JP2014219652A - Method for manufacturing laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a product having a fine concavo-convex shape integrated with a substrate with high productivity, by which degradation of transfer accuracy of a molded shape caused by shrinkage of a curable composition is decreased and a fine concavo-convex shape can be molded on a substrate comprising various raw materials including a resin and having various shapes including a curved surface by using a simple molding process and an easily available mold raw material.SOLUTION: A method for manufacturing a laminate of a cured product and a substrate is provided, which includes the steps of: (A) filling a space between a mold that can supply a curing material and a substrate with a curable composition comprising a curable raw material that is cured by contacting the curing material; (B) curing the curable composition by the curing material supplied from the die to obtain a cured product; and (C) releasing the mold from the cured product on the substrate.

Description

  The present invention relates to a method for producing a laminate of a cured product and a substrate, a method for producing a laminate of a substrate and an aggregate, and a laminate produced by these methods.

As a method of shaping a microstructure made of an inorganic material on a substrate, a method of transferring and replicating a mold shape using a curable composition such as a sol-gel material and a mold in the production of a diffraction grating or a recording medium, It has been known for a long time (see Patent Document 1 and Patent Document 2 below).
Examples of a method for forming a fine structure on a substrate using a mold include the following.
(1) Metal alkoxide, solvent, water, and catalyst are hydrolyzed in a solution consisting of metal alkoxide, the hydrolyzate solution is applied to the substrate, the solvent is removed, and polycondensation is advanced. Method of releasing after heat curing;
(2) A method of applying the hydrolysis and condensation solution to the mold, removing the solvent and curing, and then transferring it to the substrate through an adhesive;
(3) A method in which the solution subjected to hydrolysis and condensation is applied to a mold, gelled, pressed against a substrate, heated and cured, and then released;
(4) A method of using a flexible sheet or film-like mold, sandwiching the hydrolysis and condensation solution between the mold and a substrate, heating and releasing the mold after curing.

In addition to the sol-gel material, a material comprising polysilazane, a solvent, and a catalyst that can be cured at a relatively low temperature is also known as the curable composition. In Patent Document 3 below, such a material is a partition wall of a plasma display. It is used for the production of
In Patent Document 4 below, an antireflection structure is produced using polysilazane.
In Patent Document 5 below, a coating liquid is prepared by blending high refractive index fine particles with an organosilicon compound.
On the other hand, using a dispersion of inorganic fine particles and shaping with a mold while removing the dispersion medium has been known for a long time as slip casting, as described in Patent Document 6 below. It was never applied to film formation. In recent years, as disclosed in Patent Document 7 below, a method for forming a needle sheet used for a transdermal absorption sheet using a polymer solution and a breathable silicone resin mold has been developed.

JP 60-21215 A Japanese Patent Laid-Open No. 2-83226 Japanese Patent No. 3660449 JP 2011-28229 A Japanese Patent No. 4673664 Japanese Patent Laid-Open No. 62-104704 JP 2011-245055 A

A curable composition such as a sol-gel material is generally a dilute solution and has a large volume shrinkage in the curing process. Therefore, it is necessary to reduce the shrinkage and improve the transfer accuracy of the shaped shape. For this reason, as described above, methods such as shaping a condensate that has been subjected to hydrolysis and condensation in advance, or adding inorganic fine particles to the curable composition have been used.
However, in general, condensates and inorganic fine particle additives that have undergone hydrolysis and condensation have high viscosity, and a large pressure is required for shaping, and an inorganic material such as metal or glass is required as a mold material. Many. Further, in many cases, it is necessary to sinter at a high temperature of about several hundred to several hundreds of degrees after curing, so that the cured product becomes glassy, and the shape is greatly shrunk by sintering, and the resin cannot be used as a base material. There were problems such as.

On the other hand, curable compositions such as conventional sol-gel materials have fine particle surfaces previously modified with metal alkoxide and dispersed in the sol in order to disperse inorganic fine particles in the sol. Often, important properties such as the high refractive index of the material are impaired, and it has been difficult for the prior art to exceed the refractive index of 1.8 even when titania is used.
In addition, even when titania is dispersed in an organic resin binder to form a coating, the photocatalytic action of titania causes the binder to oxidize and decompose in an environment exposed to ultraviolet rays, shortening the life of the coating and reducing reliability. There was a problem.

  In view of these problems, the problem to be solved by the present invention is to reduce a decrease in the transfer accuracy of a shaped shape based on the shrinkage of the curable composition, and to use a mold material that is easy to obtain and easy to obtain. It is possible to form a fine uneven shape on a substrate composed of various materials including a resin and have various shapes including a curved surface, and a product in which the fine uneven shape is integrated with the substrate. It is to provide a method for manufacturing with good productivity. In addition, the problem to be solved by the present invention is that a cured product that is highly filled with fine particles without a minimum modification or surface modification while reducing a decrease in transfer accuracy of a shaped shape based on shrinkage of the curable composition. It is also providing the method of manufacturing the laminated body formed on the base material.

As a result of intensive investigations and repeated experiments, the present inventors have determined that the curable composition can be removed from the surface of the mold by combining the material constituting the mold and the curable composition in a specific combination. It was cured sequentially, and it was found that it was possible to reduce a decrease in the transfer accuracy of the shaped shape based on curing shrinkage. Also, paying attention to the process in which the mold shape is transferred while the curable composition is cured in the mold, it aggregates and solidifies when the fine particles are below a specific distance, and the material constituting the mold and the curable composition It was found that by making the composition in a specific combination, the curable composition was sequentially cured from the mold surface, and the transfer accuracy of the shaped shape based on curing shrinkage could be reduced, and the present invention was completed.
That is, the present invention is as follows.

[1] The following steps:
(A) a step of filling a space between a mold capable of supplying the curable material and a substrate with a curable composition containing a curable raw material that is cured by contact with the curable material;
(B) a step of obtaining a cured product by curing the curable composition with the curing material supplied from the mold; and (C) a step of peeling the mold from the cured product on the substrate.
The manufacturing method of the laminated body of hardened | cured material and a base material containing this.

