JP2003215303A - Antireflection article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an antireflection article which has reduced light reflection and the improvd visibility of display. <P>SOLUTION: In an antireflection article 10, fine irregularities 2 is provided on one surface of a transparent base material 1, and an antireflection film 3 which doesn't have fine irregularities like a dielectric multi-layered film and has a layer having a low refractive index and is constituted of a single layer or many layers is provided on the other surface. Such shape is given to the fine irregularities 2 that a period PMAX of top parts of the fine irregularities becomes equal to or shorter than a minimum wavelength λMIN in vacuum of the wavelength band of visible rays, and the sectional area occupancy ratio of the material part of the transparent base material in a horizontal section is continuously gradually reduced toward the top part from the bottom part of the fine irregularities. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a liquid crystal display, for example.
Used for various purposes such as window material of various display parts by spraying etc.
The present invention relates to an anti-reflection article that prevents surface reflection of light. [0002] 2. Description of the Related Art Various tables using a liquid crystal display or the like
Window materials or various optical elements placed on the front of the display
Often the reflection of light on the surface is a problem. For example, a liquid crystal display
Mobile phone using display (LCD) etc. for display
Then, display panel book by LCD etc. from water, dust, external force, etc.
To protect your body, put a transparent plastic on the front of the display panel.
A window material such as a backing plate is arranged and protected (Japanese Unexamined Patent Publication No.
No. 66859). However, we placed the window material
As a result, outside light is reflected on both the front and back, and the visibility of the display
Decreases. In addition, light from the display panel
Is reflected by the window material and returned to the display panel side.
The light use efficiency of the panel decreases, and the visibility decreases accordingly.
You. In addition, wasteful power consumption is necessary to compensate for this.
In mobile phones where low power consumption is important,
Is a problem. [0003] Conventionally, on the surface where light reflection is a problem,
For example, methods such as vapor deposition, sputtering, or coating
Therefore, a low-refractive-index layer single-layer film or a low-refractive-index layer and a high-refractive-index layer
Providing an anti-reflection film composed of a multilayer film with a layer
(Refer to JP-A 1-127852).
(Japanese Patent Application Laid-Open No. 2001-127852)
Information). Alternatively, as another anti-reflection treatment,
The surface is matted on a scale larger than the light wavelength, and the mirror of the uneven surface is
Diffuse light by surface reflection to reduce light (specular) reflection
Anti-glare technology (see JP-A-9-193332)
is there. This technology can improve anti-glare properties,
This prevents the rear view from appearing on the screen when looking straight ahead. [0004] However, evaporation,
Anti-reflection coating by sputtering etc. once or many times
Batch processing to form a thin film with controlled refractive index and thickness
Had to be done. On the other hand, the anti-glare technology has a light reflectance
Is not linked to an increase in light transmittance.
do not come. Therefore, the light use efficiency cannot be improved. example
For example, the display light utilization efficiency in the window material of the display unit is
You. Therefore, the applicant of the present invention has proposed a conventional anti-reflection
In order to solve the problems in the shutdown processing technology,
The repetition period disclosed in Japanese Patent Application Publication No. 70040 is smaller than the wavelength of light.
By providing the very fine irregularities below on the surface
Attempt to apply technology to reduce surface reflectance
Was. If the technology disclosed in this publication is described here,
For optical components such as lenses to reduce surface reflection,
Applying photoresist on the surface, exposing, developing, etc.
To form a resist pattern, and
By corroding the glass substrate, the surface of the optical component
This is a method of directly forming fine irregularities. However, in this method, work efficiency is poor, and
The required productivity (mass productivity) for industrial products cannot be obtained. There
Then, the applicant once applied such fine irregularities to the original (ma
After preparing on a glass substrate to be
-Used in production of compact disc production lines, etc.
Using a nickel electroforming method that has been
Duplicate and use this duplicate as the imprint (master)
To achieve mass production as an industrial product.
It worked. [0007] For example, in the case of the above-mentioned articles such as window materials,
Is the fine concave only on one of the front and back surfaces of the transparent substrate.
Light reflection is better when provided on both front and back surfaces than when provided with protrusions.
It can be prevented on both sides, and a better anti-reflection effect can be obtained.
You. However, in the case of such an article,
Surface) is exposed to the outside under the operating environment
So that it is easily scratched and
It is easy to accumulate in the recess. Therefore, the front side is fine
There is a problem that the anti-reflection effect due to unevenness is likely to decrease.
Was. For this reason, antireflection articles as window materials for display devices
Is not exposed to the outside when using anti-reflective articles.
On the back side (inside) of the transparent substrate
(Display device according to Japanese Patent Application No. 2001-185965)
Window material: not disclosed at the time of filing this patent). [0008] However, the anti-reflection effect due to the fine irregularities is not enough.
No matter what is excellent, it is easy for dirt, dust and dirt to adhere
Only the inner surface, such as the back side, excluding the outer surface exposed to the outside
The light reflection on the outer surface will still remain
There was a problem. That is, an object of the present invention is to provide an LCD or the like.
As optical components and optical elements such as window materials for various display units
Available, reduces surface reflection of light and improves light transmittance
To provide an improved anti-reflection article. [0010] Means for Solving the Problems Therefore, the above problems are solved.
The anti-reflective article according to the present invention has a
Anti-reflection fine irregularities are formed on the fine irregularities forming surface.
The other surface is composed of at least a low refractive index layer
Reflection made by forming an anti-reflection film without fine irregularities
The prevention article, wherein the fine irregularities are in a visible light wavelength band.
Is the minimum wavelength in vacuum_MIN, The most convex of the fine irregularities
The period in the part is P_MAXAnd when P_MAX≤λ_MIN And the fine irregularities are perpendicular to the direction of the irregularities.
