JP2015020410A - Laminate and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an imprint method for producing a laminate having substantially no residual film or a residual film of remarkably small thickness.SOLUTION: A production method of the laminate comprising a cured product and a base material comprises the steps of: packing a curable composition containing curable raw materials in the space between the base material and a die, which has a finely-rugged structure on the surface thereof and in which from at least a protrusion part of the finely-rugged structure, the curable raw materials can be sucked; and contacting the tip part of the protrusion part of the die with the surface of the base material since the curable raw materials are sucked from at least the protrusion part of the finely-rugged structure on the surface of the die and the volume of the curable composition in the recessed part of the die becomes smaller. The laminate produced by this method is characterized in that the finely-rugged structure is transferred to the surface of the base material and the thickness of the residual film in a portion corresponding to the protrusion part of the die, when the finely-rugged structure is transferred, is made equal to or thinner than the escape thickness of the Auger electron.

Description

  The present invention relates to a laminate and a method for producing the laminate. More specifically, the present invention relates to an imprint method for producing a laminate having substantially no residual film or a remarkably thin residual film, and a laminate produced by the method.

  Imprint lithography is known as a technique for obtaining fine patterns with high productivity. In the imprint method, the concave / convex pattern is transferred by pressing the mold against the transfer material, but the transfer material between the substrate and the mold is only thinned even if the mold is pressed with a high pressure. Since the material cannot be brought into contact, a thin film always exists even in the concave portion where the film thickness is the thinnest in the transferred material. For this reason, it is necessary to remove the film of the concave portion called a residual film in a subsequent process. In photolithography using a photo-curable resin and a photo mask, no residual film is formed, and thus reduction of the residual film is a long-standing problem in imprint lithography.

In Patent Document 1 below, as an imprint method for reducing the residual film, a light-shielding layer is provided on the convex portion of the mold to inhibit the curing of the photocurable resin, thereby preventing the concave portion of the transferred material from solidifying. A method of removing in a process is disclosed.
Further, Patent Document 2 below discloses a method of decomposing and removing a resin in a portion in contact with a convex portion of a mold using a depolymerizable polymer.
Further, Patent Document 3 below discloses a method of pressing and curing a mold composed of a hard convex portion of polyimide and PDMS on a curable resin thin film having low hardness.

JP 2004-304097 A JP 2007-220797 A JP 2010-192702 A

  However, in the imprint method described in Patent Document 1, there is a problem that providing a partial light-shielding property to a fine mold makes it difficult to produce a mold as compared with a conventional exposure method using a mask. Moreover, even if a depolymerizable polymer is used as in the imprint method described in Patent Document 2, it is difficult to put it into practical use as a method, such as it is difficult to selectively heat the decomposition part by contact with a fine mold. It is. In addition, as in the imprint method described in Patent Document 3, even if a hard mold is pressed against a soft resin with a large force, the distance between the convex tip of the mold and the substrate surface is several to several tens of nm. As you approach, the apparent viscosity of the resin increases significantly due to the interaction between the mold and the resin adhering to the vicinity of the substrate surface due to van der Waals force. Is very difficult.

As described above, all of the imprint methods for reducing the remaining film of the prior art have problems that it is difficult to produce a mold having a complicated structure as described above, and that it is difficult to implement practically as a technique.
In view of these problems of the prior art, the problem to be solved by the present invention is an imprint method for producing a laminate having substantially no residual film or a remarkably thin residual film, and has been produced by the method. It is to provide a laminate.

As a result of intensive studies and experiments to solve such problems, the present inventors focused on a method of removing the curable composition that becomes the remaining film portion during the filling to curing process, and By making the composition and the material constituting the mold into a specific combination, it is found that the residual film thickness can be remarkably reduced or eliminated by absorbing the curable composition from the tip of the convex portion of the mold, and the present invention is completed. Has been reached.
That is, the present invention is as follows.

[1] A method for producing a laminate of a cured product and a substrate, the following steps:
A curable composition having a fine concavo-convex shape on the surface and containing the curable raw material in a space between the mold and the substrate capable of absorbing the curable raw material from at least the convex portion of the fine concavo-convex structure on the mold surface Including a step of filling the product, wherein the curable raw material is absorbed from at least the convex portions of the fine concavo-convex structure on the surface of the mold, and the volume of the curable composition in the concave volume of the mold is reduced. Wherein the top of the convex portion of the mold contacts the surface of the substrate.

