivity such as ATO, tin-doped indium oxide (ITO), F-doped tin oxide (FTO), phosphorus-doped tin oxide (PTO), and aluminum-doped zinc oxide (AZO).

  The coating amount of the coating solution for forming the intermediate film varies depending on the concentration of the coating solution, but it is preferable that the coating is performed so that the thickness of the interlayer film is 10 to 300 nm, further 30 to 200 nm as described above.

  If the intermediate film is thin, the effect of improving the antireflection performance and antistatic performance may be insufficient. Even if the intermediate film is too thick, the antireflection performance is not further improved, and the transparency may be lowered, the crack may be generated and the hardness may be lowered, or may be insufficient.

  As a coating method, the bar coater method, the dip method, the spray method, the spinner method, the roll coating method, the gravure coating method, the slit coating method, etc., as in the coating method of the surface-treated inorganic oxide fine particle dispersion employed in the present invention. Is mentioned.

It is preferable to dry after applying the coating solution for forming the intermediate film, and a conventionally known method can be adopted as the drying method. For example, the drying temperature substantially removes the dispersion medium of the coating solution for forming the intermediate film. Although there is no particular limitation if possible, it is generally 50 to 120 ° C.
Thus, if necessary, an inorganic oxide fine particle layer is formed on the substrate on which the hard coat layer and the intermediate film are formed.

Formation of Inorganic Oxide Fine Particle Layer As the inorganic oxide fine particles used in the present invention, the above-described plate-like, fibrous, and chain-like inorganic oxide fine particles are used, and further, the formulas (1) to (2) What was surface-treated with an organosilicon compound is preferably used.
Examples of the method for producing fibrous and plate-like alumina hydrate fine particles that are suitably used in the plate-like, fiber-like, and chain-like inorganic oxide fine particles used in the present invention.

Preparation Method of Alumina Hydrate Fine Particles The method for producing the alumina hydrate fine particles used in the present invention is not particularly limited as long as the above-mentioned alumina hydrate fine particles are obtained, but the following methods are exemplified.

First, a basic method for producing fibrous alumina hydrate fine particles will be exemplified.
(1) A method of preparing an aluminum hydrogel slurry by adding an alkaline aqueous solution to an aqueous aluminum salt solution to neutralize it, and aging as necessary,
(2) A method of adding an alkaline aqueous solution after the aging, aging as necessary, then adding an aluminum salt aqueous solution, and aging as necessary.
(3) A method of repeating (2) above.

Alternatively, (4) a method in which an acid aqueous solution is added to a sodium aluminate aqueous solution to neutralize it to prepare an aluminum hydrogel slurry, and is aged as necessary.
(5) A method of adding an acid aqueous solution after the aging and aging as necessary, then adding a sodium aluminate aqueous solution and aging as necessary.
(6) A method of repeating (5) above.

further,
(7) A method of preparing an aluminum hydrogel slurry by mixing an aluminum salt aqueous solution and a sodium aluminate aqueous solution, and aging as necessary. In this case, (8) The method (2) or (5) may be performed, and this may be repeated as necessary.

In the present invention, the aluminum hydrogel slurry obtained by the above method is washed and used. The fine particles obtained by washing are used as the alumina hydrate fine particles used in the present invention.
As a washing method, a method of filtering and spraying, an ultrafiltration method, a method of removing cations and anions with a cation exchange resin, an anion exchange resin, both ion exchange resins, etc., a method of using these in combination The method of repeatedly performing is mentioned.

  In the above, examples of the aqueous aluminum salt solution include aqueous solutions of organic acid aluminum salts such as aluminum chloride, aluminum nitrate, aluminum sulfate, and aluminum acetate.

  Examples of the alkaline aqueous solution include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and aqueous solutions such as ammonia. In addition, conventionally known particle growth regulators such as citric acid, malic acid, lactic acid, fumaric acid, maleic acid, adipic acid, oxalic acid, malonic acid, succinic acid, tartaric acid, and phthalic acid can be blended and used.

As described above, fibrous alumina hydrate fine particles that can be used in the present invention can be prepared. The average length (L _F ) and average particle width (W _F ) of the fibrous alumina fine particles (secondary particles) are the raw materials used, neutralization conditions, aging conditions, concentration at that time, washing conditions, organic carboxylic acid, etc. It can adjust by well-known methods, such as use of a particle growth regulator.

Next, a basic method for producing plate-like alumina hydrate fine particles will be exemplified.
In the first example, an alumina hydrogel slurry is prepared in the same manner as in the case of preparing fibrous alumina hydrate fine particles. At this time, an acidic alumina hydrogel slurry is prepared, and then heated as necessary. Add basic compound to make it alkaline, then add acidic compound under heating if necessary to make acidic, then add basic compound under heating if necessary to prepare alkaline alumina hydrogel slurry To do.

  Alternatively, when an alkaline alumina hydrogel slurry is prepared, it is then made acidic by adding an acidic compound under heating, if necessary, and then made basic by adding a basic compound under heating, if necessary. Next, an acidic compound is added under heating as necessary to prepare an acidic alumina hydrogel slurry.

Subsequently, plate-like alumina hydrate fine particles can be prepared by washing the alumina hydrogel slurry by a conventionally known method.
A second example different from this is to prepare an alumina hydrogel slurry in an alkaline region by adding an acidic compound to a sodium aluminate aqueous solution with heating as necessary, and then ripen under heating to produce a primary solution. Plate-like alumina hydrate fine particles having substantially square particles can be prepared. Next, after thoroughly washing by a conventionally known method, an organic base such as tetramethylammonium hydroxide (TMAOH) is added, hydrothermally treated at a high temperature using an autoclave or the like, and then washed to remove the organic base. Thus, plate-like alumina hydrate fine particles that can be suitably used in the present invention can be prepared.

  The surface-treated inorganic oxide fine particles used in the present invention are the above-described plate-like, fiber-like, and chain-like inorganic oxide fine particles, which are hydrolyzable organosilicon compounds and / or hydrolyzable organosilicon compounds as described above. Surface treatment with hydrolyzate of

The amount of surface treatment of the inorganic oxide fine particles with the hydrolyzable organosilicon compound is such that the hydrolyzable organosilicon compound is R _n —SiO 2 _(4-n) with respect to 100 parts by weight of the inorganic oxide fine particles as the oxide (1 _{). / 2} is preferably in the range of 1 to 200 parts by weight, more preferably 5 to 100 parts by weight.

  As the surface treatment method, for example, the inorganic oxide fine particle aqueous dispersion is solvent-substituted with an alcohol such as methanol by an ultrafiltration membrane method, a predetermined amount of the hydrolyzable organosilicon compound is mixed, and hydrolyzed as necessary. For example, a method of adding an acid or alkali as water for hydrolysis and a catalyst for hydrolysis, and aging as necessary may be mentioned.

Examples of the dispersion medium for the dispersion medium surface-treated inorganic oxide fine particle dispersion include alcohols such as methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, furfuryl alcohol, and tetrahydrofurfuryl alcohol; Esters such as methyl acetate, ethyl acetate, isopropyl acetate, propyl acetate, isobutyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, cyclohexyl acetate, ethylene glycol monoacetate, ethylene glycol, Glycols such as hexylene glycol; diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol Hydrophilic solvents including ethers such as isopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monopropyl ether, propyl acetate, isobutyl acetate, butyl acetate, acetic acid Esters such as isopentyl, pentyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, cyclohexyl acetate, ethylene glycol monoacetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methylcyclohexanone, dipropyl ketone, Ketones such as methyl pentyl ketone and diisobutyl ketone; and polar solvents such as toluene. Furthermore, polar solvents such as N-methylpyrrolidone can also be used, and these may be used alone or in combination of two or more.

  The concentration of the surface-treated inorganic oxide fine particle dispersion is preferably in the range of 0.1 to 20% by weight, more preferably 0.5 to 10% by weight as the solid content. If the concentration of the surface-treated inorganic oxide fine particle dispersion is low, the thickness of the inorganic oxide fine particle layer may be thin, and desired irregularities may not be formed. Sufficient antireflection performance, antiglare performance, water repellency, strength, hardness, and scratch resistance may not be obtained.

  If the concentration of the surface-treated inorganic oxide fine particle dispersion is high, the coating properties may be lowered and the desired unevenness may not be formed depending on the coating method, and the resulting film may have poor water repellency and antireflection performance. May be sufficient.

  The surface-treated inorganic oxide fine particle dispersion is applied, but the coating method is not particularly limited as long as an inorganic oxide fine particle layer having a generally desired uneven structure can be formed. For example, a bar coater method, a dip method, a spray method, Examples thereof include a spinner method, a roll coat method, a gravure coat method, and a slit coat method.