Transparency in the cross section assuming that it was cut on the surface to be cut
The sectional area occupancy of the material portion of the base material is the most convex portion of the fine irregularities.
From the top to the most concave part
The configuration was such that it had unevenness. An antireflection article having such a structure is provided.
In the case where the light reflection on the surface of the article is
Anti-reflective coating on another surface that is prevented by
On the surface, light reflection is prevented by the antireflection film.
For this reason, when only one side is used to prevent reflection by fine irregularities
The antireflection performance is further improved as compared with. In addition, micro concave
In simple terms, convexity prevents light reflection.
On the surface of the material
When the irregularities are provided, the change in the refractive index between the surface and air is substantially reduced.
Abrupt and discontinuous because it can be gentle and continuous
Prevents light reflection, a phenomenon that occurs when the refractive index changes
Because. Moreover, the anti-reflection due to the fine irregularities is not
Even if it is convex, it has irregularities that are larger than the light wavelength
Anti-glare type that reduces light reflection by specular irregular reflection
No sudden change in refractive index at the interface between the article surface and air
The light reflectance is reduced because it is realized by summing
As a result, the light transmittance is improved. Of course, the surface with fine irregularities
The anti-reflection film formed on a different surface is also
It is not an antiglare that reduces light reflection. Therefore, light
The light transmittance can be improved as much as the reflectance is reduced. Follow
For example, an anti-reflection article is
When used for window materials, etc., improving the visibility of the display
In addition, the article can improve the use efficiency of the display light. [0013] DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described.
I do. [Outline] First, FIG.
FIG. 1 is a cross-sectional view illustrating one embodiment of an anti-sun article 10. Same figure
The anti-reflection article 10 illustrated in FIG.
To sheet-like), and the anti-reflection target surface is
Both front and back surfaces, the upper surface and the lower surface
This is a case of two planes parallel to. The anti-reflection article shown in the drawings exemplified here
For 10, the upper surface of these two drawings is the outer surface, and the lower surface is the lower surface.
The other surface is also called the inner surface. The outer surface is greasy, dusty,
This is the one that is easily stained. On the other hand, the inner surface is
On the side where dirt and dust are unlikely to adhere, such as inside the device.
Face. In FIG. 1, the inner surface of the transparent substrate 1
Fine irregularities 2 are formed for the purpose of preventing
An anti-reflection film 3 having no fine irregularities is formed on the outer surface of
It is an article of the composition made. The antireflection film 3 is a low refractive index layer
Single-layer film or multilayer film of low refractive index layer and high refractive index layer
This is an antireflection film according to a conventional method. Like this, on the inside
Is anti-reflective after anti-reflection
If you have fine irregularities on the outer surface that is easily scratched or dirty
Has been subjected to a conventional anti-reflection treatment that does not depend on the fine irregularities.
The anti-reflection function of both
Rather than only having an anti-reflection function due to fine irregularities,
Antireflection performance is further improved. Moreover, anti-reflection on the outer surface
Is more resistant to scratches and dirt
As a result, the antireflection effect is not easily reduced. The anti-reflection article 10 shown in FIG.
Means that the transparent substrate 1 is depicted as a single layer,
Is also good. For example, the antireflection article 10 illustrated in FIG.
As shown in FIG.
The transparent substrate 1 is transparent and has a different layer
Substrate body 1a and transparent fines having fine irregularities 2 on the surface
This is a configuration including the uneven layer 1b. [Fine unevenness] The fine unevenness 2 has an antireflection effect.
Has the following reasons. That is, the fine
Due to the irregularities 2, the transparent substrate 1 constituting the surface of the article and the outside
Abrupt and discontinuous refractive index changes with the field (air)
It is possible to change to a refractive index change that is gradually and gradually changing
Because. That is, the reflection of light is discontinuous at the material interface.
Because it is a phenomenon caused by a sudden change in the refractive index,
The refractive index change at the surface changes continuously and spatially
By doing so, light reflection on the article surface is reduced.
Because FIGS. 2 to 4 show the shape of the transparent substrate 1 formed on the surface thereof.
Of the refractive index distribution obtained by the fine irregularities 2
FIG. First, FIG.
Regarding the transparent substrate 1 provided on the surface, the transparent substrate 1
Occupies the space of Z ≦ 0, and the surface of the transparent substrate,
That is, the Z-axis direction is uneven on the XY plane at Z = 0.
This shows a state in which a number of fine irregularities 2 are arranged. In the present invention, the fine irregularities 2 are
, The period at the most convex portion 2t is P_MAXAnd
This P_MAXHowever, in a vacuum in the wavelength band of visible light,
Is the minimum wavelength_MINBecause it is as follows, the surface with fine unevenness
For the light that reaches the light, the medium (transparent substrate and air)
Even if there is a spatial distribution of the refractive index, it is the wavelength of interest
Since the distribution has the following size, the distribution is directly
Does not act on light, but acts as an average
I do. Therefore, the refractive index after averaging (effective refractive index)
Has a distribution that changes continuously as light progresses.
By doing so, the reflection of light can be prevented. In the present invention, the most convex portion 2t
Cycle P_MAXMeans between the most convex portions 2t of the adjacent fine irregularities 2
Distance is the largest of the
It is regularly arranged and has periodicity (adjacent fine irregularities
Although the distance between them may be the same, there is no periodicity (adjacent
(The distances between the fine irregularities are irregular). In FIG. 2, a transparent coordinate system is used as an orthogonal coordinate system.
The Z axis is set in the normal direction set on the envelope surface of
The X axis and the Y axis are set in a plane orthogonal to the X axis and the Y axis. Soshi
Now, light enters the transparent substrate from above the drawing,
Navigate the inside of the substrate and move the vicinity of the surface of the transparent substrate in the negative direction of the Z axis.