  [2] The above-mentioned [1], wherein when the top of the convex portion of the mold comes into contact with the surface of the base material, the top of the convex portion deforms along the surface of the base material and adheres to the base material. Method.

  [3] The method according to [1] or [2] above, wherein the shape near the tip of the convex portion of the mold is composed of a surface inclined with respect to the opposing substrate surface.

  [4] The method according to any one of [1] to [3], wherein the top of the convex portion of the mold is made of a rubber-like material.

  [5] The method according to [4], wherein the material of the mold is silicone rubber.

  [6] The method according to any one of [1] to [5], wherein the curable raw material is a metal alkoxide.

  [7] The method according to [6], wherein the metal of the metal alkoxide is silicon.

  [8] A laminate produced by the method according to any one of [1] to [7].

  [9] A laminate in which a fine concavo-convex structure is transferred to the surface of a substrate, and the remaining film thickness of the portion corresponding to the convex portion of the mold at the time of transfer is not more than the escape thickness of Auger electrons.

  [10] The laminate according to [9], wherein the fine uneven structure is made of an inorganic material.

  [11] The laminate according to [10], wherein the inorganic substance is a metal or a metal oxide.

  [12] The laminate according to [11], wherein the metal is silicon.

  [13] The laminate according to any one of [9] to [12], wherein the fine uneven structure includes glass.

  [14] The laminate according to any one of [9] to [13], wherein the fine concavo-convex structure includes inorganic fine particles having a particle size of 10 nm or less.

[15] A method for producing a laminate of a cured product and a substrate, the following steps:
The space between the substrate having a fine irregular shape on the surface and capable of absorbing the fine particle dispersion medium from at least the convex portion of the fine irregular structure on the mold surface and the fine particle dispersion medium and the fine particles are included. Including a step of filling the fine particle dispersion, wherein the fine particle dispersion medium is absorbed from at least the convex portions of the fine concavo-convex structure on the surface of the mold, and the volume of the curable composition in the concave volume of the mold is small. The method, wherein the top of the convex portion of the mold contacts the surface of the substrate.

  According to the imprint method of the present invention, the residual film thickness can be significantly reduced or the residual film can be substantially eliminated.

The photomicrograph of the silicone resin type surface where the convex lens shape was transferred. The photomicrograph of the silicone resin type surface where the convex lens shape was transferred. A photomicrograph of the surface of the silicone resin mold onto which the concave lens shape was transferred. When the concave mold is used, the top of the convex part of the shaped convex lens is formed as a lens having a diameter of about 7 μm, but the lower part of the convex part is not formed with a V-shaped valley and is a flat part of the substrate. The micrograph of the structure which shows that. In Comparative Example 1, when a concave mold was used, the V-shaped valley at the bottom of the convex part was completely formed from the convex part top of the shaped convex lens, and the flat part of the substrate could not be confirmed. A photomicrograph of the structure shown.

Hereinafter, an embodiment of the present invention (hereinafter abbreviated as “embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.
The manufacturing method according to the present embodiment has a fine concavo-convex shape on the surface, and a space between the base and the mold that can absorb the curable raw material from at least the convex part of the fine concavo-convex structure on the mold surface. A method for producing a laminate of a cured product and a substrate, comprising a step of filling the curable composition containing the curable raw material, wherein the curable raw material has a fine concavo-convex structure on the surface of the mold. In this method, the top of the convex portion of the mold comes into contact with the surface of the substrate by being absorbed from at least the convex portion and reducing the volume of the curable composition in the concave volume of the mold.

[Curable composition]
The curable composition used in the present embodiment includes a curable raw material such as a metal alkoxide and a curing catalyst, and may include fine particles. The cured product is obtained by curing the curable composition into a solid state, and the curing reaction may not proceed completely, and an organic functional group may remain in part. The curable composition may contain polysilazane and a curing catalyst. Water may be included in the curable composition as long as the curing reaction does not proceed significantly for a desired period and can exist stably.