  [2] The method according to [1], wherein the mold has a fine concavo-convex structure having an average pitch of 10 nm to 0.1 mm and a height / pitch ratio of 0.1 to 5 on the surface.

  [3] The method according to [1] or [2], wherein the curable material is water and the curable raw material is a metal alkoxide.

[4] The water permeation amount of the mold is 5 × 10 ⁻⁵ g · m ⁻² · s ⁻¹ or more and / or the water content in the atmospheric equilibrium of the mold is 0.5 mass% or more and 20 mass% or less. The method according to [3], wherein

  [5] A laminate of a cured product and a substrate produced by the method according to any one of [1] to [4].

[6] The following steps:
(A ′) Filling the space between the mold capable of supplying the curable material and the substrate with the curable composition in which the fine particles are dispersed in the curable raw material that is cured by contact with the curable material. Process,
(B ′) a step of obtaining a cured product by curing the curable composition with the cured material supplied from the mold, and (C ′) peeling the mold from the cured product on the substrate. Process,
The manufacturing method of the laminated body of hardened | cured material and a base material containing this.

  [7] The method according to [6], wherein the curable composition further comprises a solvent for dispersing the fine particles.

  [8] The method according to [7], wherein the mold can absorb the solvent.

[9] The method according to [8] above, wherein the permeation amount of the solvent of the mold is 1 × 10 ⁻³ g · m ⁻² · s ⁻¹ or more.

  [10] The method according to any one of [6] to [9], wherein the mold has a fine uneven structure having an average pitch of 10 nm to 0.1 mm and a height / pitch ratio of 0.1 to 5 on the surface. .

  [11] The method according to any one of [6] to [10], wherein the average particle size of the fine particles is 100 nm or less.

  [12] The method according to any one of [6] to [11], wherein the curable material is water and the curable raw material is a metal alkoxide.

[13] The method according to [12], wherein the mold has a water permeation amount of 5 × 10 ⁻⁵ g · m ⁻² · s ⁻¹ or more.

  [14] The method according to [12] or [13], wherein the moisture content in the atmospheric equilibrium of the mold is 0.5% by weight or more and 20% by weight or less.

  [15] A laminate of a cured product and a base material produced by the method according to any one of [6] to [14].

  [16] The laminate according to [15], wherein the cured product has a refractive index of 1.75 to 2.20.

  [17] The laminate according to [15], wherein the cured product has a refractive index of 1.20 to 1.40.

[18] The following steps:
(A ″) a step of filling a dispersion in which fine particles are dispersed in a solvent into a space between a mold capable of absorbing the solvent and a base material;
(B '') the mold absorbs the solvent to agglomerate the fine particles in the dispersion to obtain an agglomerate; and (C '') the agglomerate on the substrate. A process of peeling from the object,
The manufacturing method of the laminated body of a base material and an aggregate containing this.

[19] A step of sintering the aggregate on the substrate obtained in the steps (D) and (C ″) to fix the structure,
The method according to [18], further comprising:

  [20] The method according to [18] or [19], wherein the surface of the fine particles is coated with a material having a melting point lower than that of the fine particles.

  [21] A laminate produced by the method according to any one of [18] to [20].

[22] The following steps:
(A ′ ″) a step of filling a space between a mold capable of absorbing the solvent and a substrate with a curable composition that is cured by reducing the amount of the solvent contained;
(B ′ ″) a step of absorbing the solvent into the mold to cure the curable composition to obtain a cured product; and (C ′ ″) the mold on the substrate. A process of peeling from the object,
The manufacturing method of the laminated body of hardened | cured material and a base material containing this.

  [23] The method according to [22] above, wherein fine particles are dispersed in the curable composition.

[24] The method according to [22] or [23], wherein the permeation amount of the solvent of the mold is 1 × 10 ⁻³ g · m ⁻² · s ⁻¹ or more.

  [25] The method according to any one of [22] to [24], wherein the mold has a fine concavo-convex structure having an average pitch of 10 nm to 0.1 mm and a height / pitch ratio of 0.1 to 5 on the surface. .

  [26] A laminate of a cured product and a substrate produced by the method according to any one of [21] to [25].

  According to the production method of the present invention, it is possible to form a fine uneven shape with high transfer accuracy on a substrate surface composed of various materials including a resin and having various shapes including a curved surface. . In addition, a laminate in which a cured product that is highly filled with fine particles without minimal modification or surface modification is formed on a base material while reducing a decrease in transfer accuracy of a shaped shape based on shrinkage of the curable composition Can be manufactured.

It is a graph which shows the surface reflectance of the hardened | cured material which has a fine shape. It is an electron micrograph of the moth-eye structure formed on the glass surface. It is the schematic explaining the process of the method of providing the hardened | cured material which has a fine shape on the surface of a base material of this invention.

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 of the laminated body which concerns on 1st embodiment of this Embodiment is the following processes:
(A) a step of filling a space between a mold capable of supplying the curable material and a substrate with a curable composition containing a curable raw material that is cured by contact with the curable material;
(B) a step of obtaining a cured product by curing the curable composition with the curing material supplied from the mold; and (C) a step of peeling the mold from the cured product on the substrate.
Is a method for producing a laminate of a cured product and a substrate.

The manufacturing method of the laminated body which concerns on 2nd embodiment of this Embodiment is the following processes:
(A ′) Filling the space between the mold capable of supplying the curable material and the substrate with the curable composition in which the fine particles are dispersed in the curable raw material that is cured by contact with the curable material. Process,
(B ′) a step of obtaining a cured product by curing the curable composition with the cured material supplied from the mold, and (C ′) peeling the mold from the cured product on the substrate. Process,
Is a method for producing a laminate of a cured product and a substrate.

