CN100575036C - Manufacturing method of mold and base material with transferred fine pattern - Google Patents

Abstract

The invention provides a mold and a method for manufacturing a substrate having a transferred fine pattern. The mold having a fine pattern for molding a photocurable resin is characterized by comprising a transparent substrate having a chemical bond based on a functional group (x) on a surface on which the following intermediate layer (A) is formed, the intermediate layer (A) existing between the surface of the transparent substrate and the following surface layer (B), and the following surface layer (B) having a fine pattern. Intermediate layer (a): a layer comprising a fluoropolymer (1) having a reactive group (y) reactive with the functional group (x) as a fluoropolymer having a fluoroaliphatic ring structure in the main chain. Surface layer (B): a layer having a fine pattern on the surface thereof, which is formed from a fluoropolymer (2) having a fluoroaliphatic ring structure in the main chain thereof and which is substantially free of the reactive group (y).

Description

Manufacturing method of mold and base material with transferred fine pattern

technical field

The present invention relates to a mold and a method for producing a substrate having a transferred fine pattern formed of a cured product of a photocurable resin using the mold.

Background technique

In recent years, a method of forming a reverse pattern of a fine pattern on the surface of a substrate by contacting a substrate with a mold having a fine pattern on its surface (so-called nano-imprint) has attracted attention (see Patent Documents 1 and 2).

Among them, a method of manufacturing a base material with a fine pattern transferred from a cured product using a mold having a fine pattern on the surface, a base material, and a photocurable resin in sequence has attracted attention: sandwiching the photocurable resin between the mold The process of applying pressure between the fine pattern surface and the substrate surface; the process of irradiating light from the mold side to cure the photocurable resin to form the cured product; and the process of peeling the mold from the cured product.

As a mold in this manufacturing method, a quartz mold is generally used. However, this mold has low mold releasability, and when the mold is peeled off from the cured product, the fine pattern accuracy of the cured product tends to decrease. As a method of improving mold release properties, a method of coating a mold release agent on a finely patterned surface of a mold has been proposed. However, the accuracy of the fine pattern of the mold tends to decrease due to variations in the thickness of the applied release agent. In addition, in the case of continuous use of the mold, it is necessary to repeatedly apply the release agent, and the production efficiency is likely to decrease.

Patent Document 3 describes a mold formed of a tetrafluoroethylene-based polymer, an ethylene/tetrafluoroethylene-based copolymer, or a perfluoroalkoxyvinyl ether-based polymer.

Patent Document 1: Japanese Patent Application Publication No. 2004-504718

Patent Document 2: Japanese Patent Application Publication No. 2002-539604

Patent Document 3: Japanese Patent Application Publication No. 2005-515617

disclosure of invention

However, since the mold described in Patent Document 3 is formed of a specific fluorine-containing polymer, its mechanical strength and shape stability are not sufficient. In order to improve this, a method of combining this fluoropolymer with another matrix having mechanical strength and shape stability is considered. However, since the fluoropolymer is non-adhesive, other substrates are not easily combined with the mold. In particular, it is not easy to combine molds having fine patterns with high precision and other substrates by firmly bonding them. An object of the present invention is to provide a mold with a fine pattern for molding a photocurable resin, which has light transmittance, releasability, and durability, and has mechanical strength, shape stability, and dimensional accuracy of fine patterns.

That is, the gist of the present invention is as follows.

<1>: Mold, which is a mold with a fine pattern for molding a photocurable resin, characterized in that it has a transparent substrate having a chemical bond based on a functional group (x) on the surface forming the following intermediate layer (A) , an intermediate layer (A) present between the surface of the transparent substrate and a surface layer (B) described below, a surface layer (B) described below having a fine pattern.

Intermediate layer (A): a fluoropolymer (1) having a reactive group (y) reactive with the aforementioned functional group (x) as a fluoropolymer having a fluoroaliphatic ring structure on the main chain formed layer.

Surface layer (B): formed of a fluorine-containing polymer (2) which is a fluorine-containing polymer having a fluorine-containing aliphatic ring structure on the main chain and substantially does not have the aforementioned reactive group (y), and has a fine surface layer Graphical layers.

