JP2012037670A - Manufacturing method of mold for producing antireflection film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antireflection film with excellent mechanical strength, sticking resistance, and molding performance, with respect to crack or the like of an edge of a convex part of a microscopic irregular pattern in an antireflection layer.SOLUTION: An antireflection film comprises a light-transmissive substrate and an antireflection layer formed on the light-transmissive substrate and having an irregular shape on a surface formed with a period less than or equal to the wavelength of a visible light region. The antireflection layer has a bottom part formed on the light-transmissive substrate and microscopic irregularities including the irregular shape formed on the bottom part. A convex part of the microscopic irregularities includes a main part with a frustum shape rising in a tapered form to the light-transmissive substrate and an end part with a curved surface structure formed so as to cover a top plane of the main part.

Description

  The present invention relates to an antireflection film used for flat displays and the like, a mold used for manufacturing the antireflection film, and a manufacturing method thereof.

  In recent years, with the development of personal computers, in particular with the development of portable personal computers, the demand for flat panel displays has increased. Recently, the penetration rate of flat-panel televisions for home use is also increasing, and the market for flat panel displays is expanding. In addition, flat panel displays that have become widespread in recent years tend to have larger screens, and particularly for home-use liquid crystal television sets. As such a flat panel display, various display methods such as a liquid crystal display, a plasma display, and an organic EL display are adopted, and the display quality of the image is improved in any display. The purposeful research is done every day. In particular, the development of antireflection technology for the purpose of improving display quality has become one of the important technical issues common to each type of display.

  Conventionally, as such an antireflection technique, for example, a technique of obtaining an antireflection effect effective for light of a single wavelength by forming a thin film made of a low refractive index material on the surface as a single layer, A technique for obtaining an antireflection effect for light in a wider wavelength range by forming a plurality of layers in which thin films of a low refractive index substance and a high refractive index substance are alternately formed has been used. Among them, the technique using a plurality of layers has been useful in that it can obtain an antireflection effect even for light having a wider wavelength range by increasing the number of layers. It has been put to practical use.

However, there are some problems in such a technique using a plurality of layers. First, in order to form a plurality of layers having an excellent antireflection effect, it is usually necessary to form a film using a vacuum deposition method or the like, and therefore it is necessary to provide a vacuum facility when manufacturing a display device. There was a problem of becoming. Further, in the vacuum deposition method, since the film formation time is generally long, a problem of manufacturing efficiency has been pointed out. In particular, for displays used in environments with very strong ambient light, a higher antireflection function is required, so the number of layers that make up multiple layers must be increased, resulting in significant manufacturing costs. There was a problem of becoming high.
Second, even from a technical point of view, the antireflection technology using a plurality of layers makes use of the light interference phenomenon, so the antireflection effect greatly affects the incident angle and wavelength of light. There is a problem that it is difficult to obtain the same antireflection effect.

In order to deal with such problems, Patent Documents 1 to 6 disclose techniques for preventing reflection by forming on the surface a fine uneven pattern in which the uneven period is controlled to be equal to or less than the wavelength of visible light. Such a method uses the principle of a so-called moth-eye structure, and continuously changes the refractive index for light incident on the substrate, thereby eliminating the discontinuous interface of the refractive index. This prevents light reflection. Such antireflection technology using a moth-eye structure is useful in that it can prevent reflection of light in a wide wavelength range by a simple method, and its practical application is also being studied in the field of displays. .
In addition, as a fine uneven | corrugated pattern used for the said moth-eye structure, the shape where the front-end | tip is sharp in the shape containing cones and cylinders, such as a cone shape and a quadrangular pyramid shape, is common.

  However, when a fine concavo-convex pattern with a sharp tip such as a cone having a conical shape is used as the moth-eye structure, there is a problem that the fine concavo-convex pattern is liable to break because the tip is thin, In the case of a shape including a shape, there is a problem that the die-cutting property of the fine uneven pattern is not good. Further, in the case of a cylindrical shape, when a liquid having a large surface tension enters the moth-eye structure and evaporates, a phenomenon in which adjacent structures contact or stick to each other (sticking) easily occurs. When sticking occurs in 50% or more of the structure, there arises a problem that haze increases due to a decrease in the antireflection function and an increase in diffused light.

  On the other hand, the moth-eye structure is generally manufactured by using a mold (stamper or mold) having a shape obtained by inverting the fine uneven shape and transferring the uneven shape to an arbitrary resin layer. Is. Therefore, as a method for producing an antireflection film using a moth-eye structure (hereinafter sometimes referred to as “moth-eye type antireflection film”), after forming a resin layer made of a curable resin on a substrate, A method of forming a moth-eye structure on the surface of the resin layer using the mold as described above and further curing the resin layer can be used. Such a production method has an advantage that an antireflection film can be continuously produced by a simple method and high production efficiency.

  By the way, the moth-eye structure is generally manufactured by transferring the concave / convex mold to an arbitrary resin layer using a stamper (mold or mold) having a shape obtained by inverting the fine concave / convex shape. As a matter of fact, as the stamper, a stamper formed by a laser interference method (for example, see Patent Documents 1 to 3) or a stamper formed by an anodic oxidation method (for example, Patent Documents 4 to 7). Reference) is used. Among them, the anodic oxidation method has advantages in that the positions where the concave portions are formed can be made random, and the concave portions having a uniform shape over a large area can be formed. Those formed by the anodic oxidation method have come to be widely used, and researches with an eye toward improving the recess formation technology are still actively conducted.

  In a mold manufactured by such an anodic oxidation method, the opening of the formed recess is likely to have a vertical shape, and when the uneven shape is formed on the resin layer using the mold, a resin is formed in the recess. There is a problem that the layer is difficult to enter.

JP-T-2001-517319 JP 2004-205990 A JP 2004-287238 A JP 2001-272505 A JP 2002-286906 A International Publication No. 2006/059686 Pamphlet Japanese Patent No. 4265729

  The present invention has been made in view of the above problems, and provides an antireflection film excellent in mechanical strength, sticking resistance, and die-cutting properties against cracks at the tips of convex portions of a fine uneven pattern in an antireflection layer. Is the main purpose. In addition, the present invention provides an antireflection film-manufacturing mold capable of obtaining an antireflection film-manufacturing mold that allows easy entry of a resin layer into a fine hole and easy demolding when a fine concavo-convex pattern is formed into a resin layer. The main object is to provide a mold manufacturing method.

  In order to achieve the above object, the present inventors have conducted intensive research, and as a result, when a fine concavo-convex pattern having a flat convex tip, such as a truncated cone shape such as a truncated cone, is used as a moth-eye structure, an antireflection layer It was found that the problem such as cracking of the tip of the fine uneven pattern in can be solved, and further, the die-cutting property can be improved, but the antireflection function is lowered when the tip of the convex part is flat. There is a possibility that. Therefore, by adopting a moth-eye structure with a fine concavo-convex pattern having a shape with a curvature at the tip of the convex part, the mechanical strength, sticking resistance and die-cutting properties against cracks etc. of the convex part of the fine concavo-convex pattern in the antireflection layer are improved. And the antireflection function is not deteriorated. The present invention has been made based on such knowledge.

  That is, the present invention is an antireflection film comprising a light-transmitting substrate and an antireflection layer having a concavo-convex shape formed on the surface and having a period equal to or less than the wavelength of the visible light region. The antireflection layer has a base portion formed on the light-transmitting substrate, a fine unevenness formed on the base portion and having the uneven shape, and a convex portion in the fine unevenness. Is composed of a frustum-shaped main body that rises in a tapered shape with respect to the light-transmitting substrate, and a tip having a curved structure formed so as to cover the top surface of the main body. An antireflection film is provided.

  According to the present invention, the convex portion in the fine irregularities of the antireflection layer has a curved surface structure formed so as to cover the top surface of the frustum-shaped main body portion that rises in a tapered shape with respect to the light-transmitting substrate. Therefore, the antireflection film can have an excellent antireflection function and excellent mechanical strength, sticking resistance and die-cutting property against cracks at the tips of the convex portions of the fine unevenness pattern in the antireflection layer. . Moreover, since the convex part in the said fine unevenness | corrugation has the said frustum-shaped main-body part, it can be set as the antireflection film which is easy to come off from the metal mold | die used when manufacturing an antireflection film.

  In the said invention, it is preferable that the taper angle with respect to the said transparent substrate in the longitudinal cross-section of the said main-body part exists in the range of 50 degrees-87 degrees. This is because it can be more easily removed from the mold used for manufacturing the antireflection film.

  In the said invention, it is preferable that the height of the said main-body part exists in the range of 60 nm-1400 nm. This is because the antireflection layer can have a good antireflection function.

  The present invention also provides an anodic oxidation step of forming a metal oxide film having a plurality of fine holes on the surface of the metal substrate by an anodic oxidation method using a metal substrate, and etching the metal oxide film to form the fine holes. A first etching step for forming a tapered shape in the opening of the second etching step, and a second etching step for expanding the diameter of the micropores by etching the metal oxide film at an etching rate higher than the etching rate of the first etching step. The method for producing a mold for producing an antireflective film is provided, which has a fine hole forming step of forming a plurality of fine holes on the surface of the metal substrate by sequentially repeating the above.

  According to the present invention, since the first etching step is included, a tapered shape can be formed in the opening portion of the fine hole, and the resin layer easily enters the fine hole when the antireflection film is manufactured. A mold for producing an antireflection film that is easy to come off can be obtained.

  In the said invention, it is preferable that the said 1st etching process is a process performed in the electrolyte solution used at the said anodizing process immediately after the said anodizing process. This is because it is not necessary to separately prepare an etchant used in the first etching step, and a tapered shape can be easily formed in the opening of the microhole.

  Further, the present invention is a mold for producing an antireflection film comprising a metal base and a metal oxide film formed on the surface of the metal base and having a plurality of micropores, Provided is a mold for producing an antireflection film having a taper shape having a depth in a range of 60 nm to 2000 nm.

  According to the present invention, since the opening of the microhole has a tapered shape with a predetermined depth, when the antireflection film is manufactured, the mold for manufacturing the antireflection film in which the resin layer easily enters the microhole. It can be.

  The antireflection film of the present invention has the effect of being excellent in mechanical strength, sticking resistance, and die-cutting properties against cracks at the tips of convex portions of a fine uneven pattern in the antireflection layer. In addition, the method for producing a mold for producing an antireflection film according to the present invention has an effect that when producing an antireflection film, a resin layer can easily enter a fine hole, and an antireflection film production mold that can be easily removed can be obtained. Play.

It is a schematic sectional drawing which shows an example of the antireflection film of this invention. It is a schematic sectional drawing which shows an example of the antireflection layer in the antireflection film of this invention. It is the schematic explaining the shape of the fine unevenness | corrugation in an antireflection film. It is a schematic sectional drawing which shows an example of the front-end | tip part in the antireflection film of this invention. It is the schematic explaining the parameter which specifies the fine unevenness | corrugation in the antireflection film of this invention. It is a schematic sectional drawing which shows the other example of the antireflection film of this invention. It is a schematic sectional drawing which shows the other example of the antireflection film of this invention. It is a schematic sectional drawing which shows the other example of the antireflection film of this invention. It is a schematic sectional drawing which shows the other example of the antireflection film of this invention. It is process drawing which shows an example of the manufacturing method of the metal mold | die for antireflection film manufacture of this invention. It is a schematic sectional drawing which shows an example of the metal mold | die for antireflection film manufacture of this invention. It is a schematic sectional drawing which shows the other example of the metal mold | die for antireflection film manufacture of this invention. It is the schematic explaining the parameter which specifies the fine unevenness | corrugation in the metal mold | die for antireflection film manufacture of this invention.

  Hereinafter, the antireflection film of the present invention, the method for producing a mold for producing an antireflection film, and the mold for producing an antireflection film will be described in detail.

A. Antireflection film First, the antireflection film of the present invention will be described. The antireflection film of the present invention has an antireflection film comprising a light-transmitting substrate and an antireflection layer having a concavo-convex shape formed on the surface at a period equal to or less than the wavelength of the visible light region. A film, wherein the antireflection layer has a base formed on the light-transmitting substrate, and fine unevenness formed on the base and having the uneven shape, and in the fine unevenness A convex part is comprised from the front-end | tip part which has the frustum-shaped main-body part which rises in a taper shape with respect to the said light-transmitting board | substrate, and the curved-surface structure formed so that the top surface of the said main-body part might be covered. It is characterized by.

  The antireflection film of the present invention will be described with reference to the drawings. FIG. 1 is a schematic sectional view showing an example of the antireflection film of the present invention. 1A shows the entire antireflection film, and FIG. 1B shows an enlarged antireflection layer in the antireflection film shown in FIG. 1A. The antireflection film 10 illustrated in FIG. 1A is formed on the light transmissive substrate 1 and the light transmissive substrate 1, and is formed on the surface of the visible light region with a period equal to or less than the wavelength of the visible light region. And an antireflection layer 2 having an uneven shape. The antireflection layer 2 has a base portion 3 formed on the light-transmitting substrate 1 and fine unevenness 4 formed on the base portion 3 and having the above-described uneven shape. Furthermore, as illustrated in FIG. 1B, the convex portions of the fine irregularities 4 cover the frustum-shaped main body portion 4 a that rises in a tapered shape with respect to the light-transmitting substrate and the top surface of the main body portion 4 a. And a tip portion 4b having a curved surface structure.

  According to the present invention, the convex portion in the fine irregularities of the antireflection layer has a curved surface structure formed so as to cover the top surface of the frustum-shaped main body portion that rises in a tapered shape with respect to the light-transmitting substrate. Therefore, there is no problem such as breakage of the tip of the convex portion of the fine concavo-convex pattern in the antireflection layer without impairing the antireflection function, and an antireflection film excellent in mold release properties can be obtained. Moreover, since the convex part in the said fine unevenness | corrugation has the said frustum-shaped main-body part, it is easy to come off from the metal mold | die used when manufacturing an antireflection film, and the antireflection which has the mechanical strength which does not generate sticking It can be a film.

The antireflection film of the present invention has at least a light-transmitting substrate and an antireflection layer, and may have any other configuration as necessary.
Hereinafter, each structure in the antireflection film of the present invention will be described.

1. Antireflection Layer First, the antireflection layer in the present invention will be described. The antireflection layer in the present invention is formed on a light transmissive substrate described later, and imparts an antireflection function to the antireflection film of the present invention. In addition, the antireflection layer in the present invention has a concavo-convex shape (hereinafter sometimes referred to as “moth eye structure”) formed on the surface with a period equal to or less than the wavelength of the visible light region. It has a base portion formed on the substrate and fine unevenness formed on the base portion and having the uneven shape.

(1) Fine unevenness The fine unevenness used for this invention consists of uneven | corrugated shape formed with the period below the wavelength of visible light region, and the convex part in the said fine unevenness is a taper with respect to a transparent substrate. A frustum-shaped main body portion that rises like a cone and a tip portion having a curved surface structure formed so as to cover the top surface of the main body portion.

(A) Main body The main body used in the present invention has a frustum shape that rises in a tapered shape with respect to the light-transmitting substrate. In this invention, since it has the said frustum-shaped main-body part, while having a favorable antireflection function, it becomes easy to remove | deviate from the metal mold | die used when manufacturing an antireflection film. When the removal from the mold is bad, the resin for forming the main body part remains in the fine holes of the mold. The surface of the light-transmitting substrate to which the portion corresponding to the remaining portion has been transferred is in a state where there is no concavo-convex shape for exhibiting the antireflection function, which causes the inhibition of the antireflection function. Further, since the main body portion has a tapered shape, the mechanical strength is also improved, and sticking is less likely to occur than when the taper is small.

The taper angle with respect to the light-transmitting substrate in the longitudinal section of the main body is not particularly limited as long as it is an angle capable of forming a truncated cone shape that rises in a tapered shape, but is 50 ° to 87 °. It is preferably within the range, more preferably within the range of 55 ° to 85 °, and even more preferably within the range of 55 ° to 82 °. When the taper angle is larger than the above range, the main body portion is close to a columnar shape that rises vertically, and may not be easily removed from the mold used in manufacturing the antireflection film of the present invention. This is because the antireflection function may not be exhibited. Furthermore, sticking may easily occur. On the other hand, when the taper angle is smaller than the above range, the antireflection function is lowered, the wavelength dependency of the reflectance is easily received, and it may be difficult to form the main body.
The taper angle in the present invention refers to an angle formed by a straight line approximating the side surface and a straight line parallel to the light-transmitting substrate surface when the side surface in the longitudinal section of the main body is linear. , An angle represented by θ ₁ in FIG.
On the other hand, when the side surface in the longitudinal section of the main body is curved, the point on the outer periphery of the top surface of the main body and the point on the outer periphery of the bottom surface of the main body are selected and connected so as to be the shortest distance An angle formed by a straight line parallel to the surface of the light-transmitting substrate, for example, an angle represented by θ ₂ in FIG.
Here, the top surface of the main body portion is a surface including a cross section of a portion where the curvature of the side surface of the convex portion in the fine unevenness greatly changes, and the bottom surface of the main body portion is a surface where the main body portion and the base portion are in contact.
The taper angle in the present invention is the average of the measured values obtained by observing the longitudinal section of the main body portion with an electron microscope and measuring the taper angle for ten pieces. FIG. 2 is a schematic cross-sectional view showing an example of the antireflection layer according to the present invention. Since the reference numerals in FIG. 2 are the same as those in FIG. 1, description thereof is omitted here.

