JPH10300902A - Antireflection film and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To transmit internal necessary visual information and to clearly read it by providing specified low refractive index layer, medium refractive index layer and high refractive index layer and specifying the thicknesses of the respective refractive index layers and the optical thickness of the film. SOLUTION: A medium refractive index layer 3, a high refractive index layer 2 and a low refractive index layer 1 are formed in this order on a transparent substrate film 5 through a bar code layer 4. Namely, the layers comprise the low refractive index layer 1 composed of a SiOx layers, the medium refractive index layer 3 provided by applying coating material composed of a binder and superfine particles having the refractive index larger than 1.5 and the high refractive index layer 2 having electric conductivity. This antireflection film has the relation: 2.20 > the refractive index of the high refractive index layer 2>1.40, thicknesses of the respective refractive index layers 1-3 of the low refractive index layer 1 of 80-110 nm, the high refractive index layer 2 of 30-110 nm and the medium refractive index layer 3 of 80-110 nm and the optical film thickness D smaller than the wavelength of visible light (D=n.d, n: the refractive index of the refractive index of the medium refractive index layer 3, d: the thickness of the medium refractive index layer 3).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film having an optical function having an anti-glare property, and more particularly to a film for various displays such as a word processor, a computer and a television, a surface of a polarizing plate used for a liquid crystal display, and transparent plastics. Becomes a film with excellent optical properties suitable for anti-reflection film on the surface of window glass of automobiles, trains, etc., optical lenses such as lenses of sunglasses, lenses of prescription glasses, lenses of camera finder, etc. .

[0002]

2. Description of the Related Art Curve mirrors, rearview mirrors, goggles, windows, displays such as personal computers and word processors, and various other commercial displays use transparent substrates such as glass and plastic. I have. When observing visual information such as objects, characters, and figures through these transparent substrates, or observing the image from the mirror through the transparent substrate and the image from the reflective layer, the surface of these transparent substrates reflects light, There is a problem that the necessary visual information is difficult to read.

Conventionally, techniques for preventing such reflection of light include a method of applying an antireflection paint to the surface of glass or plastic, and a method of coating a glass or other transparent substrate with a thickness of 0.1 μm.
m, a method of providing an ultra-thin film such as MgF ₂ or a metal vapor-deposited film, coating an ionizing radiation-curable resin on the surface of a plastic lens, etc., and further depositing SiOx or M
There are a method of forming a film of gF ₂ and a method of further forming a coating film having a lower refractive index on a cured film of an ionizing radiation-curable resin.

The thickness of the glass is 0.1 μm.
The MgF ₂ thin film of about m will be described in more detail. When the incident light is perpendicularly incident on the thin film in the air, the specific wavelength is λ ₀ , the refractive index of the anti-reflection film for this wavelength is n ₀ , the thickness of the anti-reflection film is h, and the substrate is The refractive index of _nz
Then, the anti-reflection film prevents 100% of light reflection,
It is already known that the condition for transmitting 100% of the light needs to satisfy the relationship of the following Expressions 1 and 2. (Science library physics = 9 "Optics" 7
0-72, published in 1980 by Science Co., Ltd.).

[0005] ^{_{n 0 = (n z) 1/2}} ( Formula _{1) n 0 h = λ 0} /4 ( Equation 2) is the refractive index n _z = 1.5 in the glass, the refractive index of MgF ₂ film n ₀ = 1.38, the wavelength of the incident light λ ₀ = 5500 angstroms (reference) is known. When these numerical values are substituted into the above (Equation 2), the thickness h of the antireflection film is about 0.5.
It is calculated that 1 μm is optimal.

According to the above (Equation 1), the reflection of light is 100
In order to prevent this, a material whose refractive index of the upper coating film is close to the value of the square root of the refractive index of the lower layer on which it is provided may be selected.

[0007] The present invention is applicable to various kinds of displays, such as visual information such as objects, characters, and figures to be identified through a transparent substrate, or an image from a mirror when an image from a reflective layer is observed through a transparent substrate. The surface of the board prevents the reflection of light and transmits the necessary visual information inside,
It is an object of the present invention to provide an antireflection film that can be clearly read.

[0008]

According to the present invention, which solves the above-mentioned problems, as shown in FIG. 1 or FIG. 2, a transparent substrate film 5 is provided with a medium refractive index layer 3 through a hard coat layer 4. In the antireflection film 10 in which the high refractive index layer 2 and the low refractive index layer 1 are sequentially formed, the low refractive index layer 1 composed of a SiOx layer,
1. A medium refractive index layer 3 and a high refractive index layer 2 having conductivity, which are formed by coating a paint comprising a binder and ultrafine particles having a refractive index of 1.5 or more; 20> refractive index of high refractive index layer> refractive index of medium refractive index layer> refractive index of low refractive index layer> 1.40, low refractive index layer being 80 to 110n
m, the thickness of each refractive index layer in which the high refractive index layer is 30 to 110 nm and the medium refractive index layer is 50 to 100 nm, and the optical thickness D which is equal to or less than the wavelength of visible light (D = nd, where n : Medium-refractive index, d = thickness of medium-refractive index layer).