The manufacturing method of the laminated body according to the third embodiment of the present embodiment includes the following steps:
(A ″) a step of filling a dispersion in which fine particles are dispersed in a solvent into a space between a mold capable of absorbing the solvent and a base material;
(B '') the mold absorbs the solvent to agglomerate the fine particles in the dispersion to obtain an agglomerate; and (C '') the agglomerate on the substrate. A process of peeling from the object,
It is a manufacturing method of the laminated body of a base material and an aggregate containing.

And the manufacturing method of the laminated body which concerns on 4th embodiment of this Embodiment is the following processes:
(A ′ ″) a step of filling a space between a mold capable of absorbing the solvent and a substrate with a curable composition that is cured by reducing the amount of the solvent contained;
(B ′ ″) a step of absorbing the solvent into the mold to cure the curable composition to obtain a cured product; and (C ′ ″) the mold on the substrate. A process of peeling from the object,
Is a method for producing a laminate of a cured product and a substrate.

  In the method for manufacturing a laminate according to the first embodiment of the present embodiment, a curable composition that can be cured by supplying a curing material, a mold that can supply the curing material, and The curable composition is filled between the substrates, and the curable composition is hardened until it can be released from the mold by diffusing and supplying the curable composition from the mold to the curable composition. It is characterized by giving a thing.

  In the method for manufacturing a laminate according to the second embodiment of the present embodiment, fine particles with a minimal modification on the surface or without surface modification are dispersed in a curable raw material serving as a binder for the fine particles, By curing the curable raw material of this fine particle dispersion into a shape along the mold, a dense film highly filled with fine particles can be formed.

  In the method for producing a laminate according to the third embodiment of the present embodiment, fine particles with a minimal modification on the surface or without surface modification are dispersed in a solvent, and the solvent of the fine particle dispersion is used as a mold. It is possible to form a film in which fine particles are aggregated at a high density by agglomerating into a shape along the mold while being absorbed.

  In the method for producing a laminate according to the fourth embodiment of the present embodiment, a curable composition that can be cured by reducing the solvent contained therein, a mold that can absorb the solvent, Filled between the base materials, the solvent contained in the curable composition is absorbed in the mold, the curable composition is cured until it can be released from the mold, and the mold is peeled off, and the cured product is formed on the surface of the base material. It is characterized by giving.

[Fine particles]
The fine particles used in this embodiment are required to have a property of aggregating when the interparticle 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 and solvent]
The fine particle dispersion is obtained by dispersing the above fine particles in a solvent, and the dispersion medium (solvent) may be any material as long as the fine particles are stably dispersed, and the solvent other than water is an alcohol such as methanol, ethanol, isopropanol or the like. In addition to ketones such as acetone and methyl ethyl ketone, various esters are listed, and the appropriate amount is absorbed from the mold material and diffused and permeated through the mold material without being dissolved or decomposed. To do.
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.

[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 the above-described fine particles. The cured product is obtained by curing a curable composition containing an inorganic material into a solid state, and the curing reaction may not proceed completely, and an organic functional group may partially remain. 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 invention, the curable raw material is not particularly limited as long as it is a material that can be cured by a curing material, and can be, for example, a metal alkoxide.

[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.

[Addition of solvent, 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.
By adding an appropriate amount of solvent, such as when the curable composition contains fine particles, even if a sufficient amount of water is contained in the curable composition, the curable composition does not self-cure and is stable for a long time. Can be obtained. In this case, the curable composition can be cured by absorbing the solvent with the mold and reducing the amount of the solvent (see the fourth embodiment).
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 a non-solvent.

[Type]
The mold in the present embodiment supplies a curable material to the curable composition in contact with the mold surface and sequentially cures the curable composition from the mold surface, or at the same time, adjusts the concentration and stability of the curable composition. Absorbs the solvent for curable composition from the curable composition and cures the curable composition from the mold surface and / or absorbs the solvent (dispersion medium) for dispersing the inorganic fine particles in the fine particle dispersion from the fine particle dispersion. Then, the fine particles are aggregated, or at the same time, a curing material is supplied to the curable composition in contact with the mold surface, and the curable composition is sequentially cured from the mold surface.
Specifically, the first embodiment has a function of supplying a curable material to the curable composition in contact with the mold surface and sequentially curing the curable composition from the mold surface. Regarding the second embodiment, the solvent (dispersion medium) for dispersing the inorganic fine particles in the fine particle dispersion in contact with the mold surface is absorbed from the fine particle dispersion to aggregate the fine particles, and at the same time, contacted with the mold surface. It has a function of supplying a curable material to the curable composition and sequentially curing the curable composition from the mold surface. The third embodiment has a function of aggregating fine particles by absorbing from the fine particle dispersion a solvent (dispersion medium) for dispersing inorganic fine particles in the fine particle dispersion in contact with the mold surface. The fourth embodiment has a function of absorbing the solvent in the curable composition in contact with the mold surface from the curable composition and sequentially curing the curable composition from the mold surface.
For this reason, the mold needs to have a property of appropriately absorbing and transmitting the dispersion medium, or simultaneously holding and / or transmitting an appropriate amount of the curing material.
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.

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. In this case, the moisture content of the mold material is preferably 0.5% by mass or more, more preferably 1.0% by mass or more in atmospheric equilibrium. The upper limit is not limited as long as the material swells due to water absorption, the rigidity is greatly reduced, and the mold is not deformed.
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 are not only high in chemical resistance, but also easily absorb and permeate solvents and have high moisture permeability, and thus can be said to be materials suitable for curing. 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 may be smooth or have a fine shape. As a method of forming a fine shape on the mold surface, a fine shape is formed in advance on the surface of a substrate such as metal, glass, silicon, or resin, and a mold material heated to a glass transition temperature or a melting point or higher is pressed on the fine shape. A thermal transfer method that cools under pressure, a method of transferring a mold material solution on a fine shape and transferring the solvent by removing the solvent, an ultraviolet curable resin, a thermosetting resin, or other reactive resin on the fine shape. For example, the resin may be cured by reaction curing with heat. Among them, the method using a reactive resin is easy to continuously process, and can use a cylindrical mold to continuously transfer a fine shape onto a long film material. Can be produced. The fine shape of the mold surface needs to be 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.