In addition, the height of the main body is not particularly limited as long as it is within a range in which a desired antireflection function can be imparted to the antireflection layer in the present invention, and can be adjusted as appropriate. Here, as the height is higher, the reflectance of the antireflection layer can be lowered. On the other hand, as the height is lower, the reflectance on the long wavelength side tends to increase. For this reason, the height of the main body in the present invention is preferably in the range of 60 nm to 1400 nm, more preferably in the range of 100 nm to 1000 nm, and in the range of 120 nm to 750 nm. More preferably. If the height of the main body portion is higher than the above range, the main body portion is likely to be damaged, and sticking may easily occur. If the height of the main body portion is lower than the above range, the antireflection in the present invention. This is because the antireflection function for light on the long wavelength side of the layer may be insufficient.
The height of the main body in the present invention refers to the distance from the base surface to the top surface of the main body, for example, a distance represented by H in FIG. In addition, let the height of the said main-body part in this invention be the average value determined by the method mentioned above.

  The diameter of the top surface of the main body is not particularly limited as long as it is smaller than the diameter of the bottom of the main body, but is preferably in the range of 1 nm to 100 nm, and in the range of 2 nm to 50 nm. More preferably. This is because if the diameter of the top surface of the main body is too small, the mechanical strength is reduced and the main body is easily damaged. Moreover, if the diameter of the top surface of the main body is too large, the taper becomes small, so that sticking is likely to occur or it is difficult to remove from the mold. In addition, let the diameter of the top surface of the said main-body part in this invention be the average value determined by the method mentioned above.

  The diameter of the bottom surface of the main body is not particularly limited as long as it is larger than the diameter of the top surface of the main body, but is preferably in the range of 25 nm to 500 nm, and in the range of 50 nm to 250 nm. More preferably. When the diameter of the bottom surface of the main body portion is reduced, the space between adjacent structures is opened, and the portion not forming the structure is increased, so that the antireflection function is deteriorated. In addition, let the diameter of the bottom face of the said main-body part in this invention be the average value determined by the method mentioned above.

  The top surface shape and the bottom surface shape of the main body are not particularly limited, and examples thereof include a polygonal shape in addition to a circular shape such as a circle and an ellipse.

  The side surface shape of the main body may be linear or curved in the longitudinal section of the main body. In particular, in the present invention, it is preferable that the main body portion forms a curved side surface that is continuous with a tip portion described later. This is because, as illustrated in FIG. 2, the convex portions of the fine irregularities can be formed into a bell shape, and a good antireflection function can be obtained. Hereinafter, the reason why the antireflection function is good when the convex portion has a bell shape will be specifically described.

The principle that the moth-eye structure prevents reflection is considered as follows. The refractive index N of the space (pseudo layer a) near the apex of the moth eye structure X illustrated in FIG. 3A is 1 for the refractive index of air and the volume occupied by the moth eye structure X in the pseudo layer a. When the ratio is V _m and the refractive index of the resin constituting the moth-eye structure X is N _m , the following formula (1) is established.
N = 1 × (1−V _m ) + N _m × V _m (1)
That is, the refractive index of the pseudo layer a is given as a weighted average considering the respective volumes and refractive indexes of air and resin. The same applies to the pseudo layer b and the subsequent layers. As the substrate Y approaches the pseudo layer a to the pseudo layer k, the refractive index of the pseudo layer increases. However, as illustrated in FIG. 3B, the amount of change in the refractive index of the cone shape changes in a curved manner. In contrast, the amount of change in the refractive index of the bell shape changes almost linearly. This is because the volume ratio occupied by the moth-eye structure X can be regarded as a change in the cross-sectional area from the pseudo layer a to the pseudo layer k. This is because the bell shape changes almost linearly. Therefore, the bell-shaped moth-eye structure X has a feature that the rate of change of the refractive index in the vicinity of the substrate Y is smaller than that of the cone-shaped moth-eye structure X. When the refractive index change rate in the vicinity of the substrate Y is smaller, the refractive index between the air and the resin is reduced in a pseudo manner, and the reflectance can be reduced. Further, when the taper of the main body is small, as shown in FIG. 3B, the amount of change in the refractive index in the pseudo layer k is small, but the amount of change in the refractive index in the portion from the pseudo layer a to c is large. Therefore, the whole tends to be whitish. Therefore, the bell-shaped moth-eye structure X is superior in antireflection function to the cone-shaped moth-eye structure X and the moth-eye structure X having a small taper.
In the present invention, the refractive index distribution of the pseudo layer is optimized by appropriately adjusting the taper angle of the main body part and the radius of curvature of the tip part and defining the bell shape of the convex part in the fine unevenness. Thus, the fine unevenness can be a moth-eye structure having excellent optical characteristics.

(B) Tip portion The tip portion used in the present invention has a curved surface structure formed so as to cover the top surface of the main body portion. In the present invention, since the tip portion has a curved surface structure, there is no problem such as cracking of the leading edge of the convex portion of the fine unevenness pattern in the antireflection layer, and the antireflection film excellent in die-cutting property and can do. The curved surface structure of the tip portion can be controlled by the pressure at the time of forming the antireflection layer, the viscosity of the resin of the antireflection layer, and the like.

  The shape of the tip is not particularly limited as long as it is a curved structure formed so as to cover the top surface of the main body. In the present invention, in particular, it is preferably substantially spherical, and the radius of curvature thereof can be appropriately adjusted according to the application of the antireflection film of the present invention, for example, used in the present invention. The diameter of the top surface of the main body is preferably within a range of 1.0 to 5.0 times, more preferably within a range of 1.0 to 2.0 times. More preferably, it is in the range of 0.0 times to 1.5 times. If the curvature radius of the tip portion is larger than the above range, the tip portion becomes close to a flat shape, so that the reflectance of the antireflection layer increases, and the antireflection function of the antireflection film of the present invention may deteriorate. Because. Further, the curved surface structure is preferably spherical as illustrated in FIG. 4A, but partially sharpened and / or as illustrated in FIGS. 4B to 4C. There may be undulations. In addition, the tip end portion of the tip portion does not need to be at the center of the top surface of the main body portion, and the antireflection function does not change even if it is deviated from the center.

  Further, the height of the tip portion, that is, the distance from the top surface of the main body portion to the most distal portion of the tip portion is appropriately adjusted within a range in which a desired antireflection function can be imparted to the antireflection layer in the present invention. It is something that can be done.

(3) Convex part The convex part used for this invention is comprised from the said front-end | tip part and the said main-body part, and the antireflection function with which the antireflection layer in this invention is provided has the said convex part. Depends on period, height, interval.
The period of the convex portion is formed, a height, and spacing, P _1, Q _1, and as shown by R _1, the top portion of the tip portion from the top of the front end portion of the raised portion adjacent each respectively, in FIG 5 , The distance from the top of the tip of the protrusion to the bottom of the main body, and the shortest distance between the outer peripheries of the bottom of the main body of the adjacent protrusion. Here, FIG. 5 is a schematic diagram for explaining parameters for specifying fine irregularities in the antireflection film of the present invention, and reference numerals not described in FIG. 5 can be the same as those in FIG. The description in is omitted.

  The period of the convex portion is not particularly limited as long as it is equal to or shorter than the wavelength of the visible light region, and can be appropriately determined according to the use of the antireflection film of the present invention. Here, the period affects the wavelength dependence of the reflectance of the antireflection layer used in the present invention, and the reflectance for light on the short wavelength side in the visible light region increases as the period becomes longer. There is a tendency. On the other hand, when the period is 200 nm or less, the change in the wavelength dependence of the reflectance due to the fluctuation of the period is small. For this reason, the period of the convex portions in the present invention is preferably in the range of 80 nm to 400 nm, more preferably in the range of 100 nm to 300 nm, and in the range of 120 nm to 250 nm. Is more preferable. This is because if the period of the convex portions is shorter than the above range, the shape of the individual convex portions becomes extremely small, so that it may be difficult to form the convex portions with high accuracy. Further, if the period of the convex portion is longer than the above range, the antireflection function for light on the short wavelength side of the antireflection layer in the present invention may be insufficient. In addition, the period of the said convex part in this invention observes the longitudinal cross-section of a convex part with an electron microscope, measures the period for ten pieces, and makes it the average value of the measured value.

  The height of the convex portion can be appropriately adjusted within a range in which a desired antireflection function can be imparted to the antireflection layer in the invention, and is not particularly limited. Here, as the height is higher, the reflectance of the antireflection layer can be lowered. On the other hand, when the height is lowered, the reflectance on the long wavelength side tends to increase. Therefore, the height of the convex portion in the present invention is preferably in the range of 62 nm to 1402 nm, more preferably in the range of 100 nm to 1002 nm, and in the range of 120 nm to 752 nm. More preferably. If the height of the convex portion is higher than the above range, the individual convex portions may be easily damaged, and if the height of the convex portion is lower than the above range, the antireflection layer of the present invention This is because the antireflection function for light on the long wavelength side may be insufficient. In addition, the height of the said convex part in this invention is taken as the average value determined by the method mentioned above.

  As the interval at which the convex portions are formed increases, the reflectance tends to increase in the entire wavelength region of visible light, and as the interval decreases, the reflectance tends to decrease in the entire wavelength region of visible light. For this reason, the interval at which the convex portions are formed in the present invention can be appropriately adjusted within a range in which a desired antireflection function can be imparted to the antireflection layer in the present invention, and is particularly limited. It is not something. In addition, the space | interval of the said convex part in this invention is taken as the average value determined by the method mentioned above.

  The variation in the height of the protrusions is preferably 100 nm or less, more preferably 50 nm or less, and even more preferably 10 nm or less. This is because if the variation in the height of the convex portions is larger than the above range, unevenness may occur in the antireflection function of the antireflection layer in the present invention. Moreover, the mechanical strength of the surface comprised from the vertex of a convex part falls, and it becomes easy to receive a damage. In addition, the variation in the height of the convex portion means a difference between the maximum value and the minimum value of the measured values obtained by observing the vertical section of the convex portion with an electron microscope and measuring the height of ten pieces.

The number of convex portions per unit area can be appropriately adjusted within a range in which a desired antireflection function can be imparted to the antireflection layer in the present invention, and is not particularly limited. 50 / μm ² or more, preferably 60 / μm ² or more, and more preferably 70 / μm ² or more. If the number of the convex portions per unit area is 50 / μm ² or less, glare occurs and the antireflection function deteriorates. Moreover, the mechanical strength of the surface comprised from the vertex of a convex part falls, and it becomes easy to receive a damage.
In the present invention, the antireflection layer may have a structure other than the protrusions, but the ratio of the number of protrusions in the antireflection layer to the total number of structures in the antireflection layer is 50% or more, more preferably 60% or more, and even more preferably 75% or more. This is because if the ratio is too small, the antireflection function, the sticking resistance and the mold release property are lowered.

The regular reflectance at an incident angle of 5 ° in the wavelength region of 360 nm to 760 nm of the convex portion is preferably 0.5% or less, and more preferably in the range of 0.005% to 0.3%. Preferably, it is more preferably in the range of 0.005% to 0.1%.
Moreover, it is preferable that the haze value in the 360 nm-760 nm wavelength range of the said convex part exists in the range of 0.1%-50%.

  The convex portion can reflect all over from a short wavelength region to a long wavelength region.

(2) Base part The base part in the antireflection layer used in the present invention is formed on a light-transmitting substrate, which will be described later, and supports the fine irregularities.
The thickness of the base is preferably in the range of 0.5 μm to 150 μm, more preferably in the range of 1 μm to 100 μm, and still more preferably in the range of 2 μm to 80 μm. When the thickness of the base is within the above range, the degree of shrinkage stress of the antireflection layer can be reduced, and the antireflection film of the present invention has curl regardless of the type of the light transmissive substrate described later. This is because it can be prevented from occurring. Moreover, there exists an effect as a cushion layer and it can reinforce the mechanical damage of an antireflection layer. For example, the mechanical strength of the antireflection layer can be increased, scratch resistance can be improved, and scratch resistance can be reduced. Furthermore, the adhesion between the antireflection layer and the light transmissive substrate can be improved.

(3) Antireflection layer The antireflection layer in the present invention is usually made of a resin. The resin is not particularly limited as long as it can form the above-described fine irregularities, such as an ionizing radiation curable resin such as an ultraviolet curable resin and an electron beam curable resin, a thermosetting resin, and a thermoplastic resin. Can be mentioned. Among these, in the present invention, it is preferable to use an ionizing radiation curable resin. This is because by using the ionizing radiation curable resin, fine irregularities can be produced with high accuracy, and a good antireflection function can be imparted to the antireflection layer.

Examples of the ionizing radiation curable resin used in the present invention include acrylic resins. Examples of the acrylic resin include compounds having at least three ethylenically unsaturated double bonds. For example, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tri (meth) acrylate, tris (Acryloxyethyl) isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate, trimethylol ethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, alkyl-modified dipentaerythritol tet (Meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetra (meth) acrylate, polyurethane polyacrylate, polyester polyacrylate, etc. Ester compound of monohydric alcohol and (meth) acrylic acid; polyurethane poly (meth) acrylate, polyester poly (meth) acrylate, polyether poly (meth) acrylate, polyacryl poly (meth) acrylate, polyalkyd poly (meth) acrylate , Polyepoxy poly (meth) acrylate, polyspiroacetal poly (meth) acrylate, polybutadiene poly (meth) acrylate, polythiol polyene poly ( Data) acrylate, (meth) acrylate compound of the polysilicon poly (meth) polyfunctional compounds such acrylate.
Among these compounds having at least three or more ethylenically unsaturated double bonds, polyurethane poly (meth) acrylate and polyepoxy poly (meth) acrylate having at least six functional groups from the viewpoint of coating film strength and adhesion. Poly (meth) acrylates such as polyfunctional acrylates having 4 or more acryloyl groups in the molecule can be suitably used.
Polyepoxy poly (meth) acrylate is obtained by esterifying an epoxy group of an epoxy resin with (meth) acrylic acid and converting the functional group to a (meth) acryloyl group, and (meth) acrylic acid to bisphenol A type epoxy resin There are adducts, (meth) acrylic acid adducts to novolac type epoxy resins, and the like.
The polyurethane poly (meth) acrylate is obtained by reacting, for example, a diisocyanate and a (meth) acrylate having a hydroxyl group, or an isocyanate group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate under an excess of isocyanate groups. Some are obtained by reacting polymers with (meth) acrylates having a hydroxyl group. Alternatively, a hydroxyl group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate under hydroxyl-excess conditions can be obtained by reacting with a (meth) acrylate having an isocyanate group.
Examples of polyols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentane glycol, neopentyl glycol, hexanetriol, trimellilol propane, polytetra Examples include methylene glycol and a condensation polymer of adipic acid and ethylene glycol.
Examples of the polyisocyanate include tolylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate.
Examples of (meth) acrylates having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and ditrimethylolpropane tetraacrylate. .
Examples of (meth) acrylates having an isocyanate group include 2-methacryloyloxyethyl isocyanate and methacryloyl isocyanate.
Specific examples of the polyfunctional group having four or more acryloyl groups in the molecule include the above-described polyhydric alcohol and acrylic acid ester compounds, and a single compound or a mixture of two or more compounds is preferable.
Furthermore, a (meth) acrylic polymerizable composition described in WO2007 / 040159 can be used.
Moreover, it is desirable to add a photopolymerization initiator to the resin as appropriate. Examples of the photopolymerization initiator include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, and the like. Specifically, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, diethoxyacetophenone, gendyl dimethyl ketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, benzophenone, 2 , 4,6-trimethylbenzoin diphenylphosphine oxide, Michler's ketone, isoamyl N, N-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, and the like. It can also be used together as appropriate. In the present invention, from these ionizing radiation curable resins, a resin having a refractive index close to the refractive index of a light transmissive substrate described later can be appropriately selected and used.

  Examples of the thermosetting resin or thermoplastic resin used in the present invention include acrylic resin, polyester resin, epoxy resin, polyolefin resin, styrene resin, polyamide resin, polyimide resin, polyamideimide resin, polyurethane resin, and polyacetic acid. Vinyl resin, polyvinyl alcohol resin, polyvinyl butyral resin, polycarbonate resin, melamine resin, urea resin, alkyd resin, phenol resin, cellulose resin, diallyl phthalate resin, silicone resin, polyarylate resin, polyacetal resin, styrene-isoprene rubber, fluorine resin Etc. Moreover, these elastomers and acid-modified products can be mentioned.