[Curing material]
In the present embodiment, the curable raw material is not particularly limited as long as it is a material that can be cured by a curing material. For example, a metal alkoxide can be used.
[Metal alkoxide]
Examples of the metal of the metal alkoxide include magnesium (Mg), aluminum (Al), zinc (Zn), silicon (Si), titanium (Ti), barium (Ba), zirconium (Zr) and the like. Si) and aluminum (Al) are preferable because inorganic materials can be formed relatively easily.
The metal alkoxide is represented by the general formula MR ² _m (OR ¹ ) _nm , where M is a metal having an oxidation number n and m is an integer of 0 to (n−1). OR ¹ includes an alkoxy group such as a methoxy group, an ethoxy group, and a propoxy group, a hydroxy group, a phenoxy group, an acetoxy group, and the like, and R ² includes a phenyl group or a derivative thereof, other aryl groups, hydrogen, methyl, and the like. Group, an alkyl group such as ethyl group, a group having addition reactivity such as vinyl group, a group having ring-opening reactivity such as epoxy group, and an alkoxy group. Among alkoxy groups, those with short chains, such as methoxy groups and ethoxy groups, are preferred and stable because of their high reactivity and low shrinkage, as well as the penetration of alcohol generated during solidification into the mold material and diffusibility. For example, tetramethoxysilane (TMOS) and tetraethoxysilane (TEOS) are preferable as the silicon alkoxide (alkoxysilane).
In the case of silicon alkoxides, those having various characteristic groups are known as silane coupling agents. By mixing these, various characteristics can be imparted to the resulting surface, for example, as R ² By introducing a fluorinated alkyl group, water repellency and antifouling properties can be imparted. Moreover, mixing a plurality of metal alkoxides is preferable in order to increase the reactivity. A low condensate of about 2 to 10 mer of metal alkoxide can be used if the viscosity is acceptable, and is effective for increasing the solid content concentration of the curable composition.

[Curing material]
In the present specification, the “curing material” is a material for curing the above-described curable composition or curing material. When the curable material is a metal alkoxide, it can be water.

[Curing catalyst]
As a curing catalyst for metal alkoxide, in addition to the well-known acids or bases such as hydrochloric acid and ammonia, perchlorates, hydrochlorides, sulfates represented by ammonium perchlorate, ammonium chloride, ammonium sulfate, ammonium nitrate, sodium acetate Acids such as carboxylates, metal salts, and organometallic compounds such as zinc, cobalt, tin, titanium, and aluminum are used. Among these, tin or organotin dicarboxylic acid ester is preferable because of its high curing rate and curing reaction rate. Specific examples include tin bisneodecanoate and dioctyltin diacetate.
As the curing catalyst, one or two or more of the above various curing catalysts may be used in combination, and the addition amount is preferably 0.05 to 5% by mass with respect to the curable raw material.

[Addition of solvents, etc.]
In addition to the dispersion medium contained in the fine particle dispersion, a solvent can be added for adjusting the concentration of the fine particles and the curable composition in order to adjust the film thickness and the transfer shape. The type of the solvent is selected from the conditions such as being compatible with the curable composition without being adversely affected by the dispersion of the fine particles and being absorbed into the mold. When a fine particle dispersion medium can be used, it is often preferable to use the same dispersion medium because the dispersion state of the fine particles becomes stable.
In addition, the amount of water contained in the curable composition is such that self-curing by the contained water is substantially in the process from preparation to storage, application of the curable composition, and filling between the mold and the substrate. It must be below the amount that does not matter.
The curable composition preferably has good wettability with respect to the substrate surface, and needs to be firmly adhered to the substrate after curing, and contains a surfactant and water to improve wettability and adhesion. It is also possible to add no solvent.

[Fine particles]
The fine particles used in this embodiment preferably have the property of aggregating when the inter-particle distance becomes a specific value or less, and it is preferable to use fine particles having a particle size of 100 nm or less. This is because when the particle size is 100 nm or less, the repulsion between particles due to adsorption of solvent molecules is reduced even when dispersed in a solvent, and the distance between particles becomes close to each other and the particles tend to aggregate even with the same particle content. is there. In particular, when used for optical applications, transparency of the coating is often required, and the particle size is preferably 50 nm or less, more preferably 30 nm or less, and even more preferably 10 nm or less.
There are no particular restrictions on the material of the fine particles, mainly inorganic metals, metal oxides, etc., examples of metals include gold, platinum, palladium, silver, copper, nickel, chromium, titanium, and alloys thereof. Examples of metal oxides include magnesium (Mg), aluminum (Al), zinc (Zn), silicon (Si), titanium (Ti), barium (Ba), zirconium (Zr), tin (Sn), tungsten (W), Examples thereof include oxides of metals such as yttrium (Y), indium (In), copper (Cu), and mixtures thereof. The fine particles may not only have a homogeneous structure, but may have a structure in which two or more kinds of materials function with a concentration gradient, or may have a coating for the stability and protection of the particles. The surface of the fine particles preferably has a functional group that easily reacts with the metal alkoxide, such as a hydroxyl group, in order to facilitate bonding with the metal alkoxide.