It is preferable to dry after applying the surface-treated inorganic oxide fine particle dispersion, and a conventionally known method can be adopted as the drying method. For example, the drying temperature is substantially equal to the dispersion medium of the inorganic oxide fine particle dispersion. However, the temperature is generally 50 to 120 ° C.
When the surface treatment agent uses the organosilicon compound of the formula (2) as described above, the binder is applied to the inorganic oxide fine particle layer by applying a coating solution for the binder.

The binder contained in the binder is as described above, and a coating liquid in which the binder is dispersed is used.
As the dispersion medium for the binder coating liquid, the same dispersion medium as that of the surface-treated inorganic oxide fine particle dispersion can be used.
The concentration of the coating solution for the binder is preferably in the range of 0.05 to 20% by weight, more preferably 0.1 to 10% by weight as oxide or R _n —SiO 2 _{(4-n) / 2} .

  When the concentration of the coating liquid for the binder is in the above range, it can be uniformly applied to the inorganic oxide fine particle layer, although it varies depending on the coating method, functions as a binder for the surface-treated inorganic oxide fine particles, An inorganic oxide fine particle layer having excellent hardness and excellent adhesion to the substrate can be formed.

The coating liquid for the binder is composed of 100 parts by weight of the surface-treated inorganic oxide fine particles in the inorganic oxide fine particle layer as oxide (1), and the binder is converted into oxide (R _n -SiO _{(4-n) / 2} ) Then, the coating solution for the binder is used so as to be in the range of 1 to 200 parts by weight, more preferably 10 to 190 parts by weight.

If the coating amount of the binder coating solution is small, the adhesiveness, strength, hardness, etc. of the inorganic oxide fine particle layer to the substrate may be insufficient.
Even if the coating amount of the binder coating solution is too large, the surface unevenness and the surface roughness become small, and the water repellency and antireflection performance of the finally obtained antireflection film may be insufficient.

  The coating method for the binder coating solution is not particularly limited as long as it can be uniformly applied to the alumina hydrate fine particle layer. For example, a bar coater method, a dip method, a spray method, a spinner method, a roll coating method, a gravure coating method, The slit coat method etc. are mentioned.

  It is preferable to dry after applying the coating liquid for the binder, and a conventionally known method can be adopted as the drying method. For example, the drying temperature is particularly limited as long as the dispersion medium of the binder coating liquid can be substantially removed. Although there is no restriction | limiting, it is 50-120 degreeC in general, Preferably it is 60-100 degreeC.

  Furthermore, it can also heat-process as needed. Although heat processing temperature changes also with the kind of base material, it is preferable that it exists in the range of 130-700 degreeC, Furthermore, 150-500 degreeC.

An overcoat layer-forming coating solution is applied onto the overcoat layer-forming inorganic oxide fine particle layer as necessary to form an overcoat layer.

  In the present invention, when the hydrolyzable organosilicon compound represented by the formula (1) is used for the surface treatment, it is not always necessary to provide an overcoat layer, but it is also possible to provide it.

The components constituting the overcoat layer are as described above.
The coating solution is not particularly limited as long as it can bind to the inorganic oxide fine particle layer and improve water repellency, but in the present invention, as described above, the hydrolyzable fluorine-containing hydrolyzable organosilicon compound represented by the formula (4) is added. It is preferable to use a decomposition product.

  In addition to being able to improve water repellency by using the hydrolyzable organosilicon compound represented by formula (4), a fluorine-containing silica-based layer having a low refractive index can be formed on the inorganic oxide fine particle layer, The antireflection performance can be improved.

The overcoat layer forming coating solution preferably further contains a hydrolyzable organosilicon compound and / or a hydrolyzate represented by the following formula (5).
SiX ₄ (5)
(Wherein, X: C1-C4 alkoxy group, hydroxyl group, halogen, hydrogen)

Examples of such hydrolyzable organosilicon compounds include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.
The hydrolyzate of over-the organosilicon compound and / or a hydrolyzable organic silicon compound of the coat layer forming coating liquid to _{R n -SiO (4-n)} / 2 as 100 parts by weight, as SiO ₂ 0 to 100 It is preferable that it exists in the range of a weight part and also 0-50 weight part.

  If the amount of the hydrolyzable organosilicon compound represented by the formula (9) and / or the hydrolyzate is within the above range, the reflection is more excellent in strength, hardness, scratch resistance, etc. without reducing water repellency. A substrate with a protective film can be obtained.

As a dispersion medium for the coating liquid for forming the overcoat layer, the same dispersion medium as that for the surface-treated inorganic oxide fine particle dispersion can be used.
The concentration of the overcoat layer-forming coating solution, in terms of silica _{[R n -SiO (4-n} ) / 2 + SiO 2] 0.05~20 % by weight, still more in the range of 0.1 to 10 wt% It is preferable.

  When the concentration of the coating solution for forming the overcoat layer is low, uneven coating without a part of the overcoat layer occurs, and sufficient water repellency, strength, hardness, and scratch resistance may not be obtained. Even if the concentration of the overcoat layer forming coating solution is too high, the desired uneven structure may not be obtained, the water repellency will not be further improved, and the antireflection performance, strength, and hardness will be insufficient. There is.

The coating amount of the overcoat layer forming coating solution is [R _n -SiO _{(4-n) / 2} + SiO with respect to 100 parts by weight of the fine particles in the formed surface-treated inorganic oxide fine particle layer as oxide (1). ₂ ] is preferably in the range of 1 to 100 parts by weight, more preferably 1 to 80 parts by weight.

  If the coating amount of the overcoat layer forming coating solution is small, uneven coating with no overcoat layer occurs, and sufficient water repellency, strength, hardness, and scratch resistance may not be obtained. Even if the coating amount of the overcoat layer forming coating solution is too large, the desired uneven structure may not be obtained, and the water repellency is not further improved, and the antireflection performance, strength and hardness are insufficient. There is a case.

  The coating method of the overcoat layer forming coating solution is not particularly limited as long as it can be uniformly applied to the inorganic oxide fine particle layer. For example, a bar coater method, a dip method, a spray method, a spinner method, a roll coating method, a gravure coating method. And a slit coating method.

  It is preferable to dry after applying the overcoat layer-forming coating solution, and a conventionally known method can be adopted as the drying method. For example, the drying temperature is substantially equal to the dispersion medium of the overcoat layer-forming coating solution. However, it is generally 50 to 120 ° C, preferably 60 to 100 ° C.

Usually, heat treatment is performed for the purpose of removing the solvent. Although heat processing temperature changes also with the kind of base material, it is preferable that it exists in the range of 80-300 degreeC, Furthermore, 130-250 degreeC.
When the overcoat layer is formed and dried at 80 to 120 ° C., heat treatment is not necessary.

  By the drying / heating treatment, the bond between the inorganic oxide fine particle layer or the inorganic oxide fine particle layer containing the binder and the overcoat layer on the inorganic oxide fine particle layer is increased, and the strength, hardness, scratch resistance, and base material are increased. Adhesion can be improved.

  When the heat treatment temperature is low, the bond between the inorganic oxide fine particle layer composed of the inorganic oxide fine particles and the binder and the overcoat layer (fluorine-containing silica-based layer) on the inorganic oxide fine particle layer becomes insufficient, and the strength , Hardness, scratch resistance and adhesion to the substrate may be insufficient.

  If the heat treatment temperature is too high, the heat resistance may be exceeded depending on the type of the substrate, and the fluorine-substituted hydrocarbon group contained in the overcoat layer (fluorine-containing silica-based layer) is decomposed, resulting in water repellency, Strength, hardness, and adhesion may be insufficient.

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by these Examples.
[Example 1]
Preparation of surface-treated alumina hydrate fine particles (1) Dispersion A steam jacket heating type 100L tank made of titanium is charged with 55.987kg of pure water, and aluminum chloride hexahydrate (manufactured by Kanto Chemical Co., Inc .: deer) Special grade, AlCl ₃ .6H ₂ O concentration 98 wt%) 3.532 kg is dissolved. To this solution, 2.710 kg of sodium hydroxide (manufactured by Kanto Chemical Co., Inc .: deer special grade, NaOH concentration 48% by weight) is added and mixed. The mixture was heated to 80 ° C. with stirring and maintained for 1 hour to obtain 62.229 kg of alumina hydrogel slurry (1-1) having a pH of 4.0.

While maintaining the alumina hydrogel slurry (1-1) at 80 ° C., 0.620 kg of sodium hydroxide (manufactured by Kanto Chemical Co., Inc .: deer special grade, 48 wt% NaOH) was added and mixed, and the mixture was stirred for 80 Holding at 1 ° C. for 1 hour, 62.849 kg of alumina hydrogel slurry (1-2) having a pH of 8.5 was obtained. While maintaining this alumina hydrogel slurry (1-2) at 80 ° C., 1.314 kg of aluminum chloride hexahydrate (manufactured by Kanto Chemical Co., Inc .: deer special grade, 98 wt% AlCl ₃ .6H ₂ O) is stirred. 2.777 kg of an aluminum chloride aqueous solution dissolved in 1.463 kg of pure water was added and mixed, and kept at 80 ° C. for 1 hour with stirring to obtain 65.626 kg of alumina hydrogel slurry (1-3) having a pH of 4.5.