The antireflection layer used in the present invention may be formed by laminating on a light-transmitting substrate described later, or may be a coextruded resin of the antireflection layer and the light-transmitting substrate.
In addition, when a resin that is soluble in an organic solvent such as triacetyl cellulose (TAC), polycarbonate resin, or acrylic resin is used for the light transmissive substrate used in the present invention, the resin used in the antireflection layer is diluted in the organic solvent. In general, a method of laminating on a light transmissive substrate is used. At this time, the organic solvent to be used penetrates into the light transmissive substrate. By forming a penetrating layer that penetrates, the adhesion and the mechanical strength of the antireflection layer may be improved.

The transparency of the resin used for the antireflection layer in the present invention is preferably 80% or more, more preferably 85% or more, and more preferably 90% or more, with respect to the entire visible light wavelength range. More preferably it is.
Here, the light transmittance can be measured by, for example, a spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation.

  The antireflection function of the antireflection layer used in the present invention depends on the refractive index of the resin used for the antireflection layer and the refractive index of the light-transmitting substrate described later. That is, the smaller the difference between the refractive index of the resin used for the antireflection layer and the refractive index of the light-transmitting substrate, the more the discontinuity of the refractive index can be corrected. It can be improved. From such a viewpoint, the difference between the refractive index of the resin used in the present invention and the refractive index of the light-transmitting substrate described later is preferably in the range of 0 to 0.5, and preferably 0 to 0.2. More preferably, it is in the range of 0 to 0.1. In addition, the specific refractive index value of the resin used for the antireflection layer is determined in relation to a light-transmitting substrate described later, and a particularly preferable value is not specified. The range is 1.20 to 2.40.

  The antireflection layer used in the present invention may contain any additive as necessary in addition to the above-described resin. Examples of such additives include antistatic agents (conductive agents), refractive index adjusters, leveling agents, antifouling agents, pressure-sensitive adhesives, ultraviolet / infrared absorbers, hardeners, hardness adjusters, and fluidity. Conditioners, antioxidants, fluororesins, hydrocarbons such as liquid paraffin, paraffin wax, synthetic polyethylene wax, fatty acid amides, metal stearate, calcium stearate / magnesium stearate, lead stearate / zinc stearate, etc. Release agents such as metal soaps, fatty acid esters, silicone oils, acrylic polymers, internal or external lubricants, polarization refraction regulators such as strontium carbonate, hydrophilic agents, lipophilic agents, colorants, etc. Can be mentioned. Specifically, for example, the following substances described in JP 2009-230045 A can be mentioned.

<Antistatic agent (conductive agent)>
By adding an antistatic agent (conductive agent), dust adhesion on the surface of the antireflection layer can be effectively prevented. Specific examples of the antistatic agent (conductive agent) include quaternary ammonium salts, pyridinium salts, various cationic compounds having a cationic group such as first to third amino groups, sulfonate groups, sulfate ester bases, Anionic compounds having an anionic group such as phosphate ester base and phosphonate base, amphoteric compounds such as amino acid series and amino sulfate ester series, nonionic compounds such as amino alcohol series, glycerin series and polyethylene glycol series, tin and titanium And metal chelate compounds such as acetylacetonate salts thereof, and compounds obtained by increasing the molecular weight of the compounds listed above. In addition, a monomer or oligomer having a tertiary amino group, a quaternary ammonium group, or a metal chelate portion and polymerizable by ionizing radiation, or an organometallic compound such as a coupling agent having a functional group, etc. Polymerizable compounds can also be used as antistatic agents.

  Examples of the antistatic agent include conductive polymers, and specific examples thereof include aliphatic conjugated polyacetylene, polyacene, oliazulene, etc .; aromatic conjugated poly (paraphenylene), etc .; heterocyclic conjugated type Examples include polypyrrole, polythiophene, polyisocyannaphthene, etc .; heteroatom-containing polyaniline, polythienylene vinylene, etc .; mixed conjugated poly (phenylene vinylene), etc. In addition to these, a plurality of conjugated chains are included in the molecule. Examples thereof include a double-chain conjugated system that is a conjugated system, a conductive composite that is a polymer obtained by grafting or block-copolymerizing the conjugated polymer chain described above to a saturated polymer, and these conductive polymer derivatives. In particular, it is more preferable to use an organic antistatic agent such as polypyrrole, polythiophene or polyaniline. By using the above organic antistatic agent, it is possible to exhibit excellent antistatic performance and at the same time increase the total light transmittance of the antireflection layer and reduce the haze value. An anion such as an organic sulfonic acid or iron chloride can be added as a dopant (electron donor) for the purpose of improving conductivity and improving antistatic performance. In view of the effect of dopant addition, polythiophene is particularly preferable because of its high transparency and antistatic properties. As the polythiophene, oligothiophene can also be preferably used. The derivative is not particularly limited, and examples thereof include polyphenylacetylene, polydiacetylene alkyl group-substituted products, and the like. Further, conductive carbon nanotubes, boron and its compounds, metals, and fine powders of these metal oxides having a particle diameter of 1 μm or less can be added. For example, a metal made of titanium, aluminum, cerium, yttrium, zirconium, niobium, antimony, or a metal oxide, or a compound in which these are coated or doped on the surface is used.

  According to a preferred embodiment of the present invention, the antistatic agent is 0.01% by weight or more and 50% by weight or less with respect to the total amount of the resin composition for forming an antireflection layer, preferably the lower limit is 0.1% by weight. The upper limit is about 30% by weight or less. By adjusting to the above numerical range, it is preferable in that the anti-reflection layer can be kept transparent and anti-static performance can be imparted without affecting the anti-reflection function.

<Refractive index adjusting agent>
By adding a refractive index adjuster, it becomes possible to adjust the optical characteristics of the antireflection layer. Examples of the refractive index adjusting agent include a low refractive index agent, a medium refractive index agent, and a high refractive index agent.

1) Low refractive index agent The refractive index of the antireflection layer to which the low refractive index agent is added is less than 1.5, preferably 1.45 or less. Preferable examples of the low refractive index agent include low refractive index inorganic ultrafine particles such as silica and magnesium fluoride (all kinds of fine particles such as porous and hollow), and fluorine-based resins which are low refractive index resins. As the fluororesin, a polymerizable compound containing at least a fluorine atom in the molecule or a polymer thereof can be used. The polymerizable compound is not particularly limited, but for example, those having a curing reactive group such as a functional group that is cured by ionizing radiation and a polar group that is thermally cured are preferable. Moreover, the compound which has these reactive groups simultaneously may be sufficient. In contrast to this polymerizable compound, a polymer has no reactive groups as described above.

  As the polymerizable compound having an ionizing radiation curable group, fluorine-containing monomers having an ethylenically unsaturated bond can be widely used. More specifically, to illustrate fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluorobutadiene, perfluoro-2,2-dimethyl-1,3-dioxole, etc.) Can do. As having a (meth) acryloyloxy group, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) Ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, α-trifluoromethacryl (Meth) acrylate compounds having fluorine atoms in the molecule, such as methyl acrylate and ethyl α-trifluoromethacrylate; C 1-14 fluoroalkyl groups having at least 3 fluorine atoms in the molecule, fluorocyclo An alkyl group or a fluoroalkylene group and at least two (medium There are also fluorine-containing polyfunctional (meth) acrylic acid ester compounds having an acryloyloxy group.

  Preferable examples of the thermosetting polar group include hydrogen bond forming groups such as a hydroxyl group, a carboxyl group, an amino group, and an epoxy group. These are excellent not only in adhesion to the coating film but also in affinity with inorganic ultrafine particles such as silica. Examples of the polysynthetic compound having a thermosetting polar group include 4-fluoroethylene-perfluoroalkyl vinyl ether copolymer; fluoroethylene-hydrocarbon vinyl ether copolymer; epoxy, polyurethane, cellulose, phenol, polyimide, etc. Fluorine modified products of each resin can be mentioned.

  Polymerizable compounds having both ionizing radiation curable groups and thermosetting polar groups include acrylic or methacrylic acid moieties and fully fluorinated alkyl, alkenyl, aryl esters, fully or partially fluorinated vinyl ethers, fully or partially fluorine. Illustrative examples include fluorinated vinyl esters, fully or partially fluorinated vinyl ketones, and the like.

  Specific examples of the fluorine-containing polymer include a polymer of a monomer or a monomer mixture containing at least one fluorine-containing (meth) acrylate compound of the polymerizable compound having the ionizing radiation curable group; the fluorine-containing (meth) At least one kind of acrylate compound and no fluorine atom in the molecule such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate ( Copolymer with (meth) acrylate compound; fluoroethylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, 3,3,3-trifluoropropylene, 1,1,2-trichloro-3,3,3- Trifluoropropylene, hexafluoropropylene Homopolymers or copolymers of fluorine-containing monomer are mentioned, such as.

  Silicone-containing vinylidene fluoride copolymers obtained by adding a silicone component to these copolymers can also be used. The silicone components in this case include (poly) dimethylsiloxane, (poly) diethylsiloxane, (poly) diphenylsiloxane, (poly) methylphenylsiloxane, alkyl-modified (poly) dimethylsiloxane, azo group-containing (poly) dimethylsiloxane, Dimethyl silicone, phenylmethyl silicone, alkyl aralkyl modified silicone, fluorosilicone, polyether modified silicone, fatty acid ester modified silicone, methyl hydrogen silicone, silanol group containing silicone, alkoxy group containing silicone, phenol group containing silicone, methacryl modified silicone, acrylic Modified silicone, amino modified silicone, carboxylic acid modified silicone, carbinol modified silicone, epoxy modified silicone, mercapto modified silicone Over emissions, fluorine-modified silicones, polyether-modified silicone and the like. Among them, those having a dimethylsiloxane structure are preferable.

  Furthermore, non-polymers or polymers composed of the following compounds can also be used as the fluororesin. That is, a fluorine-containing compound having at least one isocyanato group in the molecule is reacted with a compound having at least one functional group in the molecule that reacts with an isocyanato group such as an amino group, a hydroxyl group, or a carboxyl group. Compound obtained: a compound obtained by reacting a fluorine-containing polyol such as fluorine-containing polyether polyol, fluorine-containing alkyl polyol, fluorine-containing polyester polyol, fluorine-containing ε-caprolactone modified polyol with a compound having an isocyanato group Can be used.

  According to a preferred embodiment of the present invention, it is preferable to use “fine particles having voids” as the low refractive index agent. The “fine particles having voids” can lower the refractive index while maintaining the layer strength of the antireflection layer. In the present invention, the term “fine particles having voids” means a structure in which a gas is filled with gas and / or a porous structure containing gas, and the gas in the fine particle is compared with the original refractive index of the fine particle. It means fine particles whose refractive index decreases in inverse proportion to the occupation ratio. The present invention also includes fine particles capable of forming a nanoporous structure inside and / or at least part of the surface depending on the form, structure, aggregation state, and dispersion state of the fine particles inside the coating film. It is.

  As specific examples of the inorganic fine particles having voids, silica fine particles prepared by using the technique disclosed in JP-A-2001-233611 are preferably exemplified. In addition, it may be silica fine particles obtained by the production methods described in JP-A-7-133105, JP-A-2002-79616, JP-A-2006-106714, and the like. Since the silica fine particles having voids are easy to manufacture and have high hardness itself, when mixed with a binder and added to the antireflection layer, the layer strength is improved and the refractive index is 1.20 to 1.45. It is possible to prepare within a range. In particular, as specific examples of the organic fine particles having voids, hollow polymer fine particles prepared by using the technique disclosed in JP-A-2002-80503 are preferably exemplified.

  The fine particles capable of forming a nanoporous structure inside and / or at least part of the surface of the coating are manufactured for the purpose of increasing the specific surface area in addition to the silica fine particles, and the packing column and the surface porosity Examples include controlled release materials that adsorb various chemical substances in the mass part, porous fine particles used for catalyst fixation, or dispersions and aggregates of hollow fine particles intended to be incorporated into heat insulating materials and low dielectric materials. it can. Specifically, as a commercial product, an assembly of porous silica fine particles from the product names Nippil and Nipgel manufactured by Nippon Silica Industry Co., Ltd., and a structure in which silica fine particles manufactured by Nissan Chemical Industries, Ltd. are connected in a chain form. From the colloidal silica UP series (trade name), it is possible to use those within the preferred particle diameter range of the present invention.

  The average particle diameter of the “fine particles having voids” is 5 nm or more and 300 nm or less, preferably the lower limit is 8 nm or more and the upper limit is 100 nm or less, more preferably the lower limit is 10 nm or more and the upper limit is 80 nm or less. When the average particle diameter of the fine particles is within this range, excellent transparency can be imparted to the antireflection layer.

2) High refractive index agent / medium refractive index agent The high refractive index agent and the medium refractive index agent are used for further improving the antireflection function. The refractive index of the high refractive index agent and the medium refractive index agent may be set within the range of 1.55 to 2.00, and the refractive index of the medium refractive index agent is within the range of 1.55 to 1.80. The high refractive index agent means one having a refractive index in the range of 1.65 to 2.00.

  Examples of these refractive index agents include fine particles. Specific examples thereof (indicated by the refractive index in parentheses) include zinc oxide (1.90), titania (2.3 to 2.7), and ceria (1.95). ), Tin-doped indium oxide (1.95), antimony-doped tin oxide (1.80), yttria (1.87), and zirconia (2.0).

<Leveling agent>
The leveling agent can impart an effect of slipping property, antifouling property and scratch resistance to the antireflection layer. Therefore, the leveling agent functions as an antifouling agent, a water repellent, an oil repellent, and a fingerprint adhesion preventive. Preferable leveling agents include fluorine or silicone.

<Contaminant>
The antifouling agent is mainly intended to prevent the outermost surface of the antireflection layer from being stained, and can further impart scratch resistance to the antireflection layer. As specific examples of the antifouling agent, additives that exhibit water repellency, oil repellency, and fingerprint wiping are effective. Specific examples include fluorine compounds, silicon compounds, or mixed compounds thereof. More specifically, silane coupling agents having a fluoroalkyl group, such as 2-perfluorooctylethyltriaminosilane, and the like can be mentioned, and those having an amino group can be preferably used.

<Ultraviolet / infrared absorber>
Examples of the ultraviolet absorber include benzotriazole compounds, benzophenone compounds, salicylate compounds, and the like. Examples of the infrared absorber include diimonium compounds and phthalocyanine compounds.

<High hardness agent, hardness adjusting agent, and fluidity adjusting agent>
Any of the hardener, hardness adjuster, and fluidity modifier may be used as long as they are used in the antireflection layer.

2. Next, the light transmissive substrate in the present invention will be described. The light-transmitting substrate in the present invention supports the above-described antireflection layer, and in combination with the above antireflection layer, imparts a desired antireflection function to the antireflection film of the present invention.

The light-transmitting substrate used in the present invention is not particularly limited as long as it has transparency to visible light. Among them, the light transmittance for the entire wavelength range of visible light is 80% or more. It is preferably 85% or more, more preferably 90% or more.
Here, the light transmittance can be measured by, for example, a spectrophotometer U-4100 manufactured by Hitachi High-Technologies Corporation.

The light-transmitting substrate used in the present invention preferably has a refractive index comparable to that of the resin used for the antireflection layer. As a result, in the antireflection film of the present invention, a discontinuous interface of refractive index is formed at the interface between the antireflection layer and the light-transmitting substrate, and light is reflected at the discontinuous interface. This is because the antireflection function of the antireflection film can be prevented from being impaired. Among them, the light transmissive substrate used in the present invention preferably has a difference between the refractive index of the light transmissive substrate and the refractive index of the resin in the range of 0 to 0.5. More preferably, it is in the range of 2, more preferably in the range of 0 to 0.1.
In addition, since the value of the refractive index of the light-transmitting substrate used in the present invention is determined in relation to the refractive index of the resin described above, there is no particularly preferable value. Within the range of .40.

The material constituting the light transmissive substrate used in the present invention is not particularly limited as long as it exhibits the light transmissive property described above and can obtain a light transmissive substrate having a desired refractive index. is not. In the present invention, examples of the material used for the light transmissive substrate include poly (meth) methyl acrylate, poly (meth) ethyl acrylate, methyl (meth) acrylate-butyl (meth) acrylate, and the like. Acrylic resin, polyethylene, polypropylene, polymethylpentene, cyclic olefin polymer (typically norbornene resin, etc., for example, product names “ZEONOR” manufactured by Nippon Zeon Co., Ltd., “ Polyolefin resin such as Arton ", polycarbonate resin, thermoplastic polyester resin such as polyethylene terephthalate, polyethylene naphthalate, polyamide, polyimide, polystyrene, acrylonitrile-styrene copolymer, polyethersulfone, polysulfone, triacetyl Ceruleau For example, cellulose resins such as polyvinyl acetate, ethylene-vinyl acetate copolymer, thermoplastic resins such as vinyl chloride, polyvinylidene chloride, polyether ether ketone, polyurethane, or glass (including ceramics). it can.
Moreover, you may contain arbitrary additives as needed. Examples of such additives include antistatic agents (conductive agents), refractive index adjusters, leveling agents, antifouling agents, pressure-sensitive adhesives, ultraviolet / infrared absorbers, hardeners, hardness adjusters, and fluidity. Conditioners, antioxidants, fluororesins, hydrocarbons such as liquid paraffin, paraffin wax, synthetic polyethylene wax, fatty acid amides, metal stearate, calcium stearate / magnesium stearate, lead stearate / zinc stearate, etc. Release agents such as metal soaps, fatty acid esters, silicone oils, acrylic polymers, internal or external lubricants, polarization refraction regulators such as strontium carbonate, hydrophilic agents, lipophilic agents, colorants, etc. Can be mentioned.