<2>: Mold, which is a mold with a fluorine-containing polymer layer and a transparent substrate having a fine pattern on the surface for molding a photocurable resin, and is characterized in that it has a mold formed on the intermediate layer (A) The intermediate layer (A) on the surface of the transparent substrate having the functional group (x) on the surface, and the surface layer (B) formed on the surface of the intermediate layer (A).

Intermediate layer (A): a fluoropolymer (1) having a reactive group (y) reactive with the aforementioned functional group (x) as a fluoropolymer having a fluoroaliphatic ring structure on the main chain formed layer.

Surface layer (B): formed of a fluorine-containing polymer (2) which is a fluorine-containing polymer having a fluorine-containing aliphatic ring structure on the main chain and substantially does not have the aforementioned reactive group (y), and has a fine surface layer Graphical layers.

<3>: The mold according to the aforementioned <1> or <2>, wherein the fine pattern of the mold is composed of a concave-convex structure, and the average height of the convex structure part is 1 nm to 500 μm.

<4>: The mold according to any one of the aforementioned <1> to <3>, wherein the functional group (x) is a hydroxyl group, amino group or oxirane group, and the reactive group (y) is a carboxyl group.

<5>: The mold according to any one of <1> to <4>, wherein the transparent substrate having the functional group (x) on the surface is a glass substrate into which the functional group (x) has been introduced by surface treatment.

<6>: A method for producing a base material having a transferred fine pattern formed of a cured product of a photocurable resin, wherein the mold, the base material, and the photocured material according to any one of the aforementioned <1> to <5> are used. Resin, the following steps are carried out in sequence: the step of sandwiching the photocurable resin between the fine pattern surface of the mold and the surface of the substrate to pressurize; the step of illuminating the photocurable resin from the side of the mold to cure the photocurable resin to form a cured product; And the process of peeling the mold from the cured product.

Since the transparent base and the layer having the fine pattern are firmly bonded through the specific layer, the mold of the present invention has the physical properties (mechanical strength, etc.) of the transparent base and a fine pattern with high precision. In addition, since the fine pattern portion of the mold is formed of a fluoropolymer with high non-adhesiveness, the mold of the present invention can also be molded with a highly adhesive photocurable resin. In addition, even if the mold of the present invention is used repeatedly, fine pattern parts are not easily polluted.

The best way to practice the invention

In the present invention, the compound represented by formula (1) is referred to as compound 1. Compounds represented by other formulas are also represented in the same manner.

The transparent base in the mold of the present invention is preferably a glass base (quartz, glass, etc.), a silicone resin base, or a transparent resin (fluorine-containing resin, acrylic resin, polycarbonate resin, polyimide resin, etc.) base , a glass substrate is particularly preferred due to its good mechanical strength. The shape of the transparent substrate may be planar (flat plate, etc.) or curved (cylindrical, triangular pyramid, spherical, etc.).

The light transmittance of the transparent substrate for light having a wavelength of 200 to 500 nm is preferably at least 90%, particularly preferably at least 95%. Here, the light transmittance refers to the light transmittance of a transparent substrate having a thickness of 1 mm.

The functional group (x) in the transparent base is preferably a hydroxyl group, an oxirane group or an amino group. The functional group (x) may be a functional group derived from the material of the transparent base, or a functional group imparted to the surface of the transparent base by surface treatment to introduce the functional group (x). The functional group (x) is preferably the latter functional group because its type and amount can be controlled arbitrarily.

The surface treatment method for introducing functional groups (x) is preferably a method of surface treating the transparent substrate with a silane coupling agent having a functional group (x) or surface-treating a transparent substrate with a silazane compound having a functional group (x). Methods.

The silane coupling agent with functional group (x) is preferably a silane coupling agent with amino groups (aminopropyltriethoxysilane, aminopropylmethyldiethoxysilane, aminoethyl-aminopropyltrimethoxy silane, aminoethyl-aminopropylmethyldimethoxysilane, etc.). Moreover, a silane coupling agent (glycidoxypropyltrimethoxysilane, glycidoxypropylmethyldimethoxysilane, etc.) which has an oxiranyl group is also preferable.

In the present invention, the fluorine-containing polymer (1) constituting the intermediate layer (A) and the fluorine-containing polymer (2) constituting the surface layer (B) are respectively fluorine-containing polymers having a fluorine-containing alicyclic structure on the main chain. thing. The fluoropolymer is an amorphous or non-crystalline polymer, preferably a highly transparent fluoropolymer. The light transmittances of the fluoropolymer (1) and the fluoropolymer (2) for light having a wavelength of 200 to 500 nm are each preferably at least 90%. Here, the light transmittance refers to the light transmittance of a fluoropolymer having a thickness of 100 μm.