While maintaining this alumina hydrogel slurry (1-3) at 80 ° C., 1.241 kg of sodium hydroxide (manufactured by Kanto Chemical Co., Inc .: deer special grade, 48 wt% NaOH) was added and mixed, and the mixture was stirred at 80 ° C. Holding at 1 ° C. for 1 hour, 66.867 kg of pH 9.5 alumina hydrogel slurry (1-4) was obtained. This alumina hydrogel slurry (1-4) was filled in an ultrafiltration device and concentrated until the concentration as Al ₂ O ₃ was 4.5% by weight.

Al concentration as ₂ O ₃ is at 4.5 wt% alumina hydrogel slurry (1-4) to 60 ° C. of warm pure water, washed until the concentration of sodium remaining and chlorine is 10ppm or less, Al ₂ O An alumina hydrogel slurry (1-5) having a concentration of ₃ as a weight of 5% by weight was obtained.

Next, 33 g of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: SK-1BH) was added to 1000 g of the alumina hydrogel slurry (1-5), and the mixture was stirred for 1 hour for dealkalization.
Next, after separating the cation exchange resin, 33 g of an anion exchange resin (Mitsubishi Chemical (manufactured): SANUPC) was added, and the mixture was stirred for 1 hour for deanion treatment. Next, 33 g of cation exchange resin (Mitsubishi Chemical Corporation: SK-1BH) was added again, and the mixture was stirred for 1 hour and dealkalized to obtain a hydrated alumina having a concentration of 4.8% by weight as Al ₂ O _3. A fine particle (1) dispersion was prepared.

The dispersion was subjected to solvent substitution with methanol using an ultrafiltration membrane to obtain alumina hydrate fine particles (1) methanol dispersion having a solid content concentration of 8% by weight.
Part of the alumina hydrate fine particles (1) methanol dispersion was dried, and a scanning electron micrograph (SEM) was taken and shown in FIG.

The average particle length (L _F ) and average particle width (W _PF ) were measured, and the results are shown in the table.
Next, 100 g of alumina hydrate fine particles having a solid content concentration of 8 wt% (1) tetraethoxysilane (manufactured by Tama Chemical Industry Co., Ltd .: normal ethyl silicate-A, SiO ₂ concentration of 28.8 wt%) 1 Next, 3.1 g of ultrapure water was added and stirred at 50 ° C. for 6 hours to prepare surface-treated alumina hydrate fine particles (1) methanol dispersion having a solid content concentration of 8% by weight.

  Surface-treated alumina hydrate microparticles with a solid content of 8% by weight (1) 100 g of methanol dispersion, 8 g of N-methylpyrrolidone (NMP), 192 g of propylene glycol monopropyl ether (PGME), mixed alcohol (Nippon Alcohol Sales Co., Ltd.) ): SOLMIX A-11, mixed alcohol of methanol, ethanol and isopropyl alcohol) 100 g, and then stirred at 25 ° C. for 30 minutes to form a surface having a solid content concentration of 2% by weight for forming an inorganic oxide fine particle layer A treated alumina hydrate fine particle (1) dispersion was prepared.

Preparation of coating liquid for binding material (1) Mixed alcohol (Nippon Alcohol Sales Co., Ltd .: Solmix A-11, mixed alcohol of methanol, ethanol and isopropyl alcohol) 72.5 g with water 10.0 g and concentration 61% by weight 0.1 g of nitric acid was added and stirred at 25 ° C. for 10 minutes. Next, 17.4 g of tetraethoxysilane (manufactured by Tama Chemical Industry Co., Ltd .: normal ethyl silicate-A, SiO ₂ concentration 28.8 wt%) was added and stirred at 30 ° C. for 30 minutes to hydrolyze tetraethoxysilane. (Solid content concentration 5.0 wt%, molecular weight: 1000) was obtained. Next, 333.3 g of diacetone alcohol (DAA), 666.6 g of ethylene glycol monoisopropyl ether (I-PG) and mixed alcohol (manufactured by Nippon Alcohol Sales Co., Ltd .: Solmix A-11, methanol, ethanol and isopropyl alcohol 566.67 g of mixed alcohol) was added and stirred at 25 ° C. for 30 minutes to prepare a binder coating solution (1) made of silica having a solid concentration of 0.3% by weight.

Preparation of coating liquid for overcoat layer formation (1) Mixed alcohol (Nippon Alcohol Sales Co., Ltd .: Solmix A-11, mixed alcohol of methanol, ethanol and isopropyl alcohol) 2252.5 g with water 159.0 g and concentration 61 3.3% by weight of nitric acid was added and stirred at 25 ° C. for 5 minutes. Next, 46.4 g of tridecafluorooctyltrimethoxysilane (manufactured by MOMENTIVE: TSL8257, solid concentration: 98%) was added and stirred at 25 ° C. for 5 minutes, and then treated in an autoclave at 100 ° C. for 3 hours. Thereafter, 356.39 g of PGM and 213.91 g of DAA were added and treated at 25 ° C. for 30 minutes to prepare a coating solution for forming a fluorine-containing silica-based layer having a solid content concentration of 1.50% by weight.

  Subsequently, 10 g of PGM and mixed alcohol (manufactured by Nippon Alcohol Sales Co., Ltd .: Solmix A-11, mixed alcohol of methanol, ethanol and isopropyl alcohol) were added to 100 g of fluorine-containing silica-based layer forming coating solution having a solid content concentration of 1.50% by weight. 40 g was added to prepare an overcoat layer forming coating solution (1) having a solid content concentration of 1.0%.

Preparation of hard coat layer forming coating solution (1) Silica sol (manufactured by JGC Catalysts & Chemicals Co., Ltd .: Cataloid SI-30, average particle size 12 nm, SiO ₂ concentration 40.5% by weight, dispersion medium: isopropanol, particle refraction (Rate 1.46) 1.88 g of γ-methacrylooxypropyltrimethoxysilane (Shin-Etsu Silicone Co., Ltd .: KBM-503, SiO ₂ component 81.2%) was mixed with 100 g of ultrapure water (3.1 g). The resultant was added and stirred at 50 ° C. for 20 hours to obtain a surface-treated 12 nm silica sol dispersion (solid concentration: 40.5% by weight).

Thereafter, the solvent was replaced with propylene glycol monopropyl ether (PGME) by a rotary evaporator (solid content: 40.5% by weight).
Subsequently, 51.85 g of a silica sol propylene glycol monopropyl ether dispersion having a solid content concentration of 40.5% by weight, 18.90 g of dihexaerythritol triacetate (manufactured by Kyoeisha Chemical Co., Ltd .: DPE-6A), and 1.6- Hexanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .; light acrylate SR-238F) 2.10 g, silicone leveling agent (manufactured by Enomoto Kasei Co., Ltd .; Disparon 1610) and photopolymerization initiator (Ciba Japan Co., Ltd.) )) Made: Irgacure 184, dissolved in PGME to a solid content concentration of 10% by weight) 12.60 g and 14.54 g of PGME are thoroughly mixed to form a hard coat film forming coating solution having a solid content concentration of 42.0% by weight (1 ) Was prepared.

Production of substrate with antireflection film (1) Hard coating film-forming coating liquid (1) having a solid content concentration of 42.0% by weight was prepared from a TAC film (manufactured by Panac Corporation: FT-PB80UL-M, thickness: 80 μm, refractive index: 1.51), coated by the bar coater method (# 16), dried at 80 ° C. for 2 minutes, and then cured by irradiating with 300 mJ / cm ² ultraviolet rays to form a substrate with a hard coat film did.

  Next, a dispersion of surface-treated alumina hydrate fine particles (1) with a solid content concentration of 2% by weight was applied by the bar coater method (# 3) so that the dry layer thickness was the front, and dried at 80 ° C. for 30 seconds. did. Next, the coating liquid for binding material (1) having a solid content concentration of 0.3% by weight is adjusted to the content shown in the table on the surface-treated alumina hydrate fine particles (1) layer by the bar coater method (# 3). And heated at 80 ° C. for 10 minutes.

  Next, an overcoat layer forming coating solution (1) having a solid content concentration of 1.0% by weight was applied by the bar coater method (# 4) so as to have the content shown in the table, and dried and cured at 80 ° C. for 10 minutes. Thus, a base material (1) with an antireflection film was produced.