3. Antireflection Film The antireflection film of the present invention has at least the antireflection layer and the light transmissive substrate, and is reflected on the light transmissive substrate 1 as illustrated in FIG. The anti-reflection layer 2 may be a two-layer structure, and as illustrated in FIG. 6A, the anti-reflection layer 2 and the light-transmitting substrate 1 are formed from the same material. Alternatively, as illustrated in FIG. 6B, a three-layer structure in which the antireflection layer 2 is formed so as to sandwich the light transmissive substrate 1 may be employed. FIG. 6 is a schematic cross-sectional view showing another example of the antireflection film of the present invention, and reference numerals not described in FIG. 6 can be the same as those in FIG. Omitted.

Moreover, although the antireflection film of the present invention has at least the antireflection layer and the light-transmitting substrate, any configuration may be used as necessary. The arbitrary structure used for this invention is not specifically limited, According to the use etc. of the antireflection film of this invention, the structure which can provide a desired function can be selected suitably, and can be used. . Among them, as an arbitrary configuration suitably used in the present invention, a primer layer (adhesion stable layer) formed between the antireflection layer and the light transmissive substrate, a hard coat layer, an antistatic layer, etc. Examples thereof include a functional layer and an adhesive layer formed on a surface opposite to the surface on which the antireflection layer of the light transmissive substrate is formed. The primer layer can also serve as a hard coat layer and / or an antistatic layer. Furthermore, a protective layer formed on the surface of the antireflection layer can also be used.
Here, the hard coat layer or the primer layer is formed as the functional layer, thereby improving the hardness of the antireflection film of the present invention and improving the adhesion between the antireflection layer and the light-transmitting substrate. Therefore, when the antireflection film of the present invention is used for a display device, there is an advantage that the antireflection film of the present invention can be used as a protective film for the display device.
On the other hand, since the adhesive layer is formed, for example, when the antireflection film of the present invention is used in a display device, there is an advantage that the antireflection film of the present invention can be easily bonded to another member. is there.

  The case where the antireflection film of the present invention has the hard coat layer or primer layer will be described with reference to the drawings. FIG. 7 is a schematic cross-sectional view showing an example when the antireflection film of the present invention has a hard coat layer or a primer layer. As illustrated in FIG. 7, in the antireflection film 10 of the present invention, a hard coat layer or a primer layer 5 may be formed between the antireflection layer 2 and the light transmissive substrate 1. In addition, about the code | symbol which is not demonstrated in FIG. 7, since it can be made the same as that of FIG. 1, description here is abbreviate | omitted.

  The hard coat layer or primer layer used in the present invention is not particularly limited as long as it has adhesion and hardness with a desired light-transmitting substrate. The material constituting such a hard coat layer or primer layer is composed of the same resin as that of the above-described antireflection layer and additives appropriately used. The resin is not particularly limited as long as it has adhesion and hardness with a light-transmitting substrate, and is an ionizing radiation curable resin such as an ultraviolet curable resin or an electron beam curable resin, or a thermosetting resin. And thermoplastic resins. For example, relatively low molecular weight polyester resins, polyether resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, (meth) acrylates of polyfunctional compounds such as polyhydric alcohols Monofunctional monomers such as oligomers or prepolymers such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N-vinylpyrrolidone as reactive diluents and polyfunctional monomers such as trimethylolpropane tri ( (Meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol hexa (meth) a Relate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate.

  In addition, the thickness of the hard coat layer or primer layer used in the present invention depends on the kind of material used for the hard coat layer or primer layer described above, and the hard coat layer or primer layer has a desired light-transmitting substrate. It is not particularly limited as long as it is within a range where adhesion and hardness can be imparted. Among these, the thickness of the hard coat layer or primer layer used in the present invention is preferably in the range of 0.05 μm to 50 μm, more preferably in the range of 0.1 μm to 30 μm, and 1 μm to 20 μm. More preferably, it is within the range. This is because when the thickness of the hard coat layer or primer layer is larger than the above range, the antireflection film of the present invention may be curled depending on the type of material constituting the hard coat layer or primer layer. On the other hand, if the thickness is less than the above range, it may be difficult to make the hardness of the hard coat layer to a desired level depending on the type of material constituting the hard coat layer or primer layer. Moreover, when adding the function as a primer layer, adhesiveness cannot be taken but it may peel. When a function as an antistatic layer is added, sufficient antistatic performance may not be exhibited.

As the hard coat layer or primer layer, one previously laminated on a light-transmitting substrate may be used, or one obtained by simultaneously laminating a hard coat layer or a primer layer and an antireflection layer resin may be used.
In addition, when a resin that is soluble in an organic solvent such as triacetyl cellulose (TAC), polycarbonate resin, or acrylic resin is used for the light transmissive substrate used in the present invention, the resin used for the hard coat layer or primer layer is organic. A method of diluting in a solvent and laminating on a light-transmitting substrate is common, but at this time, the organic solvent to be used penetrates into the light-transmitting substrate, and accordingly, the hard coat layer or primer layer to be used By forming a permeation layer that also penetrates a part of the resin, the adhesion may be improved and the mechanical strength of the hard coat layer or primer layer may be improved.

  Furthermore, the hard coat layer or primer layer used in the present invention preferably has a refractive index comparable to the refractive index of the antireflection layer and the refractive index of the light transmissive substrate. Thereby, a discontinuous interface of refractive index is formed at the boundary between the antireflection layer and the hard coat layer or the primer layer in the antireflection film of the present invention, and at the boundary between the hard coat layer or the primer layer and the light transmitting substrate. This is because the antireflection function of the antireflection film of the present invention can be prevented from being impaired due to the reflection of light at these boundaries. Among them, the difference between the refractive index of the hard coat layer or primer layer used in the present invention and the refractive index of the antireflection layer and the light transmissive substrate is preferably in the range of 0 to 0.5. More preferably, it is in the range of -0.2, more preferably in the range of 0-0.1.

  Next, the case where the said adhesion layer is used for the antireflection film of this invention is demonstrated, referring drawings. FIG. 8 is a schematic cross-sectional view showing an example in which an adhesive layer is used in the antireflection film of the present invention. As illustrated in FIG. 8, the antireflection film 10 of the present invention includes an adhesive layer on the surface of the light transmissive substrate 1 opposite to the surface on which the antireflection layer 2 and the hard coat layer or the primer layer 5 are formed. 6 may be formed. In addition, about the code | symbol which is not demonstrated in FIG. 8, since it can be the same as that of FIG. 1, description here is abbreviate | omitted.

  The adhesive layer used for this invention will not be specifically limited if it consists of a desired adhesive according to the use of the antireflection film of this invention. Examples of the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer include acrylic polymers, silicone polymers, polyesters, polyurethanes, polyamides, polyethers, fluorine-based and rubber-based polymers, so-called gel polymers, and the like.

  The thickness of the pressure-sensitive adhesive layer used in the present invention is preferably in the range of 1 μm to 400 μm, more preferably in the range of 1 μm to 100 μm, and still more preferably in the range of 1 μm to 50 μm. However, it is not particularly limited.

  In addition to the above-described materials, the primer layer (adhesion stable layer), hard coat layer, antistatic layer, and other functional layers used in the present invention may contain additives as necessary. . As such an additive, those similar to the additive described in the section of “1. Antireflection layer” can be used, and therefore description thereof is omitted here.

  Next, the case where the said protective layer is used for the antireflection film of this invention is demonstrated, referring drawings. FIG. 9 is a schematic cross-sectional view showing an example when a protective layer is used in the antireflection film of the present invention. As illustrated in FIGS. 9A to 9C, the antireflection film 10 of the present invention may have a protective layer 7 formed on the surface of the antireflection layer 2. As illustrated in FIG. 9A, the protective layer 7 may be formed so that only the top surface of the antireflection layer 2 is in contact with the protective layer 7, as illustrated in FIG. 9B. The antireflection layer 2 may be formed so as to be slightly recessed into the protective layer 7, and the antireflection layer 2 may be formed so as to enter the protective layer 7 as illustrated in FIG. 9C. . In addition, about the code | symbol which is not demonstrated in FIG. 9, since it can be made the same as that of FIG. 1, description here is abbreviate | omitted.

  As a method for forming a protective layer formed on the surface of the antireflection layer used in the present invention, a method of applying a protective film that expresses pressure-sensitive or heat-sensitive adhesive force, a resin having a protective function is coated, UV irradiation, There are a method of forming a film by drying, a method of melting and extruding to the surface of the antireflection layer, and forming by cooling.

The protective layer formed by the pressure-sensitive or heat-sensitive method is not particularly limited as long as it is made of a desired protective layer material according to the use of the antireflection film of the present invention. Examples of the pressure-sensitive protective layer material include acrylic polymers, silicone polymers, polyesters, polyurethanes, polyamides, polyethers, fluorine-based and rubber-based polymers, so-called gel polymers, and the like. Further, the protective layer comprises an olefin-based thermoplastic resin, ethylene / α-olefin copolymer, propylene / α-olefin copolymer, 1-butene homopolymer and copolymer, styrene-butadiene block copolymer, styrene-butadiene. You may form with the resin layer which mixed the hydrogenated substance of the block copolymer, the tackifier, and said adhesive.
Further, the protective layer comprises an unsaturated carboxylic acid graft-modified α-olefin polymer and α-olefin copolymer, a copolymer of ethylene and acrylic acid or an acrylic acid derivative, ethylene and methacrylic acid or methacrylic acid. It may be formed from a resin layer containing a copolymer with a derivative, a metal ion-crosslinked α-olefin polymer, a copolymer of ethylene and α-olefin, or the like.

  When the protective layer is formed by melt extrusion onto the surface of the antireflection layer and cooling, the protective layer materials include α-olefin polymers, copolymers of ethylene and α-olefins, and copolymers of propylene and α-olefins. A polymer can be used alone or blended. Examples of the resin to be blended include acrylic polymers, silicone polymers, polyesters, polyurethanes, polyamides, polyethers, fluorine-based and rubber-based polymers, so-called gel polymers, and the like. Also, ethylene / α-olefin copolymer, propylene / α-olefin copolymer, 1-butene homopolymer and copolymer, styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, tackifier, Saturated carboxylic acid graft-modified α-olefin polymers and α-olefin copolymers, copolymers of ethylene and acrylic acid or acrylic acid derivatives, copolymers of ethylene and methacrylic acid or methacrylic acid derivatives, metal ions Crosslinked α-olefin polymers or copolymers of ethylene and α-olefins may be mentioned.

  As a method of coating a resin having a protective function and forming a film by UV irradiation or drying, the film is formed by coating the upper surface of the antireflection layer with or without diluting with an organic solvent or an aqueous system. If necessary, drying, cooling, and UV irradiation are performed to improve the film strength. Examples of the resin used include acrylic polymers, silicone polymers, polyesters, polyurethanes, polyamides, polyethers, fluororesins and rubber polymers, so-called gel polymers, and the like.

4). Next, a method for producing the antireflection film of the present invention will be described. The antireflection film of the present invention can be produced using a generally known method as a method for producing a so-called moth-eye type antireflection film. Specifically, the following three aspects are mentioned. Can do.

(1) 1st aspect 1st aspect of the manufacturing method of the antireflection film of this invention uses the metal mold | die which has the shape which can form the fine unevenness | corrugation of the antireflection layer in this invention, and resin is used for the said metal mold | die. A filling step of filling the resin composition for forming an antireflection layer containing a resin, a placement step of placing a light-transmitting substrate on the resin composition for forming an antireflection layer filled in the mold, and the antireflection A pressure-loading step of applying a pressure capable of forming the fine irregularities in a state where the resin composition for layer formation and the light-transmitting substrate are in contact with each other; and for forming the anti-reflection layer after releasing the pressure. It is a manufacturing method which has the hardening process which hardens a resin composition, and the peeling process which peels the said metal mold | die from the cured resin composition for antireflection layer formation.
Hereinafter, each process in the manufacturing method of the antireflection film of the 1st mode is explained.

(A) Filling step The filling step in this embodiment uses a mold having a shape capable of forming fine irregularities of the antireflection layer in the present invention, and the antireflection layer forming resin contains a resin in the mold. It is a step of filling the composition.

The resin composition for forming an antireflection layer used in this embodiment contains at least a resin. The resin used in this embodiment is not particularly limited as long as fine irregularities having a desired shape can be formed. For example, the resin described in the section “1. Antireflection layer” is preferable. Can be used.
Moreover, the resin composition for forming an antireflection layer may contain an optional additive as necessary in addition to the resin. Examples of such an additive include the above-mentioned “1. Antireflection layer”. Can be used.

The viscosity of the antireflective layer forming resin composition is not particularly limited as long as the antireflective layer forming resin composition can enter the mold to a desired degree. In the range of 10 mPa · s to 10000 mPa · s, more preferably in the range of 50 mPa · s to 5000 mPa · s, and further in the range of 100 mPa · s to 3000 mPa · s. preferable.
In the case of a melt-type resin, for example, the melt flow index (MFI) at 190 ° C. is preferably 1.0 g / 10 min or more, more preferably 3.0 g / 10 min or more. More preferably, it is 0.0 g / 10 min or more.

  The mold used in the present embodiment is not particularly limited as long as fine irregularities having a desired shape can be formed on the resin composition for forming an antireflection layer. For example, “C. The mold described in the section “Film-manufacturing mold” can be preferably used.

(B) Arrangement Step The arrangement step in this embodiment is a step of disposing a light transmissive substrate on the antireflection layer forming resin composition filled in the mold.

  Examples of the light transmissive substrate used in this embodiment include those described in the above section “2. Light transmissive substrate”.

(C) Pressure load process The pressure load process in this aspect loads the pressure which can form the said fine unevenness | corrugation in the state which the said resin composition for anti-reflective layer formation and the said light-transmissive board | substrate contact | connected. It is a process. In this process, in the fine unevenness formed by a truncated cone-shaped main body portion that rises in a tapered shape with respect to the light-transmitting substrate, and a tip portion having a curved structure formed so as to cover the top surface of the main body portion. The shape of the convex portion can be formed.

  The pressure in this step is appropriately selected according to the viscosity or the like of the resin composition for forming an antireflection layer used in this embodiment, and using the above resin composition for forming an antireflection layer and the above mold. The degree to which the shape of the mold can be formed in the resin composition for forming an antireflection layer is found by repeating experiments while adjusting the pressure. For example, when the antireflection layer forming resin composition having the above-described viscosity is used, the pressure is preferably in the range of 1.0 N / cm to 50 N / cm, and 2.5 N / cm to 40 N. More preferably within the range of / cm, and even more preferably within the range of 5.0 N / cm to 25 N / cm. If the pressure is too low, the resin composition for forming an antireflection layer does not enter the mold so much that the height of the projections in the fine irregularities may not be sufficient, and the pressure is too high. This is because the anti-reflective layer forming resin composition may enter the mold too much and not come out of the mold.

  In this step, examples of the method of applying the pressure include a method using a roll press, a flat plate press, an injection press, a belt press method, a sleeve touch method, a roll touch method using an elastic metal roll, and the like.

(D) Curing Step The curing step in this embodiment is a step of curing the antireflection layer forming resin composition after releasing the pressure. The resin composition for forming an antireflection layer cured in this step is an antireflection layer in the present invention.

  In this step, the method for curing the resin composition for forming an antireflection layer is appropriately selected according to the resin contained in the resin composition for forming an antireflection layer. In the case of an ionizing radiation curable resin, an ultraviolet curing method and an electron beam curing method can be exemplified, and when the resin is a thermosetting resin, a heat curing method and a room temperature curing method can be exemplified. Moreover, when using a thermoplastic resin for the said resin, it can be hardened | cured by the cooling method which makes a cooling roll etc. contact.

(E) Peeling Step The peeling step in this embodiment is a step of peeling the mold from the cured resin composition for forming an antireflection layer.

  The peeling method in this step is not particularly limited as long as the mold can be peeled without damaging the cured resin composition for forming an antireflection layer, that is, the antireflection layer.