[Fine particle dispersion]
The fine particle dispersion is obtained by dispersing the above fine particles in a solvent, and the dispersion medium may be any material in which the fine particles are stably dispersed. Examples of the solvent other than water include alcohols such as methanol, ethanol and isopropanol, acetone. In addition to ketones such as methyl ethyl ketone, various esters may be mentioned, and the material is appropriately selected from those which are absorbed in the mold material and diffused and permeated through the mold material without dissolving or decomposing the mold material described later.
The concentration of the fine particles is selected from concentrations at which the fine particles can be stably dispersed, and is usually about several to 60% by mass depending on the kind of the particles and the dispersion medium.
When mixed with the following curable composition, a dispersion medium other than water is basically used.

[Type]
The mold in the present embodiment absorbs a curable raw material and a solvent (dispersion medium) for dispersing inorganic fine particles in the fine particle dispersion from the fine particle dispersion to aggregate the fine particles, or simultaneously contacts the mold surface. The cured material is supplied to the cured composition and has a function of sequentially curing the curable composition from the mold surface. For this reason, it is preferable that a type | mold has a property which absorbs and permeate | transmits a sclerosing | hardenable raw material and a dispersion medium moderately, or hold | maintains and / or permeate | transmits an appropriate amount of hardening materials simultaneously.
In the present invention, at least the convex portions of the fine concavo-convex structure on the surface of the mold must be able to absorb the curable raw material and the fine particle dispersion medium in order to significantly reduce or substantially eliminate the residual film thickness.

As a mold, the permeation amount of the solvent necessary for absorbing and permeating the dispersion medium is usually 1 × 10 ⁻³ g · m ⁻² · s ⁻¹ or more in order to aggregate the fine particles in several minutes to several hours. It is more preferable that the larger particle size is 5 × 10 ⁻³ g · m ⁻² · s ⁻¹ or more because fine particles can be aggregated and solidified faster. Similarly, the permeation amount of the mold with respect to the curable raw material is preferably large, but it is sufficient that the curable raw material between the convex portion of the mold and the substrate can be absorbed before the curable composition is cured.
Further, the amount of the curing material supplied from the mold for curing the curable composition may be anything that can be cured to such an extent that it can be released within a desired time. The temperature is selected appropriately from the environmental conditions such as temperature and humidity, the fine shape to be transferred, and the adhesion between the substrate and the curable composition. From the thickness of a general film and the curing time, the amount of permeation of the cured material is usually preferably 5 × 10 ⁻⁵ g · m ⁻² · s ⁻¹ or more, and more preferably 1 × because it can be solidified faster. 10 ⁻⁴ g · m ⁻² · s ⁻¹ or more. When the thickness of the curable composition is thin, the curable composition may be sufficiently cured using only the curable material contained in the mold, and not only the curable material permeability of the mold material but also the mold material possesses the curable material. It can also be selected in terms of the amount that can be achieved.
Since the permeation amounts of the solvent and the curing material are determined by the permeability of the material forming the mold and the thickness of the mold, various combinations are possible by selecting the thickness of the mold according to the permeability of the mold material.

  When a metal alkoxide is used as the curable raw material, it must be dissolved or not decomposed by a solvent containing an alcohol generated by condensation of the metal alkoxide, and preferably has an appropriate crosslinking point as a molecular structure. Specific examples include PDMS (silicone rubber) and polyurethane resin, which not only have high chemical resistance, but also easily absorb and permeate solvents and have high moisture permeability. However, depending on the type of material, it may be easily adhered to the cured product and may be difficult to release, and surface modification may be required.

In addition, as a mold material for supplying water as a curing material, a hydrophilic material is generally mentioned, and as a hydrophilic material, an acetylcellulose-based material using cellulose such as TAC (triacetylcellulose) as a raw material. Materials include polyamide materials such as nylon 6 and nylon 66, acrylic resins such as PMMA and acrylic UV curable resins, polyurethane resins, ethylene vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, and polyvinyl alcohol. Polyester (PET) may also be used.
Specifically, the material and thickness are selected from these materials in consideration of resistance to solvents and water, workability based on permeability and thickness.