, And the Z-axis coordinate is just z
Assume that it exists. Then, for the light at Z = z here,
Means that the refractive index of the medium is such that the surface of the transparent substrate 1 has specific fine irregularities 2
Strictly speaking, X is perpendicular to the Z axis at Z = z.
In the Y plane (transverse section: horizontal section), the distribution f (x,
(y, z). That is, in the XY plane
The cross section of the transparent substrate 1 has a refractive index n_b(About 1.5
Degree), the other parts, specifically the part of air a, have a refractive index
n_a(= About 1.0) (see FIG. 3). However,
In some cases, for light, its wavelength (the
If the wavelength of the light is distributed, the minimum
Wavelength λ_MINShould be considered. Spatial scale smaller than)
The refractive index distribution of the tool acts as an average
As a result, the averaged effective refractive index is the XY plane.
, The refractive index distribution f (x, y, z) in the XY plane
Integral at [0024] (Equation 1) ## EQU1 ## As a result, the effective refractive index (n_ef)of
Distribution is a function n of z only_ef(Z) (see FIG. 4). Therefore, if the fine irregularities 2 are transparent,
The cross-sectional area of the convex portion of the substrate continuously increases toward the concave portion.
Transparent substrate (within XY plane)
The area ratio between the minute and the air part is continuously
Effective refractive index n_ef(Z) is the continuation of z
Function. On the other hand, the refractive index n₀From the medium, the refractive index n₁of
Consider the case where light enters the medium. Now, for simplicity, enter
Consider an angle of incidence θ = 0 ° (normal incidence). However, the incident angle is
It is the angle with respect to the normal of the launch surface. In this case, at the medium interface
Is independent of the polarization and the angle of incidence, and
[Equation 2] is obtained. [0028] (Equation 2) Therefore, the change of the (effective) refractive index in the Z direction
Is a continuous function in the Z direction (the way light travels).
Direction), two points separated by a small distance Δz, the refractive index at Z = z
n_ef(Z) is n₀, The refractive index n at Z = z + Δz
_ef(Z + Δz) is n₁, And when If Δz → 0, then n₁→ n₀ (From the definition of the continuous function)
From [Equation 2], R → 0 ## EQU1 ## Here, more strictly speaking, in the object
Is the wavelength in vacuum of λ and the refractive index of the object is n.
Λ / n, and generally to some extent less than λ
It will be small. However, when the object is air, the refractive index is n ≒ 1.
Therefore, it may be considered that λ / n ≒ λ. However, it is used for transparent substrates
Materials usually have a refractive index of around 1.5, so the refractive index n
_bWavelength in a transparent substrate (λ / n_b) Is about 0.7λ
You. Considering this point, in the portion of the fine irregularities 2,
Looking at the part on the air side (the concave part of the fine irregularities 2), P_MAX≤λ_MIN When the condition is satisfied, the refractive index is averaged.
The effect of reducing the reflectance can be expected. However, Λ_MIN/ N_b≤P_MAX≤λ_MIN In the case of (1), the transparent substrate portion (fine irregularities)
2), the refractive index averaging
The reflectivity reduction effect cannot be expected at least completely.
And But still, the contribution of the air
Therefore, it has an antireflection effect as a whole. And P_MAX≤λ_MIN/ N_b If the condition is satisfied, the air portion, the permeability
The period P_MAXBut smaller than the shortest wavelength
Condition is completely satisfied, so the refractive index is averaged.
The anti-reflection effect is more complete. Specifically, λ_MIN
Is 380 nm, the lower limit of the visible light wavelength band, n_bAssuming 1.5
Then λ_MIN/ N_bIs 250 nm, that is, P_MAXIs 2
The thickness may be set to 50 nm or less. In addition, with reference to FIG.
In the explanation, the light from above the drawing is taken up and explained
But also reflects light from below in the drawing according to the same principle
Has a preventive effect. Next, the shape of the fine irregularities 2 is
Assuming that it was cut along a plane (XY plane) orthogonal to the direction of the unevenness
Material of the transparent substrate in the cross section (horizontal cross section)
Whether the cross-sectional area occupancy of the part is the most convex part (top) of the fine irregularities
From the bottom to the bottom (valley bottom).
Go shape. For this purpose, there should be at least
It is only necessary that some of the sides have an oblique slope.
However, as shown in Fig. 5 (C) below,
Fine irregularities of a certain shape may be used. Particularly preferably, the most convex
Completely converges to 0 at the part and completely at the most concave part
The shape converges to 1. Specifically, for example, FIG.
(B) and a shape as shown in FIG. 5 (C). However,
5 (D) or at the most convex part as shown in FIG. 5 (E).
Has a shape that is asymptotically close to 0, or
If the shape approaches asymptotically, a certain effect can be obtained.
Can be If the shape of the fine irregularities satisfies such conditions,
Any shape is acceptable. For example, the vertical cross-sectional shape of each fine unevenness 2
Is a wave-like shape formed only by a curve such as a sine wave as shown in FIG.
Shape (see also FIG. 2), as shown in FIGS. 5 (B) and 5 (C)
The shape of only a straight line such as a triangle, or the shape shown in FIG.
Trapezoidal shape in which the most convex part of a triangle forms a flat surface
Shape, the most concave part between adjacent triangles as shown in FIG. 5 (E) is flat
And the like. However, FIG. 5 (D) and FIG. 5 (E)
As shown in the figure, the shape has a flat surface in the most convex part or the most concave part.
Is the flat surface of the most convex or concave portion, and the flat surface
The larger the percentage of the area occupied, the more the change in the effective refractive index
It becomes largely discontinuous. In that respect, performance is inferior.