[Curing and shaping process]
In the shaping step, when a fine particle dispersion or a curable composition (hereinafter also referred to as a transfer liquid) is filled between the mold and the substrate and the fine particles are contained while shaping the transfer liquid. The fine particles are aggregated to cure the curable composition. In the present embodiment, in order to reduce a decrease in the transfer accuracy of the shaped shape based on aggregation and shrinkage of the transfer liquid, the dispersion medium and solvent of fine particles are absorbed from the mold surface, and the curable composition is sequentially cured. is important. This is because the volumetric shrinkage that accompanies the aggregation of the fine particle dispersion and the curing of the curable composition is supplied from the unagglomerated or uncured liquid on the substrate surface side, and the fine shape part of the mold to be transferred is first cured. This is to improve the accuracy of the transfer shape. 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 a transfer liquid between a mold having a fine shape and a substrate, a method of applying a transfer liquid to a mold having a fine shape, a substrate, or both, and adjusting so that air does not enter between them, Examples include a method of filling the transfer liquid between the mold having the fine shape and the substrate by placing the transfer liquid on the end of the mold having the fine shape or the substrate, and sequentially pressing from the end with a rubber roller or the like. It is done. At this time, the amount of the transfer liquid sandwiched between the mold having a fine shape and the substrate is preferably a minimum amount that can transfer the fine shape and compensate for shrinkage during aggregation and curing, and the amount is too large. And the shrinkage amount of the whole film after curing becomes large, and cracks are likely to occur. Further, in order to sequentially cure the curable composition from the surface of the mold having a fine shape, the atmosphere in the filling step is preferably a dry atmosphere, specifically a dry atmosphere having a dew point of −20 ° C. or less. A dry atmosphere having a dew point of −30 ° C. or lower is more preferable, and a dry atmosphere having a dew point of −40 ° C. or lower is more preferable.
The transfer liquid may be allowed to stand at room temperature after being filled between the mold having a fine shape and the substrate. However, when heated to about 40 to 80 ° C., the aggregation and curing reaction are promoted. Can be shortened. The time for mold release is that the curable composition can maintain its shape after mold release, the condition that the adhesive force between the substrate and the agglomerate or cured product is more than the mold release force, and 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. In FIG. 3, an example of the process of the method of providing the hardened | cured material which has a fine shape on the surface of a base material is shown with a schematic diagram.

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.
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.

[Surface shape of cured product]
In this Embodiment, the surface of the hardened | cured material transcribe | transferred from the type | mold may be smooth, or may have a fine shape (fine uneven | corrugated shape). The fine shape to be transferred is not particularly limited in size due to the transfer method, but from the reproducibility of the mold shape and the time required for transfer, the average pitch is 10 nm to 0.1 mm or less and the height / pitch ratio is 0. The shape of 1-5 is preferable and does not depend on the presence or absence of regularity. The fine shape has a cross-sectional shape of a rectangle, trapezoid, sine wave, etc., and is preferably a shape that allows the mold to be removed. However, when a flexible mold such as PDMS is used, the mold or the transcript is destroyed. It may include an undercut shape that can be removed with a degree of deformation.
A specific fine shape 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.
In addition, by smoothing without forming a fine shape on the mold surface, it is possible to give a smooth inorganic coating on the surface of the substrate, and not only improve scratch resistance and barrier properties by a hard and dense coating, but also wide By changing the refractive index within the range, it is possible to prevent optical loss and the like, and it becomes easy to partially change the film thickness by using a mold.

[Refractive index of cured product]
The cured product obtained according to the present invention can be filled with inorganic fine particles at a high density by absorbing a solvent or the like from a dispersion of inorganic fine particles without minimal modification or surface modification, depending on the type. Since repulsion can be performed while maintaining a large interparticle distance by electrical repulsion, a very wide range of refractive index can be obtained.
In order to obtain a high refractive index, the minimum metal alkoxide that can be shaped and sintered by a mold as it is using a dispersion of fine particles such as titania having a high refractive index, or fine particles can be connected together By adding such as above, shaping and solidifying in the mold, it is possible to obtain a film in which the amount of titania in the cured product is maximized. The latter method can also be said to be a method of simultaneously performing surface modification and bonding solidification of fine particles. When titania is used, the refractive index of the coating can be adjusted from about 1.5 to about 2.2, and in order to obtain a refractive index of 1.75 or more, more preferably 1.8 or more, the method of the present invention. Is preferred.
In order to obtain a low refractive index, a stable state in which the distance between the particles is kept large by electrical repulsion between the fine particles is formed in the curable composition, and the solid is shaped and solidified as it is. When an appropriate amount of a metal alkoxide or the like is added to a fine particle having a low refractive index such as silica, a fine aggregate is formed, and the aggregate is solidified while maintaining a space, thereby obtaining a low refractive index coating film. The index can be adjusted from about 1.45 to about 1.20, and the method of the present invention is suitable for obtaining a refractive index of 1.40 or less, more preferably 1.35 or less.

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.
[Type]
As a PDMS (silicone rubber) material for producing the mold, ELASTOSIL-RT601 manufactured by Asahi Kasei Wacker Silicone Co., and as an ultraviolet curable material, 33 parts of trimethylolpropane triacrylate which is a trifunctional or higher acrylate compound monomer, N -33 parts of N-vinyl-2-pyrrolidone as the vinyl compound monomer, 33 parts of 1,9-nonanediol diacrylate as the other monomer, 0.5 part of silicone diacrylate, 2.4 as the photopolymerization initiator 2,6-trimethylbenzoyldiphenylphosphine oxide 2 parts was mixed to prepare an ultraviolet curable resin composition A.

