JP2001252927A - Method for manufacturing article having predetermined surface shape, and mold - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a mold capable of obtaining good releasability and a method for manufacturing an article having a predetermined surface shape using the mold. SOLUTION: In the method for manufacturing the article having the predetermined surface shape by arranging a sol-gel material between a base material and a mold in a film-like state so as to bring the same into close contact with both of them and heating the same to coat the surface of the base material with the gelled film having a surface shape reverse to that of the mold, the mold is constituted by applying an adhesive reinforcing layer, which comprises at least one metal selected from the group consisting of platinum(Pt), copper(Cu), palladium(Pd) and silver(Ag), to the surface of a mold substrate, of which at least the surface comprises at least one material selected from the group consisting of titanium(Ti), aluminum(Al), silicon(Si) and oxides of them, and applying a release layer comprising gold(Au) to the adhesive reinforcing layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an article having predetermined fine irregularities on the surface of a substrate, and more particularly to a method for manufacturing a micro optical element and an information recording medium substrate.

[0002]

2. Description of the Related Art CD-ROMs, other information recording media,
The sol-gel method used to manufacture optical components such as flat plate microlenses (a lens array in which a large number of microlenses are arranged in parallel or staggered on a substrate), Fresnel lenses, diffraction grating elements, optical waveguide elements, etc. The sol-gel material applied with a constant thickness is heated while pressing a mold having a predetermined surface shape for a certain period of time, then the mold is released from the sol-gel material, and the sol-gel material is sintered again to form a solvent. Is evaporated to thereby obtain an article having a desired surface shape and film thickness.

In the sol-gel method described above,
In order to speed up the manufacturing process of an article having a predetermined surface shape, reduce the defect rate, and improve the dimensional accuracy of an article having a predetermined surface shape, a mold having a good mold release relative to the sol-gel material is used. It is essential to have the property. For this reason, a mold release film for a mold used in the sol-gel method has been studied.

[0004] In order to release a sol-gel material from a glass master, a method of forming a nickel layer on the glass master by electroforming (Japanese Patent Laid-Open No. 5-135414) has been reported.

In order to release the sol-gel material from the stainless steel substrate, a method of using a two-layer film plated with nickel and further plated with pure gold thereon (JP-A-4-376).
22) are known.

[0006]

However, the above-mentioned prior art has the following problems. First, in the above method, when a thick gelled film having a film thickness of 1 μm or more is produced, the release film on the surface of the mold is peeled off, or a part of the gelled film adheres to the mold and remains. Thus, sufficient releasability cannot be obtained. Further, in recent years, in the sol-gel method, compared to the conventional method, further speeding up the manufacturing process, lowering the defect rate and improving the dimensional accuracy are being demanded,
There is a need for a mold having even better releasability.

SUMMARY OF THE INVENTION The present invention has been made to satisfy the above-mentioned demands, and an object of the present invention is to provide a mold having good mold releasability and an article having a predetermined surface shape using the mold. It is to provide a manufacturing method of.

[0008]

According to the present invention, a sol-gel material is arranged in a film shape by closely adhering it between a substrate and a mold, and then heated to reverse the surface shape of the mold. In a method for producing an article having a predetermined surface shape, wherein a gelling film having a surface is coated on a substrate surface, the molding die includes:
Platinum (Pt), copper (Pt), copper (Ct), at least the surface of a mold substrate made of at least one material selected from the group consisting of titanium (Ti), aluminum (Al), silicon (Si), and oxides thereof. (Cu), palladium (Pd), and silver (A
g) an adhesion enhancing layer made of at least one metal selected from the group consisting of: and gold on the adhesion enhancing layer.
A method for producing an article having a predetermined surface shape, wherein the article has a release layer made of (Au).

In the present invention, gold is used as the release film on the outermost surface of the mold. Gold is an excellent material as a release film because it has good mold release properties for sol-gel materials, mechanical strength enough to withstand pressure on sol-gel materials, heat resistance, corrosion resistance, and oxidation resistance. If the thickness of the gold release film is too small, the number of repeated use is reduced,
When the thickness of the film is too large, the transferability of the mold is deteriorated.
Therefore, the thickness of the release film is preferably 200 to 1000 nm, more preferably 400 to 600 nm. The release film is more uniform and smoother by sputtering, vacuum evaporation, electroless plating, electrolytic plating, foil bonding, etc., because the smoother the surface, the higher the release properties. Is preferred.

[0010] The molding die of the present invention comprises platinum under the release film, that is, between the surface of the mold base and the release film.
(Pt), copper (Cu), palladium (Pd), and silver (Ag)
Having an adhesion enhancing layer made of at least one metal selected from the group consisting of: Specifically, platinum (Pt), copper (Cu),
A layer of palladium (Pd), silver (Ag) or an alloy thereof is coated at a predetermined thickness along the surface of the mold base. The adhesion-enhancing layer firmly adheres the release film to the mold substrate, prevents the release film from mixing with the surface layer of the mold substrate during the film formation, and forms a pure release film. It also serves as a protective layer. Platinum (Pt) is a metal that is particularly excellent in adhesion and protection with the surface of the mold base.
If the thickness of the adhesion reinforcing layer is too small, the adhesion between the release film and the surface of the mold base cannot be enhanced, and the composition of the release film is not pure gold. Conversely, if the thickness is too large, the transferability of the mold deteriorates. Therefore, the thickness of the adhesion enhancing layer is preferably from 50 to 400 nm, more preferably from 100 to 200 nm. The adhesion enhancing layer is
It is preferable that the film is uniformly and smoothly formed by a sputtering method, a vacuum evaporation method, an electroless plating method, an electrolytic plating method, or the like.

The mold base of the present invention has at least a surface made of at least one material selected from the group consisting of titanium (Ti), aluminum (Al), silicon (Si), and oxides thereof. The molding substrate may be an integral one made of titanium, aluminum, silicon, titanium oxide, aluminum oxide or silicon oxide, but for example, silicon, glass (including quartz glass), resin, metal or a composite thereof. Titanium (Ti), aluminum (Al), silicon
An underlayer made of at least one material selected from the group consisting of (Si) and these oxides may be provided. When the surface of the mold base is made of the above-described material, the release film and the adhesion enhancing layer are firmly adhered to the mold base, and the durability is improved without the possibility that the release film is peeled off from the mold. The underlayer preferably has a thickness of 20 to 300 nm, more preferably 50 to 100 nm. The underlayer is preferably formed uniformly and smoothly by a sputtering method, a vacuum evaporation method, an electroless plating method, an electrolytic plating method, or the like. As an example of the molding die substrate, for example, a substrate obtained by vacuum-depositing titanium on the surface of a silicon or quartz glass core material can be mentioned.