You. However, even in this case, the most concave part
To continuously change the effective refractive index as going to the section
Can do it. Therefore, in terms of the antireflection performance,
The smaller the area ratio of the flat surface of the most concave portion, the better. The effective refractive index n_ef(Z) from the air
As a function of the Z direction into the transparent substrate, n_aTo n_bTo
In order to change continuously, it is necessary to use
In FIG. 5, the sectional area occupancy of the transparent substrate converges to 0.
(B) or a shape as shown in FIG.
Shape) and the cross-sectional area occupancy is continuously
A shape that converges to 1 is most preferred. Next, the horizontal cross-sectional shape of each fine unevenness is as follows:
Circular (eg Figure 2), elliptical, triangular, square, rectangular
Shapes, hexagons, and other polygons are optional. In addition, horizontal cut
The surface shape extends from the most convex part to the most concave part of the fine irregularities.
Need not be the same. Therefore, the three-dimensional shape of the fine irregularities
For example, the horizontal cross section is circular and the vertical cross section is
In the case of a square shape, the three-dimensional shape of the fine irregularities is a cone, a horizontal cross-sectional shape
Of small irregularities when the shape is circular and the vertical cross section is triangular
Body shape is oblique cone, horizontal cross-section is triangular, vertical cross-section
When the shape is an equilateral triangle, the three-dimensional shape of the fine unevenness is a triangular pyramid,
When the horizontal cross-section is square and the vertical cross-section is triangle
The three-dimensional shape of the fine irregularities becomes a quadrangular pyramid. The arrangement of the fine irregularities in the horizontal plane
Is a two-dimensional arrangement as illustrated in FIG.
As shown in the perspective view of FIG.
A one-dimensional arrangement may be used, and both effects can be obtained. However
However, in the case of a one-dimensional arrangement, the relationship with the amplitude direction of the light wave
The direction in which the antireflection effect is obtained and the direction in which
Out, anisotropy occurs. Therefore, the perspective view of FIG.
The two-dimensional arrangement as exemplified in the plan views of (B) and (C)
It is preferable that there is no directionality at all. The three-dimensional shapes of the individual fine irregularities are all the same.
The number may be one, but not necessarily the same. Also individual
When the fine irregularities 2 are two-dimensionally arranged, the cycle is
All may be the same in the fine irregularities, but they are not all the same
Is also good. The height H of the fine unevenness is determined by the desired reflection.
Reduction effect and the maximum visible light band incident on the transparent substrate surface.
Determined according to the large wavelength. For example, JP-A-50-700
No. 40 (especially FIG. 3), the reflectance and fine irregularities
When designing based on the relationship between the height of light and the wavelength of light, for example,
For example, the reflectance in the visible light band is 2% (half of that of untreated glass).
Min) if the goal is to reduce it below
Small height H_MINIs 0.2λ_{M AX}That is, H_MIN≧ 0.2λ_MAX Further, the reflectance in the visible light band is 0.5% or less.
If your goal is to reduce it down, H_MIN≧ 0.4λ_MAX It is preferable that Here, λ
_MAXIs the maximum wavelength in a vacuum in the visible light wavelength band.
You. As the height H of the fine irregularities increases from zero,
Although the emissivity decreases, it is high enough to satisfy the above inequality condition.
At that point, a significant effect can be obtained. Concrete
Specifically, for example, the maximum wavelength of the emission spectrum is λ_MAX
= 640 nm fluorescent light, then H_MIN≧ 0.
2λ_MAX= 128 nm. That is, H_MINIs 12
The thickness may be set to 8 nm or more. Also, the maximum wavelength of the spectrum
Is λ_MAX= 780 nm, consider H_MIN
≧ 0.2λ_MAX= 156 nm, ie, H_MINIs 156
nm or more. Also, the minimum height H_{M IN}And period P
_MAXThe minimum height H_MIN/ Period P_MAXThe ratio of
It is about 1/2 to 4/1. Here, the specific shape and size of the fine irregularities
In the example, the vertical section is sinusoidal and the horizontal section is
Many circular conical shapes are regularly arranged in two dimensions.
Is a set placed, and the period P_MAXIs 50-250n
m, minimum height H_MINWith the period P _MAX1.5 times
And so on. [Transparent Substrate] The transparent substrate 1 has transparency.
And those having mechanical strength are preferred. For example, transparent
As a material of the base material, poly (meth) acrylate,
Ethyl poly (meth) acrylate, (meth) acrylate
Acrylic such as butyl-butyl (meth) acrylate copolymer
Resin (however, (meth) acryl is acrylic or
Means tacryl. ], Polypropylene, polymethyl
Pentene, cyclic olefin polymer (typically Norbo
There is a linen resin, etc., for example, Nippon Zeon Co., Ltd.
Product name "Zeonor" and JSR Corporation "Art"
Resin), polycarbonate
Nate resin, polyethylene terephthalate, polyethylene
Thermoplastic polyester resin such as naphthalate, polya
Amide resin, polystyrene, acrylonitrile-styrene
Copolymer, polyether sulfone, polysulfone,
Cellulosic resin, vinyl chloride resin, polyether ether
Thermoplastic resin such as terketone, polyurethane, or
Glass (including ceramics) and the like. The shape of the transparent substrate is suitable for use in antireflection articles.
There can be more various shapes. For example, as shown in FIG.
It is a flat plate as described above. In the case of a flat plate, flexibility is increased.
There may also be a sheet shape having the same. In other words, the aforementioned mechanical strength
Is not limited to rigidity. Note that a flat
In this case, the anti-reflection surface is usually the front and back, but it is not limited to this.
Not determined. The transparent substrate may be a three-dimensional three-dimensional object or the like. One
In other words, the shape of the antireflection article may be a three-dimensional three-dimensional object.
In addition, for example, in the case of the window material of the display unit, the antireflection surface
The plate is flat, but the ribs
And the like having a shape for attaching window materials. In addition,
Specific examples of the thickness when the bright base material is flat
For applications such as window materials, the thickness is usually about 0.5 to 2 mm. What
The anti-reflection surface is a flat surface due to the fine irregularities.