(2) Second Aspect In a second aspect of the method for producing an antireflection film of the present invention, the antireflection layer is formed by coating a resin composition for forming an antireflection layer containing a resin on a light-transmitting substrate. The fine irregularities can be formed using a film forming step for forming a film made of the forming resin composition and a mold having a shape capable of forming the fine irregularities of the antireflection layer in the present invention. By applying pressure, a molding step for shaping the fine irregularities in the film made of the resin composition for forming an antireflection layer, and curing the resin composition for forming an antireflection layer after releasing the pressure It is a manufacturing method which has a hardening process and the peeling process which peels the said metal mold | die from the said cured resin composition for antireflection layer formation. When the antireflection film of the present invention is long or batch-shaped, the production method of this embodiment is usually used.
Hereinafter, each process in the manufacturing method of the antireflection film of the 2nd mode is explained.

(A) Film formation process The film formation process in this aspect consists of the said resin composition for anti-reflective layer formation by coating the resin composition for anti-reflective layer formation containing resin on a transparent substrate. This is a step of forming a film.

  The light-transmitting substrate and the antireflection layer-forming resin composition used in this embodiment are the same as the contents described in the first embodiment, and a description thereof is omitted here.

  In this step, the method for applying the resin composition for forming an antireflection layer is not particularly limited as long as it can be uniformly applied onto a light-transmitting substrate. For example, dip coating, roll coating Known methods such as a method, a T-die coating method, a cast coating method, a blade coating method, a spin coating method, a bar coating method, a wire bar coating method, a casting method, and an LB method can be used. After coating, a drying process or a half curing process by heat, UV or EB can be appropriately performed.

(B) Molding process The molding process in this embodiment uses a mold having a shape capable of forming the fine irregularities of the antireflection layer in the present invention, and applies a pressure capable of forming the fine irregularities. It is a step of shaping the fine irregularities in a film made of the resin composition for forming an antireflection layer by loading. In this process, in the fine unevenness formed by a truncated cone-shaped main body portion that rises in a tapered shape with respect to the light-transmitting substrate, and a tip portion having a curved structure formed so as to cover the top surface of the main body portion. The shape of the convex portion can be formed.

About the pressure in this process and its loading method, since it is the same as that of the content described in the pressure loading process of the above-mentioned 1st mode, explanation here is omitted.
Moreover, as a metal mold | die used for this aspect, the thing similar to the said 1st aspect can be used suitably. Further, the mold may be a flat plate shape, a roll shape, or a belt shape.

(C) Curing step The curing step in this embodiment is a step of curing the antireflection layer-forming resin composition after releasing the pressure. The resin composition for forming an antireflection layer cured in this step is an antireflection layer in the present invention. In addition, about the said hardening process, since it is the same as that of the 1st aspect mentioned above, description here is abbreviate | omitted.

(D) Peeling Step The peeling step in this aspect is a step of peeling the mold from the cured resin composition for forming an antireflection layer. About the said peeling process, since it is the same as that of the 1st aspect mentioned above, description here is abbreviate | omitted.

(3) Third Aspect In a third aspect of the method for producing an antireflection film of the present invention, an antireflection layer-forming resin composition containing a resin and a light-transmitting substrate-forming resin composition containing a resin are used. Using a coextrusion step of melt coextrusion or melt coextrusion, and a mold having a shape capable of forming fine irregularities of the antireflection layer in the present invention, and applying a pressure capable of forming the fine irregularities By forming the fine irregularities on the antireflection layer forming resin composition side of the laminate composed of the coextruded resin composition for forming an antireflection layer and the resin composition for forming a light transmissive substrate. A mold forming step, a curing step of curing the laminate after releasing the pressure, and a peeling step of peeling the mold from the cured laminate.
Hereinafter, each process in the manufacturing method of the antireflection film of the 3rd mode is explained.

(A) Co-extrusion process The co-extrusion process in this aspect is a melt co-extrusion or dissolution co-extrusion of a resin composition for forming an antireflection layer containing a resin and a resin composition for forming a light-transmitting substrate containing a resin. It is a process to do.

Since the resin composition for forming an antireflection layer used in this embodiment is the same as that described in the first embodiment, description thereof is omitted here.
On the other hand, the light-transmitting substrate-forming resin composition used in this embodiment contains at least a resin. The resin used in this embodiment is not particularly limited as long as it can form a light transmissive substrate. For example, the resin described in the section “2. Light transmissive substrate” is preferable. Can be used.
Further, the antireflection layer forming resin composition and the light transmissive substrate forming resin composition used in this embodiment may be made of the same material or a modified product of the same resin.

In this step, as a method of melt coextrusion of the resin composition for forming an antireflection layer and the resin composition for forming a light transmissive substrate, for example, the resin composition for forming an antireflection layer and the light composition can be used. Examples thereof include a method in which the resin composition for forming a transmissive substrate is prepared in a state of being thermally melted within a temperature range of a glass transition temperature or more and a pyrolysis temperature or less and extruded using a multilayer T die. In this case, the T-die can be multi-layered, and the single-layer T dies are arranged in multiple rows and coated with the molten resin composition for forming a light-transmitting substrate, and then the reflected in the molten state. The resin composition for preventing layer formation can also be laminated.
Further, in this step, as a method for dissolving and extruding the antireflection layer forming resin composition and the light transmissive substrate forming resin composition, for example, the antireflection layer forming resin composition, A method in which the above light-transmitting substrate-forming resin composition is prepared in a liquid state, supplied to a multilayer coating die head, applied to a metal or resin belt or roll, and dried to form a film. Can be mentioned. In this case, the die head can be multi-layered, the single-layer coating die heads are arranged in multiple rows, and the dissolved resin composition for forming a light-transmitting substrate is applied, and then the dissolved state is applied. A resin composition for forming an antireflection layer can also be laminated.
As a method for making a liquid state, a method of dispersing or dissolving in an organic solvent, a method of dispersing or dissolving in an aqueous solution, a method of using a solution in which a polymerization initiator is added to a 100% solid monomer (for example, acrylic) Etc.

  In this step, the resin composition for forming a light transmissive substrate may be melt coextruded or melt coextruded so as to be sandwiched by the resin composition for forming an antireflection layer.

(B) Molding process The molding process in this embodiment uses a mold having a shape capable of forming the fine irregularities of the antireflection layer in the present invention, and applies a pressure capable of forming the fine irregularities. When loaded, the fine irregularities are applied to the anti-reflection layer forming resin composition side of the laminate composed of the co-extruded resin composition for forming an anti-reflection layer and the resin composition for forming a light-transmitting substrate. This is a molding process. In this process, in the fine unevenness formed by a truncated cone-shaped main body portion that rises in a tapered shape with respect to the light-transmitting substrate, and a tip portion having a curved structure formed so as to cover the top surface of the main body portion. The shape of the convex portion can be formed.

About the pressure in this process and its loading method, since it is the same as that of the content described in the pressure loading process of the above-mentioned 1st mode, explanation here is omitted.
Moreover, as a metal mold | die used for this aspect, the thing similar to the said 1st aspect can be used suitably. Further, the mold may be a flat plate shape, a roll shape, or a belt shape.

  Moreover, in this aspect, the laminate comprising the antireflection layer-forming resin composition and the light-transmitting substrate-forming resin composition coextruded in the co-extrusion step is the light-transmitting substrate-forming resin. In the case where the composition is sandwiched between the resin compositions for forming an antireflection layer, the fine irregularities are formed on the side of the resin composition for forming an antireflection layer of the laminate by this step, thereby You may form the shape of the convex part in the fine unevenness | corrugation mentioned above on the front and back both surfaces of a laminated body.

(C) Curing step The curing step in this embodiment is a step of curing the laminate after releasing the pressure. The resin composition for forming an antireflection layer in the laminate cured in this step becomes an antireflection layer in the present invention, and the resin composition for forming a light transmissive substrate in the laminate cured in this step is This is a light-transmitting substrate in the present invention.

  In this step, the method of curing the laminate is appropriately selected according to the resin contained in the antireflection layer-forming resin composition and the light-transmitting substrate-forming resin composition. For example, when the resin is an ionizing radiation curable resin, examples include an ultraviolet curing method and an electron beam curing method. When the resin is a thermosetting resin, examples include a heat curing method and a room temperature curing method. Can do. Moreover, when using a thermoplastic resin for the said resin, it can be hardened | cured by the cooling method which makes a cooling roll etc. contact.

(D) Peeling process The peeling process in this aspect is a process of peeling the said metal mold | die from the said laminated body hardened | cured. About the said peeling process, since it is the same as that of the 1st aspect mentioned above, description here is abbreviate | omitted.

B. Next, the manufacturing method of the metal mold | die for antireflection film manufacture of this invention is demonstrated. The method for producing a mold for producing an antireflection film according to the present invention comprises using a metal substrate, an anodizing step of forming a metal oxide film having a plurality of fine holes on the surface of the metal substrate by an anodic oxidation method, and the metal oxidation. A first etching step of forming a tapered shape in the opening of the micropore by etching the film; and the micropore by etching the metal oxide film at an etching rate higher than the etching rate of the first etching step. And a second etching step for enlarging the hole diameter of the metal substrate, and repeatedly performing a second etching step to form a plurality of micropores on the surface of the metal substrate.

The manufacturing method of the metal mold | die for antireflection film manufacture of this invention is demonstrated referring drawings. FIG. 10 is a process diagram showing an example of a method for producing a mold for producing an antireflection film of the present invention. As illustrated in FIG. 10, the method for manufacturing a mold for manufacturing an antireflection film according to the present invention uses a metal substrate 11 (FIG. 10A), and performs a fine hole forming step on the metal substrate 11. (FIG. 10 (b) to FIG. 10 (d)), the mold 20 for producing an antireflection film having a configuration in which fine holes are formed on the surface of the metal substrate 11 is produced (FIG. 10 (e)). ).
Here, in the fine hole forming step, the metal substrate 11 is used (FIG. 10A), and an anodic oxidation step of forming a metal oxide film 11 ′ having a plurality of fine holes on the surface of the metal substrate 11 by an anodic oxidation method. (FIG. 10B), a first etching step (FIG. 10C) for forming a tapered shape in the opening of the microhole by etching the metal oxide film 11 ′, and the metal oxide film 11 ′ The second etching step (FIG. 10 (d)) for enlarging the hole diameter of the fine holes by performing etching at an etching rate higher than the etching rate of the first etching step is sequentially repeated, so that the surface of the metal substrate 11 is finely patterned. A hole is formed.

  According to the present invention, since the first etching step is included, a tapered shape can be formed in the opening portion of the fine hole, and the resin layer easily enters the fine hole when the antireflection film is manufactured. A mold for producing an antireflection film that is easy to come off can be obtained.

The method for producing a mold for producing an antireflection film of the present invention includes a micropore forming step having at least an anodizing step, a first etching step, and a second etching step, and other optional steps as necessary. May be used.
Hereinafter, each process in the manufacturing method of the metal mold | die for antireflection film manufacture of this invention is demonstrated.

1. Micropore formation step First, the micropore formation step in the present invention will be described. In the fine hole forming step in the present invention, a metal substrate is used, and an anodic oxidation step of forming a metal oxide film having a plurality of fine holes on the surface of the metal substrate by an anodic oxidation method, and etching the metal oxide film. A first etching step for forming a tapered shape in the opening of the microhole, and a first etching step for expanding the hole diameter of the micropore by etching the metal oxide film at an etching rate higher than the etching rate of the first etching step. In this step, a plurality of fine holes are formed in the surface of the metal substrate by sequentially repeating the two etching steps.

(1) Metal substrate The metal substrate used in the present invention is not particularly limited as long as it is made of a metal capable of forming an anodized film on its surface, that is, a so-called valve metal. Examples of such a metal substrate include those made of aluminum, magnesium, titanium, silicon, etc. Among them, those made of aluminum can be suitably used. This is because aluminum is easily oxidized and an anodic oxide film is easily formed. The metal substrate used in the present invention may be composed of aluminum alone, and is formed on an arbitrary substrate so that the layer made of aluminum becomes the outermost layer by sputtering, vapor deposition, or plating. It may have a configuration. Examples of the base material used for the metal substrate include those made of rubber, resin, metal and the like.

  Moreover, the form of the metal substrate used in the present invention is not particularly limited. Therefore, in the present invention, a metal substrate having any form such as a sheet form, a roll form, a belt form, a three-dimensional form, and a film form can be suitably used. Here, the “three-dimensional metal substrate” refers to a metal substrate that is a three-dimensional object formed by injection molding or the like, and the “film-shaped metal substrate” refers to polyethylene terephthalate having a thickness of 200 μm or less, Polyester resin such as polyarylate, polyethylene naphthalate, and polybutylene terephthalate, polyolefin resin such as polypropylene, polyamide resin such as nylon 66, acrylic resin, acrylic melamine resin, silicone resin, polyimide resin, polyimide amide resin, polycarbonate resin , A metal substrate on which a resin layer such as a fluororesin is laminated, or a metal such as nickel, aluminum, stainless steel, copper, or an alloy thereof, or a surface of these alloys such as chromium, tantalum, Chita Refers copper, silver, gold, metal or inorganic or metal substrate laminated on the metal film such as a metal formed by stacking these compounds, such as silicon, or to a metal substrate made of these composites.

  The thickness of the metal substrate is not particularly limited as long as it can form a metal oxide film having a plurality of fine holes on the surface of the metal substrate and has sufficient strength as a mold. However, it can set within the range of 50 nm-100 mm, for example.

(2) Anodizing step The anodizing step in the present invention is a step of forming a metal oxide film having a plurality of fine holes on the surface of the metal substrate by an anodic oxidation method.

  The anodic oxidation method used in this step is not particularly limited as long as it is a method capable of forming a metal oxide film having fine holes formed in a desired depth and arrangement on the surface of the metal substrate. Here, the depth and arrangement of the micropores formed by the anodic oxidation method depend on the liquidity of the electrolytic solution used for the anodic oxidation, and the electrolytic solution used in this step is neutral. Even an electrolytic solution or an acidic electrolytic solution can be suitably used. Especially, in this process, it is preferable to use an acidic electrolytic solution as the electrolytic solution. This is because the use of an acidic electrolytic solution makes it possible to form micropores at random positions on the surface of the metal substrate in this step. Examples of the acidic electrolytic solution used in this step include a sulfuric acid aqueous solution, an oxalic acid aqueous solution, and a phosphoric acid aqueous solution.

  The anodic oxidation time in this step is not particularly limited as long as a metal oxide film having a plurality of fine holes having a desired shape can be formed on the surface of the metal substrate. It is appropriately set according to the electrolytic solution used in the process.

  The thickness of the metal oxide film formed by this step is not particularly limited as long as it has a plurality of fine holes having a desired shape.

(3) 1st etching process The 1st etching process in this invention is a process of forming a taper shape in the opening part of the said micropore by etching the said metal oxide film.

  In this step, the method for etching the metal oxide film is not particularly limited as long as it can form a desired tapered shape in the opening of the fine hole. Examples of such a method include an alkali etching method, an acidic etching method, and an electrolytic etching method. Although any of these methods can be used in this step, the alkali etching method has a large gloss, surface roughness, etc., and it is difficult to maintain the etching surface in a constant state. It is preferable to use an acidic etching method because it is required to always control the dissolved metal component in the bath in a certain range.

Especially in this invention, it is preferable that this process is a process performed in the electrolyte solution used at the said anodizing process immediately after the said anodizing process. This is because it is not necessary to separately prepare an etching solution used in the first etching step, and a tapered shape can be easily formed in the opening portion of the fine hole.
The electrolytic solution used in this step is the one used in the anodizing step. Specifically, an acidic electrolytic solution such as a sulfuric acid aqueous solution, an oxalic acid aqueous solution, a phosphoric acid aqueous solution, or a mixed solution thereof is used. Among them, an oxalic acid aqueous solution is preferable from the viewpoint of handling and management.
In addition, a time during which this step is performed immediately after the anodizing step in the electrolytic solution used in the anodizing step, that is, a metal oxide film having a plurality of micropores is formed on the surface by the anodizing step. The time for leaving the metal substrate as it is in the electrolytic solution used in the anodizing step is not particularly limited as long as a desired tapered shape can be formed in the opening of the micropore, For example, it is preferably 3 seconds or more, more preferably 10 seconds or more, and further preferably 60 seconds or more.
The reason why the tapered shape can be formed in the opening of the fine hole by this step is as follows.
<1> When anodizing is performed, a porous cylindrical hole is formed while forming an oxide film.
<2> When this oxide film is chemically dissolved, the outside (ie, the top surface) is exposed to the etching solution longer than the inside (ie, the bottom surface). This is because the exchange rate of the etchant that has entered the interior is slower than that of the external etchant.
<3> As a result, the amount of etching on the outside increases, resulting in a tapered shape.

  The etching rate in this step is lower than the etching rate in the second etching step described later. In the present invention, the reason why the shape formed in the opening of the microhole differs between the first etching step and the second etching step due to the difference in the etching rate is that the second etching has an etching rate higher than that of the first etching. This is because it is fast and has the effect of expanding the entire diameter of the hole formed in the tapered shape by the first etching.