For the base material with antireflection film (1), the average height of the concavo-convex structure (T _F ), the average distance between the convex parts (W _F ), the average height of the fine concavo-convex structure (T _FF ), the distance between the average convex parts ( (W _FF ), pencil hardness, adhesion, scratch resistance, water repellency, reflectance of light having a wavelength of 550 nm, antiglare property, total light transmittance and haze are measured, and the results are shown in the table. The total light transmittance and haze were measured with a haze meter (Nippon Denshoku Co., Ltd .: NDH2000), and the reflectance was measured with a spectrophotometer (Nippon Bunko Co., Ltd .: Ubest-55).

The uncoated TAC film substrate had a total light transmittance of 93.0% and a haze of 0.3%. Antiglare properties, pencil hardness, scratch resistance, water repellency and adhesion were measured by the following methods.
The total light transmittance, haze, and reflectance of light having a wavelength of 550 nm of the obtained substrate (1) with a transparent coating were measured, and the results are shown in the table. Further, antiglare properties, pencil hardness, scratch resistance, water repellency and adhesion were evaluated by the following methods and evaluation criteria, and the results are shown in the table.

Anti-glare base material with anti-glare coating with hard coat function (1) The anti-glare property of the base material is uniformly applied with black spray on the back side of the base material. Antiglare property was evaluated. The results are shown in the table.
I can't see any fluorescent lights: ◎
Fluorescent light is slightly visible: ○
Fluorescent lamp is visible but outline is blurred: △
Fluorescent light is clearly visible: ×

Pencil hardness It measured with the pencil hardness tester according to JIS-K-5600.
Evaluation criteria:
2H or more: ◎
H-2H: ○
B to H: △
B or less: ×

Using scratch-resistant # 0000 steel wool, sliding 10 times at a load of 200 g / cm ² , visually observing the surface of the film and evaluating it according to the following criteria, the results are shown in Table 1.
Evaluation criteria:
No streak injury is found: ◎
Slightly scratched streak: ○
Many scratches are found in the streak: △
The surface has been cut entirely: ×

The contact angle with water was measured with a water repellent fully automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd .: DM 700).
Adhesive water-repellent transparent coated substrate (1) The surface of the substrate (1) with 11 parallel scratches at 1mm vertical and horizontal intervals using a knife to make 100 squares, and then the cellophane tape is adhered to and peeled off. The adhesion was evaluated by classifying the number of cells remaining without peeling into the following three stages.
Number of remaining squares: ◎
Number of remaining squares 95 to 99: ○
Number of residual squares 90-94: △
Number of remaining squares: 89 or less: ×

[Example 2]
Preparation of surface-treated alumina hydrate fine particles (2) dispersion liquid 38.743 kg of pure water was put into a 100 L tank with a steam jacket, and a sodium hydroxide solution with a concentration of 48% by weight (manufactured by Kanto Chemical Co., Ltd .: special grade) 0.815 kg was added with stirring. Next, 2.740 kg of sodium aluminate (manufactured by Kanto Chemical Co., Inc .: deer grade 1, 39% by weight in terms of alumina) was dissolved in this solution with stirring.

  Furthermore, this solution was heated to 80 ° C. with stirring and held for 1 hour to obtain 42.298 kg of a completely dissolved sodium aluminate aqueous solution. Separately, 6.269 kg of pure water was put in a 10 L tank with a steam jacket, and 0.453 kg of 35% by weight hydrochloric acid aqueous solution (manufactured by Kanto Chemical Co., Ltd .: special grade) was mixed with stirring and heated. 6.722 kg of diluted hydrochloric acid aqueous solution at 80 ° C. was obtained.

  While maintaining the sodium aluminate aqueous solution at 80 ° C., dilute hydrochloric acid aqueous solution was added, and the mixture was further maintained at 80 ° C. for 1 hour with stirring to disperse the square plate-like alumina hydrate fine particles (2-a) having a pH of 11.5. 49.020 kg of liquid was obtained. <Process (a)>

  The alumina fine particle (2-a) dispersion was separated by filtration and sufficiently poured with warm pure water at 80 ° C. to obtain 6.667 kg of washed alumina hydrate fine particle (2-b) cake. <Process (b)>

  To this alumina fine particle (2-b) cake (6.667 kg), 12.983 kg of pure water was added and sufficiently stirred and dispersed to obtain 19.650 kg of alumina hydrate fine particle dispersion, which was then hydroxylated as an organic basic compound. 0.35 kg of tetramethylammonium (TMAOH) aqueous solution (manufactured by Kanto Chemical Co., Inc .: concentration 27% by weight) was added to obtain 20.0 kg of an organic basic compound-added alumina hydrate fine particle (2-c) dispersion. . <Process (c)>

  Subsequently, this basic substance-added alumina fine particle (2-c) dispersion was placed in an autoclave reactor, heated to 150 ° C. with stirring, and hydrothermally treated under autogenous pressure for 24 hours to obtain alumina hydrate fine particles (2-d ) A dispersion was obtained. <Process (d)>

  This alumina hydrate fine particle (2-d) dispersion was put in an ultrafiltration device and thoroughly washed, and washed until the residual nitrogen concentration converted to tetramethylammonium was 10 ppm or less, An alumina hydrate fine particle (2) dispersion (20.000 kg) having a solid concentration of 5% was obtained. <Process (e)>

The average particle diameter (D _P ) and average particle thickness (T _P ) of the obtained alumina hydrate fine particles (2) were measured, and the results are shown in the table. The alumina hydrate fine particles (2) were agglomerated in a form in which 5 to 10 primary crystal particles having a square shape of 30 to 50 nm and a thickness of 3 to 5 nm were laminated without overlapping at least two sides. It was a secondary particle having a size of 100 to 200 nm.

This dispersion was subjected to solvent substitution with methanol using an ultrafiltration membrane to obtain alumina hydrate fine particles (2) methanol dispersion having a solid content concentration of 8% by weight. Alumina hydrate fine particles with a solid content concentration of 8% by weight (2) 1.88 g of tetraethoxysilane (manufactured by Tama Chemical Industry Co., Ltd .: normal ethyl silicate-A, SiO ₂ concentration of 28.8% by weight) in 100 g of methanol dispersion Then, 3.1 g of ultrapure water was added, and the mixture was stirred at 50 ° C. for 6 hours to prepare a surface-treated alumina hydrate fine particle (2) methanol dispersion having a solid concentration of 8% by weight.

  Next, surface-treated alumina hydrate fine particles having a solid concentration of 8% by weight (2) 100 g of methanol dispersion, 8 g of N-methylpyrrolidone (NMP), 192 g of propylene glycol monopropyl ether (PGME), and mixed alcohol (Japan Alcohol Sales) 100 g of Solmix A-11, a mixed alcohol of methanol, ethanol and isopropyl alcohol), and then stirred at 25 ° C. for 30 minutes to obtain a solid content concentration of 2 wt. % Surface-treated alumina hydrate fine particle (2) dispersion was prepared.

Production of base material with antireflection film (2) A surface-treated alumina hydrate fine particle (2) dispersion having a solid content concentration of 2% by weight was applied to a base material with a hard coat film prepared in the same manner as in Example 1. It was applied by a coater method (# 3) and dried at 80 ° C. for 30 seconds.

  Next, in the same manner as in Example 1, the coating liquid for binder (1) having a solid content concentration of 0.3% by weight was applied by the bar coater method (# 3) so as to have the dry layer thickness shown in the table. It was cured by heating at 80 ° C. for 10 minutes. In the same manner as in Example 1, a coating solution for forming an overcoat layer (1) having a solid content concentration of 1.0% was applied by the bar coater method (# 4), dried and cured at 80 ° C. for 10 minutes to prevent reflection. A film-coated substrate (2) was produced.

For the base material with antireflection film (2), the average height (T _F ) of the concavo-convex structure, the average distance between protrusions (W _F ), the average height of the fine concavo-convex structure (T _FF ), the average distance between protrusions ( (W _FF ), total light transmittance, haze, reflectance, antiglare property, pencil hardness, scratch resistance, water repellency, adhesion are evaluated, and the results are shown in the table.

[Example 3]
Preparation of Surface Treated Alumina Hydrate Fine Particle (3) Dispersion Alumina hydrate fine particle (3) dispersion was prepared in the same manner as in step (d) of Example 2 except that it was heated at 110 ° C.

The average particle diameter (D _P ) and average particle thickness (T _P ) of the obtained alumina hydrate fine particles (3) were measured, and the results are shown in the table.
Subsequently, tetraethoxysilane (manufactured by Tama Chemical Industry Co., Ltd .: ethyl ethyl silicate-A, SiO ₂ concentration of 28.8% by weight) was added to 100 g of methanol hydrated fine particles of alumina hydrate having a solids concentration of 8% by weight. Next, 3.1 g of ultrapure water was added and stirred at 50 ° C. for 6 hours to prepare surface-treated alumina hydrate fine particles (3) methanol dispersion having a solid content concentration of 8% by weight.