[Production of PDMS type]
After mixing the two liquids, the two-part PDMS is flowed at a thickness of about 1 mm onto the following sub-micron projection shape placed in a flat bat and the Ni-type projection shape having the following micron projection shape, The liquid PDMS was degassed for 3 minutes under reduced pressure, and then cured under atmospheric pressure at room temperature for 3 hours. After the PDMS was cured, it was peeled off from the mold and post-cured in a hot air dryer at 150 ° C. for 30 minutes to obtain a PDMS type (hereinafter also referred to as a submicron protrusion-shaped PDMS type or a micron protrusion-shaped PDMS type). Each projection shape was as follows, and the Ni mold had a projection shape.
・ Submicron protrusion shape: 700 nm in diameter and 700 nm in height and rounded truncated cone-shaped protrusions arranged in a close-packed manner on a flat surface ・ Micron protrusion shape: hemispherical convex lens shape with a diameter of 9 μm and a height of 5.5 μm Lined up with fine packing on a flat surface.
The produced PDMS mold was stored in an environment of 23 ° C. and 50% RH.
In addition to the Ni mold, a smooth glass plate was used as a mold for forming a smooth film, and a smooth PDMS mold was produced by the above method.

[Production of TAC type]
Using the TAC (triacetyl cellulose film) having a thickness of 80 μm as a base material, the above-mentioned Ni having the following moth-eye shape was applied to the surface so that the ultraviolet curable resin composition A was 0.8 μm and subjected to a release treatment. A TAC mold (hereinafter referred to as a moth eye) in which a mold made by pressing, ultraviolet light containing visible light from the side of the triacetyl cellulose film was exposed (3 J / cm ² ) and cured, then released, and the moth eye shape was transferred in reverse. Also referred to as shape TAC type.). A smooth TAC type was also produced using a smooth glass plate as a mold in the same manner as PDMS. The details of the moth-eye shape are as follows.
-Moss eye shape: A round cone-shaped projection with a pitch of 280 nm and a height of 300 nm arranged on a plane in a close-packed manner.

[Preparation of PET mold]
The film used as a mold material is changed to a PET film having a thickness of 16 μm and 250 μm, and a moth-eye shape is transferred in the same manner as the TAC type, and a PET type having a thickness of 16 μm and 250 μm (hereinafter also referred to as a moth-eye shape PET type). Produced.

[Measurement of mold water and solvent (solvent) permeation amount]
About the produced type | mold, water and a solvent (solvent) permeation | transmission amount were measured. For measurement, open a 10 cm ² hole in the lid of a glass sealed container with a metal lid, cover the hole with a mold for measuring permeability, put room temperature methanol (MeOH) or water in the container, and cover the lid. The mold was placed in the downward direction and the container was covered with liquid at room temperature, and the mass reduction rate of the entire container was measured to determine the amount of permeation. In the measurement of water permeation, the surroundings of the container were dry air at room temperature with a dew point of −40 ° C. The permeation amounts of various types of methanol and water are shown in Table 1 below.

[Fine particle dispersion]
In the fine particle dispersion, titania dispersion SRD-M (containing 15% by mass of titania particles in methanol, D50 particle diameter of about 9 nm) and SRD-K (15% of titania particles in methyl ethyl ketone) as titania dispersions. Zirconia dispersion nanouse OZ-S30M manufactured by Nissan Chemical Industries as a zirconia dispersion (containing 30% by mass of zirconia particles coated with tin oxide in methanol, scattering method particle diameter of about 30 nm), Methanol silica sol (manufactured by Nissan Chemical Industries, containing 30% by mass of silica particles and having a BET particle diameter of 10 to 20 nm) was used as the silica dispersion.

[Curing composition raw material]
Tetramethoxysilane (TMOS) or tetraethoxysilane (TEOS) was used as the metal alkoxide compound, and tin bisneodecanoate or dioctyltin diacetate was used as the curing catalyst.

[Shaping the microstructure]
As a substrate for shaping the microstructure, a glass substrate obtained by cleaning the surface of a borosilicate glass plate (150 × 150 × 0.7 mm) with ultraviolet ozone was used.

[Example 1]
A titania methanol dispersion (TiO ₂ / MeOH) was dropped linearly along the edge of the substrate on the edge of the glass substrate, and one end of the surface on which the submicron protrusion-shaped PDMS structure was formed was titania. Pressed to the location where the dispersion was supplied, pressed with a roll from the back of the PDMS mold, spread the titania dispersion between the mold and the substrate, adhered to the substrate, allowed to stand at room temperature for 60 minutes, peeled off the PDMS mold and onto the glass substrate A structure was produced.
A smooth film was also produced on a glass substrate using a smooth PDMS mold. Similarly, for the zirconia dispersion, a structure and a smooth coating were produced on the substrate using a moth-eye TAC type.
The transferred structure was dissolved by rubbing with a paper clean wiper with ethanol. In the observation using the SEM, the structure was transferred at a height of about 90% of the mold shape regardless of which mold was used. When the refractive index of the smooth film was measured using an ellipsometer, the refractive index for light having a wavelength of 633 nm was 2.02 for titania and 1.67 for zirconia. In addition, when the structure on the substrate was heated with a gas torch flame of about 1400 ° C. for about 2 minutes, the glass substrate was deformed by heat, but the structure retained its shape and could be rubbed with a paper clean wiper with ethanol attached. The structure did not peel or dissolve. The refractive index of the smooth coating after heating with respect to light having a wavelength of 633 nm was 2.10 for titania and 1.70 for zirconia.

[Example 2]
A mixture of 2 parts of TMOS and 0.1 part of the curing catalyst dioctyltin diacetate was added dropwise to 8 parts of a titania methanol dispersion with stirring to prepare a curable composition A. Although the curable composition A was slightly cloudy like the titania dispersion, it was almost transparent. Using the same method as in Example 1, a structure and a smooth coating are formed on a glass substrate using a micron-projection-shaped PDMS type, a submicron-projection-shaped PDMS type, a moth-eye-shaped TAC type, and a smooth PDMS type and a curable composition A. It was prepared and left for 10 days in a room temperature environment with a humidity of 50%.
Even if the transferred structure is rubbed with a paper clean wiper with ethanol, it does not peel off or dissolve, and the structure is approximately 90 times the shape of the mold when using any mold. It was transferred at a height of%. The smooth coating was transparent, and the refractive index was measured using an ellipsometer. The refractive index for light having a wavelength of 633 nm was 1.91.