In the present invention, the hard coat layer 4
However, it is preferable that the transparent substrate film 5 has an uneven shape on the surface which is in contact with the middle refractive index layer 3 and is hard-coated directly or via a primer layer 7 and / or an adhesive layer 9 as shown in FIG. 3 is an anti-reflection film 10 provided with the same.

Further, the medium refractive index layer is preferably, with respect to the thermosetting resin and / or ionizing radiation resin 1 part by weight, ZnO ultrafine _{particles, TiO 2, CeO 2, Sb} 2 O
₅ , SnO ₂ , ITO, Y ₂ O ₃ , La ₂ O ₃ , Al ₂
The mat material selected from one or more kinds of fine particles selected from the group consisting of O ₃ , Hf ₂ O ₃ and ZrO ₂ is 0.1%.
It is an antireflection film composed of up to 20 parts by weight.

The high-refractive-index layer and the low-refractive-index layer are preferably antireflection films which are layers provided by vacuum coating.

The high refractive index layer is preferably
Plasma CVD by discharging organic siloxane source gas
Undecomposed organic siloxane is formed by SiOx
0.1 to 0.2 part of the antireflection film remaining.

Further, the high refractive index layer and the antifouling coat layer can be formed.

As shown in FIG. 3, in the first method for producing an antireflection film of the present invention, a curing reaction type uncured hard coat layer 46 is provided on a transparent substrate film 5, and then a binder and Uncured medium refractive index layer 3 comprising a composition containing fine particles having a refractive index higher than the refractive index of the binder 3
6 is applied and formed on a transparent substrate film.

Then, a laminate (see FIG. 3A) obtained by laminating and forming a mat-shaped forming film 6 having fine irregularities on the uncured hard coat layer and the middle refractive index layer is subjected to a heat treatment. And / or curing the hard coat layer and the middle refractive index layer by ionizing radiation treatment.

Further, the shaping film 6H is peeled off and removed from the cured laminate to form the medium refractive index layer 3 having irregularities on the surface of the hard coat layer 4 as shown in FIG. 3 (b).

Then, as shown in FIG. 3 (c), a high refractive index layer 2 is formed on the cured and formed medium refractive index layer 3 having irregularities by vacuum evaporation or sputtering.
An antireflection film 10 is formed by forming a low-refractive-index layer 1 composed of an x layer by vacuum deposition, sputtering or plasma CVD.

The above-mentioned second method for producing the antireflection film is characterized in that a mat and a fine particle having a refractive index higher than the refractive index of the binder are added to a mat-shaped molding film 6 having an uneven surface. An uncured medium-refractive index layer 36 made of a composition containing: is applied, and as shown in FIG. The coat layer 46 is laminated.

Then, the obtained laminate is subjected to a heat treatment and / or
Alternatively, the medium refractive index layer and the hard coat layer are cured by ionizing radiation treatment, and the shaped film 6H is formed from the cured laminate.
Is removed to form a medium refractive index layer 3 having irregularities on the surface of the hard coat layer 4 (see FIG. 4B).

Then, as shown in FIG. 4C, the high refractive index layer 2 and the low refractive index layer 4 are formed in the same manner as in the first manufacturing method.
Are laminated. If necessary, the antifouling coat layer 42 can be formed as a low refractive index layer.

Third Example of Producing the Antireflection Film of the Invention
As shown in FIG. 5A, the method of
Then, an uncured medium refractive index layer containing a binder and fine particles having a refractive index higher than that of the binder and an uncured hard coat layer 4 are applied and cured.

On the other hand, the uncured surface obtained by coating the reactive adhesive layer 9 on the transparent base film and the cured medium refractive index layer are laminated, and the obtained laminate is subjected to heat treatment and heat treatment. And / or a treatment with ionizing radiation is performed to cure the adhesive layer.
A laminate shown in FIG.

Then, the shaping film 6H is peeled off from the cured laminate to form the middle refractive index layer 3 on the transparent base film 5 via the adhesive layer 9 and the hard coat layer 4.

Then, in the same manner as in the first manufacturing method, an antireflection film 10 is formed by laminating a high refractive index layer 2 and a low refractive index layer 1 as shown in FIG.

[0025]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments will be described below with reference to the drawings.

As shown in FIG. 1 or FIG. 2, an antireflection film 10 of the present invention comprises a hard coat layer 4 having a mirror-like or irregular shape formed on one surface of a transparent base film 5.
Through the middle refractive index layer (first layer) 3 and the high refractive index layer (second layer).
2) and a low refractive index layer (third layer) 1 in this order.