  Surface-treated alumina hydrate fine particles with solid content of 8% by weight (3) 100 g of methanol dispersion, 8 g of N-methylpyrrolidone (NMP), 192 g of propylene glycol monopropyl ether (PGME), mixed alcohol (Japan Alcohol Sales Co., Ltd.) ) Manufactured by: Solmix A-11, mixed alcohol of methanol, ethanol and isopropyl alcohol) and then stirred at 25 ° C. for 30 minutes to form an alumina hydrate fine particle layer with a solid content concentration of 2% by weight. A surface-treated alumina hydrate fine particle (3) dispersion was prepared.

Production of base material with antireflection film (3) A surface-treated alumina hydrate fine particle (3) dispersion with a solid content concentration of 2% by weight was applied to the base material with a hard coat film prepared in the same manner as in Example 1. The coater method (# 3) was applied so that the layer thickness was as shown, and dried at 80 ° C. for 30 seconds. In the same manner as in Example 1, a coating liquid for binding material (1) having a solid content concentration of 0.3% by weight was applied by the bar coater method (# 3) and cured by heating at 80 ° C. for 10 minutes.

Next, in the same manner as in Example 1, a coating liquid for forming an overcoat layer (1) having a solid concentration of 1.0% was applied by the bar coater method (# 4), dried and cured at 80 ° C. for 10 minutes, and reflected. A substrate (3) with a protective film was produced. For the base material with antireflection film (3), the average height (T _F ) of the concavo-convex structure, the average distance between the convex portions (W _F ), the average height of the fine concavo-convex structure (T _FF ), the average distance between the convex portions ( (W _FF ), total light transmittance, haze, reflectance, antiglare property, pencil hardness, scratch resistance, water repellency, adhesion are evaluated, and the results are shown in the table.

[Example 4]
Preparation of Surface Treated Alumina Hydrate Fine Particle (4) Dispersion Alumina hydrate fine particle (4) dispersion was prepared in the same manner as in step (d) of Example 2 except that the mixture was heated at 180 ° C.
The average particle diameter (D _P ) and average particle thickness (T _P ) of the obtained alumina hydrate fine particles (4) were measured, and the results are shown in the table.

Subsequently, tetraethoxysilane (manufactured by Tama Chemical Industry Co., Ltd .: ethyl ethyl silicate-A, SiO ₂ concentration of 28.8% by weight) was added to 100 g of methanol hydrate with a solid content of 8% by weight of alumina hydrate fine particles. .88 g was mixed, and then 3.1 g of ultrapure water was added and stirred at 50 ° C. for 6 hours to prepare a surface-treated alumina hydrate fine particle (4) methanol dispersion having a solid content concentration of 8 wt%.

  Surface treated alumina hydrate fine particles with a solid content of 8% by weight (4) 100 g of methanol dispersion, 8 g of N-methylpyrrolidone (NMP), 192 g of propylene glycol monopropyl ether (PGME), mixed alcohol (Nippon Alcohol Sales Co., Ltd.) ) Manufactured by: Solmix A-11, mixed alcohol of methanol, ethanol and isopropyl alcohol) and then stirred at 25 ° C. for 30 minutes to form an alumina hydrate fine particle layer with a solid content concentration of 2% by weight. A surface-treated alumina hydrate fine particle (4) dispersion was prepared.

Production of base material with antireflection film (4) A dispersion of surface-treated alumina hydrate fine particles (4) having a solid content concentration of 2% by weight was applied to a base material with a hard coat film prepared in the same manner as in Example 1. It was applied by a coater method (# 3) and dried at 80 ° C. for 30 seconds. In the same manner as in Example 1, a binder coating solution (1) having a solid content concentration of 0.3% by weight was applied by a spin coater and heated at 80 ° C. for 10 minutes to be cured.

Next, in the same manner as in Example 1, a coating liquid for forming an overcoat layer (1) having a solid concentration of 1.0% was applied by the bar coater method (# 4), dried and cured at 80 ° C. for 10 minutes, and reflected. A substrate (4) with a protective film was produced. For the base material with antireflection film (4), the average height (T _F ) of the concavo-convex structure, the average distance between protrusions (W _F ), the average height of the fine concavo-convex structure (T _FF ), the average distance between protrusions ( (W _FF ), total light transmittance, haze, reflectance, antiglare property, pencil hardness, scratch resistance, water repellency, adhesion are evaluated, and the results are shown in the table.

[Example 5]
Preparation of coating liquid for overcoat layer formation (2) Mixed alcohol (manufactured by Nippon Alcohol Sales Co., Ltd .: Solmix A-11, mixed alcohol of methanol, ethanol and isopropyl alcohol) 5126 g with water 159.0 g and concentration 61% by weight Of nitric acid was added and stirred at 25 ° C. for 5 minutes. Next, 46.4 g of tridecafluorooctyltrimethoxysilane (manufactured by MOMENTIVE: TSL8257, solid concentration 98%), tetraethoxysilane (manufactured by Tama Chemical Industry Co., Ltd .: normal ethyl silicate-A, SiO ₂ concentration 28.8 wt. %) 157.9 g was added, stirred at 25 ° C. for 5 minutes, and then treated in an autoclave at 100 ° C. for 3 hours. Then, PGM356.39g and DAA213.91g were added, and it processed at 25 degreeC for 30 minutes, and prepared the coating liquid for overcoat layer formation with a solid content density | concentration of 1.50 weight%.

  Subsequently, 10 g of PGM and mixed alcohol (manufactured by Nippon Alcohol Sales Co., Ltd .: Solmix A-11, mixed alcohol of methanol, ethanol and isopropyl alcohol) were added to 100 g of fluorine-containing silica-based layer forming coating solution having a solid content concentration of 1.50% by weight. 40 g was added to prepare an overcoat layer-forming coating solution (2) having a solid concentration of 1.0%.

Production of base material with antireflection film (5) In the same manner as in Example 2, a surface-treated alumina hydrate fine particle (2) dispersion having a solid content concentration of 2% by weight was prepared in the same manner as in Example 1. It was applied to the substrate with a coating film by the bar coater method (# 3) and dried at 80 ° C. for 30 seconds. In the same manner as in Example 1, a coating material for binding material (1) having a solid content concentration of 0.3% by weight was applied by the bar coater method (# 3) and cured by heating at 80 ° C. for 10 minutes.

  Next, the overcoat layer forming coating solution (2) having a solid content concentration of 1.0% by weight was applied by the bar coater method (# 4) so as to have the content shown in the table, and dried at 80 ° C. for 10 minutes. Curing was carried out to produce a substrate (5) with an antireflection film.

For the base material with antireflection film (5), the average height (T _F ) of the concavo-convex structure, the average distance between protrusions (W _F ), the average height of the fine concavo-convex structure (T _FF ), the average distance between protrusions ( (W _FF ), total light transmittance, haze, reflectance, antiglare property, pencil hardness, scratch resistance, water repellency, adhesion are evaluated, and the results are shown in the table.

[Example 6]
Preparation of coating liquid for forming overcoat layer (3) Mixed alcohol (manufactured by Nippon Alcohol Sales Co., Ltd .: Solmix A-11, mixed alcohol of methanol, ethanol and isopropyl alcohol) to 1771.0 g and 159.0 g of water and concentration 61 3.3% by weight of nitric acid was added and stirred at 25 ° C. for 5 minutes. Next, 47.3 g of 3,3,3,3 trifluoropropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-7103, concentration: 100% by weight) was added and stirred at 25 ° C. for 5 minutes, and then in an autoclave. For 3 hours at 100 ° C. Then, PGM356.39g and DAA213.91g were added, and it processed at 25 degreeC for 30 minutes, and prepared the coating liquid for overcoat layer formation with a solid content density | concentration of 1.50 weight%.

  Then, 10 g of PGM and mixed alcohol (manufactured by Nippon Alcohol Sales Co., Ltd .: Solmix A-11, mixed alcohol of methanol, ethanol and isopropyl alcohol) are added to 100 g of an overcoat layer forming coating solution having a solid content concentration of 1.50% by weight. Was added to prepare an overcoat layer-forming coating solution (3) having a solid concentration of 1.0%.

Preparation of substrate with antireflection film (6) A dispersion of surface-treated alumina hydrate fine particles (2) having a solid content concentration of 2% by weight prepared in the same manner as in Example 2 was prepared in the same manner as in Example 1. The coated substrate with the hard coat film was applied by the bar coater method (# 3) and dried at 80 ° C. for 30 seconds. Next, a silica binder coating solution (1) having a solid content concentration of 0.3% by weight prepared in the same manner as in Example 1 was applied by the bar coater method (# 3) and heated at 80 ° C. for 10 minutes. Cured.