[Example 3]
A film was prepared using a moth-eye TAC type in the same manner as in Example 2 except that a zirconia dispersion was used as the fine particle dispersion.
Even if the transferred structure was rubbed with a paper clean wiper with ethanol, it did not peel off or dissolve, and the structure was transferred at a height of about 90% of the mold shape by observation using SEM. . The smooth coating was transparent, and the refractive index was measured using an ellipsometer. The refractive index for light having a wavelength of 633 nm was 1.65.

[Example 4]
A mixed solution of 6 parts of TEOS and 1 part of methanol was added dropwise to 4 parts of the silica dispersion with gentle stirring, and the mixture was allowed to stand at room temperature for 1 hour to prepare a mixed solution a. Mixture a was added dropwise to a mixture of 1 part of zirconia dispersion and 1 part of methanol with vigorous stirring and mixed, and then 0.1 part of tin bisneodecanoate curing catalyst was added dropwise with vigorous stirring and mixed. Composition B was prepared. A structure and a smooth coating were produced on a glass substrate using the moth-eye TAC type and the curable composition B in the same manner as in Example 2, and left for 10 days in a room temperature environment with a humidity of 50%.
Even if the transferred structure was rubbed with a paper clean wiper with ethanol, it did not peel off or dissolve, and the structure was transferred at a height of about 90% of the mold shape by observation using SEM. . The smooth coating was transparent, and the refractive index was measured using an ellipsometer. The refractive index for light having a wavelength of 633 nm was 1.50.

[Example 5]
A film was prepared using a moth-eye TAC type in the same manner as in Example 2 except that a silica dispersion was used as the fine particle dispersion.
Even if the transferred structure is rubbed with a clean wiper made of ethanol, it does not peel off or dissolve. From observation using the SEM, the structure is about 90% of the mold shape. Transcripted at height. The smooth coating was transparent, and the refractive index was measured using an ellipsometer. The refractive index for light having a wavelength of 633 nm was 1.44.

[Example 6]
A mixture of 7 parts of TEOS and 1 part of methanol was added dropwise and mixed with 3 parts of silica dispersion with gentle stirring, and then 0.1 part of tin bisneodecanoate curing catalyst was added dropwise with vigorous stirring and mixed. Composition C was prepared. A structure and a smooth coating were prepared on a glass substrate using the moth-eye TAC type and the curable composition C in the same manner as in Example 2, and left for 10 days in a room temperature environment with a humidity of 50%.
Even if the transferred structure was rubbed with a paper clean wiper with ethanol, it did not peel off or dissolve, and the structure was transferred at a height of about 90% of the mold shape by observation using SEM. . The smooth coating was transparent, and the refractive index was measured using an ellipsometer. The refractive index for light having a wavelength of 633 nm was 1.24.

[Example 7]
A structure and a smooth coating were prepared on a glass substrate using a submicron-protrusion-shaped PDMS mold in the same manner as in Example 2 except that titania methyl ethyl ketone (MEK) dispersion (TiO ₂ / MEK) was used.
Even if the transferred structure was rubbed with a paper clean wiper with ethanol, it did not peel off or dissolve, and the structure was transferred at a height of about 90% of the mold shape by observation using SEM. . The smooth coating was transparent, and the refractive index was measured using an ellipsometer. The refractive index for light with a wavelength of 633 nm was 1.89.

[Example 8]
A coating film was prepared in the same manner as in Example 3 except that a moth-eye PET mold having a thickness of 16 μm was used and the standing time was 24 hours.
Even if the transferred structure was rubbed with a paper clean wiper with ethanol, it did not peel off or dissolve, and the structure was transferred at a height of about 90% of the mold shape by observation using SEM. . The smooth coating was transparent, and the refractive index was measured using an ellipsometer. The refractive index for light having a wavelength of 633 nm was 1.66.

[Comparative Example 1]
As a standard sol-gel coating material, 10 parts of TEOS, 7 parts of water, 4.4 parts of ethanol, and 1 part of 36% hydrochloric acid were mixed and reacted at 60 ° C. for 2 hours with stirring to prepare a curable composition D. It was 3300 when the weight average molecular weight of the reaction material was measured by GPC.
A structural film was prepared on the substrate in the same manner as in Example 1 except that the standing time was 24 hours using the moth-eye shape TAC type and the curable composition D, and was left to stand for 10 days in a room temperature environment with a humidity of 50%. . Even if the transferred structure was rubbed with a clean paper wiper with ethanol, it was not peeled off or dissolved, and the structure was transferred at a height of about 60% of the mold shape by observation using SEM. .
In order to obtain the same composition of the silica component as in Example 2, 6.2 parts of the curable composition D was dropped into 8 parts of a titania methanol dispersion while stirring to prepare a curable composition E. A structural film was produced on the substrate in the same manner as in Example 1 except that the TAC type for moth-eye shape and the curable composition E was used and the standing time was 24 hours. did.
When the transferred structure was rubbed with a paper clean wiper with ethanol, it was completely peeled off and a practical film could not be obtained.

[Comparative Example 2]
Except that a moth-eye-shaped PET mold having a thickness of 250 μm was used and the standing time was set to 72 hours, an attempt was made to produce a structure on a glass substrate in the same manner as in Example 2, but the curable composition A was not cured and the structure The body could not be made.
The results are shown in Table 2 below.

[Example 9]
[Mold material]
As UV curable material for producing mold, 33 parts of trimethylolpropane triacrylate which is trifunctional or higher acrylate compound monomer, 33 parts of N-vinyl-2-pyrrolidone as N-vinyl compound monomer, etc. UV curing by mixing 33 parts of 1,9-nonanediol diacrylate, 0.5 part of silicone diacrylate and 2 parts of 2,4,6-trimethylbenzoyldiphenylphosphine oxide as a photoinitiator. Resin composition A was produced.