The low-refractive-index layer 1 is a SiOx layer, and the middle-refractive-index layer 3 is formed on a hard coat layer 4 formed into a concavo-convex shape by adding ultrafine particles having a refractive index of 1.5 or more and a binder. The high-refractive-index layer 2 is composed of a coating of
Each layer has conductivity and electromagnetic shielding properties, and the refractive index of the adjacent refractive index layer is 2.20> the refractive index of the high refractive index layer> the medium refractive index layer. (Refractive index layer)> refractive index of low refractive index layer> 1.40, and the thickness of each refractive index layer is 80 to 100 for low refractive index layer 1.
nm, the high-refractive-index layer has a range of 30 to 110 nm, and the middle-refractive-index layer 3 has a range of 50 to 100 nm, where D = nd (where n is the refractive index of the middle-refractive-index layer, and d = the middle-refractive-index. Layer thickness)
Is the antireflection film 10 whose optical thickness D calculated is equal to or less than the wavelength of visible light.

Preferably, the hard coat layer side in contact with the middle refractive index layer 3 of the hard coat layer 4 has an uneven shape,
The hard coat layer is provided directly on the transparent base material film 5 or provided with the primer layer 7 shown in FIG. 6 or via the adhesive layer 9 shown in FIG. Antireflection film 10 which may be provided with 42
It is.

The above-mentioned medium refractive index layer 3 is preferably formed by adding 1 part by weight of the thermosetting resin and / or the ionizing radiation type resin.
Ultrafine particles of ZnO (refractive index 1.90, the following values indicate the refractive index), TiO ₂ (2.3 to 2.7), CeO
₂ (1.95), Sb ₂ O ₅ (1.71), ITO (refractive index 1.95), Y ₂ O ₃ (refractive index 1.87), La ₂
O ₃ (refractive index 1.95), ZrO ₂ (refractive index 2.0
5) The mat material selected from one or more kinds of fine particles selected from the group consisting of Al ₂ O ₃ (1.63) is 0.1 to
An antireflection film 10 composed of 20 parts by weight. The ultrafine particles preferably have a higher refractive index than the binder of the medium refractive index layer and a refractive index of 1.5 or more.
The average particle size of the ultrafine particles is preferably 5 to 50 nm, more preferably 5 to 10 nm.

The high refractive index layer 2 and the low refractive index layer 1 are preferably layers provided by vacuum coating.

The high-refractive-index layer 1 made of the SiOx layer is preferably formed by plasma CVD using a discharge of an organic siloxane source gas, and is a layer in which undecomposed organic siloxane remains in the SiOx layer. .

Further, an antifouling coat layer 42 shown in FIG. 6 can be formed on the high refractive index layer 1.

The transparent substrate sheet of the present invention is formed from a stretched or unstretched film of ceramics such as glass or a transparent plastic.

In addition to ordinary optical glass, polyester,
Thermoplastic resins such as polyamide, polyimide, polypropylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal, polymethyl methacrylate, polycarbonate, and polyurethane can be used.

The transparent substrate film is provided directly or with a primer layer for strengthening the adhesion of the hard coat layer, and the hard refractive index layer 3 shown in FIG.
May be provided to provide another refraction layer.

The medium refractive index layer 3 has a lower refractive index than the high refractive index layer 2 and has a higher refractive index than the low refractive index layer 1, the hard coat layer 4 and / or the transparent substrate film 5.

The medium refractive index layer 3 is preferably made of ZnO, TiO ₂ , CeO ₂ (refractive index: 1.95) or a binder.
Sb ₂ O ₅ , SnO ₂ , ITO, Y ₂ O ₃ , La
Composition composed of ultrafine metal oxide of a mat material selected from one or more types of fine particles selected from the group consisting of ₂ O ₃ , ZrO ₂ (refractive index 2.05), Al ₂ O ₃ and Hf ₂ O ₃ An object is applied to form a coating film and provided on the base film 5.

As shown in FIG. 3, an uncured hard coat layer 46 of the above composition is applied to the transparent substrate film 5 and an uncured middle refractive index layer 36 is applied to the middle refractive index layer 3. It is processed and laminated with the shaping film 6 in an uncured state, cured by heating and / or ionizing radiation treatment, and formed by peeling the shaping film 6.

As shown in FIG. 4, an uncured medium-refractive-index layer 36 and a hard coat 46 are provided on a shaping film 6 having an uneven shape, and an adhesive layer 9 is provided on a transparent base film, if necessary. The medium refractive index layer can be formed by a transfer method of laminating, curing and shaping.

