JP5159265B2 - Substrate with transparent film and coating liquid for forming transparent film - Google Patents

Description

The present invention relates to a substrate with a transparent film on which an uneven transparent film excellent in antireflection performance and antiglare performance is formed, and a coating liquid for forming a transparent film for forming the transparent film.

  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 coating 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 surface of the substrate. Thus, a method for forming an antireflection coating is known (see, for example, JP-A-7-133105 (Patent Document 1) and the like). 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.

Further, in the display device or the like, it is also known to form irregularities on the surface in order to impart antiglare properties (sometimes referred to as antiglare properties). (JP 2002-169001 (Patent Document 2), JP 2002-71904 (Patent Document 3), JP 2001-281411 (Patent Document 4), JP 2001-34350 (Patent Document) 5))
Further, the inventors of the present application disclosed in Japanese Patent Application Laid-Open No. 2003-12965 (Patent Document 6) two kinds of fine particles having different average particle diameters, different conductive fine particles having a small particle size and low refractive index fine particles having a large particle size. It has been proposed that a conductive film excellent in antireflection performance can be formed by a single application by using a coating solution containing.
JP 7-133105 A JP 2002-169001 A JP 2002-71904 A JP 2001-281411 A JP 2001-34350 A JP 2003-12965 A

  However, in the conventional method of forming a multilayer film as described in Patent Documents 1 to 5, it is necessary to perform a process of applying a paint, drying, and curing as necessary, for each paint, Adhesion was insufficient, and there were problems with productivity and economy. Further, the method of Patent Document 6 has low anti-glare performance because of no anti-glare performance, and when used in a display device, the display performance is insufficient.

As a result of intensive studies in view of such problems, the present inventors have found that inorganic oxide fine particles having a large average particle diameter to such an extent that irregularities can be formed on the surface, and low refractive index silica-based hollow fine particles having a small average particle diameter. The transparent film containing (B) was found to have antiglare performance and excellent antireflection performance, and the present invention was completed.

The configuration of the present invention is as follows.
[1] A substrate with a transparent coating on which a transparent coating having irregularities is formed,
The transparent coating comprises metal oxide particles (A) having an average particle diameter (DpA) in the range of 0.5 to 5 μm;
A substrate with a transparent coating comprising silica-based hollow fine particles (B) having a mean particle size (DpB) in the range of 5 to 200 nm and a refractive index in the range of 1.10 to 1.40 and a matrix component.
[2] The substrate with a transparent coating according to [1], wherein the metal oxide particles (A) are silica-based hollow fine particles having a refractive index in the range of 1.10 to 1.40.
[3] The average film thickness of the transparent film is in the range of 1 μm to 10 μm,
The unevenness of the transparent coating is such that the difference between the average height of the convex portion (T convex) and the average height of the concave portion (T concave) (T convex) − (T concave) is in the range of 30 to 1500 nm [1] or [2] A substrate with a transparent coating.
[4] The content of the metal oxide particles (A) in the transparent film is in the range of 10 to 70% by weight, and the content of the silica-based hollow fine particles (B) is in the range of 5 to 50% by weight. The substrate with a transparent coating according to [1] to [3], wherein the total content of the metal oxide particles (A) and the silica-based hollow fine particles (B) is in the range of 20 to 80% by weight.
[5] Metal oxide particles (A) having an average particle diameter (DpA) in the range of 0.5 to 5 μm and average particle diameter (DpB) in the range of 5 to 200 nm, and a refractive index of 1.10 to 1 A coating solution for forming a transparent film comprising silica-based hollow fine particles (B) in the range of 40, a matrix component and a solvent.
[6] The coating liquid for forming a transparent film according to [5], wherein the metal oxide particles (A) are silica-based hollow fine particles having a refractive index in the range of 1.10 to 1.40.
[7] The concentration of the metal oxide particles (A) is in the range of 0.1 to 10% by weight as the solid content, and the concentration of the silica-based hollow fine particles (B) is 0.1 to 10% by weight as the solid content. The coating liquid for forming a transparent film according to [5] or [6], wherein the concentration of the matrix-forming component as a solid content is in the range of 1 to 30% by weight.

  According to the present invention, the desired unevenness can be formed on the surface of the base material by applying and drying the coating for forming a transparent film once, and the anti-reflection performance and anti-glare performance as well as excellent adhesion and strength to the base material. In addition, it is possible to provide a coating solution for forming a transparent film that can form a transparent film that is excellent in productivity and economy. The obtained substrate with a transparent coating can be suitably used for a display screen such as an LCD display, a plasma display, a projection display, an EL display, or a CRT display.

Hereinafter, first, the transparent film-coated substrate according to the present invention will be specifically described.
Substrate with a transparent coating The substrate with a transparent coating according to the present invention is formed by forming a transparent coating having irregularities on the surface thereof.

The transparent coating comprises metal oxide particles (A) having an average particle diameter (DpA) in the range of 0.5 to 5 μm,
Silica-based hollow fine particles (B) having an average particle diameter (DpB) in the range of 5 to 200 nm and a refractive index in the range of 1.10 to 1.40;
It is characterized by comprising a matrix component.

FIG. 1 is a schematic sectional view showing an example of the substrate with a transparent coating according to the present invention.
The metal oxide particles (A) with a large average particle diameter are arranged on the surface of the substrate, and silica-based hollow fine particles with a small average particle diameter and other white spots are present as matrix components around the transparent coating. The surface of has an unevenness derived from large particles (A).

As the base material , cellulose base materials such as triacetyl cellulose film (TAC), diacetyl cellulose film, acetate butyrate cellulose film, polyester base materials such as polyethylene terephthalate and polyethylene naphthalate, polyethylene film, polypropylene film, Polyolefin-based substrates such as cyclic polyolefin films, polyamide-based substrates such as nylon-6 and nylon-66, etc., as well as polyacrylic films, polyurethane-based films, polycarbonate films, polyether film, polyethersulfone films , Base materials such as polystyrene film, polymethylpentene film, polyetherketone film, and acrylonitrile film. In addition, a coated substrate in which another coating such as a hard coat film is formed on such a substrate can also be used.