A coating solution for forming an overcoat layer (3) having a solid concentration of 1.0% by weight is applied by the bar coater method (# 4), dried and cured at 80 ° C. for 10 minutes, and a substrate with an antireflection film (6) Manufactured.
For the base material with antireflection film (6), the average height (T _F ) of the concavo-convex structure, the average distance between convex portions (W _F ), the average height of the fine concavo-convex structure (T _FF ), the average distance between convex portions ( (W _FF ), total light transmittance, haze, reflectance, antiglare property, pencil hardness, scratch resistance, water repellency, adhesion are evaluated, and the results are shown in the table.

[Example 7]
Production of base material with antireflection film (7) In the same manner as in Example 1, a coating liquid for forming a hard coat film (1) having a solid content concentration of 42.0% by weight was applied to a PET film (Toyobo Co., Ltd .: A4300, thickness). : 188μm) applied to the bar coater method (# 3) by the bar coater method (# 16), dried at 80 ° C. for 2 minutes, and then cured by irradiating with 300 mJ / cm ² ultraviolet rays to form a substrate with a hard coat film Formed.
Next, in the same manner as in Example 2, the surface-treated alumina hydrate fine particle (2) dispersion having a solid content concentration of 2% by weight was applied on the base material with a hard coat film so as to have the thickness of the table. Dry at 30 ° C. for 30 seconds.

Next, in the same manner as in Example 1, a coating liquid for binding material (1) having a solid content concentration of 0.3% by weight was applied by the bar coater method (# 3) and cured by heating at 80 ° C. for 10 minutes. .
In the same manner as in Example 1, the overcoat layer forming coating solution (1) was applied by the bar coater method (# 4), dried and cured at 80 ° C. for 10 minutes to produce a substrate (7) with an antireflection film. did.

For the base material with antireflection film (11), the average height (T _F ) of the concavo-convex structure, the average distance between the convex portions (W _F ), the average height of the fine concavo-convex structure (T _FF ), the average distance between the convex portions ( (W _FF ), total light transmittance, haze, reflectance, antiglare property, pencil hardness, scratch resistance, water repellency, adhesion are evaluated, and the results are shown in the table.

[Example 8]
Preparation of surface-treated chain silica fine particles (5) dispersion 334 g of a sodium silicate aqueous solution (SiO ₂ / Na ₂ O molar ratio: 3.1) having a SiO ₂ concentration of 24% by weight was diluted with 1266 g of pure water to obtain SiO ₂ 1600 g of a sodium silicate aqueous solution (pH 11) having a concentration of 5% by weight was prepared. To this sodium silicate aqueous solution, 320 g of a cation exchange resin (Mitsubishi Chemical Co., Ltd .: SK-1BH) was added and stirred for 1 hour, after which the ion exchange resin was separated and dealkalized at pH 4.0, solid content concentration 5 % 1500% silicic acid solution was prepared. Subsequently, 3500 g of pure water was added and diluted to a solid content concentration of 1.9%. This solution was put into a separable flask, heated to 40 ° C., 100 g of 10% aqueous ammonium acetate solution was added, the pH was adjusted to 4.1 with acetic acid, and the mixture was heated for 2 hours. Next, the pH was adjusted to 10.5 with a 5% aqueous ammonia solution. Then, it heated up at 95 degreeC and heated at 90 degreeC for 2 hours. After cooling to 40 ° C., a silica sol was obtained.

The obtained silica sol was concentrated using an ultrafiltration membrane (Asahi Kasei Kogyo Co., Ltd .: SIP-1013) until the SiO ₂ concentration became 13% by weight, and then concentrated on a rotary evaporator to obtain a 44 μm mesh nylon. Filtration through a filter prepared an inorganic oxide fine particle (B1-2) dispersion having a SiO ₂ concentration of 20% by weight.

This dispersion was subjected to solvent substitution with methanol using an ultrafiltration membrane to obtain a methanol dispersion having a solid concentration of 8% by weight.
The average linear particle diameter (D _C ) of the obtained chain silica fine particles (5) was 12 nm, the number of connections was 10, and the average length (L _C ) was 120 nm.

Subsequently, tetraethoxysilane (manufactured by Tama Chemical Industry Co., Ltd .: normal ethyl silicate-A, SiO ₂ concentration 28.8 wt%) was added to 100 g of chain silica fine particles having a solid content concentration of 8 wt% (5) methanol dispersion. 88 g was mixed, then 3.1 g of ultrapure water was added, and the mixture was stirred at 50 ° C. for 6 hours to prepare a surface-treated chain silica fine particle (5) methanol dispersion having a solid content concentration of 8% by weight.

  Surface-treated chain silica fine particles having a solid concentration of 8% by weight (5) 100 g of methanol dispersion, 8 g of N-methylpyrrolidone (NMP), 192 g of propylene glycol monopropyl ether (PGME), mixed alcohol (Nippon Alcohol Sales Co., Ltd.) Manufactured by Solmix A-11, mixed alcohol of methanol, ethanol and isopropyl alcohol), and then stirred at 25 ° C. for 30 minutes to form a solid content concentration of 2% by weight for forming an inorganic oxide fine particle layer A treated chain silica fine particle (5) dispersion was prepared.

Production of substrate with antireflection film (8) A dispersion of surface treated chain silica fine particles (5) having a solid content concentration of 2% by weight prepared in the same manner as in Example 2 was prepared in the same manner as in Example 1. It was applied to a substrate with a hard coat film by the bar coater method (# 3) and dried at 80 ° C. for 10 minutes. In addition, the binder is not contained.

  Next, an overcoat layer forming coating solution (1) having a solid content concentration of 1.0% prepared in the same manner as in Example 1 was applied by the bar coater method (# 4), dried and cured at 80 ° C. for 10 minutes. Thus, a base material (8) with an antireflection film was produced.

For the base material with antireflection film (8), the average height (T _F ) of the concavo-convex structure, the average distance between convex portions (W _F ), the average height of the fine concavo-convex structure (T _FF ), the average distance between convex portions ( (W _FF ), total light transmittance, haze, reflectance, antiglare property, pencil hardness, scratch resistance, water repellency, adhesion are evaluated, and the results are shown in the table.

[Example 9]
Production of base material with antireflection film (9) In the same manner as in Example 2, a surface-treated alumina hydrate fine particle (2) dispersion having a solid content concentration of 2% by weight was prepared in the same manner as in Example 1. It was applied to the substrate with a coating film by the bar coater method (# 3) and dried at 80 ° C. for 10 minutes. In addition, the binder is not contained.

  Next, a coating solution (1) for forming an overcoat layer having a solid content concentration of 1.0% by weight was applied by the bar coater method (# 4), dried and cured at 80 ° C. for 10 minutes, and a substrate with an antireflection film ( 9) was manufactured.

For the substrate with antireflection film (9), the average height (T _F ) of the concavo-convex structure, the average distance between convex portions (W _F ), the average height of the fine concavo-convex structure (T _FF ), the average distance between convex portions ( (W _FF ), total light transmittance, haze, reflectance, antiglare property, pencil hardness, scratch resistance, water repellency, adhesion are evaluated, and the results are shown in the table.

[Example 10]
Preparation of Surface Treated Alumina Hydrate Fine Particles (10) Dispersion Liquid Alumina Hydrate Fine Particles having a solid content of 8% by weight prepared as in Example 1 (1) Tridecafluorooctyltrimethoxysilane was added to 100 g of methanol dispersion liquid. (MOMENTIVE made: TSL8257, solid content concentration 55% by weight) 5.66 g was added and stirred at 25 ° C. for 30 minutes. Next, 3.80 g of water and 0.20 g of acetic acid having a concentration of 10% by weight were added and stirred at 20 ° C. for 10 minutes, followed by treatment in an autoclave at 100 ° C. for 3 hours to obtain a solid concentration of 8.0% by weight. A surface-treated alumina hydrate fine particle (10) methanol dispersion was prepared.

  Surface-treated alumina hydrate fine particles with a solid content of 8% by weight (10) 100 g of methanol dispersion, 8 g of N-methylpyrrolidone (NMP), 192 g of propylene glycol monopropyl ether (PGME), mixed alcohol (Japan Alcohol Sales Co., Ltd.) ) Manufactured by: Solmix A-11, mixed alcohol of methanol, ethanol and isopropyl alcohol) and then stirred at 25 ° C. for 30 minutes to form an alumina hydrate fine particle layer with a solid content concentration of 2% by weight. A surface-treated alumina hydrate fine particle (10) dispersion was prepared.