It is preferable to select a material having an expansion coefficient similar to that of the release film as the material of the mold core. Mold cores made of resin have the advantage that they can be easily micro-processed and easily formed into a desired shape, and glass or metal mold cores have high heat resistance and mechanical strength, and are durable. Are better.

The mold according to the present invention has a concave portion or a convex portion on its surface. Examples of the concavo-convex portion include a spherical shape, a conical shape, a pyramid shape, and a slit shape having an arbitrary cross section. The spherical, conical, and pyramidal shapes are provided in an arbitrary number in the entire or partial area of the release film. On the other hand, when a slit is provided as a concave portion, the slit may be provided linearly or arbitrarily in a curved shape.
It may be provided in a lattice shape.

The above-mentioned mold base is formed by, for example, precisely etching the surface of a glass substrate having a flat surface to form a concave shape having a desired shape. Using this as a seed mold, a convex metal matrix can be produced by electroless and electrolytic plating methods. Also, using the concave mold as a mother mold, a convex metal seed mold is produced by the plating method, and the seed mold is further plated by the plating method.
A concave metal matrix can be manufactured. These convex or concave mother dies can be used as the mold core material in the present invention. In the above plating method, metals such as nickel and chromium are preferably used. Further, using the seed mold produced by the above-described method, a resin mold can be produced by a 2P molding method using an ultraviolet curable resin, and this can be used as a mold core material in the present invention.

The article having a predetermined surface shape produced by the present invention has on its surface a gelled film having a surface having a shape inverted from the surface shape of the mold. Therefore, by setting the surface of the mold to a desired shape, a read-only optical information recording medium (CD-RO
M), an article having a predetermined surface shape such as a flat microlens or various optical components such as a grating element can be manufactured.

In the production method according to the present invention, the raw material of the sol-gel material may be a dialkyl dialkoxy silane, an alkyl trialkoxy silane, a trialkoxy silane containing an aryl group or an aryl group substituent, an aryl group or an aryl group substituent. A dialkoxysilane, a trihalogenated silane containing an aryl group or a substituted aryl group, a dihalogenated silane containing two substituted aryl groups or an aryl group, a fluorine-containing alkyltrialkoxysilane, a tetraalkoxysilane,
Tetraalkoxytitanium, tetraalkoxyzirconium, trialkoxyaluminum, tetrahalogenated silane, titanium tetrahalide, zirconium tetrahalide, aluminum trilahalide, and the like are used. As an example of a preferable combination among these, (A) a silane compound represented by the following formula (1),

## STR1 ## ^{_{R 1 m SiX 4-m ··}} (1) wherein R ¹ is an alkyl group and X is an alkoxyl group or a halogen atom, m is 1 or 2, (B) the following formula A silane compound represented by (2),

R ² SiY ₃ ... (2) wherein R ² is an aryl group or a substituted aryl group;
Y is an alkoxyl group or a halogen atom, and (C) a silane compound represented by the following formula (3):

## STR3 ## R ³ SiZ ₃ · · (3) wherein R ³ is a fluorine-containing alkyl group, and Z is an alkoxyl group or a halogen atom, a, the component (A) 0 to 95 mol%, Component (B) is 0 to 95 mol%, provided that the total of components (A) and (B) is 30 to 1%.
Raw materials for sol-gel materials containing 00 mol% (preferably 30 to 95 mol%) and 0 to 70 mol% (preferably 5 to 70 mol%) of the component (C). Hereinafter, this sol-gel material will be described in detail.

As a raw material of the sol-gel material in the present invention, an alcohol is added as a solvent to a mixed solution of at least one of the components (A) and (B) and the component (C). As the alcohol to be added, a lower alcohol having 1 to 4 carbon atoms, particularly, methanol or ethanol having a small boiling point is suitably used. The reason is that after the hydrolysis, the alcohol can be quickly removed from the solution by a heat treatment at a relatively low temperature. The amount of alcohol to be added is preferably from 0.3 to 3 times, more preferably from 0.5 to 1.5 times, in terms of molar ratio, the total of the components (A), (B) and (C). It is twice.

The raw material of the sol-gel material includes component (A),
A catalyst for hydrolyzing the components (B) and (C) is added. As the catalyst, an acid catalyst is preferably used. As the acid catalyst, it is preferable to use at least one acid catalyst among formic acid, acetic acid, tetrafluoroacetic acid, propionic acid, oxalic acid, hydrochloric acid, nitric acid, and sulfuric acid in the form of an aqueous solution.
The amount of the acid catalyst to be added varies depending on the type of the acid and the strength as a protonic acid (weak acid, strong acid). If the amount is too small, the progress of the hydrolysis / spraying condensation reaction is slow, and if it is too large, the condensation reaction is too advanced. The molecular weight becomes too large, and a precipitate or a coating solution is apt to gel, which is not preferable. The film-forming liquid contains the silane compounds (A), (B) and (C) in the form of unhydrolyzed product therein, and the silane compounds (A), (B) and ( 0.5 to 40% and 0.5 with respect to the content of C)
Among these acid catalysts, an organic acid which is a weak acid is preferably used in order to make it easier to contain each of them in an amount of up to 60%. Among organic acids, formic acid is particularly preferably used because of its low molecular weight and easy evaporation. The amount of the acid catalyst to be added is, for example, in the case where formic acid is used as the acid catalyst, expressed as a molar ratio, and 0.5% when the total of the components (A), (B) and (C) is 1 mol. It is preferably from 5 mmol to 5 mmol, more preferably from 0.7 mmol to 2 mmol.

It is preferable that water is added in a stoichiometric ratio necessary for hydrolysis. If the amount of water added is less than the stoichiometric ratio, unreacted silane compounds (A), (B) and (C) tend to volatilize during heat treatment for gelation. Usually, the amount of water to be added is 1.1 to 30 times the required stoichiometric ratio, including the water of the aqueous catalyst solution, and is expressed as a molar ratio, and the components (A), (B) and (C) Is preferably 2 to 20 times, more preferably 3 to 10 times the total of In addition, when an article manufactured by the present invention, for example, an optical element is used in proximity to various memories and other electronic circuits, the chlorine contained in the optical element may shorten the life of these electronic circuits. Therefore, it is preferable to use a chlorine-free acid catalyst as the acid catalyst.