In the fluorine-containing polymer (1) and the fluorine-containing polymer (2), having a fluorine-containing alicyclic structure on the main chain means that one or more carbon atoms constituting the ring of the fluorine-containing aliphatic ring in the polymer are The carbon atoms that make up the backbone of a polymer. The atoms constituting the fluorine-containing alicyclic ring may contain oxygen atoms, nitrogen atoms, etc. in addition to carbon atoms. A preferable fluorinated alicyclic ring is a fluorinated alicyclic ring having 1 to 2 oxygen atoms. The number of atoms constituting the fluorine-containing alicyclic ring is preferably from 4 to 7.

The carbon atoms constituting the main chain are derived from the carbon atoms of the polymerizable double bond in the case of a polymer obtained by polymerizing a cyclic monomer, and in the case of a polymer obtained by cyclopolymerizing a diene monomer. 4 carbon atoms in 2 polymerizable double bonds.

The cyclic monomer refers to a monomer having a fluorine-containing aliphatic ring and a polymerizable double bond between carbon atoms and carbon atoms constituting the fluorine-containing aliphatic ring, or a monomer having a fluorine-containing aliphatic ring and constituting the fluorine-containing aliphatic ring. A monomer having a polymerizable double bond between the carbon atoms of the ring and the carbon atoms outside the fluorine-containing aliphatic ring.

The diene monomer means a monomer having two polymerizable double bonds.

The cyclic monomer is preferably the following compound 1 or the following compound 2 (wherein ^X1 represents a fluorine atom or a perfluoroalkoxy group with 1 to 3 carbons, ^R1 and ^R2 represent a fluorine atom or a carbon number 1 ~6 perfluoroalkyl, ^X2 and ^X3 respectively represent a fluorine atom or a perfluoroalkyl group with 1 to 9 carbons.).

Specific examples of compound 1 include the following compounds.

Specific examples of compound 2 include the following compounds.

The diene monomer is preferably a monomer represented by the formula CF ₂ =CF-Q-CF=CF ₂ . However, Q represents a perfluoroalkylene group which may have an etheric oxygen atom having 1 to 3 carbon atoms. When Q is a perfluoroalkylene group having an etheric oxygen atom, the etheric oxygen atom may exist at one end of the group, may exist at both ends of the group, or may exist at the end of the group. between carbon atoms. From the viewpoint of cyclopolymerization, it is preferably present at one terminal of the group.

The aforementioned monomers form a fluoropolymer comprising at least one monomer unit selected from the following monomer unit (A), the following monomer unit (B) and the following monomer unit (C) by cyclopolymerization. In the fluoropolymer obtained by cyclopolymerizing a diene monomer, the carbon atoms in the main chain are derived from the four carbon atoms of the two polymerizable double bonds.

Specific examples of the aforementioned monomers include the following compounds.

CF ₂ =CFOCF ₂ CF=CF ₂

CF ₂ =CFOCF(CF ₃ )CF=CF ₂

CF ₂ =CFO CF ₂ CF ₂ CF=CF ₂

CF ₂ =CFOCF(CF ₃ )CF ₂ CF=CF ₂

CF ₂ =CFOCF ₂ CF(CF ₃ )CF=CF ₂

CF ₂ =CFOCF ₂ OCF=CF ₂

CF ₂ =CFOC(CF ₃ ) ₂ OCF=CF ₂

CF ₂ = CF CF ₂ CF = CF ₂

CF ₂ = CF CF ₂ CF ₂ CF = CF ₂

In the cyclic monomer and the diene monomer, the ratio of the number of fluorine atoms bonded to carbon atoms to the total number of hydrogen atoms bonded to carbon atoms and the total number of fluorine atoms bonded to carbon atoms is preferably at least 80%. , particularly preferably 100%.