As a substrate used in the present invention, a triacetyl cellulose film (TAC) can be suitably used because of its close refractive index.
Transparent coating The transparent coating comprises metal oxide particles (A), silica-based hollow fine particles (B), and a matrix component.
(i) Metal oxide particles (A)
The average particle diameter of the metal oxide particles (A) is preferably in the range of 0.5 to 5 μm, more preferably 1 to 3 μm.

When the average particle size of the metal oxide particles (A) is small, desired irregularities may not be provided on the transparent film, and sufficient antiglare performance may not be obtained.
Even if the average particle diameter of the metal oxide particles (A) is too large, the transparent film becomes excessively uneven, and in this case as well, flickering or sufficient antiglare performance may not be obtained.

The refractive index of the metal oxide particles (A) is not particularly limited, but it is desirable to use silica particles or hollow silica-based particles having a low refractive index. The refractive index may be 1.10 to 1.50, further 1.10 to 1.45. Among these, hollow silica-based particles are preferable because a transparent film having a low refractive index and excellent antireflection performance can be obtained. Details of the hollow silica-based particles will be described later.

The metal oxide particles (A) used in the present invention are preferably surface-treated with an organosilicon compound represented by the following formula (1).
_{R n -SiX 4-n (1} )
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms or a silanol group) , Halogen, hydrogen, n: an integer of 0 to 3)
Examples of the organosilicon compound represented by the formula (1) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane. , Methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, 3,3,3- Trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxy Silane, 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- (meth) a Acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, butyltrimethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilaoctyltriethoxysilane, decyltriethoxysilane, butyltriethoxysilane, isobutyl Triethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, 3-ureidoisopropylpropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyltriethoxysilane, perfluorooctylethyltriiso Propoxysilane, trifluoropropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β ( Minoechiru) .gamma.-aminopropyltrimethoxysilane, N- phenyl--γ- aminopropyltrimethoxysilane, .gamma.-mercaptopropyltrimethoxysilane, trimethylsilanol, methyltrichlorosilane, and the like.

For the surface treatment of the metal oxide particles (A), a conventionally known method can be adopted.For example, a predetermined amount of the organosilicon compound is added to an alcohol dispersion of silica particles, water is added thereto, and if necessary Then, hydrolysis is carried out by adding an acid or alkali as a catalyst for hydrolysis. At this time, the weight ratio _{(R n -SiX (4-n} ) / 2 weight of the amount of organosilicon compound as _{R n -SiX (4-n)} / 2 of the metal oxide particles (A) and organic silicon compound / Weight of metal oxide particles (A)) is preferably in the range of 0.01 to 0.5, more preferably 0.02 to 0.25.

When the weight ratio is small, since the amount of the organosilicon compound is small, the affinity with the matrix-forming component or the dispersion medium in the coating liquid for forming a transparent film described later is low, and the stability is insufficient. In some cases, the metal oxide particles (A) may aggregate, and regular irregularities may not be formed on the surface of the transparent coating.

Even if the weight ratio exceeds the above range, the dispersibility is not further improved, and the economical efficiency is lowered only by increasing the number of expensive organosilicon compounds.
An organic solvent dispersion of the metal oxide particles (A) subjected to the surface treatment can be obtained by substituting with an organic solvent. As the organic solvent, it is preferable to use an organic solvent similar to a coating liquid for forming a transparent film described later.

The content of the metal oxide particles (A) in the transparent film is preferably 5 to 70% by weight, more preferably 10 to 50% by weight, in terms of solid content.
When the content of the metal oxide particles (A) in the transparent film is small, the density of the unevenness on the surface of the transparent film is decreased, and the antiglare performance may be insufficient. Even if the content of metal oxide particles (A) is too much,
The film thickness of the transparent film may be non-uniform, and the adhesion to the substrate, the film strength, and the scratch resistance may be insufficient.
(ii) Silica-based hollow fine particles (B)
As silica-based hollow fine particles (B), Japanese Patent Application Laid-Open No. 2001-23361 filed by the present applicant.
The silica-based fine particles having cavities inside disclosed in JP-A No. 1 and JP-A No. 2003-192994 have a low refractive index, are fine particles in a colloidal region, and are excellent in dispersibility and can be suitably used. .
The average particle diameter (DpB) of the silica-based hollow fine particles (B) is preferably in the range of 5 to 200 nm, more preferably 10 to 100 nm.

If the silica-based hollow fine particles (B) are small, it is difficult to obtain low refractive index fine particles, and even if obtained, the refractive index may exceed 1.40, and the antireflection performance of the transparent coating is insufficient. There is a case. When the silica-based hollow fine particles (B) are large, unnecessary irregularities may be formed on the surface of the transparent coating, and the haze value of the transparent coating may be increased.

The refractive index of the silica-based hollow fine particles (B) is 1.10 to 1.40, more preferably 1.10 to 1.35.
It is preferable that it exists in the range.
It is difficult to obtain particles having a refractive index below the lower limit of this range. If the refractive index is high, the antireflection performance is insufficient or the reflection of the transparent coating depends on the refractive index of the substrate or the lower layer film. Due to the high rate, the photopic contrast may be insufficient.

The silica-based hollow fine particles (B) used in the present invention are preferably surface-treated with an organosilicon compound in the same manner as the metal oxide particles (A). When silica-based hollow fine particles (B) are surface-treated with an organosilicon compound, they have a high affinity with the matrix-forming component or dispersion medium in the coating solution for forming a transparent film, good dispersion stability, and uniformity in the coating solution A transparent film excellent in adhesion to the substrate, film strength, and scratch resistance can be obtained.