In the present invention, at least one of the components (A) and (B), which are the raw materials of the sol-gel material,
A solution comprising the component (C), the alcohol solvent, water and the catalyst is held at room temperature for 90 to 120 minutes with stirring to hydrolyze each alkoxysilane to prepare a sol-gel material. Thereafter, the mixture is further kept at room temperature to 140 ° C., more preferably at 70 to 100 ° C., for 6 to 30 hours to be dehydrated.
While the polycondensation reaction proceeds, the solvent in the solution, water,
It is preferable to vaporize and evaporate the alcohol and water which are the products of the dehydration / polycondensation reaction. As a result, the weight and volume of the solution is reduced to 25-35% by weight and volume% of the original formulation. Accordingly, shrinkage after film formation can be suppressed as much as possible to prevent cracking of the film, and a cured film can be formed without generating bubbles in the film at the time of final heating. If the dehydration / polycondensation reaction proceeds too much, the viscosity of the solution becomes too high, and it is difficult to coat the surface of the mold or the substrate. Conversely, if the method of conducting the dehydration / polycondensation reaction is insufficient, generation of bubbles in the film at the time of final heating cannot be prevented. It is preferable to control the method of conducting the dehydration / polycondensation reaction by selecting the temperature and the holding time so that the viscosity of the solution is 10 ³ poise or less.

The above-mentioned sol-gel material is closely adhered between a base material and a mold, and is arranged in a film form. The gel film having a surface in which the surface shape of the mold is inverted by heating is coated. The following two methods can be typically given as a process for molding an optical element.

In a first method (hereinafter referred to as a mold pouring method), a liquid of a sol-gel material is poured into a mold, heated, and the article substrate is brought into contact with the liquid and further heated to join the substrate and the molded film.
This is a final heating method after release. That is, the mold having minute irregularities is kept horizontal, and a liquid sol-gel material having a viscosity of 10 ³ poise or less is poured onto the mold, so that the sol-gel material fills the recesses of the mold.
Instead of pouring, the mold may be immersed in a bath of the sol-gel material, or a method of applying a liquid of the sol-gel material to the surface of the mold with a brush may be used. In this state, the sol-gel material filled on the mold is kept at 140 to 180 ° C. for 20 to 120 minutes until the viscosity of the sol-gel material becomes 10 ⁴ to 10 ⁸ poise to advance the dehydration / polycondensation reaction.

Then, the base material is brought into close contact with the mold, and the sol-gel material is brought into contact with the surface of the base material so as not to form a gap therebetween.
The sol-gel material is kept at 180 ° C. for 10 to 120 minutes to substantially complete the dehydration / polycondensation reaction of the sol-gel material and to gel. Next, by peeling off the mold and releasing the mold, the polysiloxane film, which is a soft gelling film, having a concavo-convex shape obtained by inverting the concavo-convex shape of the mold, is bonded to the surface of the base material. Is formed. If the mold release is performed too early, the polysiloxane film is too soft and the surface irregularities are deformed by its own weight. Therefore, the above heating is performed until this deformation does not occur.

Next, this is finally heated at 180 to 350 ° C. for 10 to 150 minutes to polycondensate the remaining silanol groups of the polysiloxane film and vaporize the water generated by the polycondensation, so that the film has a thickness. The volume shrinks slightly in the direction to form a dense film. In this way, an optical element or other article coated with a film having a surface having a shape inverted from the surface shape of the mold is obtained.

In the second molding method (hereinafter, referred to as a substrate pouring method), a liquid of a sol-gel material is directly poured onto a substrate surface and heated to obtain a plastic film (the viscosity of the liquid is 10 ⁴ to 1).
0 pressing a mold to ⁸ when it is poise) to the membrane of the article substrate surface, a method of heating as is, after the transfer molding, and release the mold, carrying out final heating. That is, the surface of the article substrate to be coated is kept horizontal and the viscosity is 1
A liquid sol-gel material of not more than 0 ³ poise is poured on the base material, and the sol-gel material is spread on the base material in a film shape so as to have a predetermined thickness. In that state, 140-180 ° C. until the viscosity of the poured sol-gel material becomes 10 ⁴ to 10 ⁸ poise.
For 20 to 120 minutes to advance the dehydration / polycondensation reaction. Then, a mold having minute irregularities is pressed on the film-like sol-gel material to apply a pressure of 0.5 to 120 kg /.
cm ² , at a temperature of 160 ° C. to 350 ° C. for 60 seconds to 60 minutes,
By holding the sol-gel material, the dehydration / polycondensation reaction of the sol-gel material is almost completed and gelled. Then, by peeling the mold, a polysiloxane film, which is a gelled film having an uneven shape obtained by inverting the uneven shape of the mold on the surface, is formed in a state of being bonded to the surface of the base material. Then, for example, 18
By final heating at 0 to 350 ° C. for 10 to 150 minutes, the remaining silanol groups of the polysiloxane film are polycondensed, and the water generated by the polycondensation is vaporized,
The film shrinks slightly in the thickness direction to form a dense film.
In this way, an optical element or other article coated with a film having a surface having a shape inverted from the surface shape of the mold is obtained.

Thus, according to the present invention, 350
Excellent heat resistance to withstand temperature of 1 ° C. and a maximum thickness (film thickness measured at the convex portions of the surface irregularities) of 1 μm to 1 mm, preferably 20 to 1 mm
1.50 μm, close to the refractive index of general glass 1.50
It has a refractive index of 1.54 and a fine uneven shape, for example, 1
Predetermined value width (concavo-convex pitch) in the range of μm to 500 μm
And a film made of an organopolysiloxane formed along the main surface or along a direction perpendicular to the main surface with surface irregularities having a height of a predetermined value in the range of 5 to 500 μm. It is formed on a substrate in a shape.

The base material used in the present invention is a flat plate,
A shape such as a curved plate is used. 20 as base material
It is desirable that the amount of warpage of the substrate surface at 0 ° C. and 20 ° C. (thermal deformation length in a direction perpendicular to the surface per unit length in the surface direction of the substrate) is within ± 5 μm per cm. If the amount of warpage exceeds this range, the substrate and the film may peel or crack at the interface during the film forming process. Therefore, it is preferable to select the material, dimensions and shape of the substrate.