However, the present invention is not limited to this. Also anti-reflective
The film formation surface may be flat or curved. Incidentally, the fine unevenness 2 is a part of the transparent substrate 1.
A transparent substrate including the fine irregularities 2
Is fine, like the anti-reflection article 10 illustrated in FIG.
As a continuous object made of the same material including
1B, the anti-reflection article 10 illustrated in FIG.
As described above, the transparent substrate 1 is placed in a portion (fine
The uneven layer 1b) and the portion not including the fine unevenness (the transparent base material)
For example, as a configuration in which two layers of
Is also good. In the former case, for example, a transparent base made of resin
Injection molding makes transparent substrates fine, including fine irregularities
It can be formed by a method of forming at once with unevenness. Ma
In the latter case, for example, a glass
Or a transparent substrate made of resin
Curing of ionizing radiation curable resin etc. on the desired surface of bright substrate
2P method (Photo-polymeriza)
at the same time as the shaping of the layer with fine irregularities
Can be formed. Also, injection molding method
But insert molding, or two-color molding if all resin
It can be formed by a method. Note that these exemplary methods are
Displacement, uneven shape for fine uneven shaping was previously formed
Use (shaping) mold. [Method of Manufacturing Mold for Forming Fine Asperities]
It is used for shaping (forming) fine irregularities on a transparent substrate.
The type obtained will be described. Fine irregularities are already tangible and transparent
Substrate material (transparent substrate body), directly formed on each one
(Japanese Patent Application Laid-Open No. 50-70040 described above).
Reference). In this method, the anti-reflective article is a single item
There is no problem in the case where small-scale production is sufficient. I
However, anti-reflective materials that require mass production as industrial products
In the case of products, it takes time to manufacture and the cost is high.
U. Therefore, considering industrial productivity and cost,
Make a mold and shape fine irregularities with this shaping mold
Is preferred. Further, as the shaping mold, the fine uneven shape is most preferable.
Do not use the prototype originally formed, once from the prototype, or
Duplicate produced through duplication process by molding and reversing at least twice
It is preferable to use a mold. In other words, first the prototype
(This is also called the original version or mother version)
Later, one or more replication operations to make a duplicate from this prototype
Performed twice or more times, and as a result,
This is also called this version or master version)
And use it. By using such a shaping mold,
This is a method excellent in industrial productivity, cost, and the like. For example,
Even if this version is damaged, can this version be easily reproduced?
It is. As a prototype which is a base of a shaping mold, a necessary fine
As long as fine irregularities are formed, the manufacturing method
There are basically no particular restrictions on productivity, cost, etc.
An appropriate one may be used with due consideration. Prototype fabrication is fine
Step of first forming an uneven shape for shaping the fine unevenness 2
The fine processing technology in the semiconductor field, etc.
Where light (including electron beam) is used for pattern formation
A so-called exposure method can be used. However, in the case of semiconductors, the uneven shape
As for the shape, the side surface is usually a vertical surface, and as in the present invention, it
In the present invention, it is not necessary to perform
And fine processing. The fine processing technology corresponding to the exposure method includes:
For example, an electron beam drawing method can be used. In this method,
After forming a resist layer on a glass substrate,
The resist layer is exposed and developed by a drawing method to
To form a resist pattern layer. After this, a corrosion mask
Dry the glass substrate using the resist pattern layer
Corrosion due to etching, etc.
Fine irregularities are formed. At this time, when etching,
Then, a slope is formed by etching. In addition, glass base
The resist pattern layer itself as a corrosion mask during plate corrosion
May be used directly, but a deep uneven shape with a slope
For this purpose, it is preferable to use chrome or the like on a glass substrate.
After forming a metal layer, a resist film is formed
A turn layer is obtained.
What was used as a metal pattern layer was replaced with a corrosion mask
It is good to use it. In forming a pattern on a resist film,
As another exposure method for electron beam lithography, laser lithography
Also available. In laser writing, holograms and diffraction gratings
Laser interferometry, which is used for manufacturing
You. In the case of a diffraction grating, it is a one-dimensional arrangement, but the angle is
If multiple exposures are changed, a two-dimensional arrangement is also possible. However
However, in laser interferometry, the fine irregularities obtained are usually regular
In the electron beam lithography method, a predetermined pattern
Turn information is stored as digital data in a storage device
In accordance with the drawing pattern information, the O
N, OFF, or intensity is modulated. Therefore, rule arrangement
Besides, irregular arrangement is also possible. Also, laser drawing
The drawing method and the electron beam drawing method each have advantages and disadvantages.
Considering the specifications, objectives, productivity, etc.,
Select an item. Next, the above prototype is used as a shaping mold.
As a method for producing a replication mold, a known method, for example,
Perform plating of metal such as nickel on the prototype and peel off the plating layer.
If it is stripped, a metal replica can be made (electroforming). Some
Is a plating of this duplicate mold again
Through many or more duplication operations such as
A shaping mold may be manufactured. In addition, the excipient used in the photopolymerization method is used.
The shape of the shape is plate, sheet, block, etc.
Possible, appropriately selected according to the shape, application, etc. of the antireflective article
Just do it. The shaping mold is made of a metal such as nickel.
May be used, but use resin products such as silicone resin
You may. For example, a continuous sheet-like sheet made of resin
Is also a possible shaping type. As described above, the transparent base material is formed by using the shaping mold.
On the other hand, as a specific method of forming (replicating) fine irregularities
Are, for example, hot pressing (embossing), injection molding,
2P method (Photo-polymerization)
Method), known replication methods such as the sol-gel method, or fine irregularities
Various methods such as laminating method of shaping sheet, transferring method of fine uneven layer
Seeding method, application of anti-reflective article, material of transparent substrate, etc.