The content of the silica-based hollow fine particles (B) in the transparent film is preferably in the range of 1 to 50% by weight , more preferably 2 to 25 % by weight as the solid content.
If the content of the silica-based hollow fine particles (B) is small, the refractive index of the transparent coating will not be sufficiently low, so the reflectance of the transparent coating will be high and the antireflection performance will be insufficient or the contrast in the bright place will be insufficient. May be. If the content of the silica-based hollow fine particles (B) is high, it may be difficult to form sufficient irregularities due to too much silica-based hollow fine particles (B) in the transparent film, and sufficient anti-glare performance May not be obtained.

The amount ratio of the silica-based hollow fine particles (B) to the metal oxide particles (A) is such that (A) :( B) is 70: 1 to 5:35, preferably 50: 2 to 10:25 It is desirable to be in range.
When the metal oxide particles (A) having a specific size and the silica-based hollow fine particles (B) are combined in such a quantitative ratio, desired irregularities are formed.

In order to adjust the unevenness, if a large unevenness is formed, a metal oxide particle (A) having a large particle size and a silica-based hollow fine particle (B) having a small particle size may be used.
As the matrix component , a silicone (sol-gel) matrix component, an organic resin matrix component, or the like is used.

As the silicone matrix component, a hydrolyzed polycondensate of an organosilicon compound similar to the formula (1) is preferably used. Examples of the organic resin-based matrix component include known thermosetting resins, thermoplastic resins, electron beam curable resins, and the like as coating resins.

  Examples of such resins include conventionally used thermoplastic resins such as polyester resins, polycarbonate resins, polyamide resins, polyphenylene oxide resins, thermoplastic acrylic resins, vinyl chloride resins, fluororesins, vinyl acetate resins, and silicone rubbers. , Urethane resin, melamine resin, silicon resin, butyral resin, reactive silicone resin, phenol resin, epoxy resin, unsaturated polyester resin, thermosetting acrylic resin, UV curable acrylic resin, etc., UV curable type An acrylic resin etc. are mentioned. Further, it may be a copolymer or modified body of two or more of these resins. In the case of a thermosetting resin, the matrix component is a polymer.

  These resins may be emulsion resins, water-soluble resins, and hydrophilic resins. Further, in the case of a thermosetting resin, it may be an ultraviolet curable type or an electron beam curable type, and in the case of a thermosetting resin, a curing catalyst, a sensitizer, and a stabilizer are included. It may be.

  The content of the matrix component in the transparent coating is preferably in the range of 25 to 94% by weight, more preferably 30 to 90% by weight as the solid content. When the content of the matrix component in the transparent film is less than 25% by weight as the solid content, the strength and scratch resistance of the transparent film may be insufficient.

  If the content of the matrix component in the transparent film is too large, the amount of one of the particles is small, so that the transparent film having the effects of the present invention, that is, both the antireflection performance and the antiglare performance may not be obtained. . Moreover, when there is little content, the intensity | strength and abrasion resistance of a film may fall.

The film thickness of the transparent film is preferably 1 to 10 μm, more preferably 2 to 8 μm in terms of average film thickness. Here, the average film thickness refers to the average value of the average height of convex portions (T convex) and the average height of concave portions (T concave) of the transparent coating. The average film thickness of the transparent coating is the size of the metal oxide particles (A) (
Smaller than (diameter). The convex portions are formed from the metal oxide particles (A), and the average height (T convex) of the convex portions is higher than the size of the metal oxide particles (A).

  If the film thickness of the transparent coating is too small, it becomes difficult to form the unevenness itself. If the average thickness of the transparent coating is too thick, depending on the size of the particles (A) and (B), the transparent coating may crack, or if the substrate is plastic, etc., curling (curving or warping) There is.

The difference between the average height of convex portions (T convex) and the average height of concave portions (T concave) (T convex)-(T concave) depends on the size of particles (A) and (B). 30 to 1500 nm, and more preferably in the range of 50 to 1000 nm. If this difference is small, the unevenness becomes insufficient and sufficient antiglare properties may not be obtained.
When (T-convex)-(T-concave) is large, the surface scattering of light may be large and appear whitish.

In the present invention, a part of the film of the substrate with the transparent film is peeled off, the average film thickness of the transparent film, the height of the convex part (T convex)
And the height of the recess (T-concave) are measured using a laser microscope (manufactured by Keyence Corporation: VE-3000).

In the present invention, the metal oxide particles (A) and the silica-based hollow fine particles (B) are mixed without being separated. Further, the metal oxide particles (A) may be a single layer, thereby forming irregularities. Furthermore, the metal oxide particles (A) may be arranged in two or more layers, thereby forming irregularities. Also good. Silica-based hollow fine particles (B) fill the space between the metal oxide particles (A), and anti-glare properties are exhibited, but the silica-based hollow fine particles (B) adhere to the surface of the metal oxide particles (A). You may do it.

Next, the coating liquid for forming a transparent film according to the present invention will be specifically described.
Transparent Film Forming Coating Liquid The transparent film forming coating liquid according to the present invention is characterized by comprising the metal oxide (A), the silica-based hollow fine particles (B), a matrix forming component and a solvent. .

The concentration of the metal oxide particles (A) in the coating solution for forming a transparent coating is preferably in the range of 0.1 to 10% by weight, more preferably 0.2 to 5% by weight as the solid content. When the concentration of the metal oxide particles (A) is low, regular and sufficient irregularities cannot be formed on the surface of the transparent coating, and thus the antiglare performance may be insufficient. If the concentration of the metal oxide particles (A) is high, the film thickness of the transparent film may not be uniform, or regular irregularities may not be formed on the surface of the transparent film, and thus the antiglare performance may not be sufficiently exhibited. In addition, the scratch resistance of the transparent film may be insufficient.