The substrate preferably has a coefficient of linear expansion of 1.5 × 10 ⁻⁵ / ° C. or less. If the linear expansion coefficient of the substrate is more than 1.5 × 10 ^-5 / ° C., if a plastics substrate having a high thermal expansion coefficient such as polypropylene (9~15x10 ^-5 / ℃), the organopolysiloxane film This is because, during the molding process, the base material and the film are separated at the interface or the film is cracked. Normal inorganic glass is 1.5
It has a coefficient of linear expansion of less than x10 ^-5 / ° C. Preferably, at least the surface of the substrate is an oxide. If the surface of the substrate in contact with the organopolysiloxane film is not an oxide, the adhesive strength is reduced in the process of forming the film, and in some cases, the substrate and the film are separated at the interface. Examples of preferable materials of the base material include silicate glass, borate glass, oxide glass such as phosphate glass, quartz, ceramics, silicon, metal, epoxy resin, glass fiber reinforced polystyrene, and the like. . The organopolysiloxane film does not bond with the metal as it is,
If the surface of the metal is treated in advance with an oxidizing agent, it can be used as a substrate.

When an object transparent to light of a desired wavelength, for example, visible light, ultraviolet light or infrared light is used as the substrate in the present invention, the article having the predetermined surface shape of the present invention is Function as a transmission optical element such as a lens, a diffraction grating, and a prism. When a transparent or opaque material is used as the substrate, a metal (aluminum, silver, etc.) or a dielectric film (magnesium fluoride, titanium oxide, etc.) is formed on the organopolysiloxane film. It is suitable for use as reflective optical elements such as reflective diffraction gratings and Fresnel reflectors, CD-ROMs and other information recording media.

As the sol-gel material, methyl, ethyl, isopropyl, and 3, which are relatively less reactive,
The surface of an article having a predetermined surface shape molded using one having a functional group such as a 3,3-trifluoropropyl group or a phenyl group shows a good release property with respect to a sol-gel material. Therefore, the article having this predetermined surface shape can be used as it is as a mold for a sol-gel material without requiring a gold release film or the like, and produces an article having a surface shape obtained by inverting the surface of the mold. be able to.

[0031]

Embodiments of the present invention will be described below in detail with reference to the drawings. The mold of the present invention,
(1) For example, a read-only optical information recording medium (CD-RO
M), a mold for manufacturing various optical components such as flat microlenses or grating elements,
Or (2) a master mold for producing a replica mold for producing the optical component.

Hereinafter, the case of using the master mold of the above (2) as an example will be mainly described in detail. In FIG. 1, a master mold 10 is disposed in a press (not shown) to manufacture a replica mold 11, and is fixed to a flat holding member 12 and a lower surface of the holding member 12. Plate-shaped mold base, adhesion enhancing layer 17 provided on the molding side surface of the base, and release film 1 provided thereon
The molding die base is composed of a mold core material 13 and a base layer 18 provided on the surface thereof.

The mold core 13 is, for example, any one of resin, silicon wafer, glass, metal and a combination thereof. Specifically, the mold core 13 has an expansion coefficient similar to that of the release film 15 and the sol-gel material. Epoxy resin,
Silicon wafer (Si), quartz glass, aluminum (A
l), silver (Ag), chrome steel (SUS), copper (Cu) -based alloys including brass, nickel (Ni) -based alloys, and the like.

Here, when a resin such as an epoxy resin is used as the mold core 13, it is easier to process and mold than when a glass or metal mold core is used. On the other hand, for example, a silicon wafer (S
i), quartz glass, aluminum (Al), silver (Ag), chrome steel
When using glass or metal such as (SUS), brass-containing (Cu) -based alloy, nickel (Ni) -based alloy, etc., better strength and heat resistance than when using resin core material Is obtained. In addition, when the mold core 13 is an epoxy resin, in order to withstand heat and pressure during heat molding of the sol-gel material,
It is preferable to provide a support such as glass or metal.

The mold core 13 has a plurality of grooves formed on the surface facing the replica mold 11. Each groove has a substantially V-shaped cross-sectional shape and the same dimension, and is arranged in parallel with each other. The surface of the mold core 13 is coated with a base layer 18, an adhesion enhancing layer 17, and a release film 15, which will be described later, and the surface 14 of the mold 10 has a groove 16 having the same shape as the groove on the surface of the mold core 13. Are formed.

As shown in FIG. 2, such a mold core 13
Is provided with an underlayer 18 having good affinity with the mold core 13 over the entire molding side surface 14. Specifically, titanium (Ti), aluminum (Al), silicon (Si) and / or
Alternatively, an oxide film thereof is formed. The underlayer 18
It has a thickness of 0 nm. If the mold core 13 is made of titanium (T
The base layer 18 may not be provided when the base layer 18 is made of at least one material selected from the group consisting of i), aluminum (Al), silicon (Si), and oxides thereof.

The adhesion reinforcing layer (protective film) 17 is
8, specifically, platinum (Pt), copper (Cu), palladium (Pd), silver (Ag) and alloys thereof, and are formed along the longest layer of the underlayer 18. Among these metals, the one that is particularly excellent in adhesion to the underlayer is platinum.
(Pt).

The release film 15 is formed of gold (Au) and is formed along the adhesion enhancing layer 17. This release film 15
It is preferable that the film be uniformly and smoothly formed by a sputtering method, a vapor deposition method, or a plating method because the smoother the surface, the higher the releasability. Gold (Au) is also excellent in heat resistance and corrosion resistance. The composition of the adhesion enhancing layer having the best adhesion to the gold (Au) film is platinum (Pt).

On the other hand, as shown in FIGS. 1 and 2, a replica mold 11 is coated with a flat substrate 19 made of, for example, quartz glass or the like, and is coated on the substrate 19 with a constant thickness before press molding. After press molding, the sol-gel material 21 is formed by inverting the surface shape of the mold 10 and transferring to the gelled film 20 having a surface shape obtained by press-molding the sol-gel material 21 (indicated by a two-dot chain line in FIG. 2). Become.

The sol-gel material may contain the above-mentioned components (A), (B) and (C).
Further, it may be one containing at least one of the organic-inorganic composites represented by the following formulas (4) and (5).

R _n SiX ′ _4-n (4) where R is a hydrocarbon group having 1 to 4 carbon atoms or
A substituted or unsubstituted aryl group, X ′ is an alkoxyl group or a halogen atom, and n is an integer of 1 or 2.

Embedded image MX '' _P ··· (5) wherein, M is Si, Ti, Zr, or a metal atom of Al, X '' is an alkoxyl group or a halogen atom, p is 3 or 4 Is an integer.