In the fluoropolymer (1) and the fluoropolymer (2), from the viewpoint of the transparency of the fluoropolymer, the ratios of repeating units having a fluorinated alicyclic structure to all monomer units are respectively It is preferably at least 20 mol%, more preferably at least 40 mol%, and particularly preferably consists of repeating units having a fluorine-containing alicyclic structure on the main chain. Here, the repeating unit having a fluorine-containing aliphatic ring structure refers to a monomer unit formed by polymerization of a cyclic monomer or a monomer unit formed by cyclopolymerization of a diene monomer.

The repeating unit having a fluorinated alicyclic structure in the fluoropolymer (2) and the repeating unit having a fluorinated alicyclic structure in the fluoropolymer (1) are preferably the same repeating unit. In this case, the intermediate layer (A) and the surface layer (B) are bonded more firmly, and there is an effect that the durability of the mold is improved.

The fluoropolymer (1) has a reactive group (y). The type of reactive group (y) is appropriately selected according to the type of functional group (x). The reactive group (y) when the functional group (x) is a hydroxyl group, an oxiranyl group or an amino group is preferably a carboxyl group or a derivative thereof, particularly preferably a carboxyl group.

On the other hand, the fluoropolymer (2) does not substantially have a reactive group (y). Substantially not having a reactive group (y) means that the content of the reactive group (y) in the fluoropolymer (2) is below the detection limit. In addition, it is preferable that the fluorine-containing polymer (2) does not substantially have a reactive group other than the reactive group (y).

The fluorinated polymer (1) and the fluorinated polymer (2) can be obtained by known methods, respectively. For example, the fluorine-containing polymer (1) whose reactive group (y) is a carboxyl group is obtained by polymerizing a diene monomer or a cyclic monomer in the presence of a hydrocarbon radical polymerization initiator. A fluorine-containing polymer having a fluorine-containing alicyclic structure is obtained by heat-treating the fluorine-containing polymer in an oxygen atmosphere, and then immersing it in water. In addition, by bringing this fluoropolymer into contact with fluorine gas, a fluoropolymer (2) substantially free of reactive groups (y) can be obtained.

The surface layer (B) in the present invention has fine patterns on its surface. The fine pattern is preferably a fine pattern composed of a concavo-convex structure.

The portion constituting the convex structure in the uneven structure exists in the form of lines or dots on the surface of the surface layer (B), and the shape of the lines or dots is not particularly limited. The linear convex structure part is not limited to a straight line, and may be in a curved or bent shape. In addition, this line may exist in parallel in many stripes. The cross-sectional shape (the cross-sectional shape in the direction perpendicular to the extending direction of the line) of the linear convex structure is not particularly limited, and examples thereof include a rectangle, a trapezoid, a triangle, and a semicircle. The shape of the dot-like convex structure is not particularly limited either. For example, cylindrical or tapered shapes such as rectangles, squares, rhombuses, hexagons, triangles, circles, etc., hemispherical shapes, polyhedral shapes, and the like can be exemplified.

The average value of the width (width of the bottom) of the linear convex structure portion is preferably from 1 nm to 500 μm, particularly preferably from 10 nm to 300 μm. The average value of the bottom surface length of the dot-shaped convex structure portion is preferably from 1 nm to 500 μm, particularly preferably from 10 nm to 300 μm. Here, the length of the bottom surface of the dot-shaped convex structure refers to the length in the direction perpendicular to the extending direction when the dot extends in a shape close to a line, and refers to the maximum length of the bottom surface shape in other cases.

The average value of the heights of the linear and dot-shaped convex structures is preferably from 1 nm to 500 μm, particularly preferably from 10 nm to 300 μm, most preferably from 10 nm to 10 μm. In addition, the thickness of the surface layer (B) is preferably at least the height of the highest convex structure.

In the portion where the concavo-convex structure is densely packed, the average value of the distance between adjacent convex structure portions (distance between bottoms) is preferably from 1 nm to 500 μm, particularly preferably from 10 nm to 300 μm. Therefore, their smallest dimension in the convex structures is preferably 500 μm or less. The lower limit is preferably at most 1 nm. The minimum size refers to the smallest item among the width, length and height of the above-mentioned convex structure portion.

The mold of the present invention is a mold having a fluorine-containing polymer layer having a fine pattern on the surface and a transparent substrate for molding a photocurable resin, preferably having a functional group formed on the surface forming the intermediate layer (A) ( The intermediate layer (A) composed of fluoropolymer (1) on the surface of the transparent substrate of x) and the finely patterned layer composed of fluoropolymer (2) formed on the surface of the intermediate layer (A) The surface layer (B) of the mold.