May be appropriately selected according to the conditions. Among them, the tangible transparent base material
The method of forming fine irregularities is hot pressing (embossing).
Method), 2P method, sol-gel method, lamination of fine irregular shaped sheet
And a transfer method of a fine uneven layer. This
In the hot pressing method (embossing method), a transparent substrate is generally heated.
It can exhibit plastically deformable state such as plastic resin
It is applied when it is made of a material such as a resin. On the other hand, 2P
Method, laminating method of fine irregular shaped sheet (or plate),
In the transfer method of the fine uneven layer, the transparent substrate is made of inorganic material such as glass.
It is a method that can be applied even when it consists of Also, Solge
The transparent method uses a heat-resistant inorganic material such as glass
This is a method that can be applied when it consists of The sol-gel method (JP-A-6-64907)
And the like) as a thickener with metal alkoxide, etc.
A composition containing polyethylene glycol or the like is applied,
While the metal is soft to shape the irregularities, and then
After final drying and heat treatment, as an inorganic coating film
This is a method for forming fine irregularities. In addition, fine irregularities
A sheet (or board) is a sheet or board made of resin
Fine irregularities have already been shaped by using a shaping mold, etc.
Things. The resin is listed as a material for the transparent substrate
Resin or the like can be used. The irregular shaped sheet (or plate)
Is attached to the transparent substrate by an adhesive or heat fusion. The method for transferring the fine uneven layer is based on
Transfer sheet with a transfer layer laminated on
Transfer on the front side (that is, the transfer sheet on the side of the support sheet
Transfer surface with a fine uneven layer in which fine unevenness is provided in advance on the layer surface)
And transfer the fine uneven layer to the transparent substrate by transfer.
To form a fine uneven layer on a transparent substrate.
You. For this reason, the support sheet of the transfer sheet is
On the side surface, fine irregularities with an irregular shape reverse to the target fine irregularities
Use a sheet provided with. In addition, the support sheet
Uses the above-mentioned fine irregular shaped sheet or the like. Also support
The fine uneven layer on the body sheet is made of thermoplastic resin such as acrylic resin.
Resins, thermosetting resins such as urethane resins, ultraviolet rays and electrons
Ionizing radiation curable resins such as acrylates that cure with radiation
For example, by applying a coating liquid made of a transparent resin such as Next, the transparent base material is simultaneously formed at the time of molding.
In addition to the injection molding method, the 2P method
And the like. In the injection molding method, fine irregularities are formed on the mold surface.
Using the injection mold that is provided, fine irregularities are applied to the injection molding method
Therefore, it is formed. According to this method, the resin is used for transparency.
The bright substrate itself and the fine irregularities can be formed simultaneously by molding.
Since it is possible, this method is extremely excellent in mass productivity. Injection
In order to provide fine irregularities for forming fine irregularities on the mold,
By mounting the shaping mold obtained as described above on the mold surface, etc.
good. In the 2P method, the transparent substrate itself is fine.
This is a method of forming irregularities at the same time. Further, the transparent substrate is formed at the same time when the transparent substrate itself is formed.
As a method for forming fine irregularities, a transparent substrate is made of glass.
In some cases, glass can be plastically deformed by heating
It is possible to apply a hot pressing method
Fine irregularities may be formed at the same time as the molding of. Note that among the various forming methods described above,
1 (B), the transparent substrate 1 and the fine irregularities 2 are integrated.
In the case of the hot structure, hot press method (embossing method), injection molding
Method, 2P method, etc., and as shown in FIG.
A transparent base having fine irregularities 2 on its surface
The structure in which the fine unevenness layer 1b is laminated is obtained by an injection molding method.
(Two-color molding method of the main body and the uneven portion), 2P method, sol-gel
Method, laminating method of fine irregular shaped sheet (or plate),
It is obtained in the case of a transfer method of a fine uneven layer or the like. Further, the fine uneven layer formed by the 2P method, the transfer method, etc.
When formed as a fat layer, the resin must be transparent.
There is no particular limitation, but in order to make it hard to
Thermosetting resin such as urethane resin, epoxy resin, etc.
Resins, acrylate-based ionizing radiation-curable resins, etc. are preferred.
Good. Further, the fine irregularities are formed on the transparent base material main body.
When forming as an uneven layer, the transparent substrate body and the fine concave
If necessary, an adhesive layer or the like may be interposed between the convex layers.
good. The adhesive layer may be a known adhesive or a silane coupling agent.
And the like. [Anti-Reflection Film] The anti-reflection film 3 is an anti-reflection film.
The principle does not depend on the fine irregularities unique to the present invention as described above,
It is a layer by various conventionally known methods. However, conventionally known
Even if it is a method, the surface is scaled at the scale of light wavelength or more.
With irregularities on the matte surface,
Anti-glare technology that diffuses light to reduce light (specular) reflection
Excluding the light reflection prevention method. It is for the purpose of the present invention
Is to improve light transmittance as well as to prevent light reflection.
Anti-reflection with anti-glare technology reduces light transmittance accordingly
Because you do. Therefore, as a specific example of the antireflection film,
Has at least a low refractive index layer and is composed of a single layer or multiple layers
It is a film to be performed. Single layer low refractive index as anti-reflective coating
Although only a layer can provide a corresponding anti-reflection effect,
The low refractive index layer and the high refractive index layer
The outermost layer is a low-refractive-index layer.
And a dielectric multilayer film for obtaining a light reflection preventing effect. Low refractive index layer and high refractive index in dielectric multilayer film
Typically, a metal oxide thin film is used for each index layer.
Is done. For example, a high refractive index layer usually has a refractive index of 1.5.