The concentration of the silica-based hollow fine particles (B) in the coating liquid for forming a transparent film is preferably 0.1 to 10% by weight as a solid content. When the concentration of the silica-based hollow fine particles (B) is less than 0.1 % by weight as a solid content, a transparent coating film having a desired low refractive index cannot be obtained, and the reflectance of the transparent coating film is increased, resulting in insufficient antireflection performance. Or the photopic contrast may be insufficient. When the concentration of the silica-based hollow fine particles (B) exceeds 10 % by weight as the solid content, the total solid content concentration of the coating solution also increases, and the coating property is deteriorated and it becomes difficult to form a uniform transparent film. In some cases, the smoothness of the transparent film may be lost, or voids may be formed inside the transparent film, causing light scattering, haze value of the transparent film may be increased, and scratch resistance may be insufficient. is there.

The quantity ratio of the particles (A) and (B) is as described above.
(iii) Matrix-forming component As the matrix-forming component, a silicone-based matrix-forming component, an organic resin-based matrix-forming component, or the like is used.

As the silicone-based matrix-forming component, an organosilicon compound represented by the following formula (1) and / or a hydrolyzate or hydrolyzed polycondensate thereof is preferably used.
_{R n -SiX 4-n (1} )
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms or a silanol group) , Halogen, hydrogen, n: an integer of 0 to 3)
As such an organosilicon compound represented by the formula (1), those described above are used. Examples of the organic resin matrix forming component include known thermosetting resins, thermoplastic resins, electron beam curable resins, and the like as coating resins. As such a resin, for example, the above-mentioned thermoplastic resin, thermosetting resin (including ultraviolet curable resin and electron beam curable resin), and the like are used. In addition, in the case of a thermosetting resin, the thing before superposition | polymerization, such as a monomer, an oligomer, and a prepolymer, is used.

  These resins may be emulsion resins, water-soluble resins, and hydrophilic resins. Further, in the case of a thermosetting resin, it may be an ultraviolet curable type or an electron beam curable type, and in the case of a thermosetting resin, a curing catalyst may be included.

The concentration of the matrix-forming component in the coating solution for forming a transparent coating is preferably in the range of 0.5 to 30% by weight, more preferably 1 to 20% by weight as the solid content.
If the concentration of the matrix-forming component is low, there are too many fine particles relative to the matrix, and the film thickness of the transparent coating becomes non-uniform or regular irregularities cannot be formed on the surface of the transparent coating. Insufficient or scratch resistance of the transparent film may be insufficient. If the concentration of the matrix forming component is too high, the amount of fine particles is too small relative to the matrix, so that the antireflection performance and antiglare performance may be insufficient, or the effect of improving the bright place contrast may be insufficient.
(Iv) Solvent The solvent used in the present invention is not particularly limited as long as it can dissolve or disperse the matrix forming component and the polymerization initiator and can uniformly disperse the metal oxide particles (A) and the silica-based hollow fine particles (B). In addition, a conventionally known solvent can be used.

Specifically, alcohols such as water, methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, hexylene glycol, isopropyl glycol; acetic acid Esters such as methyl ester, ethyl acetate, butyl acetate; ethers such as diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetone Ketones such as acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, toluene, cyclohexanone, isophorone and the like.
(v) Polymerization initiator In the coating liquid for forming a transparent film of the present invention, when the matrix forming component is a thermosetting resin (including an electron beam curable resin and an ultraviolet curable resin), a polymerization initiator is used as necessary. Can be used.

The polymerization initiator is not particularly limited as long as the matrix-forming component can be polymerized and cured, and can be appropriately selected depending on the resin, and conventionally known polymerization initiators can be used.
For example, in addition to polymerization initiators such as acylphosphine oxides, acetophenones, propiophenones, benzyls, benzoins, benzophenones, and thioxanthones, cationic photopolymerization initiators and the like can be mentioned.

  The concentration of the polymerization initiator in the coating solution for forming a transparent film varies depending on the type of the matrix-forming component, but when the matrix-forming component and the polymerization initiator are solids, 0.1 to 20% by weight of the matrix-forming component, Furthermore, it is preferable that it exists in the range of 0.5 to 10 weight%.

  If the content of the polymerization initiator is small, the transparent film may be insufficiently cured. Moreover, when there is too much content of a polymerization initiator, stability of a coating liquid may become inadequate. Further, it may contain a sensitizer, a stabilizer and the like together with the polymerization initiator.

  The concentration of the coating solution for forming the transparent film (that is, the total concentration of the particles (A), (B), the matrix-forming component, and other components) is generally in the range of 1 to 50% by weight, further 2 to 30% by weight as the solid content. It is preferable that it exists in.

If the concentration of the coating solution for forming the transparent coating is low, the concentration of the metal oxide particles (A) is also low, and irregularities with a regular unevenness of 30 nm or more cannot be formed on the transparent coating surface, resulting in poor antiglare performance. May be sufficient. If the concentration of the coating solution for forming the transparent film is too high, regular irregularities cannot be formed on the surface of the transparent film, and thus the antiglare performance may not be sufficiently exhibited, and the scratch resistance of the transparent film is insufficient. It may become. Such a coating liquid according to the present invention can be prepared by mixing the above-described components by a cultivated land method.

A conventionally well-known method can be employ | adopted as a method of forming a transparent film using the coating liquid for transparent film formation concerning this invention. Specifically, the coating liquid for forming a transparent film is formed by a known method such as dipping, spraying, spinner, roll coating, bar coating, slit coater printing, gravure printing, or micro gravure printing. It is possible to form a transparent film by applying, drying and curing by a conventional method such as ultraviolet irradiation, heat treatment, etc., but in the present invention, a roll coating method, a slit coater printing method, a gravure printing method, a micro gravure printing method. Is recommended.
[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
[Example 1]
Preparation of coating liquid (A-1) for forming transparent coating As metal oxide particles, silica particles (manufactured by Catalyst Chemical Industry Co., Ltd .: silica microbead P-500, average particle diameter 2 μm, particle refractive index 1.45, powder Body) 20 g is suspended in 180 g of methanol, 4 g of γ-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-5103, SiO ₂ component 81.2 wt%) is mixed, and 10 g of ultrapure water is added. The resulting mixture was stirred at 50 ° C. for 5 hours to obtain a surface-treated silica particle dispersion (solid content concentration: 11.2% by weight).