In the mold of the present invention, the transparent substrate has the functional group (x) before the intermediate layer (A) is formed on its surface. By forming the intermediate layer (A) on the surface of the transparent substrate, a part or all of the functional groups (x) form a chemical bond with a part or all of the reactive groups (y) of the fluoropolymer (1). When a part of the functional group (x) of the transparent base forms a chemical bond, the transparent base in the mold of the present invention further has the functional group (x). On the other hand, when all the functional groups (x) of the transparent base form chemical bonds, the transparent base in the mold of the present invention does not have the functional group (x).

In any case, chemical bonds formed by functional groups (x) and reactive groups (y) exist on the surface of the transparent substrate after the intermediate layer (A) is formed. As the chemical bond, an ester bond in which the reactive group (y) is a carboxyl group and the functional group (x) is a hydroxyl group or an oxiranyl group, an ester bond in which the reactive group (y) is a carboxyl group and the functional group (x) is An amide bond in the case of an amino group, etc. Therefore, in the mold of the present invention, the transparent substrate and the intermediate layer (A) are firmly bonded by chemical bonds.

In addition, in the mold of the present invention, since the fluorine-containing polymer (1) constituting the middle layer (A) and the fluorine-contained polymer (2) constituting the surface layer (B) have a common structure (that is, have fluorine-containing Aliphatic ring structure) fluorine-containing polymer, so the intermediate layer (A) and the surface layer (B) are firmly bonded. Therefore, the present invention can provide a mold with high mold releasability, which can appropriately select the type and shape of the transparent base and has arbitrary strength and shape.

As a specific form of the mold of the present invention, as a mold for forming a photocurable resin having a fine pattern on the surface, a transparent substrate having a light transmittance of 90% or more for light having a wavelength of 200 to 500 nm and a mold formed A mold of a fluorine-containing polymer having a fluorine-containing aliphatic ring structure on the main chain and treated with fluorine gas on the substrate.

As the method of manufacturing the mold of the present invention, a method of sequentially performing the following step M1, the following step M2, the following step M3, and the following step M4 can be exemplified.

[Process M1]

A solution obtained by dissolving the fluorine-containing polymer (1) in a fluorine-containing solvent is coated on the surface side of a transparent substrate having a functional group (x) on the surface, and then the fluorine-containing solvent is removed by drying, so that the fluorine-containing polymer (1) ) formed on the surface side of the transparent substrate having a functional group (x) on the surface.

[Process M2]

A solution obtained by dissolving the fluorine-containing polymer (2) in a fluorine-containing solvent is coated on the surface side of the intermediate layer (A), and then the fluorine-containing solvent is removed by drying, so that the layer composed of the fluorine-containing polymer (2) ( B ^P ) A step of forming on the surface of the intermediate layer (A).

[Process M3]

After heating the layer (B ^P ) to a temperature above the glass transition temperature of the fluoropolymer (2), or heating the mold with the reverse pattern of the fine pattern to a temperature above the glass transition temperature, the surface will have The reverse pattern of the mold of the reverse pattern of the fine pattern is pressed on the layer (B ^P ) side.

[Process M4]

After cooling the layer (B ^P ) and the mold to a temperature below the glass transition temperature of the fluoropolymer (2), the mold is peeled off, and the transfer fine pattern formed on the mold is made of the fluoropolymer (2). A step of forming the surface layer (B) on the surface of the intermediate layer (A).

The drying in step M1 is performed at a temperature at which chemical bonds can be formed between some or all of the functional groups (x) of the transparent substrate and some or all of the reactive groups (y) of the fluoropolymer (1). The temperature in drying is usually 100° C. or higher.

The drying in the step M2 is preferably performed at a temperature not lower than the glass transition temperature of the fluoropolymer (1) and not lower than the glass transition temperature of the fluoropolymer (2). In this case, the intermediate layer (A) and the layer (B ^P ) are bonded with high strength.

The present invention provides a method for manufacturing a base material having a transferred fine pattern formed by a cured product of the photo-curable resin using the mold, the base material, and the photo-curable resin manufactured through the above-mentioned steps: The process of pressurizing the resin between the fine pattern surface of the mold and the substrate surface (hereinafter referred to as process 1); the process of curing the photocurable resin to form a cured product by irradiating light from the mold side (hereinafter referred to as process 2) ); a step of peeling the mold from the cured product (hereinafter referred to as step 3).