Production of substrate with antireflection film (10) In the same manner as in Example 2, a surface-treated alumina hydrate fine particle (10) dispersion having a solid content concentration of 2% by weight was prepared in the same manner as in Example 1. The substrate with a coating film was applied by the bar coater method (# 3), and dried and cured at 80 ° C. for 10 minutes to produce a substrate with antireflection film (10). In addition, the binder is not contained. Also, no overcoat layer is formed.

For the base material with antireflection film (10), the average height (T _F ) of the concavo-convex structure, the average distance between convex portions (W _F ), the average height of the fine concavo-convex structure (T _FF ), the distance between average convex portions ( (W _FF ), total light transmittance, haze, reflectance, antiglare property, pencil hardness, scratch resistance, water repellency, adhesion are evaluated, and the results are shown in the table.

[Example 11]
Preparation of Surface Treated Alumina Hydrate Fine Particle (11) Dispersion Alumina hydrate fine particles (1) methanol dispersion having a solid content concentration of 8% by weight was obtained in the same manner as in Example 1.

Subsequently, 100 g of alumina hydrate fine particles having a solid content concentration of 8% by weight (1) tetraethoxysilane (manufactured by Tama Chemical Industry Co., Ltd .: normal ethyl silicate-A, SiO ₂ concentration of 28.8% by weight) 2 After addition of .70 g and 1.75 g of ultrapure water, the mixture was stirred at 50 ° C. for 6 hours. Thereafter, 2.83 g of tridecafluorooctyltrimethoxysilane (manufactured by MOMENTIVE: TSL8257, solid content concentration 55%) was added and stirred at 25 ° C. for 5 minutes, and then treated at 100 ° C. for 3 hours in an autoclave. A surface-treated alumina hydrate fine particle (11) methanol dispersion having a concentration of 8.0% by weight was prepared.

  Next, surface-treated alumina hydrate fine particles with a solid content concentration of 8% by weight (11) 100 g of methanol dispersion, 8 g of N-methylpyrrolidone (NMP), 192 g of propylene glycol monopropyl ether (PGME), and mixed alcohol (Japan Alcohol Sales) 100 g of Solmix A-11, a mixed alcohol of methanol, ethanol and isopropyl alcohol), and then stirred at 25 ° C. for 30 minutes to obtain a solid content concentration of 2% by weight for forming an inorganic oxide fine particle layer A surface-treated alumina hydrate fine particle (11) dispersion was prepared.

Production of substrate (11) with antireflection film A surface-treated alumina hydrate fine particle (11) dispersion having a solid content concentration of 2% by weight was produced in the same manner as in Example 2 in the same manner as in Example 2. The substrate with a coating film was applied by the bar coater method (# 3), dried and cured at 80 ° C. for 10 minutes to produce a substrate with antireflection film (11). In addition, the binder is not contained. Also, no overcoat layer is formed.

For the substrate with antireflection film (17), the average height (T _F ) of the concavo-convex structure, the distance between the average protrusions (W _F ), the average height of the fine concavo-convex structure (T _FF ), the distance between the average protrusions ( (W _FF ), total light transmittance, haze, reflectance, antiglare property, pencil hardness, scratch resistance, water repellency, adhesion are evaluated, and the results are shown in the table.

[Example 12]
Preparation of substrate with antireflection film (12) A surface-treated alumina hydrate fine particle (2) dispersion having a solid content concentration of 2% by weight, prepared in the same manner as in Production Example 2, was applied to a TAC film (manufactured by Panac Corporation: FT-PB80UL-M, thickness: 80 μm, refractive index: 1.51) was applied by the bar coater method (# 3) so as to have the dry layer thickness shown in the table, and dried at 80 ° C. for 30 seconds.

  Next, in the same manner as in Example 1, the coating liquid for binder (1) having a solid content concentration of 0.3% by weight was applied by the bar coater method (# 3) so as to have the dry layer thickness shown in the table. It was cured by heating at 80 ° C. for 10 minutes. In the same manner as in Example 1, a coating solution for forming an overcoat layer (1) having a solid content concentration of 1.0% was applied by the bar coater method (# 4), dried and cured at 80 ° C. for 10 minutes to prevent reflection. A film-coated substrate (12) was produced.

For the substrate with antireflection film (12), the average height (T _F ) of the concavo-convex structure, the distance between the average protrusions (W _F ), the average height of the fine concavo-convex structure (T _FF ), the distance between the average protrusions ( (W _FF ), total light transmittance, haze, reflectance, antiglare property, pencil hardness, scratch resistance, water repellency, adhesion are evaluated, and the results are shown in the table.

[Example 13]
Preparation of coating solution (1) for forming an intermediate film ATO sol dispersion (manufactured by JGC Catalysts & Chemicals Co., Ltd .: ELCOM V-3560, average particle size 8 nm, ATO concentration 20.5% by weight, dispersion medium: methanol, ethanol and isopropyl 58.5 g of alcohol mixed alcohol (Nippon Alcohol Sales Co., Ltd .: Solmix AP-11), particle refractive index 1.75), methanol, ethanol and isopropyl alcohol mixed alcohol (Nippon Alcohol Sales Co., Ltd .: Solmix AP-11) 16.82 g, PGME 8.64 g, pentaerythritol triacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate PE-3A, resin concentration 100% by weight) to 8.0 g with a photoinitiator (Ciba Specialty Co., Ltd.) ) Made: Irgacure 184) Add 8.0g and mix well to get a solid content of 3.0% by weight Film-forming coating liquid (1) was prepared.

Preparation of substrate with antireflection film (13) After forming a hard coat layer in the same manner as in Production Example 12, coating solution for forming an intermediate film having a solid concentration of 3.0% by weight by the bar coater method (# 4) (1) was applied so as to have the dry layer thickness shown in the table, dried at 80 ° C. for 2 minutes, and then cured by irradiating with 300 mJ / cm ² of ultraviolet rays to form an intermediate film.

  Next, in the same manner as in Example 1, the coating liquid for binder (1) having a solid content concentration of 0.3% by weight was applied by the bar coater method (# 3) so as to have the dry layer thickness shown in the table. It was cured by heating at 80 ° C. for 10 minutes. Next, in the same manner as in Example 1, the coating liquid for binder (1) having a solid content concentration of 0.3% by weight was applied by the bar coater method (# 3) so as to have the dry layer thickness shown in the table. It was cured by heating at 80 ° C. for 10 minutes. Next, in the same manner as in Example 1, an overcoat layer-forming coating solution (1) having a solid concentration of 1.0% was applied by the bar coater method (# 4), dried and cured at 80 ° C. for 10 minutes. A substrate (13) with an antireflection film was produced.

For the base material with antireflection film (13), the average height (T _F ) of the concavo-convex structure, the distance between the average protrusions (W _F ), the average height of the fine concavo-convex structure (T _FF ), the distance between the average protrusions ( (W _FF ), total light transmittance, haze, reflectance, antiglare property, pencil hardness, scratch resistance, water repellency, adhesion are evaluated, and the results are shown in the table.

[Comparative Example 1]
Production of substrate with antireflective coating (R1) A surface-treated alumina hydrate fine particle (2) dispersion having a solid content concentration of 2% by weight was prepared in the same manner as in Example 2 in the same manner as in Example 1. It was applied to the substrate with a coating film by the bar coater method (# 3) and dried at 80 ° C. for 30 seconds.

  Next, the coating liquid for binder (2) was applied by the bar coater method (# 3) so that the content shown in the table was obtained in the same manner as in Example 1 except that the solid content concentration was 5% by weight. Curing was carried out at 10 ° C. for 10 minutes.

  A coating solution (1) for forming a fluorine-containing silica-based layer having a solid content concentration of 1.0% by weight prepared in the same manner as in Example 1 was applied by the bar coater method (# 3), and dried and cured at 80 ° C. for 10 minutes. Thus, a base material (R1) with an antireflection film was produced.

For the base material with antireflection film (R1), the average height (T _F ) of the concavo-convex structure, the distance between the average protrusions (W _F ), the average height of the fine concavo-convex structure (T _FF ), the distance between the average protrusions ( (W _FF ), total light transmittance, haze, reflectance, antiglare property, pencil hardness, scratch resistance, water repellency, adhesion are evaluated, and the results are shown in the table.

[Comparative Example 2]
Preparation of surface-treated alumina hydrate fine particle (R2) dispersion Alumina hydrate fine particle (R2) dispersion was prepared in the same manner as in step (d) of Example 1 except that the mixture was heated at 150 ° C. The average length (L _F ) and average particle width (W _PF ) of the obtained alumina hydrate fine particles (R2) were measured, and the results are shown in the table.