Separately, 100 g of silica-based hollow fine particle dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: through rear 1420, average particle size 50 nm, concentration 20.5 wt%, dispersion medium: isopropanol, particle refractive index 1.30) is perfluoro. 10 g of octylethyltriethoxysilane (manufactured by Toray Dow Corning Co., Ltd .: AY43-158E, 26.6 wt% of SiO ₂ component) was mixed, 10 g of ultrapure water was added, and the mixture was stirred at 40 ° C. for 5 hours for surface treatment. A silica-based hollow fine particle-dispersed sol was obtained (solid content: 19.3% by weight).

Next, 144.6 g of the surface-treated silica particle dispersion and 69.9 g of the surface-treated silica-based hollow fine particle dispersion, and 24.3 g of hexaerythritol tripentaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) as a hydrophobic matrix. , 0.35 g of photoinitiator (Irgacure 184 manufactured by Ciba Specialty Inc., dissolved in IPA, solid content concentration 10%) and 13.2 g of isopropanol as a solvent, 8.0 g of methyl isobutyl ketone, propylene glycol monomethyl ether 6 0.0 g was mixed well to prepare a coating liquid for forming a transparent film (A-1).
Preparation of substrate with transparent coating (1) Coating solution (A-1) for forming transparent coating was applied to a triacetyl cellulose (TAC) film (thickness: 0.8 mm, refractive index: 1.50) with # 14 barco. After coating with a coater and drying at 70 ° C. for 1 minute, a high-pressure mercury lamp (80 W / cm) was irradiated for 1 minute to cure, thereby preparing a substrate (1) with a transparent coating. 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 Table 1.

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).
Further, antiglare properties, adhesion, and pencil hardness were evaluated by the following methods and evaluation criteria, and the results are shown in Table 1.
The back surface of the antireflection film-coated substrate (1) with an antiglare hard coat function was evenly applied with black spray, and the reflection of the fluorescent lamp was visually confirmed from a 30 W fluorescent lamp to evaluate the antiglare property. The results are shown in Table 1.

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: ×
1 on the surface of the substrate with anti-reflection coating with adhesive hard coat function (1) at intervals of 1 mm in length and width with a knife
One parallel scratch was made to make 100 squares, cellophane tape was adhered to this, and when the cellophane tape was peeled off, the number of squares remaining after the coating was not peeled The adhesion was evaluated by classifying into 4 stages. The results are shown in Table 1.

Number of remaining squares: ◎
Number of remaining squares 90-99: ○
Number of remaining squares: 85 to 89: Δ
Number of remaining squares: 84 or less: ×
Pencil hardness It measured with the pencil hardness tester according to JIS-K-5400.
Difference in average film thickness / T-convex-T-concave part The film of the substrate with transparent coating (1) is partially peeled off, and the average film thickness of the transparent film, the height of the convex part (T-convex) and the height of the concave part (T-concave ) Was measured using a laser microscope (manufactured by Keyence Corporation: VE-3000). The results are shown in Table 1.
[Example 2]
Preparation of coating liquid for forming transparent film (A-2) In the same manner as in Example 1, 96.4 g of the surface-treated silica particle dispersion, 69.9 g of the surface-treated silica-based hollow fine particle dispersion, hexagonal as the hydrophobic matrix Erythritol tripentaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) 29.7g, photoinitiator (Irgacure 184 manufactured by Ciba Specialty Co., Ltd., dissolved in IPA, solid content concentration 10%) 0.43
g and a solvent, 13.2 g of isopropanol, 8.0 g of methyl isobutyl ketone, and 6.0 g of propylene glycol monomethyl ether were sufficiently mixed to prepare a coating solution (A-2) for forming a transparent film.
Preparation of substrate with transparent film (2) A substrate with transparent film (2) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (A-2) was used. Total light transmittance, haze, reflectivity, antiglare property, adhesion, pencil hardness and average film thickness, height of convex part (T convex) and concave part of the obtained substrate with transparent coating (2) The difference from the height (T-concave) was measured, and the results are shown in Table 1.
[Example 3]
Preparation of coating liquid for forming transparent film (A-3) In the same manner as in Example 1, 192.9 g of a surface-treated silica particle dispersion, 69.9 g of a surface-treated silica-based hollow fine particle dispersion, hexagonal as a hydrophobic matrix Erythritol tripentaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) 18.9g, photoinitiator (Irgacure 184 manufactured by Ciba Specialty Co., Ltd., dissolved in IPA, solid content concentration 10%) 0.2
7 g and 13.2 g of isopropanol as a solvent, 8.0 g of methyl isobutyl ketone, and 6.0 g of propylene glycol monomethyl ether were sufficiently mixed to prepare a coating solution (A-3) for forming a transparent film.
Preparation of substrate with transparent film (3) A substrate with transparent film (3) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (A-3) was used.
Total light transmittance, haze, reflectance, anti-glare property, adhesion, pencil hardness and average film thickness, height of convex part (T convex) and concave part of the obtained substrate with transparent coating (3) The difference from the height (T-concave) was measured, and the results are shown in Table 1.
[Example 4]
Preparation of coating liquid for forming transparent coating (A-4) As metal oxide particles, silica particles (manufactured by Catalytic Chemical Industry Co., Ltd .: true sphere SW1.0, average particle diameter 1 μm, particle refractive index 1.45, powder ) 20 g suspended in 180 g methanol and γ −
4 g of acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-5103,
SiO ₂ component 81.2 wt%) were mixed, ultrapure water was added 10 g, to obtain a silica particle dispersion in which the surface treatment by stirring for 5 hours at 50 ° C. (solids concentration 11.2 wt%) .