  The mold surface has a fine concavo-convex structure. As a method for imparting a fine concavo-convex structure to the mold surface, a fine concavo-convex structure is previously formed on a substrate surface of metal, glass, silicon, resin, etc., and the fine concavo-convex structure is formed on the fine concavo-convex structure. Thermal transfer method in which mold material heated above glass transition temperature and melting point is pressed and cooled under pressure, method of transferring mold material solution on fine concavo-convex structure and removing solvent, ultraviolet light on fine concavo-convex structure Examples thereof include a method in which a reactive resin such as a curable resin or a thermosetting resin is applied and the resin is reacted and cured by ultraviolet rays or heat and transferred. Among these, the method using a reactive resin is easy to continuously process, and can use a cylindrical mold to continuously transfer a fine concavo-convex structure on a long film material. Is preferable in that it can be manufactured. The fine concavo-convex structure on the mold surface is preferably prepared in consideration of the dimensional change caused by absorbing the dispersion medium in the curable composition with the mold.

If necessary, the surface of the mold may be subjected to a fluorine or silicone mold release treatment to such an extent that the supply of solvent or water on the surface is not significantly hindered, or a mold release component may be included in the material itself.
In order to efficiently eliminate the curable composition between the convex part of the mold and the substrate and selectively collect the curable composition in the concave part of the mold, the shape of the convex part of the mold is in contact with the substrate. It is preferable to incline with respect to a base material so that a contact area may increase gradually. That is, the shape in the vicinity of the tip of the convex portion of the mold is preferably composed of a surface inclined with respect to the opposing substrate surface. In order to incline the convex side surface of a mold having a fine concavo-convex structure, in addition to the method of forming an incline on the side surface in advance when a fine concavo-convex structure is provided on the substrate surface of metal, glass, silicon, resin, etc., the fine concavo-convex structure It is possible to employ a method of scraping the mold base material by impinging argon plasma particles after applying ashing or a method of ashing with oxygen plasma.

[Curing and shaping process]
In the shaping step, a curable composition (hereinafter also referred to as transfer liquid) is filled between the mold and the substrate, and the curable composition is cured while shaping the transfer liquid. In the present embodiment, in order to reduce transfer accuracy deterioration of the shaped shape based on aggregation and shrinkage of the transfer liquid, the curable raw material and the fine particle dispersion medium are absorbed from at least the convex portion of the mold surface, and the curable composition is obtained. It is important to cure the layers sequentially. This is because the volume shrinkage due to the aggregation of the fine particle dispersion and the curing of the curable composition is supplied from the unaggregated or uncured transfer liquid on the substrate surface side, while the fine shape portion of the mold to be transferred is first This is because the accuracy of the transfer shape is increased by curing. From the viewpoint of realizing this aggregation and curing order, the base material is preferably glass, polyethylene terephthalate (PET), cyclic olefin polymer (COP), polystyrene (PS), or the like that hardly absorbs water. The material can be appropriately selected according to the required shape accuracy.

  As a method of filling the transfer liquid between the mold having the fine concavo-convex structure and the base material, the transfer liquid is applied to the mold having the fine concavo-convex structure, the base material, or both so that air does not enter between them. Or a method of filling the transfer liquid between the mold having a fine shape and the substrate by placing the transfer liquid on the end of the mold or substrate having a fine concavo-convex structure and sequentially pressing from the end with a rubber roller or the like. Etc. At this time, it is preferable that the amount of the transfer liquid sandwiched between the mold having the fine concavo-convex structure and the substrate is a minimum amount that can transfer the fine concavo-convex structure and compensate for shrinkage during aggregation and curing. If the amount is too large, the amount of shrinkage of the entire film after curing increases and cracks are likely to occur. Further, in order to sequentially cure the curable composition from the surface of the mold having a fine concavo-convex structure, the atmosphere in the filling step is preferably a dry atmosphere, specifically a dry atmosphere having a dew point of −20 ° C. or less. More preferably, the drying atmosphere has a dew point of −30 ° C. or lower, and still more preferably the drying atmosphere has a dew point of −40 ° C. or lower.

  The solvent content and filling amount of the transfer liquid are such that the solvent and the curable raw material in the transfer liquid are finally absorbed from the mold surface, and the volume of the curable composition in the recess volume of the mold is reduced. It is necessary that the amount of protrusions is in contact with the substrate. Here, the concave portion volume of the mold means a volume of a space between the mold and the base material when the mold having the fine concavo-convex structure starts to contact the base material. In order for the convex part of the mold to come into contact with the base material, specifically, it can be adjusted by the amount of the solvent in the transfer liquid. When the amount of the solvent is increased, the amount of liquid absorbed from the mold surface increases. It becomes easy to contact the convex part of the substrate. It is also preferable to control the amount of transfer liquid when the transfer liquid is filled between the mold and the substrate in order to improve reproducibility.