Subsequently, tetraethoxysilane (manufactured by Tama Chemical Industry Co., Ltd .: ethyl ethyl silicate-A, SiO ₂ concentration of 28.8% by weight) was added to 100 g of an alumina hydrate fine particle (R2) methanol dispersion having a solid content of 8% by weight. Next, 3.1 g of ultrapure water was added, and the mixture was stirred at 50 ° C. for 6 hours to prepare a surface-treated alumina hydrate fine particle (R2) methanol dispersion having a solid content concentration of 8 wt%.

  100 g of surface-treated alumina hydrate fine particles (R2) methanol dispersion with a solid content concentration of 8% by weight, 8 g of N-methylpyrrolidone (NMP), 192 g of propylene glycol monopropyl ether (PGME), mixed alcohol (Nippon Alcohol Sales Co., Ltd.) ): SOLMIX A-11, mixed alcohol of methanol, ethanol and isopropyl alcohol) 100 g, and then stirred at 25 ° C. for 30 minutes to form a surface having a solid content concentration of 2% by weight for forming an inorganic oxide fine particle layer A treated alumina hydrate fine particle (R2) dispersion was prepared.

Production of antireflection film-coated substrate (R2) In Example 1, except that a surface-treated alumina hydrate fine particle (R2) dispersion having a solid content concentration of 2% by weight was used, and the layer thickness was as shown in the table. In the same manner, a substrate with antireflection film (R2) was produced.

Concerning the base material with antireflection film (R2), the average height (T _F ) of the concavo-convex structure, the average distance between convex portions (W _F ), the average height of the fine concavo-convex structure (T _FF ), the average distance between convex portions ( (W _FF ), total light transmittance, haze, reflectance, antiglare property, pencil hardness, scratch resistance, water repellency, adhesion are evaluated, and the results are shown in the table.

[Comparative Example 3]
Preparation of surface-treated alumina hydrate fine particle (R3) dispersion Alumina hydrate fine particle (R3) dispersion was prepared in the same manner as in step (d) of Example 2 except that it was heated at 250 ° C.

The average particle diameter (D _P ) and average particle thickness (T _P ) of the obtained alumina hydrate fine particles (R3) were measured, and the results are shown in the table.
This dispersion was subjected to solvent replacement with methanol using an ultrafiltration membrane to obtain an alumina hydrate fine particle (R3) methanol dispersion having a solid concentration of 8% by weight. Subsequently, tetraethoxysilane (manufactured by Tama Chemical Industry Co., Ltd .: ethyl ethyl silicate-A, SiO ₂ concentration 28.8% by weight) was added to 100 g of an alumina hydrate fine particle (R3) methanol dispersion having a solid content of 8% by weight. .88 g was mixed, and then 3.1 g of ultrapure water was added and stirred at 50 ° C. for 6 hours to prepare a surface-treated alumina hydrate fine particle (R3) methanol dispersion having a solid content concentration of 8 wt%.

  100 g of surface-treated alumina hydrate fine particles (R3) methanol dispersion with a solid content concentration of 8% by weight, 8 g of N-methylpyrrolidone (NMP), 192 g of propylene glycol monopropyl ether (PGME), mixed alcohol (Nippon Alcohol Sales Co., Ltd.) ): SOLMIX A-11, mixed alcohol of methanol, ethanol and isopropyl alcohol) 100 g, and then stirred at 25 ° C. for 30 minutes to form a surface having a solid content concentration of 2% by weight for forming an inorganic oxide fine particle layer A treated alumina hydrate fine particle (R3) dispersion was prepared.

Production of substrate with antireflection film (R3) In Example 1, the substrate with antireflection film (R3) was prepared in the same manner except that the surface-treated alumina hydrate fine particle (R3) dispersion having a solid content concentration of 2% by weight was used. R3) was produced.

For the base material with antireflection film (R3), the average height of the concavo-convex structure (T _F ), the average distance between convex parts (W _F ), the average height of the fine concavo-convex structure (T _FF ), the average distance between convex parts ( (W _FF ), total light transmittance, haze, reflectance, antiglare property, pencil hardness, scratch resistance, water repellency, adhesion are evaluated, and the results are shown in the table.

[Comparative Example 4]
Production of base material with antireflection film (R4) A surface-treated alumina hydrate fine particle (2) dispersion having a solid content concentration of 2% by weight was prepared in the same manner as in Example 2 in the same manner as in Example 1. It was applied to the substrate with a coating film by the bar coater method (# 3) and dried at 80 ° C. for 30 seconds.

Next, in the same manner as in Example 1, a coating liquid for binding material (1) having a solid content concentration of 0.3% by weight was applied by the bar coater method (# 3) and cured by heating at 80 ° C. for 10 minutes. .
The overcoat layer forming coating solution (4) prepared in the same manner as in Example 1 except that the solid content concentration was 0.05% by weight was adjusted to the content shown in the table by the bar coater method (# 3). This was coated, dried and cured at 80 ° C. for 10 minutes, and an antireflection film-coated substrate (R4) was produced.

For the base material with antireflection film (R4), the average height of the concavo-convex structure (T _F ), the average distance between the convex portions (W _F ), the average height of the fine concavo-convex structure (T _FF ), the average distance between the convex portions ( (W _FF ), total light transmittance, haze, reflectance, antiglare property, pencil hardness, scratch resistance, water repellency, adhesion are evaluated, and the results are shown in the table.

[Comparative Example 5]
Production of substrate with antireflection film (R5) A surface-treated alumina hydrate fine particle (2) dispersion having a solid content concentration of 2% by weight was prepared in the same manner as in Example 2 in the same manner as in Example 2. It was applied to the substrate with a coating film by the bar coater method (# 3) and dried at 80 ° C. for 30 seconds. Next, in the same manner as in Example 1, a coating liquid for binding material (1) having a solid content concentration of 0.3% by weight was applied by the bar coater method (# 3) and cured by heating at 80 ° C. for 10 minutes. .

  The overcoat layer-forming coating solution (5) prepared in the same manner as in Example 1 except that the solid content concentration was 1.5% by weight was adjusted to the content shown in the table by the bar coater method (# 12). This was coated, dried and cured at 80 ° C. for 10 minutes, and an antireflection film-coated substrate (R5) was produced.

For the base material with antireflection film (R5), the average height of the concavo-convex structure (T _F ), the average distance between convex parts (W _F ), the average height of the fine concavo-convex structure (T _FF ), the average distance between convex parts ( (W _FF ), total light transmittance, haze, reflectance, antiglare property, pencil hardness, scratch resistance, water repellency, adhesion are evaluated, and the results are shown in the table.

Claims (4)

A substrate with an antireflection film having an antireflection film having a contact angle with water of 130 to 180 °, a reflectance (Rf) of 2% or less, and a haze of 10% or less on a resin substrate,
The antireflection film, and an inorganic oxide particle layer comprising the surface treated inorganic oxide particles, and a overcoat layer having the overcoat layer on the inorganic oxide fine particle layer,
The surface-treated inorganic oxide fine particles are surface-treated with a hydrolyzable organosilicon compound represented by the following formula (1) and / or (2) or a hydrolyzate of the hydrolyzable organosilicon compound: Fine particles,
The surface treatment amount of the surface-treated inorganic oxide fine particles is such that the hydrolyzable organosilicon compound is R _n —SiO _{(4-n) / 2} with respect to 100 parts by weight of the inorganic oxide fine particles (as oxide). 1 to 200 parts by weight,
The surface of the antireflection film has a concavo-convex structure, the average height (T _F ) of the protrusions is 30 to 500 nm, the average distance between the protrusions (pitch width) (W _F ) is 50 to 1000 nm,
The surface of the convex part of the concave-convex structure further has fine irregularities, the average height (T _FF ) of the fine convex part is 3 to 50 nm, and the average convex part distance (W _FF ) of the fine convex parts Is smaller than the average inter-convex distance (W _F ) of the convex portions, and is 3 to 50 nm.
R _n -SiX _4-n (1)
(In the formula, R is a fluorine-substituted hydrocarbon group having 1 to 10 carbon atoms and may be the same or different. X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a halogen, Hydrogen, n is an integer of 1 to 3)
R _n -SiX _4-n (2)
(In the formula, R is a hydrocarbon group (excluding fluorine substitution) which may be substituted with a (meth) acryloyl group having 1 to 10 carbon atoms, an amino group, or a mercapto group, and is the same as each other. X is an alkoxy group having 1 to 4 carbon atoms, hydroxyl group, halogen, hydrogen, and n is an integer of 0 to 3). Antireflection according to claim 1, wherein the average height (T _F) and the distance between the average protrusion (W _F) and the ratio of (T _F / W _F) is 0.1 to 10 Substrate with film.   The base material with an antireflection film according to claim 1, wherein the inorganic oxide fine particle layer contains a binder.   The base material with an antireflection film according to claim 1, further comprising a hard coat layer between the base material and the inorganic oxide fine particle layer.