As such a sol-gel material 20, a silane-based material is particularly preferred. The reason is that the use of the silane-based sol-gel material 20 has an advantage that the hydrolysis and condensation polymerization of the raw materials proceed relatively gently, so that the low viscosity state required for press molding can be maintained for a long time. In addition, a raw material represented by the formula (4) in which an organic chain is substituted to be effective for maintaining a low viscosity has advantages such as being general, easily available, and inexpensive.

Further, the sol-gel material 20 in this embodiment preferably has a functional group which shows good releasability from other sol-gel materials after solidification. Specific functional groups include a relatively poorly reactive methyl group,
Examples thereof include an ethyl group, an isopropyl group, a 3,3,3-trifluoropropyl group, and a phenyl group.

Next, a procedure for manufacturing the replica mold 11 using the above-described mold 10 and a procedure for manufacturing an article having a predetermined surface shape using the replica mold 11 will be described. First, by starting the press device, the mold 10 is brought closer to the sol-gel material 20, and the release film 1 is released.
5, the molding surface 14 is applied to the sol-gel material 20 for a certain time,
In addition, it is pressed at a constant pressure and heated to a predetermined temperature. Next, after the mold 10 is released from the sol-gel material 20, the solvent is removed by sintering the sol-gel material 20 again. The mold 10 may be heated without releasing the mold. Replica mold 1 thus manufactured
Reference numeral 1 denotes a surface shape obtained by inverting and transferring each groove 16 formed on the molding surface 14.

Next, using this replica mold 11,
Another sol-gel material is pressed again to produce an article having a new predetermined surface shape. The article having a predetermined surface shape manufactured in this way has the same shape and dimensions as the molding surface 14 of the molding die 10 described above, and is a replica of the molding die 10. When such a replica is formed of a sol-gel material having a functional group having relatively low reactivity, which is the same as the material of the replica mold 11, the replica mold 11 can be easily released after press molding. The groove 16 formed on the molding surface 14 of the mold 10 was transferred and reproduced on the surface of the replica. A gold (Au) reflection coat was deposited on this replica, and the diffraction efficiency was measured. The result was the same value as the diffraction efficiency of the mold 10.

According to the above embodiment, the molding die 1
0 on the molding surface 14 and the release film 1 of gold.
5 is provided, good mold releasability with respect to the sol-gel material 20 is obtained, and a mold with excellent durability is obtained in which the surface of the mold release film 15 hardly undergoes a change with time such as oxidation. A mold having improved strength of the entire release film can be obtained. Therefore, in manufacturing the replica mold 11, it is possible to speed up the manufacturing process of the replica mold 11 and reduce the defect occurrence rate as compared with the related art,
In addition, the dimensional accuracy can be improved, and the number of samples from one molding die 10 can be increased.

In the case where the mold core is made of a material other than at least one material selected from the group consisting of titanium (Ti), aluminum (Al), silicon (Si) and oxides thereof. Since the underlayer of this material is provided on the surface of the mold core material, the release film is formed more in comparison with the case where the release film is directly provided on a mold substrate other than the above-mentioned materials. It can be made difficult to peel off from the mold base, thereby improving the durability of the mold. Further, when the mold core material is any of resin, silicon wafer (Si), glass, metal and a combination thereof, the molding surface 14
Regardless of the size of the area, the release film can be easily thinned.

According to the molding die 10, since the molding surface 14 is provided with the concave groove 16 and other irregularities,
Using this mold, a read-only optical information recording medium (C
Various optical components such as a D-ROM), a flat microlens or a grating element can be manufactured.

In order to manufacture such an optical component, the mold 10 can be used as a master mold for manufacturing the replica mold 11. And
Since the replica mold 11 is molded by pressing the mold 10 configured as described above, it is possible to speed up the manufacturing process, reduce the defect occurrence rate, and reduce the dimensional accuracy as compared with the related art. Can be improved. Further, using the replica mold 11 thus manufactured, a similar replica can be further manufactured. When a product of an optical component such as a diffraction grating or a microlens array is used as the base or the mold core 13 of the molding die 10,
An article having a predetermined surface shape manufactured using the obtained replica mold 11 (having a surface shape inverted from the surface shape of the mold 10) has a surface shape of the optical component described above.
Since it has the surface shape transferred as it is without inversion,
It has almost the same performance as the above optical components. However, in this case, it is preferable that the thickness of the adhesion enhancing layer and the release film be as small as possible in order to prevent mold collapse.

In particular, according to this embodiment, when the sol-gel material 20 has a functional group exhibiting releasability, when the sol-gel material 20 comes into contact with the release film 15, the predetermined functional group is replicated. Since the outer layer of the mold 11 is formed, the mold 10 can be more easily released from the replica mold 11. This is because such functional groups are poorly reactive,
This is considered to be due to the fact that the sol-gel material is likely to be oriented outward when polymerized because it is relatively bulky.

Since the outwardly oriented functional groups form the outer layer, the replica mold 11 does not essentially require a gold release film and is excellent in the other sol-gel materials 20. The mold releasability is obtained, so that the replica can be easily and smoothly manufactured. Then, a large number of replica molds 11 are manufactured in this way, and the articles having a predetermined surface shape formed by these replica molds 11 are also used as optical components such as gratings, microlenses, and microlens arrays. You can do it.

(Modification) As the molding die 10, in addition to the replica molding die 11 shown in FIGS.
The replica molds 31, 41, and 51 shown in FIGS. In addition,
19 in FIGS. 3 to 5 is similar to 19 in FIGS.
It is a flat substrate formed of quartz glass or the like.

In the replica mold 31 shown in FIG. 3, by forming grooves 16 in a lattice pattern on the molding surface 14 of the mold 10 shown in FIGS. 1 and 2, a cross lattice is formed on the surface of the sol-gel material 20. I have. Further, the replica mold 41 shown in FIG. 4 is similar to the mold surface 1 of the mold 10 shown in FIGS.
By providing a concave spherical surface in the sol-gel material 4,
Are formed with a large number of convex spherical surfaces. The replica mold 51 shown in FIG. 5 has a convex arc on the surface of the sol-gel material 20 by providing a semicircular groove in the molding surface 14 of the mold 10 shown in FIGS. Are formed in large numbers.