The photocurable resin in the present invention is not particularly limited as long as it is cured by light to form a cured product. The mold of the present invention has high transparency over a wide range of light wavelength regions. Therefore, the wavelength of light in illumination is not particularly limited. The wavelength of light is preferably from 200 to 500 nm, particularly preferably from 200 to 400 nm that can cure general photocurable resins at low temperatures.

The photocurable resin in the present invention is preferably a photocurable resin containing a polymerizable compound and a photopolymerization initiator. The polymerizable compound is not particularly limited as long as it is a compound having a polymerizable group, and may be any of a polymerizable monomer, a polymerizable oligomer, and a polymerizable polymer. The photopolymerization initiator refers to a photopolymerization initiator that initiates a radical reaction or an ion reaction by light. In addition, the system temperature in Step 1, Step 2 and Step 3 is preferably not higher than the glass transition temperature of the fluoropolymer (2).

As a specific embodiment of the step 1, the following step 11, the following step 12, and the following step 13 can be mentioned, for example.

Step 11: a step of arranging a photocurable resin on the surface of the substrate, sandwiching the substrate and the mold with the photocurable resin in contact with the pattern surface of the mold, and pressurizing.

Step 12: a step of disposing the photocurable resin on the pattern surface of the mold, and then sandwiching the substrate and the mold with the surface of the substrate in contact with the photocurable resin, and pressurizing.

Step 13: Combine the substrate and the mold, form a gap between the surface of the substrate and the graphic surface of the mold, then fill the gap with a photocurable resin, and sandwich the photocurable resin between the graphic surface of the mold and the substrate Then carry out the process of pressurization.

The treated substrate obtained by the production method of the present invention has a transferred fine pattern formed of a cured product of the photocurable resin on the surface. The transferred fine pattern is a fine pattern in which the fine pattern of the mold of the present invention is reversed. The transferred fine pattern is preferably a structure having a concavo-convex structure formed of a cured product of a photocurable resin (hereinafter also referred to as a concavo-convex structure). The concave-convex structure may have a layered structure consisting of a continuum having a concave-convex shape on the surface, or may have a structure composed of a collection of independent protrusions. The former refers to a structure composed of a layer of cured photocurable resin covering the surface of the substrate, and the surface of the layer of cured photocurable resin has an uneven shape. The latter refers to a structure in which a plurality of protrusions formed of a cured product of a photocurable resin independently exist on the surface of a base material and form a concavo-convex shape together with recesses formed on the surface of the base material. In either case, the portion (protrusion) forming the convex structure is formed of a cured product of the photocurable resin. In addition, the concavo-convex structure may have both of these two structures at different positions on the surface of the substrate.

The processed base material obtained by the manufacturing method of the present invention can be used as optical elements such as microlens arrays, optical waveguides, optical switches, Fresnel zone plates, binary elements, blazed grating elements, photonic crystals, AR (anti-reflection) Coating materials, biochips, chips for μ-TAS (micro total analysis system), microreactor chips, recording media, display materials, catalyst carriers, filters, sensor parts, etc.

Example

Hereinafter, although an Example is given and demonstrated to this invention, this invention is not limited to these Examples.

[Example 1] Production example of polymer (P)

100 g of CF ₂ =CFOCF ₂ CF ₂ CF=CF ₂ , 0.5 g of methanol, and 0.7 g of ((CH ₃ ) ₂ CHOCOO) ₂ were added to an autoclave (made of pressure-resistant glass), and polymerization was carried out by suspension polymerization. Polymer (P) is obtained. The polymer (P) is a polymer composed of monomer units represented by the following formula (p), and has an intrinsic viscosity of 0.34 dl/g in perfluoro(2-butyltetrahydrofuran) at 30°C. The glass transition temperature of the polymer (P) was 108°C.