(4) Second Etching Step The second etching step in the present invention is a step of enlarging the diameter of the fine holes by etching the metal oxide film at an etching rate higher than the etching rate of the first etching step. . In the present invention, normally, the tapered shape is not formed in the opening portion of the fine hole by the second etching step, and the diameter of the hole having the tapered shape formed by the first etching step is increased uniformly.

  In this step, the method of etching the metal oxide film at an etching rate higher than the etching rate of the first etching step may be a method of expanding the hole diameter of the fine holes formed in the metal oxide film to a desired level. For example, there is no particular limitation. As such a method, an etching method similar to the method described in the first etching step can be given.

  The etching rate in this step is higher than the etching rate in the first etching step and is not particularly limited as long as the diameter of the micropores can be enlarged, but the etching rate in the first etching step is not limited. Thus, it is preferably 1.2 times or more, more preferably 1.5 times or more, and further preferably 2.0 times or more. This is because if the ratio is 1.2 times or less, the effect of sufficiently expanding the hole diameter is reduced.

As an etching solution used in this step, for example, an aqueous sulfuric acid solution, an aqueous oxalic acid solution, an aqueous phosphoric acid solution, an aqueous chromic acid solution, or a mixed solution thereof is used. An alkaline aqueous solution such as sodium hydroxide is used. Among these, an aqueous phosphoric acid solution is preferable from the viewpoint of handling and management.
The concentration of the etching solution is appropriately adjusted according to the type of the etching solution used in this step, the metal substrate used in the present invention, and the like, for example, 0.005M to 2.0M. It is preferably within the range, and more preferably within the range of 0.01M to 1.5M. This is because if the concentration of the etchant used in the second etching step is higher than the above range, the metal oxide film may be completely removed by the second etching step. This is because if the concentration is lower than the above range, the etching rate in the second etching step is lowered, and sufficient pore diameter expansion processing cannot be performed.
The etching time in this step is appropriately adjusted according to the etching solution used in this step, the metal substrate used in the present invention, processing temperature, concentration, etc., for example, in the range of 1 minute to 60 minutes. Is preferably within the range of 2 minutes to 30 minutes. If the etching time of the second etching step is longer than the above range, the metal oxide film is completely removed by the second etching step, the wall between the holes becomes thin, the strength becomes weak, and the resin enters. If the etching time of the second etching step is shorter than the above range, the fine holes cannot be sufficiently enlarged, and a desired shape may not be obtained. Because.

(5) Micropore forming step In this step, the degree of repetition when the anodic oxidation step, the first etching step, and the second etching step are sequentially repeated is as follows. It is repeated a plurality of times until fine pores that are uniform enough to be used as This step may end with the anodizing step or the second etching step.

  In this step, the number of times that the anodic oxidation step, the first etching step, and the second etching step are sequentially repeated can be appropriately determined according to the shape of the target micropore. It is a thing and is not specifically limited. Further, in this step, the number of times that these steps are sequentially repeated is appropriately adjusted together with etching conditions such as an etching solution and an etching time according to the target etching amount.

  The shape of the fine holes formed on the surface of the metal substrate by this step is not particularly limited as long as the opening has a tapered shape. About the shape of the said micropore, since it can be made to be the same as that of what is described in the term of "C. metal mold | die for antireflection film" mentioned later, description here is abbreviate | omitted.

2. Arbitrary process The manufacturing method of the metal mold | die for antireflection film manufacture of this invention has the said micropore formation process at least, and may have another arbitrary processes as needed. Examples of such a process include a mold release process, a water washing process, and a drying process.

Especially, in this invention, it is preferable to have a mold release process process which performs a mold release process to the metal mold | die for antireflection film obtained by the said micropore formation process. It is because it can provide mold release property to the metal mold for antireflection film obtained by this invention by having a mold release process process. Since the mold for producing an antireflection film has releasability, there is an advantage that when the antireflection film is produced, the antireflection film can be easily taken out from the mold for producing the antireflection film.
The release treatment method is not particularly limited as long as it does not fill the fine holes of the metal oxide film in the antireflection film production mold. For example, a release agent may be used to produce the antireflection film. Examples thereof include a method of applying to a metal mold, a method of laminating a release agent on the metal mold for producing an antireflection film by a sputtering method, and the like. Examples of the release agent include fluorine compounds, silicone compounds, aliphatic amide compounds, paraffin compounds, and the like.

3. Applications The method for producing a mold for producing an antireflection film of the present invention can be used as a method for newly producing a mold for producing an antireflection film. The antireflection film produced using the mold for producing an antireflection film produced according to the present invention is usually disposed and used on the outermost surface of a display device or the like. However, the moth-eye structure formed on the surface of the anti-reflection film not only has an anti-reflection function, but improves the adhesion to the arbitrary layer when an arbitrary layer is formed on the moth-eye structure, for example, by an anchor effect. The function of making it possible can also be achieved. For this reason, the use of the antireflection film produced using the antireflection film production mold produced according to the present invention is not limited to the use disposed on the outermost surface of the display device as described above, For example, it may be arranged in an optical member having a configuration in which a plurality of layers are laminated, and may be used in an aspect that exhibits an antireflection function and an adhesion improving function by the anchor effect.

  Moreover, the manufacturing method of the metal mold | die for antireflection film manufacture of this invention can be used also as a method of reproducing | regenerating the metal mold | die for used antireflection film. That is, in the used antireflection film manufacturing mold, the micropores formed on the surface become non-uniform, and the performance of the manufactured antireflection film deteriorates if it is used continuously. It will be. Therefore, by using the used antireflection film manufacturing mold as the metal substrate in the present invention and carrying out the method of the present invention, the fine holes can be made uniform again and reused. For this reason, the manufacturing method of the metal mold | die for antireflection film manufacture of this invention can be used also as a reproduction | regeneration method of a metal mold | die.

C. Next, the mold for producing an antireflection film of the present invention will be described. The mold for producing an antireflection film of the present invention is a mold for producing an antireflection film comprising a metal substrate and a metal oxide film having a plurality of fine holes formed on the surface of the metal substrate, wherein the fine holes The opening has a tapered shape with a depth in the range of 60 nm to 2000 nm.

  The mold for producing an antireflection film of the present invention will be described with reference to the drawings. FIG. 11 is a schematic cross-sectional view showing an example of a mold for producing an antireflection film of the present invention. An antireflection film manufacturing mold 20 illustrated in FIG. 11 includes a metal base 11 and a metal oxide film 11 ′ formed on the surface of the metal base 11 and having a plurality of micropores. The portion has a tapered shape with a depth D within a predetermined range.

  According to the present invention, since the opening of the fine hole has a taper shape with a predetermined depth, when the antireflection film is produced, the resin layer easily enters the fine hole and is easily removed. It can be used as a mold.

  The metal substrate is the same as that described in the above-mentioned section “B. Method for producing mold for producing antireflection film”, and thus the description thereof is omitted here. Hereinafter, the other structure in the metal mold | die for antireflection film manufacture of this invention is demonstrated.

  The metal oxide film in the present invention is formed on the surface of a metal substrate and has a plurality of fine holes. The metal oxide film is usually formed by anodizing a metal substrate. The thickness of the metal oxide film is not particularly limited, and can be appropriately selected according to a target mold for producing an antireflection film.

The metal mold for producing an antireflection film of the present invention is characterized by having a tapered shape having a depth within a predetermined range at the openings of a plurality of fine holes of the metal oxide film. The depth of the tapered shape at the opening of the micropores may be in the range of 60 nm to 2000 nm, but is preferably in the range of 100 nm to 1200 nm, and is preferably in the range of 120 nm to 800 nm. Is more preferable. If the depth of the taper shape is deeper than the above range, the transferred portion of the micropores may be easily damaged in the antireflection film manufactured using the mold for manufacturing the antireflection film of the present invention. This is because sticking may easily occur or it may be difficult to remove from the mold. On the other hand, if the depth of the tapered shape is shallower than the above range, it is difficult to form the tapered shape, and the antireflection function may be deteriorated.
Here, the taper-shaped depth in the opening portion of the microhole means a distance from the opening surface of the microhole to the deepest portion of the taper shape, and is a distance represented by D in FIG. Depending on the shape of the fine holes, the depth of the tapered shape may be the same as the depth of the fine holes. The taper-shaped depth in the present invention is the average value of the measured values obtained by observing the longitudinal section of the micropores with an electron microscope and measuring the taper-shaped depth of ten.

The taper angle in the longitudinal section of the opening of the fine hole is not particularly limited as long as it is an angle capable of forming a tapered shape, but is preferably in the range of 50 ° to 87 °. More preferably, it is within the range of 55 ° to 85 °, and further preferably within the range of 55 ° to 82 °. When the taper angle in the longitudinal section of the opening of the fine hole is larger than the above range, the opening becomes close to a vertical shape, and it is difficult for the resin layer to enter the fine hole of the mold when manufacturing the antireflection film. Because there is. In addition, it is difficult to remove from the mold. On the other hand, if the taper angle in the longitudinal section of the opening of the microhole is smaller than the above range, it may be difficult to form the opening. In addition, the antireflection function becomes inferior.
Here, the taper angle in the longitudinal section of the opening of the microhole is formed by a straight line approximating the side wall and a straight line parallel to the opening surface when the side wall in the longitudinal section of the microhole is linear. Refers to an angle, for example, the angle represented by θ ₃ in FIG. On the other hand, when the side wall in the vertical cross section of the microhole is curved, the point on the outer periphery of the opening surface of the microhole and the point on the outer periphery of the surface formed by the transverse cross section of the tapered deepest part in the microhole are defined as the shortest distance. The angle formed by the straight line selected and tied in such a way and the straight line parallel to the opening surface is the angle represented by θ ₄ in FIG. In addition, the said taper angle in this invention is taken as the average value determined by the method mentioned above. FIG. 12 is a schematic cross-sectional view showing another example of the mold for producing an antireflection film of the present invention. The reference numerals in FIG. 12 are the same as those in FIG.

  The fine hole in the present invention is not particularly limited as long as the opening has a tapered shape with a predetermined depth, and the shape of the tip is narrow with respect to the opening. The shape of the tip of the fine hole may be, for example, a pointed shape, a flat shape, or a curved shape. Among these, in the present invention, it is preferable that the shape of the tip of the fine hole is a curved surface. This is because, in the case of a curved surface shape, the resin is likely to enter uniformly and variation in shape is reduced. On the other hand, in the case of a planar shape, if the resin fills the planar shape, it may not come off.

The shape of the opening surface of the micropore is not particularly limited, and examples thereof include a round shape such as a circle and an ellipse, and a polygonal shape.
The diameter of the opening surface of the micropore, that is, the pore size of the micropore is not particularly limited, but is preferably in the range of 25 nm to 500 nm, and in the range of 50 nm to 250 nm. Is more preferable. When the hole diameter of the fine holes is 25 nm or less, the space between adjacent structures in the antireflection film becomes large, so that the portion where the structures are not formed increases and the antireflection function deteriorates. In addition, let the said hole diameter in this invention be the average value determined by the method mentioned above.

  The period of the micropores is not particularly limited, and can be appropriately determined according to the use of the antireflection film produced using the antireflection film production mold of the present invention. Here, the period of the micropores affects the wavelength dependency of the reflectance of the antireflection film manufactured using the mold for manufacturing the antireflection film of the present invention, and becomes more visible as the period becomes longer. The reflectance for light on the short wavelength side in the light region tends to increase. On the other hand, when the period is 200 nm or less, the change in the wavelength dependence of the reflectance due to the fluctuation of the period is small. For this reason, the period of the micropores is preferably in the range of 80 nm to 400 nm, and more preferably in the range of 100 nm to 300 nm. In addition, the said period in this invention is taken as the average value determined by the method mentioned above.

  In addition, the depth of the micropores also affects the wavelength dependence of the reflectance of the antireflection film produced using the mold for producing the antireflection film of the present invention. The rate can be lowered, while the reflectance on the long wavelength side tends to increase as the depth becomes shallower. For these reasons, the depth of the micropores is preferably in the range of 60 nm to 2000 nm, and more preferably in the range of 100 nm to 800 nm. In addition, the said depth in this invention is taken as the average value determined by the method mentioned above.

  In addition, as the interval between the micropores becomes wider, the reflectance tends to increase in the entire wavelength region of visible light in the antireflection film produced using the mold for producing the antireflection film of the present invention. The reflectance tends to decrease in the entire wavelength region of visible light. For this reason, the interval between the micropores is preferably in the range of 0 nm to 100 nm, and more preferably in the range of 5 nm to 80 nm. In addition, the said space | interval in this invention is taken as the average value determined by the method mentioned above.

Here, the period, depth, and interval of the micropores are as shown by P ₂ , Q ₂ , and R ₂ in FIG. 13, respectively, from the top of the tip to the top of the tip in each adjacent microhole. The distance, the distance from the top of the tip of the minute hole to the opening surface, and the shortest distance between the outer peripheries of the opening surfaces of adjacent minute holes. FIG. 13 is a schematic diagram for explaining parameters for specifying fine irregularities in the mold for producing an antireflection film of the present invention.

  The variation in the depth of the micropores is preferably 100 nm or less, more preferably 50 nm or less, and even more preferably 10 nm or less. This is because if the variation in the depth of the micropores is larger than the above range, unevenness may occur in the antireflection function of the antireflection film produced using the mold for producing the antireflection film of the present invention. The variation in the depth of the micropores means a difference between the maximum value and the minimum value of the measured values obtained by observing the longitudinal cross section of the micropores with an electron microscope and measuring the depth of 10 pieces.

  In the present invention, the step between the opening surfaces of the adjacent micropores (hereinafter referred to as small undulations) is preferably 100 nm or less, more preferably 80 nm or less, and 50 nm or less. Further preferred. This is because if the small undulation exceeds 100 nm, the surface can be visually recognized as a scratch, and the antireflection function becomes non-uniform.

In the present invention, the step between the opening surfaces of the micropores separated by 500 nm or more (hereinafter referred to as large waviness) is preferably 10 μm or less, and more preferably in the range of 500 nm to 2 μm. preferable. This is because, when the swell is 500 nm or more, if the large swell is 10 μm or less, the antireflection function is not affected, and even if it is visually observed, it is not understood (deceived).
As a method for creating large waviness on the surface of the metal substrate, the surface of the metal substrate or the support of the metal substrate is roughened to form irregularities, the surface of the metal substrate or the support of the metal substrate is roughened, and irregularities are formed. After laminating the metal substrate by sputtering, plating, vapor deposition, roughening the surface of the metal substrate or the support of the metal substrate, forming irregularities, laminating the resin, and smoothing the irregularities , A method of laminating a metal substrate by a sputtering method, a plating method, a vapor deposition method, a method of laminating a resin on the surface of the metal substrate or a support of the metal substrate, forming an unevenness, and then laminating the metal substrate, silica on the surface, Examples include a method of laminating a resin containing metal or metal oxide particles on a metal substrate or a support of the metal substrate, forming irregularities, and then laminating the metal substrate.
As a method for roughening the surface of the metal substrate or the support of the metal substrate, mechanical treatment, electrochemical treatment, anodization, embossing method, polishing method, etching method, wet plating method, dry plating method, thermal spraying method, Examples include a method in which a photolithography method, a surface heat treatment method, a sol-gel method, and the like are appropriately used alone or in combination.
Mechanical treatment methods include sand blast method, shot blast method, grit blast method, blast method such as glass bead blast method, synthetic resin hair made of synthetic resin such as nylon, polypropylene, and vinyl chloride resin, Brush graining method using brush hair (material) such as non-woven fabric, animal hair, steel wire, wire graining method using metal wire, brush polishing method while supplying slurry containing abrasive (brush grain method) And buffing methods such as a ball grain method and a liquid honing method, and a shot peening method.
As an electrochemical treatment method, there is a method using a direct current or an alternating current in an aqueous electrolyte solution containing hydrochloric acid, nitric acid or sulfuric acid and chloride ion or nitrate ion.
Examples of the embossing method include roll embossing or single-wafer press-type embossing that presses a roll mold or a single-wafer press mold imparted with a large wavy shape on the surface and transfers the shape by 50% or more.
As the polishing method, barrel polishing method using a rotary barrel or vibration barrel, buff polishing method, leuter polishing method, abrasive flow polishing method, electrolytic polishing method, chemical polishing method, chemical composite polishing method, electrolytic composite polishing method , Chemical mechanical polishing, CMP polishing and the like.
Examples of the etching method include chemical etching, electrolytic etching, and dry etching using sputtering.
Examples of the wet plating method include an electroplating method, an electroless plating method, a hot dip galvanizing method, a hot dip aluminum plating method, and an insoluble anode method.
Examples of dry plating include physical vapor deposition (PVD) such as vacuum vapor deposition, resistance heating, sputtering, ion plating, and chemical vapor deposition (CVD) such as atmospheric pressure CVD, reduced pressure CVD, and plasma CVD. .
Flame spraying methods using metal, ceramics, plastics, cermets, carbides, and abradables as materials include flame flame spraying, powder flame spraying, flame flame spraying, explosive spraying (D gun), etc. Examples include arc spraying, plasma spraying (low pressure plasma spraying / atmospheric plasma spraying / water plasma spraying), electric spraying methods such as line explosion spraying, high-speed flame spraying, and cold spray spraying.
Surface heat treatment methods include bubbles on the surface, brushing, cratering, cracking, crystal growth treatment, bulking, convection dissipation patterning, sinking dissipation Examples include a method of forming a shape by a method such as patterning, dissipating patterning, agglomeration of particles, or nano buckling.
Further, a plasma ashing method in which undulations are formed on the surface using plasma can also be used.
Methods for laminating a resin on a metal substrate or its support include spraying, electrodeposition, dipping, dip coating, roll coating, T-die coating, cast coating, blade coating, spin coating, bar A known method such as a coating method, a wire bar coating method, a casting method, an LB method, an electrostatic coating method, a powder coating method, or a method of coating a tube or a sleeve can be used. After coating, a drying process or a half curing process by heat, UV or EB can be appropriately performed.
Examples of the resin used include ionizing radiation curable resins such as ultraviolet curable resins and electron beam curable resins, thermosetting resins, thermoplastic resins, and the like, for example, acrylic resins, polyester resins, epoxy resins, polyolefins. Resin, styrene resin, polyamide resin, polyimide resin, polyamideimide resin, polyurethane resin, polyvinyl acetate resin, polyvinyl alcohol resin, polyvinyl butyral resin, polycarbonate resin, melamine resin, urea resin, alkyd resin, phenol resin, cellulose resin, diallyl Examples thereof include phthalate resin, silicone resin, polyarylate resin, polyacetal resin, styrene-isoprene rubber, and fluorine resin. Moreover, there are these elastomers and acid-modified products.
The formation of large undulations can be achieved when the anodizing step, the first etching step, and the subsequent second etching step described in the above section “B. You may give as a pre-process of a process process, and you may process after this process process. Or you may carry out before and after this process process. Furthermore, it may be performed after the anodic oxidation step in the present processing step, or may be performed after the first etching step, and further, a combination thereof can be used.