The above is used (2.3 to 2.7), and ZnO
(Refractive index: 1.90, hereinafter the numerical value in parentheses indicates the refractive index),
TiO_Two(2.3-2.7), CeO_Two(1.95), S
b_TwoO_Five(1.71), SnO_Two(1.997), In_TwoO
_Three(2.00), Y_TwoO_Three(1.87), La_TwoO_Three(1.
95), Al_TwoO_Three(1.63), HfO_Two(2.0
0), ZrO_Two(2.05), ITO [Indium tin
Oxide] (1.95) and the like. This
Among them, the refractive index is 1.7 particularly at the point of high refractive index.
Metal oxides of from 8 to 2.4 are preferred.
O, TiO_Two, SnO_Two, In_TwoO_Three, ZrO_TwoAnd this
These mixed oxides are preferred. On the other hand, low refractive index layers
For example, those having a refractive index of 1.42 to 1.51 are used.
And SiO_Two, SiO, SiO_x, (However, x <2),
A metal oxide composed of chill group-containing silica or the like is used.
In addition, methyl group-containing silica is, for example, hexamethyl
Disiloxane (HMDSO), tetramethyldisiloxa
(Silicone) containing methyl group such as TMDSO
Formed by a plasma CVD method using a compound as a source gas.
(See JP-A-2000-338307).
See). And a low refractive index layer made of these metal oxides
And high refractive index layer, sputtering method, plasma CVD
It is formed by a known thin film forming method such as a method. High refractive index layer and low refractive index in dielectric multilayer film
Specific examples of the combination of the refractive index layer, for example, a high refractive index layer
Using an ITO film (refractive index 2.002) for the low refractive index layer
SiO_TwoUsing a film (refractive index: 1.452), transparent substrate side
From the ITO film (thickness 25 nm) / SiO_TwoMembrane (thick
25 nm) / ITO film (85 nm thick) / SiO_Twofilm
(Having a thickness of 92 nm) and four layers. In addition, this
These films can be formed by a sputtering method. Further, another specific example of the dielectric multilayer film will be described.
For example, for example, an ITO film (having a thickness of 25
nm) / SiO_TwoFilm (thickness 25 nm) / ITO film (thickness
85 nm) / Silica film (95 nm thick)
It is a layer film. In addition, this silica film is formed by a plasma CVD method.
The other is formed by a sputtering method. Further, as the antireflection film, magnesium fluoride
Thin single layer with low refractive index material such as
Film or powder of these low refractive index substances
-A coating film of an anti-reflective paint made into a dispersed paint in
You. It should be noted that an anti-reflection film should be provided on a transparent substrate.
At this time, a hard core for increasing the surface strength of the anti-reflection film is used.
Primer layer to increase adhesion to transparent substrates and transparent substrates
May be used in combination as appropriate. Hard coat layer is anti-reflective coating
It is preferable to provide between the transparent base material in terms of antireflection
You. On the other hand, the primer layer is between the antireflection film and the transparent substrate.
When a hard coat layer is also provided,
Between coat layer and transparent substrate, anti-reflective coating and hard coat layer
It is provided between or at both positions. As the hard coat layer, depending on the application,
Known ones may be used. For example, as a hard coat layer
Is a thermosetting resin such as urethane resin and epoxy resin,
Ionizing radiations such as acrylates that cure with external or electron beams
Formed as a cross-linked cured product of a curable resin such as a curable resin
be able to. [Use of antireflection article] Antireflection article of the present invention
An article is first shaped as a film (or sheet).
G), plate, three-dimensional shape, etc. are arbitrary, and the use is particularly limited.
Not something. However, fine irregularities for anti-reflection
Be careful about dirt and scratches
Good. Therefore, the surface on which the fine unevenness is formed is preferably on the outer surface.
Can be used on the inner side without being exposed, and one anti-reflection coating
The use which can be used by making the side the outer surface side is preferable. In addition,
The applications to which the present invention can be applied include the following applications.
It is not limited. For example, a table in various devices such as a cellular phone
It is the window material of the indicator. In these displays, display such as LCD
On the front of the panel, a resin window material that became a plate or molded product
Be placed. For anti-reflective articles as window material,
As an anti-reflection film, forming the fine irregularities unique to the present invention on the inner surface side
Good face. The display unit is a display panel such as an LCD.
In addition to mechanical analog meters such as watches.
The display may be performed by any mechanical means such as these.
But it's fine. In addition, although the window material has a flat shape,
Some have projections and the like around from the viewpoint of design. A device having a display unit with a window as described above
In addition to mobile phones and watches, personal computers
PDA or personal digital assistant such as computer, electronic notebook,
Desk or CD player, DVD player, MD player
Various portable types such as layers and semiconductor memory type music players
Music player, video tape recorder, IC recorder
Coders, video cameras, digital cameras, label pudding
Electronic devices such as rice cookers, electric rice cookers, electronic pots,
There are electric products such as a rinsing machine. Further, a film (or sheet) or a plate
For anti-reflective articles, use for transparent touch panels, etc.
Transparent substrates such as transparent electrode films and transparent plates.
You. Transparent touch panel adds input function to display
Although it is a product, display on LCD, CRT, etc. on the product assembly
Since it is assembled as a separate part from the panel,
Air gaps remain between the bright touch panels, causing light reflection. There
The transparent base material that forms the back side of the transparent touch panel
Has fine irregularities peculiar to the present invention on its back (inner) side.
Anti-reflective article with an anti-reflective coating on the front side (outer surface)
Then, light reflection can be prevented. The transparent touch panel is, for example, an electronic
PDAs such as notebooks or portable information terminals (devices), or
Car navigation system, POS (point of sale
Terminal), portable order entry terminal, ATM (cash automatic
Deposit payment machine), facsimile, fixed telephone terminal, mobile
Phones, digital cameras, video cameras, personal computers,
Display for socon, television receiver, for television
Monitor displays, ticket vending machines, measuring instruments, calculators, electronics
Electronic devices such as musical instruments, copiers, ECRs (cash register machines), etc.