The ratio (weight ratio) of the ultrafine particles to the binder in the medium refractive index layer is preferably 1 to 20 for the ultrafine particles with respect to 1 for the binder, and if it is less than 1, the antireflection effect is reduced. If it exceeds 300, there is a problem that the sticking property of the ultrafine particles is reduced and the tendency to fall off is increased.

The uneven shape provided with the middle refractive index layer of the present invention is as follows:
In addition to being provided on the shaped hard coat layer 3, the adhesive layer 9 and the primer layer 7, which are layers provided on the transparent substrate film, can be provided with the same function by forming an uneven shape. The uneven shape of the hard coat layer 4 is in direct contact with the middle refractive index layer 3, and the refractive index is formed smaller than the refractive index of the middle refractive index layer.

The above-mentioned reactive resin for forming the medium refractive index layer or the hard coat layer which satisfies the requirements is preferably a resin having an acrylate functional group, for example, a polyester having a relatively low molecular weight, (Meth) acrylates of polyfunctional compounds such as polyether, acrylic resin, epoxy resin, polyurethane, alkyd resin, spiroacetal resin, polybutadiene, polythiolpolyene resin, and polyhydric alcohol (hereinafter, acrylate and methacrylate Are described as (meth) acrylate) and monofunctional such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, vinyltoluene and N-vinylpyrrolidone which are reactive diluents. monomer,
And polyfunctional monomers such as trimethylolpropane tri (meth) acrylate and hexanediol (meth)
Acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6 hexanediol di (meth) acrylate,
A material containing a relatively large amount of neopentyl glycol di (meth) acrylate or the like is used.

Further, when the above-mentioned ionizing radiation-curable resin is used as an ultraviolet-curable resin, acetophenones, benzophenones, Michler benzoyl benzoate, α-amyloxime ester, and the like may be used as a photopolymerization initiator. Thioxanthones and n- as photosensitizers
It is preferable to use a mixture of butylamine, triethylamine, tri-n-butylphosphine and the like.

The above ionizing radiation-curable resin may contain the following reactive organosilicon compound.

A compound represented by R _m Si (0R ′) _n , wherein R and R ′ each represent an alkyl group having 1 to 10 carbon atoms, m + n = 4, and m and n are each an integer. . More specifically, tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetra Pentaethoxysilane, tetrapenta-iso-propoxysilane, tetrapenta-n-propoxysilane, tetrapenta-n-
Butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane,
Examples include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, dimethylpropoxysilane, dimethylbutoxysilane, methyldimethoxysilane, methyldiethoxysilane, hexyltrimethoxysilane and the like.

The thickness of the hard coat layer 4 is preferably
It is formed to a thickness of 0.5 to 6 μm, more preferably 3 μm or more. When the thickness is less than 0.5 μm, the hardness of the medium refractive index layer, the high refractive index layer, and the low refractive index layer formed on the transparent substrate film cannot be maintained. Hard performance can be imparted to the prevention film.

Making the hard coat layer unnecessarily thick not only impairs the flexibility of the antireflection film, but also
A curing time is required, and there are restrictions on productivity and cost.

In the present invention, the term “hard performance” or “hard coat” means a hardness higher than H in a pencil hardness test shown in JIS K5400.

The material used for the high refractive index layer 2 of the present invention has a higher refractive index than the binder of the middle refractive index layer and a refractive index of 1.5 or more increases the refractive index of the high refractive index layer. Therefore, a material similar to the fine particle material used for the medium refractive index layer can be used. The high refractive index layer is formed using one or more kinds of materials selected from the above, and is formed by vacuum deposition or sputtering. And
The thickness d is 80 to 110 nm, and the resulting refractive index n is 1.90 to 2.10. The highest refractive index among the layers of the present invention is used. The product (optical thickness D) of the refractive index n and the thickness d is set to be equal to or less than the wavelength of visible light, so that reflection of light is prevented and visible light is transmitted optimally.

The high refractive index layer is preferably made of a sputtered ITO film and has a surface resistance of 10 ³ Ω.
/ □ or less is desirable.

Further, in this case, it is preferable that the binder of the middle refractive index layer comprises a heat and / or ionizing radiation curable organosilicon compound. Thereby, the above-mentioned ITO
Adhesion with the layer can be further improved.

The ultrafine particles of the medium refractive index layer are
The use of rO ₂ particles is particularly preferred for further improving the durability.

The low refractive index layer of the present invention is made of SiOx (x is 1.5 to 4.0), and is plasma-treated by using CVD, preferably organic siloxane as a raw material gas under the condition that no other inorganic vapor deposition source is present. It can be formed by CVD. Then, the film to be deposited is maintained at a temperature as low as possible.

The SiOx layer (low-refractive-index layer) of the present invention contains undecomposed organic siloxane, and carbon is allowed to remain at 0.1 to 0.2 with respect to silicon.
The effect of maintaining the flexibility and adhesiveness of x can be further improved.