The mold for forming the replica mold 31 has a large number of substantially quadrangular pyramid-shaped concave portions formed in a matrix on the molding surface. In addition, replica mold 41
In a molding die for molding, a large number of spherical concave portions are formed in a matrix on the molding surface. Further, a molding die for molding the replica molding die 51 has a large number of substantially semicircular cross-sectional grooves formed in parallel on a molding surface. The replica molds 31, 41, 51 can also be used as gratings or micro lenses by themselves.

[Examples] Next, the materials and thicknesses of the substrate, the release film, the base film, and the adhesion enhancing layer (protective layer), the film forming method, and the presence or absence of the base film and the adhesion enhancing layer were changed. Prototype mold,
An article having a predetermined surface shape was manufactured using these molds.

The evaluation of the releasability, the transferability, the number of service life and the overall evaluation of these molds were evaluated according to the following criteria. To evaluate the release property, after pressing the mold against the sol-gel material at a constant pressure for a certain period of time, investigate that the mold can be released easily and quickly from the sol-gel material. The percentage of the area that was released without adhering to the surface was measured, and the results were evaluated as follows: ◎: 100% (extremely good),…: 90% or more and less than 100% (good), Δ:
70% or more and less than 90 (slightly poor), ×... Less than 70% (bad) ”. Further, the transferability was evaluated by measuring the variation in the diffraction efficiency of the obtained diffraction grating and the focal length of the microlens.
%, Variation of focal length 10% or less (very good), ○
... Diffraction efficiency of 50% or more and less than 60%, variation in focal length of more than 10% and 25% or less (good);
0% or more and less than 50%, the variation of the focal length was more than 25% and less than 50% (somewhat poor), ×... The service life indicates the maximum number of times the mold can be used repeatedly without peeling of the release film of the mold. The overall evaluation is, in addition to the releasability and transferability, taking into account, for example, the ease of film formation and durability of the release film, corrosion resistance, heat resistance, etc. Good, Δ: somewhat poor, ×: poor ”.

As each mold base or mold core, the first
And the second mold core were selectively used. First mold core material By a photoresist method, about 1000 linear V-grooves (groove width 25 μm, groove depth 1) were formed on the surface of a silicon wafer by a photoresist method.
5 μm, groove cross section: triangular, spacing between adjacent grooves (measured at the center of the groove, about 25 μm), average thickness 2.0 mm
2.5 cm x 2.5 cm silicon diffraction grating
Was prepared as a mold core material.

Second mold core material A transparent quartz glass plate having a size of 2 mm × 36 mm × 36 mm is coated with a metal film having a high hydrofluoric acid resistance (thickness: 1 μm) by sputtering. And subjecting a metal film to a surface of one side of the quartz glass plate by a photoresist process to form holes having a diameter of about 1 μm in a pitch of 240 μm in a vertical direction and a horizontal direction, respectively, and then performing an aqueous hydrofluoric acid solution Etching was performed for a predetermined period of time, and then the metal film was removed. Thereby, 120μ
150 semi-spherical arc-shaped concave portions having a radius of curvature of m, 150 closely in the vertical direction, and 150 closely in the horizontal direction.
A quartz glass core having 2,500 pieces was obtained. This is used as a second mold core.

[Example 1] A first mold core (diffraction grating) was placed in a vacuum evaporation apparatus, and an 80 nm-thick titanium (Ti) film was formed as a base layer on the surface of the mold core. And a 170 nm-thick platinum (Pt) as a protective layer on the titanium film.
Was formed. Next, this was put into a vacuum sputtering apparatus, and a 53 nm-thick gold (Au) film was formed as a release film on the platinum layer by a sputtering method to obtain a molding die. This mold had a gold surface, and the reflection of the fluorescent lamp seemed to interfere.

0.19 mol of phenyltriethoxysilane and 0.04 mol of dimethyldiethoxysilane and (3,
3,3 trifluoropropyl) trimethoxysilane 0.0
4 mol was stirred in a beaker. 0.25 mol of ethanol was added to this liquid and stirred, and 1.75 mol of water (31.5 mol) was added.
An aqueous solution obtained by dissolving formic acid to 0.1% by weight in g) was further added thereto, followed by stirring for 2 hours. The liquid separated into two layers at the beginning of stirring, but became a transparent and homogeneous solution after stirring for 2 hours. When this solution was heated in an oven at 80 ° C. for 12 hours, ethanol, an aqueous solution of formic acid, water generated by the polycondensation reaction, and the like were volatilized. As a result, the solution, which initially had a weight of about 103.3 g and a volume of about 100 cm ³ , had its weight and volume reduced to about 30% to a weight of about 27 g and a volume of about 30 cm ³ . The liquid thus obtained is used as a sol-gel solution.

The sol-gel solution was applied on the surface of the mold to form a layer having a thickness of about 60 μm, and heated at 140 ° C. for 7 minutes. By this heat treatment, a plastically deformable gel film (viscosity: 10 ⁴ to 10 ⁸ poise) was formed on the mold. Thereafter, a thickness of 3.0 was applied to the coating surface (gel film).
2.5 kg square quartz glass substrate on 2 mm pressure 2 kg
The substrate was heated at 200 ° C. for 30 minutes while being pressed at a pressure of / cm ² , and bonded to a quartz glass substrate. Then, after the coating film was completely gelled, it was naturally cooled in air, the mold was separated from the quartz glass substrate, released, and further heated at 350 ° C. for 15 minutes. As a result, a film on which the shape of the mold was transferred (average film thickness: 30 μm)
Was obtained on the surface of the quartz glass substrate.
In order to measure the diffraction efficiency of this diffraction grating, a gold (Au) reflection coat having a reflectance of 60% (wavelength: 1550 nm) was formed on its surface by a sputtering method. The process of manufacturing the above-described diffraction grating was repeated 30 times to produce 30 diffraction gratings.

The surface of the mold was observed under a microscope before and after use to determine whether or not the release film was separated from the mold. As a result, no release of the release film from the mold was observed. In addition, the mold was easily and quickly released from the sol-gel material. And this state did not change even if the production was repeated 30 times as described above.

The diffraction efficiency of the obtained diffraction grating was measured and observed with a microscope. The measurement of diffraction efficiency is
The laser light of 1550 nm obtained from the wavelength tunable laser light source is incident on the diffraction grating, and the intensity of the diffracted light is measured by a photodetector, and the amount of light incident on the diffraction grating is measured by the same photodetector, and the two are compared. The diffraction efficiency was evaluated.