Used for office equipment or electrical products such as washing machines and microwave ovens.
Used. The use of the antireflection article of the present invention
Various optical elements are also included. [0083] The present invention will be described in more detail with reference to the following examples. [Embodiment 1] Reflection having a configuration as shown in FIG.
The prevention article 10 was produced as follows. Shapes fine irregularities
Glass substrate with a thickness of 3mm in order to make a shaping mold
Photosensitive resin (Sipley)
Co. , Inc., Inc. Product name "Micropost
  S1805 ") to form a resist layer having a thickness of 600 nm
And an argon ion laser
The operation of exposing the light from two directions at an incident angle of 50 °
This was performed twice while rotating the lath substrate by 90 degrees. Then develop
Liquid (manufactured by Sipley Co., Inc., trade name "D
Develop the resist layer with "eveloperCONC")
By doing so, the laser with the desired fine irregularities formed
An original plate (mother) consisting of a glass substrate
Plate). Next, from this mother plate, an electroplating method was applied.
Therefore, the mass of the nickel-plated plate having a thickness of 80 μm is
The slab was prepared as a shaping mold. On the other hand, the substrate body 1a having a thickness of 80 μm
Front side of triacetyl cellulose resin (TAC) film
Antireflection film 3 made of a dielectric multilayer film
Was formed. The antireflection film 3 is made of an oxide
Ion film (thickness 100 nm) / ITO film (thickness 40 nm)
/ Three-layer silicon oxide film (80 nm thick)
It was formed by a sputtering method. Then, the surface to be the back side of the base material body 1a
In contrast, using ultraviolet-curing ionizing radiation-curable resin
The fine uneven layer 1b having the fine unevenness 2 is formed by the 2P method.
Formed. Specifically, ionizing radiation is applied to the back surface of the substrate body.
The curable resin was potted (coating amount converted: 2 g /
m^Two) After that, press the above-mentioned shaping mold from above the resin mass
With the resin spread over the sheet surface and pressed
In the condition, the substrate is irradiated with ultraviolet rays from the
After the fat is cured by photopolymerization, the shaping mold is peeled off,
A fine uneven layer was formed. As described above, sheet-like reflection
A protected article was obtained. Then, the fine unevenness 2 of the antireflection article
Is the height H by observation with an atomic force microscope._MINIs 20
0 nm, period P_MAXHas a shape of 300 nm, as shown in FIG.
With a large number of fine irregularities regularly arranged in a square lattice shape vertically and horizontally
there were. [Comparative Example 1]
Example 1 was the same as Example 1 except that the formation of
Similarly, an antireflection article was produced. [Evaluation of Performance] Reflection of Examples and Comparative Examples
For the prevention products, the light transmittance in the visible light band (
And the reflectance (luminous reflectance) were measured. as a result,
In the antireflection article of Example 1, the transmittance was 98.4%,
The emissivity was 0.6%. In contrast, conventional anti-reflection
In the antireflection article of Comparative Example 1 having only the stop film, the transmittance was 95.
2%, reflectance 4.0%, both performances inferior to Example 1.
Was. The antireflection article of Example 1 was antireflection.
Light is not diffused and the transmittance has been improved.
Was done. [0091] According to the antireflection article of the present invention, the article table
Surface light reflection is prevented by both fine irregularities and anti-reflective coating
When only one side is anti-reflective with fine irregularities
In comparison, the antireflection performance is further improved. Moreover, those
As a result, the light transmittance improves as much as the light reflectivity decreases.
Therefore, when used as a window material for a display unit such as a display,
Improve the visibility of the display and use the display light
It is an article that can raise the rate.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view illustrating an antireflection article of the present invention in two embodiments. FIG. 2 is a diagram (part 1) for conceptually explaining the distribution of the effective refractive index obtained by fine irregularities. FIG. 3 is a diagram (part 2) for conceptually explaining the distribution of the effective refractive index obtained by fine irregularities. FIG. 4 is a diagram (part 3) for conceptually explaining the distribution of the effective refractive index obtained by fine irregularities. FIG. 5 is a cross-sectional view illustrating some (vertical) cross-sectional shapes of fine unevenness. FIG. 6 is a cross-sectional view illustrating some arrangements of fine irregularities in a horizontal plane. DESCRIPTION OF SYMBOLS 1 Transparent substrate 1a Transparent substrate main body 1b Fine unevenness layer 2 Fine unevenness 2t Most convex portion 3 (of fine unevenness 2) Antireflection film 10 Antireflection article n Refractive index n _a Refractive index (air) n _b Refractive index (transparent substrate) n ₀ Refractive index n ₁ Refractive index n _ef (Z) Effective refractive index H _MIN Minimum height of fine irregularities P _MAX Period R Reflectivity λ _MIN Minimum wavelength λ _MAX maximum wavelength

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Claims (1)

Claims: 1. A surface of a transparent substrate having fine irregularities for antireflection formed thereon, and at least a low refractive index layer having no such fine irregularities on a surface different from the surface on which the fine irregularities are formed. An anti-reflection article comprising an anti-reflection film formed of a single layer or a multilayer, wherein the fine irregularities have a minimum wavelength in a vacuum of a visible light wavelength band in a vacuum of λ _MIN . The period at the most convex part of the fine irregularities is P
_{When MAX} , the relationship of P _MAX ≦ λ _{MIN is} satisfied, and the cutting of the material portion of the transparent base material in the cross section when it is assumed that the fine unevenness is cut on a surface orthogonal to the uneven direction. An antireflection article wherein the area occupancy is such that the area occupancy increases gradually from the most convex portion to the most concave portion of the fine irregularities.