  The transfer rate of the mold for producing the antireflection film of the present invention is appropriately adjusted according to the viscosity and pressure of the resin used at the production of the antireflection film, but may be 50% or more. That is, the mold for producing an antireflection film of the present invention has a micropore shape enough to obtain a fine uneven pattern having sufficient physical properties to be used as an antireflection film even if the transfer rate is not 100%. It can be molded into the resin layer. Therefore, at the tip portion of the resin layer that has entered the fine hole of the mold, a bottom surface or a side wall of the fine hole, or a portion that does not contact the bottom surface and the side wall is generated. Here, the transfer rate refers to the ratio of the depth at which the resin layer enters with respect to the depth of the fine holes. Since the penetration depth of the resin layer is the same as the height of the convex portion of the molded product, the transfer rate is the ratio of the height of the convex portion of the molded product to the depth of the fine holes.

  The method for producing the antireflection film production mold of the present invention is not particularly limited as long as it is a method capable of producing the antireflection film production mold having the above-described configuration. And the method described in the section “Method for producing mold for production of antireflection film”.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

  Hereinafter, the present invention will be specifically described by giving examples.

[Example 1]
(Production of anti-reflection film mold)
First, a rolled aluminum plate having a purity of 99.50% is polished so that the surface roughness Rz is 30 nm as a small undulation and the large undulation is 1 μm, and then a conversion voltage is obtained in an electrolyte solution of a 0.02 M oxalic acid aqueous solution. Anodization was performed for 120 seconds under the conditions of 40 V and 20 ° C. Next, as a first etching process, an etching process was performed for 60 seconds with the electrolytic solution after anodization. Subsequently, as a second etching process, a pore size expansion process was performed with a 1.0 M aqueous phosphoric acid solution for 150 seconds. Further, the above steps were repeated, and these were added five times in total. Thereby, an anodized alumina film was formed on the aluminum substrate. Finally, a fluorine mold release agent was applied and the excess mold release agent was washed to obtain a mold for producing an antireflection film.

[Example 1-1]
(Preparation of antireflection film)
An ultraviolet curable resin composition (viscosity: 500 mPa · s) was applied and filled so that the surface of the antireflection film-producing mold obtained in Example 1 was covered and had a thickness of 20 μm, and light was applied on it. A 80 μm thick triacetyl cellulose film (refractive index: 1.48) as a transparent substrate was bonded from an oblique direction, and the bonded body was pressed with a rubber roller under a load of 10 N / cm. . After confirming that the uniform composition was applied to the entire mold, ultraviolet rays were irradiated from the film side with an energy of 2000 mJ / cm ² to photocur the ultraviolet curable resin composition. Then, it peeled from the metal mold | die and obtained the antireflection film.

[Example 1-2]
(Preparation of antireflection film)
A polyethylene terephthalate film having a viscosity of 200 mPa · s and a light-transmitting substrate having a thickness of 125 μm (manufactured by Toray Industries Inc., base layer refractive index 1.66, coated surface refractive index 1. 58) An antireflection film was obtained in the same manner as in Example 1-1 except that the load at the time of bonding was changed to 2.5 N / cm.

[Example 1-3]
(Preparation of antireflection film)
The viscosity of the UV-curable resin composition used is 3000 mPa · s, the light-transmitting substrate is an acrylic film with a thickness of 125 μm (Mitsubishi Rayon, refractive index 1.49), and the load at the time of bonding is changed to 25 N / cm. Except having done, it carried out similarly to Example 1-1, and obtained the anti-reflective film.

[Example 2]
(Production of anti-reflection film mold)
First, an aluminum cylinder provided with rotating shafts at both ends of an extruded aluminum pipe having a purity of 99.85% is subjected to surface polishing so that the surface roughness Rz is 80 nm. Then, anodization was performed for 20 seconds under conditions of a formation voltage of 55 V and 20 ° C. Next, as a first etching process, an etching process was performed for 30 seconds with the electrolytic solution after anodization. Subsequently, as the second etching treatment, a pore size enlargement treatment was performed with a 0.5 M phosphoric acid aqueous solution for 10 minutes. Further, the above steps were repeated, and these were added four times in total. As a result, an anodized alumina film was formed on the aluminum cylinder. Finally, a fluorine mold release agent was applied and the excess mold release agent was washed to obtain a mold for producing an antireflection film.

[Example 2-1]
(Preparation of antireflection film)
An ultraviolet curable resin composition (viscosity: 100 mPa · s) containing a solvent that penetrates triacetylcellulose is thickened on a 80 μm thick triacetylcellulose film (refractive index: 1.48) as a light-transmitting substrate. After applying to a thickness of 40 μm and removing the solvent by drying, it was pressure-bonded to the antireflection film-producing mold obtained in Example 2 with a rubber roller under a load of 25 N / cm. After confirming that the uniform composition was applied to the entire mold, ultraviolet rays were irradiated from the film side with an energy of 2000 mJ / cm ² to photocur the ultraviolet curable resin composition. Then, it peeled from the metal mold | die and obtained the antireflection film.

[Example 3]
(Production of anti-reflection film mold)
First, after polishing the nickel substrate so that the surface roughness Rz is 60 nm, an acrylic resin layer having a thickness of 20 μm is formed, and an aluminum thin film having a purity of 99.99% and a thickness of 2 μm is formed on the surface by sputtering. Then, anodization was performed for 120 seconds in an electrolytic solution of 0.05 M oxalic acid aqueous solution under the conditions of a formation voltage of 40 V and 20 ° C. Next, as a first etching process, an etching process was performed for 120 seconds with the electrolytic solution after anodization. Subsequently, as the second etching process, a pore diameter expansion process was performed with a 0.7 M phosphoric acid aqueous solution for 150 seconds. Further, the above steps were repeated, and these were added a total of 8 times. Thereby, an anodized alumina film was formed on the aluminum thin film. Finally, a fluorine mold release agent was applied and the excess mold release agent was washed to obtain a mold for producing an antireflection film.

[Example 3-1]
(Preparation of antireflection film)
The surface of the mold for producing the antireflection film obtained in Example 3 was covered, and an acrylic resin (melt viscosity 6 g / 10 min) heated and melted at 200 ° C. was extruded so that the thickness became 500 μm, and the mold was filled with metal. The belt was pressed with a load of 50 N / cm for 2 seconds. It was confirmed that a uniform resin film was formed on the entire mold, and the acrylic resin was cured by cooling from the surface with air cooling. Then, it peeled from the metal mold | die and obtained the antireflection film.

[Example 3-2]
(Preparation of antireflection film)
An antireflection film was obtained in the same manner as in Example 3-1, except that the acrylic resin was changed to a polycarbonate resin (melt viscosity 1 g / 10 min) and a thickness of 1000 μm.

[Example 4]
(Production of anti-reflection film mold)
First, an aluminum cylinder provided with rotating shafts at both ends of an extruded aluminum pipe having a purity of 99.85% is polished so that the surface roughness Rz is 50 nm, and the surface has a purity of 99.99% and a thickness of 2 μm. An aluminum thin film was formed by sputtering, and anodized in an electrolytic solution of 0.05 M oxalic acid aqueous solution for 120 seconds under conditions of a conversion voltage of 75 V and 20 ° C. Next, as a first etching process, an etching process was performed for 60 seconds with the electrolytic solution after anodization. Subsequently, as a second etching process, a pore size expansion process was performed with a 2.0 M phosphoric acid aqueous solution for 300 seconds. Further, the above steps were repeated, and these were added 12 times in total. Thereby, an anodized alumina film was formed on the aluminum thin film. Finally, a fluorine mold release agent was applied and the excess mold release agent was washed to obtain a mold for producing an antireflection film.

[Example 4-1]
(Preparation of antireflection film)
UV curable composition containing 40% silica having an average particle diameter of 5 nm including a solvent which penetrates triacetyl cellulose in a triacetyl cellulose film (produced by Fuji Film Co., Ltd., refractive index: 1.48) as a light transmissive substrate. After applying a resin composition (viscosity 100 mPa · s) to a thickness of 50 μm, the solvent is removed by drying, and 20% antimony pentoxide having an average particle size of 8 nm is contained, and the solvent does not contain an ultraviolet curable resin. After laminating the composition (viscosity 500 mPa · s) to a thickness of 20 μm, it was pressure-bonded to the antireflection film-producing mold obtained in Example 4 with a rubber roller under a load of 15 N / cm. After confirming that the uniform composition was applied to the entire mold, ultraviolet rays were irradiated from the film side with an energy of 1500 mJ / cm ² to photocur the ultraviolet curable resin composition. Then, it peeled from the metal mold | die and obtained the antireflection film.

[Example 5]
(Production of anti-reflection film mold)
First, a stainless steel substrate formed by a rolling method is polished as a small undulation so that the surface roughness Rz is 10 nm, and then a large undulation of 1.5 μm is formed by blasting, and an acrylic melamine resin is formed on the surface. 10 μm was laminated. Further, an aluminum thin film having a purity of 99.99% and a thickness of 2 μm was formed on the surface by sputtering, and anodized in an electrolytic solution of 0.3 M oxalic acid aqueous solution for 20 seconds at a conversion voltage of 75 V and 20 ° C. Was given. Next, as a first etching process, an etching process was performed for 120 seconds with the electrolytic solution after anodization. Subsequently, as the second etching process, a pore size expansion process was performed with a 1.0 M phosphoric acid aqueous solution for 15 minutes. Further, the above steps were repeated, and these were added 20 times in total. Thereby, an anodized alumina film was formed on the aluminum thin film. Finally, a fluorine mold release agent was applied and the excess mold release agent was washed to obtain a mold for producing an antireflection film.

[Example 5-1]
(Preparation of antireflection film)
An ultraviolet curable resin composition (viscosity: 500 mPa · s) was applied and filled so that the surface of the antireflection film production mold obtained in Example 5 was covered and had a thickness of 20 μm. A 125 μm polyethylene terephthalate film (two-layer type, base part refractive index of 1.66, coated surface refractive index of 1.58, manufactured by Toray Industries, Inc.) is obliquely bonded as a transparent substrate, and then the bonded bonded body is made of rubber. Crimping was performed with a roller at a load of 10 N / cm. After confirming that the uniform composition was applied to the entire mold, ultraviolet rays were irradiated from the film side with an energy of 2000 mJ / cm ² to photocur the ultraviolet curable resin composition. Then, it peeled from the metal mold | die and obtained the antireflection film.

[Example 6]
(Production of anti-reflection film mold)
First, an acrylic resin containing silica particles having an average particle diameter of 1 μm and 10 μm in a polyethylene terephthalate film having a thickness of 25 μm (manufactured by Toray Industries Co., Ltd., two-layer type, base part refractive index 1.66, coated surface refractive index 1.58). In the electrolyte solution of 0.05M oxalic acid aqueous solution, a resin layer is applied, and an aluminum layer having a thickness of 2 μm is laminated by vapor deposition on a surface having a large undulation with a height of 0.8 μm and a pitch of 50 μm to 100 μm. Then, anodization was performed for 120 seconds under the conditions of a conversion voltage of 30 V and 20 ° C. Next, as a first etching process, an etching process was performed for 120 seconds with the electrolytic solution after anodization. Subsequently, as a second etching process, a pore size expansion process was performed with a 0.5 M aqueous phosphoric acid solution for 150 seconds. Further, the above steps were repeated, and these were added six times in total. Thereby, an anodized alumina film was formed on the aluminum layer. Finally, a fluorine mold release agent was applied and the excess mold release agent was washed to obtain a mold for producing an antireflection film.

[Example 6-1]
(Preparation of antireflection film)
A two-part curable resin composition obtained by adding 2 parts by weight of an isocyanate curing agent to 100 parts by weight of a polyester resin (viscosity 30 mPa · s) diluted with ethyl acetate was obtained in Example 6 by a gravure roll coating method. Thickness that was uniformly coated and filled to a thickness of 3 μm on the surface of the mold for producing the antireflection film and dried with ethyl acetate, and then the two-component curable resin layer surface was prepared as a light-transmitting substrate After being bonded to a polycarbonate film having a thickness of 50 μm (Mitsubishi Chemical Corporation, refractive index: 1.59), it was pressurized with a load of 25 N / cm between a heat roll and a rubber roll set at a temperature of 60 degrees. Furthermore, an aging treatment was performed at 40 ° C. for 5 days while the mold and the light-transmitting substrate were laminated via the two-component curable resin layer. Thereafter, the mixture was allowed to cool to room temperature for 24 hours, and then peeled off from the mold to obtain an antireflection film.

[Example 6-2]
(Preparation of antireflection film)
As a primer layer, a 50 μm thick polyethylene terephthalate film (manufactured by Toray Industries, Inc.) prepared as a light-transmitting substrate was a two-part curable resin composition in which 50 parts by weight of an isocyanate curing agent was added to 100 parts by weight of a polyester resin. A two-layer type was applied to the base part with a refractive index of 1.66 and a coating surface refractive index of 1.58), and was dried with hot air at 80 ° C. for 30 seconds. Further, an ultraviolet curable resin composition (viscosity 30 mPa · s) was applied on the primer layer so as to have a thickness of 5 μm, and then the antireflection film production mold obtained in Example 6 was applied with a rubber roller. Crimping was performed with a load of 5 N / cm. After confirming that the uniform composition was applied to the entire mold, ultraviolet rays were irradiated from the film side with an energy of 2000 mJ / cm ² to photocur the ultraviolet curable resin composition. Then, it peeled from the metal mold | die and obtained the antireflection film.

[Comparative Example 1]
(Production of anti-reflection film mold)
First, a rolled aluminum plate having a purity of 99.50% is polished as a small undulation so that the surface roughness Rz is 30 nm, and then formed in a 0.02M oxalic acid aqueous solution with a conversion voltage of 40 V and 20 ° C. Anodization was performed for 120 seconds under the conditions. Next, the first etching process was not performed, and immediately as the second etching process, a pore diameter expansion process was performed for 150 seconds with a 1.0 M aqueous phosphoric acid solution. Further, the above steps were repeated, and these were added five times in total. Thereby, an anodized alumina film was formed on the aluminum substrate. Finally, a fluorine mold release agent was applied and the excess mold release agent was washed to obtain a mold for producing an antireflection film.

[Comparative Example 1-1]
(Preparation of antireflection film)
An ultraviolet curable resin composition (viscosity 15000 mPa · s) was coated and filled so that the surface of the antireflection film production mold obtained in Comparative Example 1 was covered and had a thickness of 20 μm. A 80 μm thick triacetyl cellulose film (refractive index: 1.48) as a transparent substrate was bonded from an oblique direction, and the bonded body was pressed with a rubber roller under a load of 10 N / cm. . After confirming that the uniform composition was applied to the entire mold, ultraviolet rays were irradiated from the film side with an energy of 2000 mJ / cm ² to photocur the ultraviolet curable resin composition. Then, it peeled from the metal mold | die and obtained the antireflection film.