The low refractive index layer thus formed has a surface contact angle of 40 to 180 degrees with water.
It is composed of an Ox layer and is therefore excellent in preventing dust adhesion.

A polarizing plate obtained by laminating the anti-reflection film 10 having the above-described structure with a polarizing element, or a cathode ray tube having the anti-reflection film 10 bonded to the surface has a clear image and no reflection. Things.

A clear image without reflected light is displayed even in a liquid crystal display device incorporating the above-mentioned polarizing plate.

[0058]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments will be described below in more detail with reference to the drawings.

Example 1 A biaxially stretched polyethylene terephthalate film having a thickness of 50 μm (Toray Industries, Inc.) was used as the shaping film 6 shown in FIG.
ZrO ₂ on one side of
Fine particle coating liquid No. A coating liquid (trade name, manufactured by Sumitomo Osaka Cement Co., Ltd.) comprising 1275 (0.3 parts by weight of a binder (ionizing radiation-curable organosilicon compound) per 100 parts by weight of ZrO ₂ fine particles) having a thickness of 57 nm (dried thickness: An uncured medium refractive index layer 36 (refractive index: 1.74) was applied with a wire bar so as to obtain the same.

On the other hand, an ultraviolet curable resin (PET-D3)
1: PET film having a thickness of 188 μm (A-4)
350 # 188 Toyobo Co., Ltd.) with a thickness of 6μ
m, and the solvent component was dried to form an uncured hard coat layer 46.

Next, the uncured medium refractive index layer 36 provided on the shaping film 6 and the uncured hard coat layer 46 provided on the transparent substrate film 5 are laminated and pressed so as to be in contact with each other. 480 mJ (10 m / min) of ultraviolet light is applied to cure the uncured middle refractive index layer 36 and the hard coat layer 46 to form the middle refractive index layer 3 and the hard coat layer 4, and to form the shaped film 6. Peeled off.

As shown in FIG. 4B, the transparent substrate film 5 excluding the release molding film 6H is provided with a medium refractive index layer 3
Are embedded and transferred to the surface of the hard coat layer 4, and the hard coat layer 4 and the middle refractive index layer 3 are laminated and formed on the transparent substrate film 5.

Further, as shown in FIG. 4C, an ITO sputtering (refractive index: 2.
0), the degree of vacuum was 5 × 10 ⁻⁶ torr, the substrate temperature was room temperature, argon was 100 scc / min, and oxygen was 5 scc / min.
min was introduced, and the deposition rate was set to 1.6 Å / s under a condition of 105 nm to form a high refractive index layer 2.

The high refractive index layer 2 is further provided with Si
O ₂ (refractive index: 1.46) and a vacuum degree of 5 × 10 ⁻⁶ to
A low refractive index layer 1 having a thickness of 85 nm was formed at rr, a substrate temperature of room temperature, and a deposition rate of 26 Å / s.

On the side of the low refractive index layer 2, a fluorine surfactant FC-772 (trade name, manufactured by 3M) was further applied with a wire bar to a thickness of 2 nm to form the antireflection film 10 of Example 1. Was prepared.

Example 2 As shown in FIG. 5, a 50 μm-thick shaped film 6 whose surface was treated with an acrylic melamine resin
-19 (trade name, manufactured by Reiko Co., Ltd.)
₂ Fine particle coating liquid No. 1221 (coating liquid consisting of 0.3 parts by weight of a binder (ionizing radiation curable organosilicon compound) per 100 parts by weight of ZrO ₂ fine particles: trade name, manufactured by Sumitomo Osaka Cement Co., Ltd.) having a film thickness of 57
nm of uncured middle refractive index layer 36 (refractive index 1.
74) was provided by coating with a wire bar.

Then, on the side of the middle refractive index layer 36, an ultraviolet curable resin (PET-D31: trade name, manufactured by Dainichi Seika Kogyo Co., Ltd.) was applied so as to have a thickness of 8 μm. Was dried to form an uncured hard coat layer 46.

Next, an ultraviolet ray of 480 mJ (10 m / mi) was applied to the uncured medium refractive index layer 36 and the hard coat layer 46.
n) Irradiation was performed to cure the uncured medium refractive index layer and the uncured resin layer, respectively, to provide the medium refractive index layer 3 and the hard coat layer 4 on the molding film 6.

As a result, the ultrafine particles of the middle refractive index layer 3 are embedded and transferred to the surface of the transparent cured resin layer 4, and the hard coat layer 4 and the middle refractive index layer 3 are laminated on the transparent release film 8. Been formed.