Separately, a silica-based hollow fine particle dispersed sol surface-treated in the same manner as in Example 1 was obtained (solid content: 19.3% by weight).
Next, 144.6 g of the surface-treated silica particle dispersion and 69.9 g of the surface-treated silica-based hollow fine particle dispersion, and 24.3 g of hexaerythritol tripentaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) as a hydrophobic matrix. , 0.35 g of photoinitiator (Irgacure 184 manufactured by Ciba Specialty Inc., dissolved in IPA, solid content concentration 10%) and 13.2 g of isopropanol as a solvent, 8.0 g of methyl isobutyl ketone, propylene glycol monomethyl ether 6 0.0 g was mixed well to prepare a coating solution for forming a transparent film (A-4).
Preparation of substrate with transparent film (4) Substrate with transparent film (4) The same procedure as in Example 1 was applied except that the coating liquid for forming a transparent film (A-4) was applied using a # 8 bar coater. ) Was prepared.

Total light transmittance, haze, reflectance, anti-glare property, adhesion, pencil hardness and average film thickness, height of convex part (T convex) and concave part of the obtained substrate with transparent coating (4) The difference from the height (T-concave) was measured, and the results are shown in Table 1.
[Example 5]
Preparation of coating liquid for forming transparent film (A-5) As metal oxide particles, silica particles (manufactured by Catalyst Kasei Kogyo Co., Ltd .: true sphere SW4.0, average particle diameter 4 μm, particle refractive index 1.45, powder ) 20 g suspended in 180 g methanol and γ −
4 g of acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-5103,
SiO ₂ component 81.2 wt%) were mixed, ultrapure water was added 10 g, to obtain a silica particle dispersion in which the surface treatment by stirring for 5 hours at 50 ° C. (solids concentration 11.2 wt%) .

Separately, a silica-based hollow fine particle dispersed sol surface-treated in the same manner as in Example 1 was obtained (solid content: 19.3% by weight).
Next, 144.6 g of the surface-treated silica particle dispersion and 69.9 g of the surface-treated silica-based hollow fine particle dispersion, and 24.3 g of hexaerythritol tripentaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) as a hydrophobic matrix. , 0.35 g of photoinitiator (Irgacure 184 manufactured by Ciba Specialty Inc., dissolved in IPA, solid content concentration 10%) and 13.2 g of isopropanol as a solvent, 8.0 g of methyl isobutyl ketone, propylene glycol monomethyl ether 6 0.0 g was mixed well to prepare a coating solution for forming a transparent film (A-5).
Preparation of transparent coated substrate (5) Transparent coated substrate (5) was prepared in the same manner as in Example 1 except that the coating solution (A-5) for forming a transparent coating was applied using a # 20 bar coater. ) Was prepared.
Total light transmittance, haze, reflectance, anti-glare property, adhesion, pencil hardness and average film thickness, height of convex part (T convex) and concave part of the obtained substrate with transparent coating (5) The difference from the height (T-concave) was measured, and the results are shown in Table 1.
[Example 6]
Preparation of coating liquid for forming transparent film (A-6) In the same manner as in Example 1, 144.6 g of a surface-treated silica particle dispersion, 28.0 g of a surface-treated silica-based hollow fine particle dispersion, hexagonal as a hydrophobic matrix Erythritol tripentaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) 32.4 g, photoinitiator (Irgacure 184 manufactured by Ciba Specialty Co., Ltd., dissolved in IPA, solid content concentration 10%) 0.3
5 g and 13.2 g of isopropanol as a solvent, 8.0 g of methyl isobutyl ketone, and 6.0 g of propylene glycol monomethyl ether were sufficiently mixed to prepare a coating solution for forming a transparent film (A-6).
Preparation of substrate with transparent film (6) A substrate with transparent film (6) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (A-6) was used. Total light transmittance, haze, reflectance, anti-glare property, adhesion, pencil hardness and average film thickness, height of convex part (T convex) and concave part of the obtained substrate with transparent coating (6) The difference from the height (T-concave) was measured, and the results are shown in Table 1.
[Example 7]
Preparation of coating solution for forming transparent film (A-7) In the same manner as in Example 1, 120.5 g of the surface-treated silica particle dispersion, 111.9 g of the surface-treated silica-based hollow fine particle dispersion, hexagonal as the hydrophobic matrix Erythritol tripentaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) 18.9 g, photoinitiator (Irgacure 184 manufactured by Ciba Specialty Co., Ltd., dissolved in IPA, solid content concentration 10%)
27 g and 13.2 g of isopropanol as a solvent, 8.0 g of methyl isobutyl ketone, and 6.0 g of propylene glycol monomethyl ether were sufficiently mixed to prepare a coating solution (A-7) for forming a transparent film.
Preparation of substrate with transparent film (7) A substrate with transparent film (7) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (A-7) was used. Total light transmittance, haze, reflectance, anti-glare property, adhesion, pencil hardness and average film thickness of the obtained transparent film-coated substrate (7), the height of the convex part (T convex) and the concave part The difference from the height (T-concave) was measured, and the results are shown in Table 1.
[Example 8]
Preparation of substrate with transparent coating (8) A coating solution for forming a transparent coating (A-1) prepared in the same manner as in Example 1 was prepared from a triacetyl cellulose (TAC) film (thickness: 0.8 mm, refractive index: 1). .50) with a # 8 bar coater, dried at 70 ° C. for 1 minute, and then cured by irradiation with a high pressure mercury lamp (80 W / cm) for 1 minute to form a substrate (8) with a transparent coating. Prepared. Total light transmittance, haze, reflectance, anti-glare property, adhesion, pencil hardness and average film thickness, height of convex portion (T convex) and concave portion of the obtained substrate with transparent coating (8) The difference from the height (T-concave) was measured, and the results are shown in Table 1.
[Example 9]
Preparation of substrate with transparent coating (9) A coating solution for forming a transparent coating (A-1) prepared in the same manner as in Example 1 was prepared from a triacetyl cellulose (TAC) film (thickness: 0.8 mm, refractive index: 1). .50) with a # 20 bar coater, dried at 70 ° C. for 1 minute, and then cured by irradiation with a high pressure mercury lamp (80 W / cm) for 1 minute to form a substrate (9) with a transparent coating. Prepared. Total light transmittance, haze, reflectance, anti-glare property, adhesion, pencil hardness and average film thickness, height of convex part (T convex) and concave part of the obtained substrate with transparent coating (9) The difference from the height (T-concave) was measured, and the results are shown in Table 1.
[Example 10]
Preparation of coating liquid for forming transparent film (A-10) As metal oxide particles, silica-based hollow fine particle dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: Thruria S special product, average particle size 0.5 μm, concentration 10.5) % By weight, dispersion medium: isopropanol, particle refractive index 1.20) and 4 g of γ-acrylooxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-5103, SiO ₂ component 81.2 weight) %) Was added, 10 g of ultrapure water was added, and the mixture was stirred at 50 ° C. for 5 hours to obtain a surface-treated silica particle dispersion (solid content concentration: 11.2 wt%).