[Mold making]
Ni having a moth-eye shape obtained by using a triacetyl cellulose film (TAC) having a thickness of 80 μm as a base material, applying the UV curable resin composition (1) to the surface so as to have a thickness of 0.8 μm, and performing a release treatment. The mold was pressed, and ultraviolet light was exposed (3 J / cm ² ) from the triacetylcellulose film side to be cured, and then released to obtain a mold A in which the moth-eye shape was transferred by reversal. The moth-eye shape has a height of 300 nm and round cone-shaped protrusions that are closely packed on a plane at a pitch of 280 nm. The Ni mold has a conical protrusion. The produced mold A was stored in an environment of 23 ° C. and 50% RH.

[Curable composition]
As a metal alkoxide compound, 8 parts of tetramethoxysilane, 2 parts of trimethoxymethylsilane, 0.2 part of dibutyltin diacetate and 0.06 part of acetic acid were mixed to prepare curable composition F.

[Shaping the microstructure]
As a substrate for shaping the fine structure, a borosilicate glass plate (150 × 150 × 0.7 mm) whose surface was cleaned with ultraviolet ozone was used. First, the curable composition F is dropped linearly along the edge of the substrate at the edge of the substrate, and one end of the surface on which the structure of the mold A is formed is placed to the place where the curable composition F is supplied. The resin mold was pressed with a roll from the back side of the mold A, and the curable composition F was spread between the mold and the substrate so as to adhere to the substrate. After 20 minutes, the mold A was peeled off to produce a structure on the substrate. After the mold A was peeled off, the substrate was left for one week to proceed with curing. This shaping operation was performed in an environment of 23 ° C. and 50% RH.
About the obtained borosilicate glass plate with a moth-eye structure, the reflectance with respect to visible light was measured. The results are shown in FIG. Also, an electron micrograph of the surface is shown in FIG.

[Example 10]
In Example 9, the curable composition F was spread between the mold and the substrate, adhered to the substrate, then left in an oven at 60 ° C. for 5 minutes, and then the mold A was peeled off. A structure was fabricated on the substrate.

[Example 11]
As curable composition G, a mixture of 7 parts of tetramethoxysilane and 3 parts of phosphoric acid-based curing catalyst X-40-2039A manufactured by Shin-Etsu Chemical Co., Ltd. was prepared. Except for using the curable composition G, except that the mold similar to Example 9 was used, the curable composition G was spread between the mold and the substrate, adhered to the substrate, and the resin mold was peeled off after 10 minutes. A structure was fabricated on the substrate in the same manner as in Example 9.

[Example 12]
As curable composition H, a mixture of 4 parts of tetramethoxysilane tetramer and 6 parts of phosphoric acid-based curing catalyst X-40-2039A manufactured by Shin-Etsu Chemical Co., Ltd. was prepared. Except for using the curable composition H, except that the mold similar to Example 9 was used, the curable composition H was spread between the mold and the substrate and adhered to the substrate, and the resin mold was peeled off after 30 minutes. A structure was fabricated on the substrate in the same manner as in Example 9.

[Example 13]
100 parts of trimethylolpropane EO-modified triacrylate (Aronix M-350 manufactured by Toagosei Co., Ltd.), a trifunctional or higher acrylate compound monomer as an ultraviolet curable material for producing a mold, and BASF Irgacure as a photopolymerization initiator 184 parts by weight and 5 parts of 2- (perfluorohexyl) ethyl methacrylate were mixed, and a mold B was prepared as the ultraviolet curable resin composition B in the same manner as in Example 9. A structure was fabricated on the substrate in the same manner as in Example 9 except that the mold B was used.

[Example 14]
Using a PMMA film with a thickness of 125 μm as the mold material, using a Ni mold having a moth-eye shape, pressurizing at 140 ° C. and 2 MPa for 5 minutes, then cooling to room temperature while maintaining the pressure, and the moth-eye on the PMMA film surface A mold C in which the shape was inverted and transferred was produced. A structure was fabricated on the substrate in the same manner as in Example 9 except that this mold C was used.

[Example 15]
A structure was produced on a substrate in the same manner as in Example 9 except that the film used as the mold material was changed to an ethylene / polyvinyl alcohol copolymer (EVOH) film having a thickness of 60 μm.

[Example 16]
A structure was produced on the substrate in the same manner as in Example 9 except that the film used as the mold material was changed to a polyamide 6 (PA6) film having a thickness of 100 μm.

[Example 17]
The film used as the mold material is changed to a PET film with a thickness of 16 μm, and the curable composition G is spread between the mold and the substrate by using the curable composition G, and is closely adhered to the substrate. A structure was produced on the substrate in the same manner as in Example 9 except for peeling.

[Example 18]
Using a 200 μm thick thermoplastic polyurethane resin (TPU) film as the mold material, pressurizing at 140 ° C. and 2 MPa for 5 minutes using a Ni mold having a moth-eye shape, and then cooling to room temperature while maintaining the pressure Then, a mold D in which the moth-eye shape was inverted and transferred to the TPU film surface was produced. A structure was produced on the substrate in the same manner as in Example 9 except that this mold D was used.

[Example 19]
Implemented except that SIRAGUSITAL-B4373 (C) (composition containing organically modified silicone, tetraethoxysilane, dibutyltin diacetate, isopropyl alcohol and methanol as solvents) manufactured by New Technology Creation Laboratory was used as curable composition I Using the same material as in Example 9, the curable composition I was spread between the mold and the substrate, closely adhered to the substrate, and the resin mold was peeled off after 20 hours. The body was made.

[Example 20]
As the curable composition J, 2.5 parts of aluminum tri-sec-butoxide in which the metal of the metal alkoxide used was changed to Al, 2 parts of isopropyl alcohol as a solvent, 0.5 part of ethyl acetate as a stabilizer, dibutyltin didioxide A structure was produced on the substrate in the same manner as in Example 9 using the same material as in Example 9 except that 0.1 part of acetate was added.