  The transfer liquid may be allowed to stand at room temperature after being filled between the mold having the fine concavo-convex structure and the base material. However, heating to about 40 to 80 ° C. promotes aggregation and curing reaction. The time to mold can be shortened. The time of mold release is a condition that satisfies the condition that the curable composition can retain its shape after mold release, that the adhesive force between the substrate and the agglomerate or cured product is greater than or equal to the mold release force, and that the mold release force is sufficiently small To select as appropriate. Also, in the initial stage after filling with the transfer liquid, the mold swells with the dispersion medium, increasing its size and increasing the release force. Therefore, after the dispersion medium diffuses from the mold surface into the mold, the mold shrinks. It is preferable to release the mold.

When using the curable composition, the mold (hereinafter, also referred to as a mold film) can be used as a protective film without being peeled off until use.
For shaping, after the curable composition is cured to such an extent that the mold can be peeled off, the mold is peeled off and the curable composition is sufficiently cured by moisture in an external atmosphere such as in the air. This is preferable in order to shorten the time until the selection and the curing conditions of the curable composition. In the curing of the curable composition, it is preferable to give sufficient moisture and temperature within a range that does not adversely affect the substrate and to stir the atmosphere, and in some cases, steam can be sprayed.
In addition, it is also possible to shape a fine concavo-convex structure only by a fine particle dispersion containing no curable raw material in the curable composition due to agglomeration of fine particles. In this case, at least the convex portions of the fine concavo-convex structure on the surface of the mold must be able to absorb the fine particle dispersion medium in order to significantly reduce or substantially eliminate the residual film thickness. In addition, it is preferable to perform sintering in order to firmly bond the fine particles after peeling of the mold.

When the substrate has a curved shape, if the mold film can follow the cylindrical side, it can be shaped in the same way as a flat surface using the above method, but the curved surface cannot be followed by a flat film, such as a spherical shape. In this case, the mold film is pre-molded by thermoforming to match the curved surface of the substrate, or the mold film is made of a stretchable material, and the mold film is pulled along the curved surface of the substrate. It can be shaped.
In addition, by using a flexible mold such as PDMS, it is possible to superimpose various shapes by a plurality of shaping, for example, a submicron size shape on a micron size shape. Or a micron-sized shape can be formed on a submicron-sized shape.

[Surface shape of cured product]
In the present embodiment, the fine shape or the concavo-convex structure to be transferred is not particularly limited in size due to the transfer method, but the average pitch is 10 nm to 0.1 mm or less from the reproducibility of the mold shape and the time required for transfer. And a shape having a height / pitch ratio of 0.1 to 5 is preferable, and does not depend on the presence or absence of regularity. The fine shape or the concavo-convex structure is preferably a shape in which the shape of the cross section is made of a rectangle, trapezoid, sine wave, etc., and basically a shape that can be removed from the mold, but when using a flexible mold such as PDMS, the mold or transfer It may include an undercut shape that can be removed by deformation that does not destroy the object.
A specific fine shape or concavo-convex structure can be appropriately selected according to a desired application. For example, for a wire grid polarizer base material application, a pitch of 100 to 150 nm, a height of about 80 to 150 nm, a line and space structure having a line width of 0.1 to 0.4 times the pitch, and an antireflection application, For light extraction applications of LEDs and OLEDs having a pitch of about 100 to 300 nm and a cone-to-conical shape having a height / pitch ratio of about 0.8 to 1.5, which is called a moth-eye structure, the pitch is 0. A structure in which frustoconical shapes with a height of 8 to 2 μm and a height / pitch ratio of about 0.8 to 1.5 are densely arranged. For infrared emitters for thermophotovoltaic power generation, the aperture width and depth are the wavelengths of emitted infrared rays. For the purpose of light diffusion and condensing, a lens with a pitch of about 1 to 20 μm and a height / pitch ratio of about 0.2 to 2, various irregularities such as prisms Structure, bacteria, cell and microorganism adhesion / reproduction control Applications include various concavo-convex structures such as a cylinder having a pitch of 0.1 to 20 μm and a height / pitch ratio of about 0.2 to 2, a truncated cone and a line and space.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, these are described for description and the range of this invention is not limited to the following Example.
[Mold making]
As a material for producing a mold, ELASTOSIL RT601 manufactured by Asahi Kasei Wacker Silicone Co. is used as an addition reaction curable silicone resin, and a microlens array shape HT-MLA-09 manufactured by Holoolols having a diameter of 9 μm and a height of 5.5 μm is microstructured. Transcribed as. The microlens array shape has a convex lens shape transferred on the silicone resin surface (hereinafter convex) and a concave lens shape transferred on the silicone resin surface that is the reverse of the convex shape (hereinafter concave). Two kinds of were prepared. When the transfer shape on the surface of the silicone resin was observed with a microscope, both the convex mold (Figs. 1 and 2) and the concave mold (Fig. 3) showed good transfer. A pointed sphere that was parallel to the surface of the substrate was negligible except for the tip of the sphere.