Separately, 100 g of silica-based hollow fine particle dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: through rear 1420, average particle size 50 nm, concentration 20.5 wt%, dispersion medium: isopropanol, particle refractive index 1.30) is perfluoro. 10 g of octylethyltriethoxysilane (manufactured by Toray Dow Corning Co., Ltd .: AY43-158E, 26.6 wt% of SiO ₂ component) was mixed, 10 g of ultrapure water was added, and the mixture was stirred at 40 ° C. for 5 hours for surface treatment. A silica-based hollow fine particle-dispersed sol was obtained (solid content: 19.3% by weight).

Next, 144.6 g of the surface-treated silica-based hollow fine particle dispersion sol and 69.9 g of the surface-treated silica-based hollow fine particle dispersion liquid, hexaerythritol tripentaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) as the hydrophobic matrix 24. To 3 g, photoinitiator (Irgacure 184, manufactured by Ciba Specialty Co., Ltd., dissolved in IPA, solid content concentration 10%) 0.35 g
Further, 13.2 g of isopropanol, 8.0 g of methyl isobutyl ketone, and 6.0 g of propylene glycol monomethyl ether were sufficiently mixed as a solvent to prepare a coating solution (A-10) for forming a transparent film.
Preparation of substrate with transparent film (10) A substrate with transparent film (10) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (A-10) was used.

Total light transmittance, haze, reflectance, anti-glare property, adhesion, pencil hardness and average film thickness, height of convex part (T convex) and concave part of the obtained substrate with transparent coating (10) The difference from the height (T-concave) was measured, and the results are shown in Table 1.
[Comparative Example 1]
Preparation of coating liquid for forming transparent film (A-R1) As metal oxide particles, silica particles (Catalyst Chemical Industries, Ltd .: silica microbead P-500, average particle diameter 2 μm, particle refractive index 1.45, powder Body) 20 g is suspended in 180 g of methanol, 4 g of γ-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-5103, SiO ₂ component 81.2 wt%) is mixed, and 10 g of ultrapure water is added. The resulting mixture was stirred at 50 ° C. for 5 hours to obtain a surface-treated silica particle dispersion (solid content concentration: 11.2% by weight).

Next, 144.6 g of the surface-treated silica particle dispersion and 37.8 g of hexaerythritol tripentaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) as a hydrophobic matrix.
In addition, 0.54 g of photoinitiator (Irgacure 184 manufactured by Ciba Specialty Inc., dissolved in IPA, solid content concentration 10%) and 13.2 g of isopropanol as a solvent, 8.0 g of methyl isobutyl ketone, propylene glycol monomethyl ether A coating solution for forming a transparent film (A-R1) was prepared by thoroughly mixing 6.0 g.
Preparation of substrate with transparent film (R1) A substrate with transparent film (R1) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (A-R1) was used. Total light transmittance, haze, reflectance, anti-glare property, adhesion, pencil hardness and average film thickness, height of convex part (T convex) and concave part of the obtained substrate with transparent coating (R1) The difference from the height (T-concave) was measured, and the results are shown in Table 1.
[Comparative Example 2]
Preparation of coating liquid for forming transparent film (A-R2) Silica-based hollow fine particle dispersion sol (manufactured by Catalyst Kasei Kogyo Co., Ltd .: through rear 1420, average particle diameter 50 nm, concentration 20.5 wt%, dispersion medium: isopropanol, 100 g of particle refractive index 1.30) is mixed with 10 g of perfluorooctylethyltriethoxysilane (manufactured by Toray Dow Corning Co., Ltd .: AY43-158E, SiO ₂ component 26.6% by weight), and 10 g of ultrapure water is added. Thus, a silica-based hollow particle-dispersed sol having been surface-treated by stirring at 40 ° C. for 5 hours was obtained (solid content 19.3% by weight).