Further, on the side of the hard coat layer 4, a urethane-based two-part curable adhesive: LX-660 / KW75 = 4/1
(DIC product name) provided by wire bar coating so as to have a thickness of 10 μm, and a triacetyl cellulose film FT-UV80 (Fuji Photo Film Co., Ltd. product) as a transparent substrate film 5 Name)
Were laminated and aged at 40 ° C. for 7 days to complete the curing of the adhesive, to form a transparent cured adhesive layer 46, and the mold film 6 was peeled off. And exfoliated shaping film 6H
Is sputtered on the surface of the medium refractive index layer 3 except for the same conditions as in Example 1 to form the high refractive index layer 2.
iO ₂ was laminated by a plasma CVD method to produce the antireflection film 10 of Example 2.

Example 3 The transparent substrate film 2 shown in FIG.
Biaxially stretched polyethylene terephthalate film TP
On one side of ET (Toyobo A-4350),
An uncured hard coat layer 46 similar to that used in Example 1 was coated at a thickness of 8 μm, and a coating solution comprising 0.4 parts by weight of a binder to 100 parts by weight of TiO ₂ fine particles (manufactured by Sumitomo Osaka Cement Co., Ltd.) Was coated so as to have a thickness of 57 nm, and an uncured medium refractive index layer 36 (refractive index: 1.74) was coated with a wire bar.

Then, the surface of the uncured medium refractive index layer 36 and the shaping film 6 used in Example 1 were laminated and cured.

Then, in the same manner as in Example 1, the hard coat layer 4 and the middle refractive index layer 3 having the uneven shape were formed, and the release molding film 6H was released.

Further, on the side of the middle refractive index layer 3, a high refractive index layer 2 of 105 nm made of ITO sputtering (refractive index: 2.0) and SiO ₂ (refractive index: 1.46) were deposited on the side of 85.
to form a low refractive index layer 1.

On the side of the low refractive index layer 2, the fluorine-based surfactant FC-772 used in Example 1 was further coated in a thickness of 2 nm.

The above Example 1 is different from ZrO ₂ in that
The anti-reflection film 10 of Example 3 using iO ₂ was produced.

Comparative Example 1 As shown in FIG.
88 μm PET film (A-4350 # 188
On one side of Toyobo Co., Ltd. (trade name), a hard coat layer 45 was provided with a thickness of 8 μm, and further a refraction layer 26 in which MgO (refractive index: 1.72) was deposited to a thickness of 57 nm was provided. Next, in the same manner as in Example 1, an antireflection film 10H of a comparative example having a refraction layer 27 formed by ITO sputtering and a refraction layer 28 formed by deposition of SiO ₂ was formed.

COMPARATIVE EXAMPLE 2 The second refraction layer of Comparative Example 1 was formed by sputtering ITO.
An antireflection film of Comparative Example 2 having the same configuration as that of Comparative Example 1 was produced except that the deposition was replaced with iO ₂ .

On one side of the base film 5 where the hard coat layer 45 was provided at 8 μm, MgO (refractive index: 1.
The refraction layer 26 was formed by vapor-depositing 72) to have a thickness of 57 nm. Next, the antireflection film 10H of the comparative example provided with the high refractive layer 27 (film thickness 100 nm) formed by TiO ₂ vapor deposition and the refractive layer 28 (85 nm film thickness) formed by SiO ₂ vapor deposition.
Was configured.

Comparative Example 3 As shown in FIG. 6, a hard coat layer 45 having a thickness of 8 μm was provided on a transparent substrate film 5 in the same manner as in Comparative Example 1.

Further, on the side of the hard coat layer 45, I
TO sputtering (refractive index: 2.0), vacuum degree 5
× 10 ^-6 torr, substrate temperature is room temperature, argon is 100
Scc / min, oxygen 5 scc / min were introduced, the deposition rate was 1.6 Å / s, and the film thickness was 25.
Under the condition of nm, the first refractive index layer 26 was formed.

The first refractive index layer 26 further includes
SiO ₂ (refractive index: 1.43) The degree of vacuum 5 × 10 ^-6
The second refractive index layer 27 having a thickness of 20 nm was formed at Torr, a substrate temperature of room temperature, a deposition rate of 2 Å / s, and the like.

Further, ITO sputtering was performed on the second refraction layer 27 side, the degree of vacuum was 5 × 10 ⁻⁶ torr, the substrate temperature was room temperature, argon was 100 scc / min, and oxygen was 5 s.
cc / min, and a deposition rate of 1.6 Å / s and a film thickness of 120 nm.
A third refractive index layer 28 was formed.

The third refractive index layer 28 is made of SiO.
₂ Deposition was performed at a vacuum degree of 5 × 10 ⁻⁶ torr, a substrate temperature of room temperature, a deposition rate of 2 Å / s, and a thickness of 10
The antireflection film of Comparative Example 3 was manufactured by forming the fourth refractive index layer 29 having a thickness of 0 nm.