[Comparative Example 1-2]
(Preparation of antireflection film)
The UV curable resin composition (viscosity 5 mPa · s) was applied and filled so that the surface of the antireflection film production mold obtained in Comparative Example 1 was covered and had a thickness of 20 μm. A 80 μm thick triacetyl cellulose film (made by Fuji Film Co., Ltd., refractive index: 1.48) is bonded obliquely as a light transmissive substrate, and the bonded body is loaded with a rubber roller at a load of 80 N / cm. Crimped with. After confirming that the uniform composition was applied to the entire mold, ultraviolet rays were irradiated from the film side with an energy of 2000 mJ / cm ² to photocur the ultraviolet curable resin composition. Then, it peeled from the metal mold | die and obtained the antireflection film.

[Comparative Example 2]
(Production of anti-reflection film mold)
First, a rolled aluminum plate having a purity of 99.50% is polished so that the surface roughness Rz is 30 nm as a small undulation and the large undulation is 1 μm. Anodization was performed for 120 seconds under the conditions of 30 V and 20 ° C. Next, the first etching treatment was not performed, and immediately as the second etching treatment, a pore diameter enlargement treatment was performed with a 0.5 M phosphoric acid aqueous solution for 150 seconds. Further, the above steps were repeated, and these were added 50 times in total. Thereby, an anodized alumina film was formed on the aluminum substrate. Finally, a fluorine mold release agent was applied and the excess mold release agent was washed to obtain a mold for producing an antireflection film.

[Comparative Example 2-1]
(Preparation of antireflection film)
An ultraviolet curable resin composition (viscosity 5 mPa · s) was applied and filled so that the surface of the antireflection film production mold obtained in Comparative Example 2 was covered and had a thickness of 20 μm. An 80 μm triacetyl cellulose film (manufactured by Fuji Film Co., Ltd., refractive index: 1.48) was bonded as a transparent substrate from an oblique direction, and the bonded body was pressed with a rubber roller under a load of 80 N / cm. After confirming that the uniform composition was applied to the entire mold, ultraviolet rays were irradiated from the film side with an energy of 2000 mJ / cm ² to photocur the ultraviolet curable resin composition. Then, it peeled from the metal mold | die and obtained the antireflection film.

[Evaluation 1]
(Observation of cross section of mold for manufacturing antireflection film by scanning electron microscope)
The anti-reflection film manufacturing mold is cut vertically with a focused ion beam, and the cross section of the mold is observed using a scanning electron microscope S-4500 manufactured by Hitachi High-Technologies. The hole diameter, period, depth, and shape of the opening were measured.

  In the antireflection film-manufacturing mold obtained in Example 1, it was confirmed that a micropore having a pore diameter of approximately 0.5 nm was formed in the back of a tapered micropore having a pore diameter of approximately 100 nm. The period was 110 nm, and the depth of the micropores was 220 nm. Further, it was confirmed that a tapered shape was formed in the opening portion of the fine hole, the depth of the tapered shape was 215 nm, and the taper angle was 77 °.

  In the anti-reflection film manufacturing mold obtained in Example 2, it was observed that fine holes with a pore diameter of about 2 nm were formed at the back of the tapered fine holes with a pore diameter of about 120 nm, and the period of the fine holes was Was 130 nm and the depth of the micropores was 340 nm. In addition, it was confirmed that a tapered shape was formed in the opening portion of the fine hole, the depth of the tapered shape was 320 nm, and the taper angle was 80 °.

  In the anti-reflection film manufacturing mold obtained in Example 3, it was observed that micropores with a pore diameter of approximately 3 nm were formed in the back of the tapered micropores with a pore diameter of approximately 95 nm. Was 105 nm and the micropore depth was 330 nm. Further, it was confirmed that a tapered shape was formed in the opening portion of the fine hole, the depth of the tapered shape was 300 nm, and the taper angle was 82 °.

  In the antireflection film-manufacturing mold obtained in Example 4, it was observed that micropores with a pore diameter of approximately 6 nm were formed in the back of the tapered micropores with a pore diameter of approximately 160 nm, and the period of the micropores Was 190 nm and the depth of the micropores was 430 nm. Further, it was confirmed that a tapered shape was formed in the opening portion of the fine hole, the depth of the tapered shape was 400 nm, and the taper angle was 80 °.

  In the anti-reflection film manufacturing mold obtained in Example 5, it was observed that fine holes with a hole diameter of about 10 nm were formed in the back of the tapered fine holes with a hole diameter of about 200 nm, and the period of the fine holes was Was 180 nm and the depth of the micropores was 1150 nm. In addition, it was confirmed that a tapered shape was formed in the opening of the fine hole, the depth of the tapered shape was 1080 nm, and the taper angle was 85 °.

  In the antireflection film manufacturing mold obtained in Example 6, it was observed that a micropore having a pore diameter of approximately 0.5 nm was formed in the back of a tapered micropore having a pore diameter of approximately 75 nm. The period was 80 nm, and the depth of the micropores was 90 nm. In addition, it was confirmed that a tapered shape was formed in the opening of the fine hole, the depth of the tapered shape was 87 nm, and the taper angle was 67 °.

  In the antireflection film manufacturing mold obtained in Comparative Example 1, no micropores were observed in the back of the micropores having a pore diameter of approximately 105 nm, the micropore period was 110 nm, and the micropore depth was 220 nm. Met. Moreover, it was confirmed that the vertical shape was formed in the opening part of the micropore, and the depth of the vertical shape was 220 nm.

  In the anti-reflection film manufacturing mold obtained in Comparative Example 2, it was observed that micropores with a pore diameter of approximately 0.1 nm were formed in the back of the micropores with a pore diameter of approximately 75 nm, and the period of the micropores was The depth of the micropores was 8050 nm and 2050 nm. Moreover, it was confirmed that the vertical shape was formed in the opening part of a micropore, and the depth of the vertical shape was 2012 nm.

[Evaluation 2]
(Observation of antireflection film surface and cross section by scanning electron microscope)
The surface of the antireflection film was observed using a scanning electron microscope S-4500 manufactured by Hitachi High-Technologies. Moreover, a cross section was produced with a glass slice, and the cross section of the film was observed using a scanning electron microscope S-4500 manufactured by Hitachi High-Technologies. From the obtained image, the period of the convex portions in the fine irregularities, The height, the shape of the main body and the tip were measured.

(Reflectivity of antireflection film)
Black tape was affixed to the back surface of the antireflection film, and 5 ° incident absolute reflectance to the film surface was measured using a self-recording spectrophotometer UV-3100 manufactured by Shimadzu Corporation.

(Appearance of antireflection film)
Black tape was affixed to the back surface of the antireflection film and visually confirmed.

(Anti-reflection film sticking)
The antireflection film was immersed in water and taken out, and then air-dried for 24 hours. After confirming that no water droplets remained on the surface, the surface of the film was observed using a scanning electron microscope S-4500 manufactured by Hitachi High-Technologies. The presence or absence of sticking was confirmed from the obtained image.

(Wipe cloth for antireflection film)
The antireflection film was rubbed with a load of 50 g / cm ^{2 with} flannel and allowed to stand for 12 hours, and then the surface of the film was observed using a scanning electron microscope S-4500 manufactured by Hitachi High-Technologies. From the obtained image, it was confirmed whether or not the structure was damaged.

(Displacement of antireflection film from mold for manufacturing antireflection film)
The surface of the antireflection film was observed using a scanning electron microscope S-4500 manufactured by Hitachi High-Technologies. The damage state of the structure on the film surface was observed from the obtained image.

  The surface structure of the mold was transferred to the surface (transfer surface) of the antireflection film obtained in Example 1-1. The transfer surface has a convex shape with a period of 110 nm, a height of the convex part of 210 nm, and a main body part having a tapered shape with a taper angle of 77 ° and a tip part having a radius of 4 nm. The structure was formed. The removal from the mold was carried out without problems. The 5 ° regular reflectance was 0.02%. The appearance was not white and could withstand practical use. In addition, no sticking occurred, and wiping with a cloth suppressed damage, and there was no problem in practical use.

  The surface structure of the mold was transferred to the surface (transfer surface) of the antireflection film obtained in Example 1-2. The transfer surface has a convex shape with a convex period of 110 nm, a convex part height of 218 nm, and a main body part having a tapered shape with a taper angle of 77 ° and a tip part having a radius of 1 nm. The structure was formed. The removal from the mold was carried out without problems. The 5 ° regular reflectance was 0.05%. The appearance was not white and could withstand practical use. In addition, no sticking occurred, and wiping with a cloth suppressed damage, and there was no problem in practical use.

  The surface structure of the mold was transferred to the surface (transfer surface) of the antireflection film obtained in Example 1-3. The transfer surface has a convex shape with a period of 110 nm, a height of the convex part of 190 nm, and a main body portion having a tapered shape with a taper angle of 77 ° and a tip portion having a radius of 10 nm. The structure was formed. The removal from the mold was carried out without problems. The 5 ° regular reflectance was 0.01%. The appearance was not white and could withstand practical use. In addition, no sticking occurred, and wiping with a cloth suppressed damage, and there was no problem in practical use.

  The surface structure of the mold was transferred to the surface (transfer surface) of the antireflection film obtained in Example 2-1. The transfer surface has a convex portion period of 130 nm, a convex portion height of 298 nm, a main body portion having a taper shape having no curvature, a taper angle of 80 °, and a tip portion having a radius of 9 nm. An arc-shaped structure was formed. The removal from the mold was carried out without problems. The 5 ° regular reflectance was 0.01%. The appearance was not white and could withstand practical use. In addition, no sticking occurred, and wiping with a cloth suppressed damage, and there was no problem in practical use. Moreover, the solvent permeation layer was recognized by the light transmissive board | substrate from the result of the component analysis of the antireflection film using the energy dispersive X-ray detector attached to the scanning electron microscope S-4500 made from Hitachi High-Technologies.

  The surface structure of the mold was transferred to the surface (transfer surface) of the antireflection film obtained in Example 3-1. The transfer surface has a convex shape with a period of 105 nm, a height of the convex part of 295 nm, and a main body part having a tapered shape with a taper angle of 82 ° and a tip part having a radius of 10 nm. The structure was formed. The removal from the mold was carried out without problems. The 5 ° regular reflectance was 0.04%. The appearance was not white and could withstand practical use. In addition, no sticking occurred, and wiping with a cloth suppressed damage, and there was no problem in practical use.

  The surface structure of the mold was transferred to the surface (transfer surface) of the antireflection film obtained in Example 3-2. The transfer surface has a convex shape with a period of 105 nm, a height of the convex part of 280 nm, and a main body part having a taper shape with a curvature, a taper angle of 82 °, and a tip part with a radius of 15 nm. The structure was formed. The removal from the mold was carried out without problems. The 5 ° regular reflectance was 0.08%. The appearance was not white and could withstand practical use. In addition, no sticking occurred, and wiping with a cloth suppressed damage, and there was no problem in practical use.

  The surface structure of the mold was transferred to the surface (transfer surface) of the antireflection film obtained in Example 4-1. The transfer surface has an arc shape with a convex period of 190 nm, a convex part height of 406 nm, a main body part having a tapered shape, a taper angle of 80 °, and a tip part having a radius of 6 nm. The structure was formed. The removal from the mold was carried out without problems. The 5 ° regular reflectance was 0.01%. The appearance was not white and could withstand practical use. In addition, no sticking occurred, and wiping with a cloth suppressed damage, and there was no problem in practical use. Further, the surface resistivity was low, and good antistatic performance was exhibited. Moreover, the solvent permeation layer was recognized by the light transmissive board | substrate from the result of the component analysis of the antireflection film using the energy dispersive X-ray detector attached to the scanning electron microscope S-4500 made from Hitachi High-Technologies.

  The surface structure of the mold was transferred to the surface (transfer surface) of the antireflection film obtained in Example 5-1. The transfer surface has an arc shape with a convex period of 180 nm, a convex part height of 934 nm, and a main body part having a tapered shape with a taper angle of 85 ° and a tip part having a radius of 20 nm. The structure was formed. The removal from the mold was carried out without problems. The 5 ° regular reflectance was 0.1%. The appearance was not white and could withstand practical use. In addition, no sticking occurred, and wiping with a cloth suppressed damage, and there was no problem in practical use.

  The surface structure of the mold was transferred to the surface (transfer surface) of the antireflection film obtained in Example 6-1. The transfer surface has a convex period of 80 nm, a convex part height of 88 nm, a main body part having a taper shape having no curvature, a taper angle of 67 °, and a tip part having a radius of 1 nm. An arc-shaped structure was formed. The removal from the mold was carried out without problems. The 5 ° regular reflectance was 0.35%. The appearance was not white and could withstand practical use. In addition, no sticking occurred, and wiping with a cloth suppressed damage, and there was no problem in practical use.

  The surface structure of the mold was transferred to the surface (transfer surface) of the antireflection film obtained in Example 6-2. The transfer surface has a convex period of 80 nm, a convex part height of 88 nm, a main body part having a taper shape having no curvature, a taper angle of 67 °, and a tip part having a radius of 1 nm. An arc-shaped structure was formed. The removal from the mold was carried out without problems. The 5 ° regular reflectance was 0.4%. The appearance was not white and could withstand practical use. In addition, no sticking occurred, and wiping with a cloth suppressed damage, and there was no problem in practical use.

  The surface structure of the mold was transferred to the surface (transfer surface) of the antireflection film obtained in Comparative Example 1-1. The transfer surface was formed with a cylindrical structure having a convex portion period of 110 nm, a convex portion height of 58 nm, a main body portion having a vertical shape, and a tip portion having a flat shape. The removal from the mold was bad, and there were many portions where there was no structure on the surface of the transfer surface, that is, a portion that could not be peeled off from the mold. The 5 ° regular reflectance was 2.0%. The appearance was also whitish and could not be used practically. In addition, sticking occurred.

  The surface structure of the mold was transferred to the surface (transfer surface) of the antireflection film obtained in Comparative Example 1-2. The transfer surface was formed with a columnar structure having a convex portion period of 110 nm, a convex portion height of 220 nm, a main body portion having a vertical shape, and a tip portion having a flat shape. The removal from the mold was bad, and there were many portions where there was no structure on the surface of the transfer surface, that is, a portion that could not be peeled off from the mold. The 5 ° regular reflectance was 1.0%. The appearance was also whitish and could not be used practically. In addition, sticking occurred.

  The surface structure of the mold was transferred to the surface (transfer surface) of the antireflection film obtained in Comparative Example 2-1. On the transfer surface, a sharp conical structure having a period of convex portions of 80 nm, a convex portion height of 2050 nm, a main body portion having a vertical shape, and a tip portion having a radius of 0.05 nm is formed. It was. The removal from the mold was bad, and there were many portions where there was no structure on the surface of the transfer surface, that is, a portion that could not be peeled off from the mold. The 5 ° regular reflectance was 1.1%. In addition, sticking occurred, and the cloth was damaged by wiping.

DESCRIPTION OF SYMBOLS 1 ... Light transmissive board | substrate 2 ... Antireflection layer 3 ... Base part 4 ... Fine unevenness 4a ... Main-body part 4b ... Tip part 5 ... Hard-coat layer or primer layer 6 ... Adhesive layer 7 ... Protective layer 10 ... Antireflection film 11 ... Metal substrate 11 '... Metal oxide film 20 ... Mold for manufacturing antireflection film

Claims (6)

An antireflective film having a light transmissive substrate and an antireflective layer formed on the light transmissive substrate and having a concavo-convex shape formed on the surface with a period equal to or less than a wavelength of a visible light region,
The antireflection layer has a base portion formed on the light-transmitting substrate, a fine unevenness formed on the base portion and having the uneven shape, and the convex portion in the fine unevenness is the A reflection comprising a frustum-shaped main body portion that rises in a tapered shape with respect to a light-transmitting substrate and a tip portion having a curved structure formed so as to cover the top surface of the main body portion. Prevention film.   2. The antireflection film according to claim 1, wherein a taper angle with respect to the light transmissive substrate in a longitudinal section of the main body is within a range of 50 ° to 87 °.   The antireflection film according to claim 1 or 2, wherein a height of the main body is in a range of 60 nm to 1400 nm.   An anodizing step of forming a metal oxide film having a plurality of fine holes on the surface of the metal base by an anodizing method using a metal base, and a tapered shape at the opening of the fine holes by etching the metal oxide film A first etching step for forming the metal oxide film and a second etching step for expanding the diameter of the micropores by sequentially etching the metal oxide film at an etching rate higher than the etching rate of the first etching step. The manufacturing method of the metal mold | die for antireflection film characterized by having the micropore formation process which forms a several micropore in the surface of the said metal base | substrate by this.   5. The mold for producing an antireflection film according to claim 4, wherein the first etching step is a step performed immediately after the anodizing step in the electrolytic solution used in the anodizing step. Production method. A mold for producing an antireflection film comprising a metal substrate and a metal oxide film formed on the surface of the metal substrate and having a plurality of fine holes,
A mold for producing an antireflection film, wherein the opening of the fine hole has a tapered shape, and the depth of the tapered shape is in the range of 60 nm to 2000 nm.

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