Then, 69.9 g of the surface-treated silica-based hollow fine particle dispersion, hexaerythritol tripentaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) 40 as a hydrophobic matrix
. To 5 g, photoinitiator (Irgacure 184 manufactured by Ciba Specialty Co., Ltd., dissolved in IPA,
(Solid content 10%) 0.58 g and 13.2 g of isopropanol, 8.0 g of methyl isobutyl ketone, and 6.0 g of propylene glycol monomethyl ether as a solvent were mixed thoroughly to form a coating solution for forming a transparent film (A-R1 ) Was prepared.
Preparation of substrate with transparent film (R2) A substrate with transparent film (R2) was prepared in the same manner as in Example 1 except that the coating liquid for forming a transparent film (A-R2) was used. Total light transmittance, haze, reflectance, anti-glare property, adhesion, pencil hardness and average film thickness, height of convex part (T convex) and concave part of the obtained substrate with transparent coating (R2) Measure the difference from the height (T-concave)
The results are shown in Table 1.
[Comparative Example 3]
Preparation of coating liquid for forming transparent film (A-R3) As metal oxide particles, silica particle aqueous dispersion (manufactured by Catalyst Kasei Kogyo Co., Ltd .: Spherica slurry, average particle size 0.3 μm, particle refractive index 1.45) , 100 g of SiO ₂ concentration is suspended in 100 g of methanol, and 4 g of γ-acrylooxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-5103, SiO ₂ component 81.2 wt%) is mixed. , 10g of ultrapure water
Was added and stirred at 50 ° C. for 5 hours to obtain a surface-treated silica particle dispersion (solid content concentration: 11.2% by weight).

Separately, a silica-based hollow fine particle dispersed sol surface-treated in the same manner as in Example 1 was obtained (solid content: 19.3% by weight). Next, 144.6 g of the surface-treated silica particle dispersion and 69.9 g of the surface-treated silica-based hollow fine particle dispersion, and 24.3 g of hexaerythritol tripentaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) as a hydrophobic matrix. , Photoinitiator (Irgacure 184, manufactured by Ciba Specialty Co., Ltd., dissolved in IPA, solid content concentration 10%)
35 g and 13.2 g of isopropanol as a solvent, 8.0 g of methyl isobutyl ketone, and 6.0 g of propylene glycol monomethyl ether were sufficiently mixed to prepare a coating solution for forming a transparent film (A-R3).
Preparation of substrate with transparent coating (R3) A substrate with transparent coating (R3) was prepared in the same manner as in Example 1 except that the coating solution for forming a transparent coating (A-R3) was used. Total light transmittance, haze, reflectance, anti-glare property, adhesion, pencil hardness and average film thickness, height of convex part (T convex) and concave part of the obtained substrate with transparent coating (R3) The difference from the height (T-concave) was measured, and the results are shown in Table 1.
[Comparative Example 4]
Preparation of coating liquid for forming transparent film (A-R4) As metal oxide particles, silica particles (manufactured by Catalyst Kasei Kogyo Co., Ltd .: true sphere SW 7.0, average particle diameter 7 μm, particle refractive index 1.45, powder ) 20 g suspended in 180 g methanol and γ −
4 g of acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-5103,
SiO ₂ component 81.2 wt%) were mixed, ultrapure water was added 10 g, to obtain a silica particle dispersion in which the surface treatment by stirring for 5 hours at 50 ° C. (solids concentration 11.2 wt%) .

Separately, a silica-based hollow fine particle dispersed sol surface-treated in the same manner as in Example 1 was obtained (solid content: 19.3% by weight). Next, 144.6 g of the surface-treated silica particle dispersion, 69.9 g of the surface-treated silica-based hollow fine particle dispersion, and 24.3 g of hexaerythritol tripentaacrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) as a hydrophobic matrix. , 0.35 g of photoinitiator (Irgacure 184 manufactured by Ciba Specialty Corporation, dissolved in IPA, solid content concentration 10%) and 13.2 g of isopropanol as solvent, 8.0 g of methyl isobutyl ketone, 6.0 g of propylene glycol monomethyl ether Were mixed well to prepare a coating solution for forming a transparent film (A-R3).
Preparation of substrate with transparent coating (R4) A substrate with transparent coating (R4) was prepared in the same manner as in Example 1, except that the coating solution for forming a transparent coating (A-R4) was used. Total light transmittance, haze, reflectance, anti-glare property, adhesion, pencil hardness and average film thickness, height of convex part (T convex) and concave part of the obtained substrate with transparent coating (R4) The difference from the height (T-concave) was measured, and the results are shown in Table 1.

The schematic sectional drawing which shows an example of the base material with a transparent film of this invention is shown.

Claims (5)

A substrate with a transparent film on which a transparent film having irregularities on the surface is formed,
The transparent coating comprises silica particles (A) having an average particle size (DpA) in the range of 0.5 to 5 μm;
The silica particles (A) are composed of silica-based hollow fine particles (B) having a mean particle diameter (DpB) in the range of 5 to 200 nm and a refractive index in the range of 1.10 to 1.40, and a matrix component. A substrate with a transparent coating, characterized by being silica-based hollow fine particles having a refractive index in the range of 1.10 to 1.40 . The transparent film has an average film thickness in the range of 1 μm to 10 μm,
The unevenness of the transparent film is characterized in that the difference between the average height of the convex portions (T convex) and the average height of the concave portions (T concave) (T convex) − (T concave) is in the range of 30 to 1500 nm. The substrate with a transparent film according to claim 1.   The content of silica particles (A) in the transparent coating is in the range of 10 to 70% by weight, the content of silica-based hollow fine particles (B) is in the range of 5 to 50% by weight, and the metal oxide particles The substrate with a transparent coating according to claim 1 or 2, wherein the total content of (A) and silica-based hollow fine particles (B) is in the range of 20 to 80% by weight. Silica particles (A) having an average particle diameter (DpA) in the range of 0.5 to 5 μm and average particle diameters (DpB) in the range of 5 to 200 nm, and the refractive index in the range of 1.10 to 1.40. It consists of a certain silica-based hollow fine particle (B), a matrix component, and a solvent, and the silica particle (A) is a silica-based hollow fine particle having a refractive index in the range of 1.10 to 1.40. Coating liquid for forming a transparent film. The concentration of the silica particles (A) is in the range of 0.1 to 10% by weight as the solid content, and the concentration of the silica-based hollow fine particles (B) is in the range of 0.1 to 10% by weight as the solid content, The coating liquid for forming a transparent film according to claim 4, wherein the concentration of the matrix-forming component is in the range of 1 to 30% by weight as a solid content.

Images