As a result, the efficiency of the 26th-order diffracted light of the obtained diffraction grating was 60%, while the diffraction efficiency of the 26th-order diffracted light of the mold was 60% (1550 nm), and the transfer was performed with good reproducibility. I found out.

On the other hand, as a result of observation with a microscope, the depth of the diffraction grating is 15 μm and the pitch is 25 μm, whereas the article having a predetermined surface shape has a depth of 14.7 to 1 μm.
5.3 μm, the pitch is 24.2 to 25.1 μm,
It was found that the image was transferred with high accuracy. As shown in Table 1, the results of these Examples 1 were that the evaluation of the releasability and the evaluation of the transferability were both “◎”, and the number of times of use was 30 or more.
The overall evaluation is “◎”.

[0065]

Table 1 Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 2 Type core material or substrate Si Si Si Si Si---------------------------- Quartz glass Underlayer material TiTiNi-Ti Underlayer forming method Evaporation Evaporation Plating method-Evaporation Protective layer material Pt---Pt Protective layer formation method Evaporation---Evaporation Release layer material Au Au Au Ni Ni Au Release layer Molding method Sputtering method Sputtering method Sputtering method Electroforming method Sputtering method Releasability ◎ ○ △ × ◎ Transferability ◎ △ △ × ◎ Number of service life 30 or more 5 0 0 30 or more Overall evaluation ◎ ○ △ × ◎ ────── ──────────────────────────────

Comparative Example 1 The procedure of Example 1 was repeated except that a platinum protective layer was not provided and titanium and gold were formed in the preparation of the first mold in Example 1. The diffraction grating was molded multiple times.

This mold was able to maintain good releasability and transferability up to the first to fifth times in forming the diffraction grating, but after the sixth time, the gold (Au) thin film was peeled off onto the sol-gel film. The releasability was greatly reduced.

[Comparative Example 2] In the preparation of the first mold in Example 1, a platinum protective layer was not provided, and a nickel underlayer was formed instead of a titanium underlayer (by electroless plating). , 1.0 μm thick), except that the diffraction grating was formed a plurality of times in the same manner as in Example 1.

In this mold, when forming the diffraction grating, the mold was not completely released from the first time, and a part of the sol-gel composition remained on the mold. The film remaining on the mold could be removed by ultrasonic cleaning with alcohol or the like, but the mold could not be completely released no matter how many times.
Therefore, the evaluation of the releasability and the transferability and the overall evaluation are “Δ”.

[Comparative Example 3] In the preparation of the first molding die in Example 1, a protective layer of platinum and an underlayer of titanium were not provided, and a nickel release layer (by electroforming) was used instead of the gold release layer. , 1.0 μm thick), except that the diffraction grating was formed a plurality of times in the same manner as in Example 1.

In this mold, when the diffraction grating was formed, the mold releasability was not obtained from the first time. When the mold and the diffraction grating were peeled off with force, the sol-gel material partially adhered to the molding surface of the mold. Then, defective products occurred. For this reason, the evaluation of the releasability, the transferability and the overall evaluation are “x”.

Example 2 A titanium base layer, a platinum protective layer, and a gold release film were formed on the surface of the second mold core in the same manner as in Example 1 to form a mold. I got

A glass substrate having a thickness of 3.0 mm and a thickness of 2.5 mm
cm square quartz glass substrate (linear expansion coefficient: 1.0 × 10 ⁻⁵⁾
/ ° C) was subjected to ultrasonic alkali cleaning and pure water cleaning. Example 1
Pour the same sol-gel solution as used in the above on the surface of the quartz glass substrate to form a layer having a thickness of about 200 μm,
Start heating at 160 ° C and gradually increase to 180 ° C over 20 minutes
And kept for 40 minutes. This heat treatment allows a plastically deformable gel film (viscosity: 10 ⁴⁾ on the quartz glass substrate.
~ 10 ⁸ poise) could be formed. Next, the mold was pressed against the gel film, and a heat treatment was performed at 250 ° C. for 20 minutes while being pressed at a press pressure of ² kg / cm ² . Thereafter, the mold was released. As a result, a fine uneven plate having a film on which the shape of the mold was transferred was adhered to the surface of the quartz glass substrate. The fine uneven plate obtained by releasing the mold is
After heating for about 1 minute, the film thickness of the flat
m, the maximum film thickness from the top of the semicircle is 170 μm22,
A flat microlens in which 500 minute convex lenses were arranged was obtained. Then, the above manufacturing process was repeated 30 times to produce 30 flat microlenses.

The surface of the mold was observed under a microscope before and after use to determine whether the release film would peel from the mold. It was found that the release film did not peel from the mold at all. In addition, the mold was easily and quickly released from the sol-gel material. And this state did not change even if the production was repeated 30 times as described above.

In each of the first to thirty times, the spherical surface formed on the flat microlens has a radius of curvature of about 110 μm and a focal length of about 1800 μm (wavelength 155 μm).
0 nm), and no difference was observed in the shape of the 1st to 30th flat plate microlenses. Therefore,
The evaluation of the release property and the evaluation of the transfer property are both ““ ”, the number of service times is 30 or more, and the overall evaluation is“ ◎ ”.

From the above results, in Examples 1 and 2, a gold (Au) thin film as a release film, a platinum layer as a protective layer, and a titanium layer as a base layer are provided on the molding surface of the mold. Therefore, it can be seen that, compared to Comparative Examples 1 to 3, a good releasability for the sol-gel material was obtained, and the durability of the mold was excellent.

Example 3 The diffraction grating obtained by the procedure of Example 1 (a product not formed with a gold (Au) reflective film coat) was used as a mold (replica mold). Press molding was performed on the gel film having the same composition as in Example 1 in the same manner as in Example 1. After press molding, the mold (replica mold) was easily released, and a diffraction grating having the same pitch and depth as the original diffraction grating was obtained.

A gold reflective coat was deposited on the thus obtained diffraction grating in the same manner as in Example 1 and the diffraction efficiency was evaluated. The 26th-order diffraction efficiency was the same as that of the diffraction grating obtained in Example 1. , 60% (1550 nm), indicating that the image was transferred with good reproducibility. And also in this embodiment,
As in Examples 1 and 2, the evaluation of the releasability and the evaluation of the transferability were both “◎”, the service life was 30 times or more, and the overall evaluation was “◎”.