[Curable composition]
As a metal alkoxide compound, a curable composition A obtained by adding 1% by mass of tin neodecanoate to tetramethoxysilane, a silica fine particle dispersion “Methanol silica sol” (30% by mass of silica fine particles) manufactured by Nissan Chemical Co., Ltd. Containing methanol dispersion) A curable composition B was prepared by adding 1 part by mass and 2 parts by mass of methanol. Further, a curable composition obtained by adding 1 part by mass of curable composition A and 5 parts by mass of methanol to 4 parts by mass of zirconia fine particle dispersion “SZR-M” (manufactured by Sakai Chemical Co., Ltd.). C was produced.

[Shaping the microstructure]
As a substrate for shaping the fine structure, the surface of an ITO-coated glass plate (50 × 50 × 1.2 mm) having a surface resistance of 10 Ω / sq was used after ultraviolet ozone cleaning.

[Example 1]
The curable composition B is dropped linearly along the edge of the substrate at the edge of the substrate, and one end of the surface on which the concave structure is formed is pressed against the place where the curable composition B is supplied, Gently push the curable composition B between the mold and the substrate by pressing it with a rubber roll from the back side of the substrate, and let it adhere to the substrate. After leaving at room temperature for 60 minutes, the mold is peeled off to produce a structure on the substrate, and the humidity is 50%. It was left for 10 days in a room temperature environment.
Similarly, a structure was produced on the substrate using a convex mold.
In the observation using a microscope, when a concave structure is used, the top of the convex part of the shaped convex lens is formed as a lens having a diameter of about 7 μm, but the lower part of the convex part is a V-shaped valley. It was not formed and was a plane part of the substrate (FIG. 4). In addition, when the convex type is used, the formed concave lens shape edge protrusion is formed, but the lower part of the concave portion is not formed with a spherical lens shape but is a flat portion of the substrate.

When elemental analysis of the portion where the planar portion of these substrates was observed by Auger electron spectroscopy, In and Sn based on ITO were detected from any portion, and thus there was a SiO ₂ film on the substrate. Even so, it was found that the escape depth of Auger electrons was several nm or less.
The substrate on which the structure is transferred using the concave mold and the convex mold does not peel off or dissolve even when rubbed with a paper clean wiper with ethanol attached, and the conductive paint is separated by about 20 mm into dots. After coating and drying in two places, the conduction between these two points was measured at a voltage of 1.5 V. Both the concave and convex shapes showed good conductivity, and the portion where the flat portion of the substrate was visible was electrically It turned out to be conductive.

[Example 2]
Using the curable composition A, a structure was produced on the substrate using a concave mold in the same manner as in Example 1.
In the observation using a microscope, the structure is formed only at the top of the convex part of the shaped convex lens with a diameter of about 2 μm, and the lower part of the convex part is not formed with a V-shaped valley but is a flat part of the substrate. It was. Even if the substrate to which the structure is transferred is rubbed with a paper clean wiper with ethanol attached, the structure does not peel off or dissolve, and the planar portion of the substrate can be seen in the conductivity evaluation using a conductive paint. The part was found to be electrically conductive.

[Example 3]
Using the curable composition C, a structure was produced on the substrate using a concave mold in the same manner as in Example 1.
In the observation using a microscope, the structure has a convex lens-shaped convex top portion formed as a lens having a diameter of about 7 μm, but the lower portion of the convex portion is not formed with a V-shaped valley, and the plane of the substrate It was a department. Even if the substrate to which the structure is transferred is rubbed with a paper clean wiper with ethanol attached, the structure does not peel off or dissolve, and the planar portion of the substrate can be seen in the conductivity evaluation using a conductive paint. The part was found to be electrically conductive.