[Comparative Example 3]
Except for using a PET film having a thickness of 250 μm as a film used as a mold base material, an attempt was made to produce a structure on a substrate in the same manner as in Example 9, but the curable composition F was placed between the mold and the substrate. Although the mold was peeled after 20 hours after being spread and closely adhered to the substrate, the curable composition F was hardly cured and a structure could not be produced on the substrate.
The results of Examples 9 to 20 and Comparative Example 3 are shown in Table 3 below.

  The present invention is a method for imparting a cured product that may have a fine surface shape to the surface of a substrate. The shaping process has a high transfer accuracy of the shaped shape, is simple and highly productive, and an inexpensive mold. Since a raw material can be used, it becomes possible to manufacture microstructures of various shapes on a substrate with high productivity and at low cost. Therefore, the present invention improves the light extraction efficiency of an antireflection film with a moth-eye structure having a fine protrusion shape, a wire grid polarizer, a wavelength slope, an optical element such as a filter or a diffraction grating, and a light emitter such as an LED or an organic EL. As a member for structures, optical waveguides, infrared emitters for thermophotovoltaic power generation, solar cell surface and internal light collection patterns, biochips, microreactor chips, recording media, etc., especially heat resistance, UV resistance, It can be suitably used for applications that require the ability to exceed the performance limits of organic materials such as chemical properties and etching resistance, and by combining the surface characteristics and structure of the inorganic material that constitutes the cured product, It can also be used for hydrophilic member applications.

Claims (26)

The following steps:
(A) a step of filling a space between a mold capable of supplying the curable material and a substrate with a curable composition containing a curable raw material that is cured by contact with the curable material;
(B) a step of obtaining a cured product by curing the curable composition with the curing material supplied from the mold; and (C) a step of peeling the mold from the cured product on the substrate.
The manufacturing method of the laminated body of hardened | cured material and a base material containing this.   The method according to claim 1, wherein the mold has a fine concavo-convex structure having an average pitch of 10 nm to 0.1 mm and a height / pitch ratio of 0.1 to 5 on the surface.   The method according to claim 1 or 2, wherein the curable material is water and the curable raw material is a metal alkoxide. The water permeation amount of the mold is 5 × 10 ⁻⁵ g · m ⁻² · s ⁻¹ or more and / or the water content in the atmospheric equilibrium of the mold is 0.5 mass% or more and 20 mass% or less, The method of claim 3.   The laminated body of the hardened | cured material manufactured by the method of any one of Claims 1-4, and a base material. The following steps:
(A ′) Filling the space between the mold capable of supplying the curable material and the substrate with the curable composition in which the fine particles are dispersed in the curable raw material that is cured by contact with the curable material. Process,
(B ′) a step of obtaining a cured product by curing the curable composition with the cured material supplied from the mold, and (C ′) peeling the mold from the cured product on the substrate. Process,
The manufacturing method of the laminated body of hardened | cured material and a base material containing this.   The method according to claim 6, wherein the curable composition further comprises a solvent for dispersing the fine particles.   The method of claim 7, wherein the mold is capable of absorbing the solvent. The method according to claim 8, wherein the permeation amount of the solvent of the type is 1 × 10 ⁻³ g · m ⁻² · s ⁻¹ or more.   The method according to any one of claims 6 to 9, wherein the mold has a fine concavo-convex structure having an average pitch of 10 nm to 0.1 mm and a height / pitch ratio of 0.1 to 5 on the surface.   The method according to any one of claims 6 to 10, wherein an average particle diameter of the fine particles is 100 nm or less.   The method according to any one of claims 6 to 11, wherein the curable material is water, and the curable raw material is a metal alkoxide. The method according to claim 12, wherein the permeation amount of the mold is 5 × 10 ⁻⁵ g · m ⁻² · s ⁻¹ or more.   The method according to claim 12 or 13, wherein the moisture content in the atmospheric balance of the mold is 0.5 wt% or more and 20 wt% or less.   The laminated body of the hardened | cured material manufactured by the method of any one of Claims 6-14, and a base material.   The laminate according to claim 15, wherein the cured product has a refractive index of 1.75 to 2.20.   The laminated body of Claim 15 whose refractive index of the said hardened | cured material is 1.20-1.40. The following steps:
(A ″) a step of filling a dispersion in which fine particles are dispersed in a solvent into a space between a mold capable of absorbing the solvent and a base material;
(B '') the mold absorbs the solvent to agglomerate the fine particles in the dispersion to obtain an agglomerate; and (C '') the agglomerate on the substrate. A process of peeling from the object,
The manufacturing method of the laminated body of a base material and an aggregate containing this. (D) a step of fixing the structure by sintering the aggregate on the base material obtained in the step (C ″),
The method of claim 18, further comprising:   The method according to claim 18 or 19, wherein a surface of the fine particles is coated with a material having a melting point lower than that of the fine particles.   The laminated body manufactured by the method of any one of Claims 18-20. The following steps:
(A ′ ″) a step of filling a space between a mold capable of absorbing the solvent and a substrate with a curable composition that is cured by reducing the amount of the solvent contained;
(B ′ ″) a step of absorbing the solvent into the mold to cure the curable composition to obtain a cured product; and (C ′ ″) the mold on the substrate. A process of peeling from the object,
The manufacturing method of the laminated body of hardened | cured material and a base material containing this.   The method according to claim 22, wherein fine particles are dispersed in the curable composition. The method according to claim 22 or 23, wherein the permeation amount of the solvent of the type is 1 × 10 ⁻³ g · m ⁻² · s ⁻¹ or more.   The method according to any one of claims 22 to 24, wherein the mold has a fine concavo-convex structure having an average pitch of 10 nm to 0.1 mm and a height / pitch ratio of 0.1 to 5 on the surface.   The laminated body of the hardened | cured material manufactured by the method of any one of Claims 21-25, and a base material.