[Examples 4 to 6] The vacuum deposited films of platinum as the protective layer in Example 1 were each replaced with a vacuum deposited film of copper, palladium and silver (each having the same thickness of 170 nm as the platinum film). A diffraction grating was produced in the same manner as in Example 1 except for the above. These were evaluated for release properties, transfer properties and the like in the same manner as in Example 1, and the results are shown in Table 2,
The evaluation of the releasability and the transferability were both “◎”, the number of times of use was 30 or more, and the overall evaluation was “◎”.

[0080]

[Table 2] Example 4 Example 5 Example 6 Example 6-------------------------- −−−−−−−−−−−−−−− Mold core material Si Si Si Underlayer material Ti Ti Ti Underlayer molding method Vapor deposition Vapor deposition Protective layer material Cu Pd Ag Protective layer forming method Vapor deposition Vapor deposition Release layer Material Au Au Au Release layer forming method Sputtering method Sputtering method Sputtering method Releasability ◎ ◎ ◎ Transferability ◎ ◎ ◎ Number of service life 30 or more 30 or more 30 or more Overall evaluation ◎ ◎ ◎ ─────────── ──────────────

[Examples 7 to 10] Titanium (TiO 2, Example 7), aluminum (Al, Example 8) and alumina (Al ₂ O ₃₎ , Example 9) instead of the vacuum-deposited film (the film thickness is 80 nm, which is the same as the titanium film),
And Example 2 except that no underlayer was provided (Example 10)
A microlens was manufactured in the same manner as described above. The results of evaluation of the releasability and transferability of these in the same manner as in Example 2 are shown in Table 3. Or more or 20 times, and the overall evaluation was ““ ”.

[0082]

[Table 3] ─────────────────────────────────── Example 7 Example 8 Example 9 Example 10 ----------------------------------------------- Core material or substrate Quartz glass Quartz glass Quartz glass Quartz glass Underlayer material TiO ₂ Al Al ₂ O ₃ (None) Underlayer forming method Vapor deposition Vapor deposition Deposition Protective layer material Pt Pt Pt Pt Protective layer forming method Vapor deposition Vapor deposition Deposition Release layer material Au Au Au Au Release layer forming method Sputtering method Sputtering method Sputtering method Sputtering method Releasability ◎ ◎ ◎ ◎ Transferability ◎ ◎ ◎ ◎ Number of service life 30 or more 30 or more 30 or more 20 Overall evaluation ◎ ◎ ◎ ◎ ──────────────── ───────────────────

In the present invention, the sol-gel composition, the molding surface, the base material, the material of the underlayer and the protective layer, the type of the functional group, and the film thickness exemplified in the above-mentioned Examples 1 to 10 and the above-described embodiment are exemplified. However, the present invention is not limited to the film forming method.

[0084]

As described above, according to the present invention, it is possible to obtain a mold having a good release property with respect to a sol-gel material, and to manufacture the mold compared with a conventional article or mold having a predetermined surface shape. It is possible to achieve a high-speed process, a low defect rate, and an improvement in dimensional accuracy. In addition, the mold of the present invention has excellent durability, and there is little possibility that the release film peels off from the mold base and adheres to the sol-gel material. The number of times that the mold is used repeatedly increases, and a mold that does not lose the releasability semipermanently can be obtained. Further, according to the present invention, since fine irregularities can be provided on the surface of the release film, various optical components such as a read-only recording medium (CD-ROM), a flat microlens, and a grating element can be manufactured.

[Brief description of the drawings]

FIG. 1 is a perspective view schematically showing a method for molding a replica mold using a master mold in the present invention.

FIG. 2 is a sectional view of a master mold and a replica mold.

FIG. 3 is a perspective view showing another replica mold.

FIG. 4 is a perspective view showing another replica mold.

FIG. 5 is a perspective view showing another replica mold.

[Explanation of symbols]

10 Master mold, 11 Replica mold, 13
Mold core material, 15 release film, 17 adhesion enhancement layer, 18 base layer.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Hiroaki Yamamoto 3-5-11 Doshomachi, Chuo-ku, Osaka Japan F-term in Sheet Glass Co., Ltd. 4F202 AA33 AA49 AC06 AH73 AH75 AH79 AJ02 AJ06 AJ09 AJ11 CA01 CA09 CA19 CB01 CD03 CD12 CD22 CK11 CM26 5D121 CA01 CA03 CA06 CA07 DD07

Claims (12)

[Claims] 1. A gelled film having a surface in a shape in which the sol-gel material is brought into close contact with a substrate and a mold and arranged in a film shape and then heated to reverse the surface shape of the mold. In the method for producing an article having a predetermined surface shape, which is coated on a material surface, at least the surface of the molding die is made of titanium (T
i), aluminum (Al), silicon (Si), and platinum (Pt), copper (Cu), palladium on the surface of a mold substrate made of at least one material selected from the group consisting of oxides thereof. (Pd) and an adhesion enhancing layer made of at least one metal selected from the group consisting of silver (Ag), and a release layer made of gold (Au) coated on the adhesion enhancing layer A method for producing an article having a predetermined surface shape. 2. The method according to claim 1, wherein the adhesion enhancing layer has a thickness of 50 to 400 nm. 3. The method for manufacturing an article having a predetermined surface shape according to claim 1, wherein the release layer has a thickness of 200 to 1000 nm. 4. The mold base according to claim 1, wherein a base material of the at least one material is coated on a surface of a mold core made of silicon, glass or resin. A method for producing an article having a predetermined surface shape. 5. The method according to claim 4, wherein the underlayer has a thickness of 20 to 300 nm. 6. The method according to claim 4, wherein the mold core is made of silicon or quartz glass, and the underlayer is made of titanium. 7. A mold for press-molding a sol-gel material, wherein at least the surface has at least one selected from the group consisting of titanium (Ti), aluminum (Al), silicon (Si), and oxides thereof. Platinum (Pt), copper (Cu), palladium (Pd),
And an adhesion enhancing layer composed of at least one metal selected from the group consisting of silver and silver (Ag), and a release layer composed of gold (Au) coated on the adhesion enhancing layer. A molding die characterized by the following. 8. The mold according to claim 7, wherein said adhesion enhancing layer has a thickness of 50 to 400 nm. 9. The mold according to claim 7, wherein said release layer has a thickness of 200 to 1000 nm. 10. The mold base according to claim 7, wherein a surface of a mold core made of silicon, glass, or resin is covered with an underlayer of the at least one material. Mold. 11. The mold according to claim 10, wherein said underlayer has a thickness of 20 to 300 nm. 12. The mold according to claim 10, wherein said mold core is made of silicon or quartz glass, and said base layer is made of titanium.