[Comparative Example 1]
A curable composition D was prepared by adding 1 part of a silica fine particle dispersion “methanol silica sol” (30% by mass of silica fine particles containing methanol dispersion) of Nissan Chemical Co. to 1 part of the curable composition A. A structure was produced on the substrate using a concave mold in the same manner as in Example 1 except that the curable composition D was used. In the observation using a microscope, the V-shaped valley at the bottom of the convex part was completely formed from the top of the convex part of the shaped convex lens, and the flat part of the substrate could not be confirmed (FIG. 5). ). Conductivity evaluation using a conductive paint revealed that there was no electrical continuity, and ITO was not exposed on the surface of the substrate onto which the structure was transferred.

[Comparative Example 2]
As a material for producing a mold, an easy-adhesive PET film having a thickness of 188 μm and an ultraviolet curable resin PAK-01 manufactured by Toyo Gosei Co., Ltd. were used, and a concave shape was produced by transferring the shape of the microlens array onto the PET film. An attempt was made to produce a structure on the substrate in the same manner as in Example 1 except that this PET film base was used, but the curable composition B was cured even when left at room temperature for 2 days. No structure was obtained.

  According to the imprint method of the present invention, the residual film thickness can be significantly reduced or the residual film can be substantially eliminated. Therefore, the method for producing a laminate according to the present invention includes a line-and-space structure in a wire grid polarizing plate substrate application, a moth-eye structure in an antireflection application, LED, and OLED as a method for obtaining a fine pattern with high productivity. Structure with closely arranged frustoconical shapes for light extraction applications, structures for infrared emitters for thermophotovoltaic power generation, various uneven structures for light diffusion and light collection applications, adhesion / reproduction control of bacteria, cells and microorganisms It can be suitably used for the production of a laminate having various uneven structures such as a cylinder, a truncated cone and a line and space.

Claims (15)

It is a manufacturing method of the laminated body of hardened | cured material and a base material, Comprising: The following processes:
A curable composition having a fine concavo-convex shape on the surface and containing the curable raw material in a space between the mold and the substrate capable of absorbing the curable raw material from at least the convex portion of the fine concavo-convex structure on the mold surface Including a step of filling the product, wherein the curable raw material is absorbed from at least the convex portions of the fine concavo-convex structure on the surface of the mold, and the volume of the curable composition in the concave volume of the mold is reduced. Wherein the top of the convex portion of the mold contacts the surface of the substrate.   The method according to claim 1, wherein when the convex top portion of the mold contacts the surface of the base material, the convex top portion deforms along the base surface and adheres to the base material.   The method according to claim 1 or 2, wherein the shape in the vicinity of the tip of the convex portion of the mold is composed of a surface inclined with respect to the opposing substrate surface.   The method according to claim 1, wherein the top of the convex portion of the mold is made of a rubbery material.   5. The method of claim 4, wherein the mold material is silicone rubber.   The method according to claim 1, wherein the curable raw material is a metal alkoxide.   The method of claim 6, wherein the metal of the metal alkoxide is silicon.   The laminated body manufactured by the method of any one of Claims 1-7.   A laminate in which a fine concavo-convex structure is transferred to the surface of a substrate, wherein the remaining film thickness of the portion corresponding to the convex portion of the mold at the time of transfer is equal to or less than the escape thickness of Auger electrons.   The laminate according to claim 9, wherein the fine concavo-convex structure is composed of an inorganic material.   The laminated body of Claim 10 whose said inorganic substance is a metal or a metal oxide.   The laminate according to claim 11, wherein the metal is silicon.   The laminated body of any one of Claims 9-12 in which the said fine concavo-convex structure contains glassy.   The laminate according to any one of claims 9 to 13, wherein the fine uneven structure includes inorganic fine particles having a particle diameter of 10 nm or less. It is a manufacturing method of the laminated body of hardened | cured material and a base material, Comprising: The following processes:
The space between the substrate having a fine irregular shape on the surface and capable of absorbing the fine particle dispersion medium from at least the convex portion of the fine irregular structure on the mold surface and the fine particle dispersion medium and the fine particles are included. Including a step of filling the fine particle dispersion, wherein the fine particle dispersion medium is absorbed from at least the convex portions of the fine concavo-convex structure on the surface of the mold, and the volume of the curable composition in the concave volume of the mold is small. The method, wherein the top of the convex portion of the mold contacts the surface of the substrate.