Example 4 The film thickness of the middle refractive index layer (ZrO ₂ : n = 1.74) was 90 n
m The thickness of the high refractive index layer (ITO: n = 2.0) is 40 nm, and the thickness of the low refractive index layer (SiO ₂ : n = 1.46) is 100
An antireflection film was produced in the same manner as in Example 1 except that the thickness was changed to nm.

Comparative Example 4 Although not shown, the PET film 5 was provided with the hard coat layer 45 used in Comparative Example 4 in a thickness of 7 μm in the same manner as in Comparative Example 4, and further comprised of a first refractive layer and a second refractive layer. As the refractive layer of the layer, ITO and SiO ₂ were used in this order (λ / 4−λ /
4) Optical film thickness, that is, vapor deposition laminated film thickness of 69 nm, 94 n
m to form an antireflection film of Comparative Example 5.

With respect to the samples obtained in the examples and comparative examples, the spectrum diagram of the antireflection film was measured, and a region having a low reflectance of 1% or less and a surface characteristic (surface resistance: measured by a four-terminal method; Contact angle: Contact angle measuring instrument made by Elma Mode
1 G1; moisture resistance test: visual evaluation of change in appearance after standing for 48 hours in an environment of 50 ° C. and 95% relative humidity; and dynamic friction coefficient) were measured and evaluated.

FIG. 9 and Table 1 show the measurement results.

[0089]

[Table 1] The anti-reflection film of the present invention, as described above, the base film, a hard coat layer, a medium refractive index layer, a high refractive index layer and a low refractive index layer in the order, and the hard coat layer, It is formed of a thermosetting or ionizing radiation curable resin. Therefore, it is possible to provide an antireflection film that is firmly and stably bonded to the base film and has excellent antiglare properties.

Further, although the refractive layers of the antireflection films of Examples 1 and 2 were composed of three layers, the same antireflection effect as that of the four-layer product of Comparative Example 2 was obtained.
It is also advantageous in that the number of steps can be reduced as compared with a layered product.

[Brief description of the drawings]

FIG. 1 is a sectional view showing a basic layer configuration of an antireflection film of the present invention.

FIG. 2 is a cross-sectional view showing a configuration in which a medium refractive index layer having an uneven shape is added to the antireflection film of the present invention.

3 (a), 3 (b) and 3 (c) are schematic sectional views showing steps of a first manufacturing method of the present invention.

FIGS. 4 (a), 4 (b) and 4 (c) are schematic sectional views showing steps of a second manufacturing method of the present invention.

5 (a), 5 (b) and 5 (c) are schematic sectional views showing steps of a third manufacturing method of the present invention.

FIG. 6 is a schematic sectional view showing another configuration of the present invention.

FIG. 7 is a schematic sectional view showing a configuration of a comparative example.

FIG. 8 is a schematic sectional view showing a configuration of another comparative example.

FIG. 9 is a view showing a reflection spectrum in a visible light part of a part of the antireflection films of Examples and Comparative Examples of the present invention.

[Description of Signs] 1 Low refractive index layer 2 High refractive index layer 3 Medium refractive index layer 36 Uncured medium refractive index layer 4 Hard coat layer 42 Antifouling coat layer 45 Hard coat layer of comparative example 46 Uncured hard coat Layer 5 Transparent substrate film 6 Molding film 6H Release molding film 7 Primer layer 9 Adhesive layer 96 Uncured adhesive layer 10 Antireflection film 10H Antireflection film of comparative example 10 Antireflection film 26 First refraction layer 27 First 2nd refraction layer 28 3rd refraction layer 29 4th refraction layer

Claims (15)

[Claims] An anti-reflection film comprising a transparent substrate film, a medium refractive index layer, a high refractive index layer, and a low refractive index layer formed in this order via a hard coat layer, wherein the SiOx layer A low-refractive-index layer, a medium-refractive-index layer composed of a coating of a binder and ultrafine particles having a refractive index of 1.5 or more, and a high-refractive-index layer; .20> Refractive index of high refractive index layer> Refractive index of medium refractive index layer>
The refractive index of the low refractive index layer has a relationship of> 1.40, the low refractive index layer has a thickness of 80 to 110 nm, and the high refractive index layer has a relationship of 30 to 1.
An optical thickness D (D = n · d, where n is a refractive index of a medium refractive index) having a thickness of each refractive index layer of 10 nm and a middle refractive index layer of 50 to 100 nm and not more than the wavelength of visible light. Antireflection film having a refractive index, d = thickness of a medium refractive index). 2. The anti-reflection film according to claim 1, wherein an irregular shape is formed on a surface of said hard coat layer which is in contact with said middle refractive index layer. 3. The anti-reflection film according to claim 1, wherein said hard coat layer is provided directly on said transparent substrate film or via a primer layer and / or an adhesive layer. 4. The method according to claim 1, wherein the middle refractive index layer comprises a thermosetting resin, and / or
Or 1 part by weight of ionizing radiation type resin and ZnO, T
iO ₂ , CeO ₂ , Sb ₂ O ₅ , SnO ₂ , ITO, Y
₂ O ₃ , La ₂ O ₃ , Al ₂ O ₃ , Hf ₂ O ₃ and Z
The antireflection film according to claim 1, comprising one or more ultra-fine particles 0.1 to 20 parts by weight selected from the group consisting of and rO _2. 5. The antireflection film according to claim 1, wherein the high refractive index layer and the low refractive index layer are layers provided by vacuum coating. 6. The low-refractive-index layer is formed by plasma CVD using a discharge of a source gas of an organosiloxane, so that 0.1 to 0.2 part of undecomposed carbon remains with respect to silicon. 2. The antireflection film according to 1. 7. The antireflection film according to claim 1, wherein an antifouling coating layer is further provided on said low refractive index layer. 8. A hard coat layer on a transparent substrate film,
A method for producing an antireflection film comprising forming a middle refractive index layer, a high refractive index layer and a low refractive index layer in this order, wherein an uncured hard coat layer is formed on a transparent substrate film, and a binder Forming an uncured medium refractive index layer composed of a composition containing fine particles having a refractive index higher than the refractive index of the binder on a transparent substrate film; The surface of the medium refractive index layer is shaped by laminating a mat-shaped shaping film 6 having fine irregularities, and the obtained laminate is cured by heat treatment and / or ionizing radiation treatment. Forming a medium refractive index layer having a smooth or fine uneven surface on a transparent substrate film by removing the shaping film from the above, a high refractive index layer on the medium refractive index layer, vacuum deposition or sputtering The high refractive index layer A method for producing an antireflection film, comprising a step of forming a low refractive index layer made of a SiOx layer thereon by vacuum deposition, sputtering or plasma CVD. 9. A hard coat layer on a transparent substrate film,
A method for producing an antireflection film, comprising forming a middle refractive index layer, a high refractive index layer, and a low refractive index layer in this order, comprising: Forming an uncured medium refractive index layer made of a composition containing fine particles having a refractive index higher than the refractive index of the binder; and forming the uncured medium refractive index layer on a transparent substrate film. A cured hard coat layer is laminated, and the obtained laminate is cured by heat treatment and / or ionizing radiation treatment, and the molded film is peeled and removed from the cured laminate to have a smooth or fine uneven surface. Forming a middle refractive index layer having on the transparent base material film, further forming a high refractive index layer on the middle refractive index layer by vacuum evaporation or sputtering, and forming a SiOx layer on the high refractive index layer. Sputter low refractive index layer Comprising the step of forming the ring or a plasma CVD, method of manufacturing the anti-reflection film. 10. A method for producing an antireflection film, comprising: forming a medium refractive index layer, a high refractive index layer, and a low refractive index layer on a transparent substrate film via a hard coat layer in order. Is coated and cured on a mirror-like or mat-like molding film, an uncured medium refractive index layer and an uncured hard coat layer containing a binder and fine particles having a refractive index higher than that of the binder. Forming a middle refractive index layer and a hard coat layer, and laminating an uncured surface coated with a reactive adhesive layer on a transparent substrate film and the cured middle refractive index layer. Curing the adhesive layer by heating and / or ionizing radiation treatment of the obtained laminate; removing the release film from the cured laminate to remove the release film; And hard coat layer A high refractive index layer is further formed on the medium refractive index layer by vacuum evaporation or sputtering, and a low refractive index layer composed of a SiOx layer is formed on the high refractive index layer by sputtering or plasma CVD. A method for producing an anti-reflection film, comprising a step of forming the film. 11. The antireflection film according to claim 1, wherein the high refractive index layer is formed of a sputtered ITO film, and has a surface resistance of 10 ³ Ω / □ or less. 12. The antireflection film according to claim 1, wherein the binder of the middle refractive index layer comprises a heat and / or ionizing radiation curable organosilicon compound. 13. The method according to claim 13, wherein the ultrafine particles of the medium refractive index layer are ZrO _2.
2. The anti-reflection film according to claim 1, comprising particles. To 14. transparent substrate film on, through the hard coat layer, middle refractive index layer, the high refractive index layer and a low refractive index layer is a reflection preventing film formed by formed in this order, SiO _x A low-refractive-index layer composed of a layer, a medium-refractive-index layer composed of a coating of a paint composed of a binder and ultrafine particles having a refractive index of 1.5 or more, and a high-refractive-index layer having conductivity. 2.20> refractive index of high refractive index layer> refractive index of medium refractive index layer> refractive index of low refractive index layer>
1. Ultra-fine particles of the middle refractive index layer are composed of ZrO ₂ particles,
Anti-reflection film. 15. The antireflection film according to claim 1, wherein said high refractive index layer has conductivity.