[Example 2] Production example of a solution composition (hereinafter referred to as composition 1) containing a polymer (hereinafter referred to as polymer (11)) having a fluorine-containing alicyclic structure in the main chain and having a carboxyl group

Polymer (P) was heat-treated at 300°C for 1 hour in a hot air circulating furnace under atmospheric pressure, then immersed in ultrapure water at 110°C for 1 week, and then dried at 100°C in a vacuum dryer for 24 hours. Polymer (11) is obtained. As a result of measuring the infrared absorption spectrum of the polymer (11), a peak derived from a carboxyl group was confirmed. Polymer (11) was processed into a film with a film thickness of 100 μm, and the light transmittance of light with a wavelength of 200 to 500 nm was measured and found to be 93% or more. A perfluorotributylamine solution containing 1% by mass of the polymer (11) was prepared, and the solution was filtered with a membrane filter (pore diameter: 0.2 μm, made of PTFE) to obtain a composition 1.

[Example 3] Solution composition (hereinafter referred to as composition 2) containing a polymer (hereinafter referred to as polymer (21)) having a fluorine-containing alicyclic structure on the main chain and not having a reactive group Manufacturing example

The polymer (P) was charged into an autoclave (made of nickel, with an inner volume of 1 L), and after replacing the inside of the autoclave with nitrogen three times, the pressure was reduced to 4.0 kPa (absolute pressure). After introducing fluorine gas diluted to 14 volume % with nitrogen into the autoclave to 101.3 kPa, the inner temperature of the autoclave was maintained at 230° C. for 6 hours. The contents of the autoclave were recovered to obtain polymer (21). As a result of measuring the infrared absorption spectrum of polymer (21), no peaks derived from carboxyl groups were confirmed. The polymer (21) was processed into a film with a film thickness of 100 μm, and the light transmittance of light with a wavelength of 200 to 500 nm was measured and found to be 95% or more. A perfluorotributylamine solution containing 9% by mass of the polymer (21) was prepared, and the solution was filtered with a membrane filter (pore diameter: 0.2 μm, made of PTFE) to obtain a composition 2.

[Example 4] Manufacturing example of a mold (prototype example 1)

A silane coupling agent with an amino group (Shin-Etsu Chemical Co., Ltd.: KBE-903) containing 0.5% by mass and an ethanol solution of 5% by mass of water were applied by spin coating to a light with a wavelength of 200 to 500 nm. More than 90% of the quartz substrate (length 25mm × width 25mm × thickness 1mm) on. After the quartz substrate was washed with water, it was heated and dried at 70° C. for 1 hour, and a surface treatment was performed to introduce amino groups derived from the silane coupling agent onto the surface of the quartz substrate.

Next, the composition 1 obtained in Example 2 was applied to the surface-treated surface of the quartz substrate by spin coating, and heated and dried at 180° C. for 1 hour to volatilize the perfluorotributylamine in the composition 1. Simultaneously, the amino group on the surface of the quartz substrate was chemically bonded to the carboxyl group of the polymer (11) to obtain a quartz substrate in which a layer composed of the polymer (11) forming an amide bond with the amino group was formed on the surface.

Next, the composition 2 obtained in Example 3 was coated on this layer by the spin coating method, and heated and dried at 180°C for 1 hour to volatilize the perfluorotributylamine in the composition 2. As a result, a quartz substrate in which a layer (layer thickness: 1.3 μm) of the polymer (21) was formed on the outermost surface was obtained.

Then, a silicon mold having a concavo-convex structure in which concavities with a depth of 100 nm and a width of 0.7 μm are arranged at intervals of 9.3 μm was heated to 120° C., and pressure-bonded to a polymer (21) at 2.0 MPa (absolute pressure). Layer side for 10 minutes. After reducing the temperature of the mold and the quartz substrate to below 30 °C, peel off the mold.

As a result, the outermost surface of the polymer (21) made of a quartz substrate, a polymer (11) layer, and a polymer (21) layer was obtained with a fine pattern (100 nm high x 0.7 μm wide) at intervals of 9.3 μm. Concave-convex structure of the convex structure) mold.

[Example 5] Production example of a mold for photocurable resin molding (prototype example 2)

The same ethanol solution and quartz substrate as in Example 4 were prepared, and a similar surface-treated quartz substrate was obtained. Next, the composition 1 obtained in Example 2 was applied on the surface-treated surface of the quartz substrate by the spin coating method, and heated and dried at 180° C. for 1 hour. The composition 2 obtained in Example 3 was coated on the surface by spin coating, and heated and dried at 180° C. for 1 hour to obtain a quartz substrate on which a thin film (thickness: 1.3 μm) of the polymer (21) was formed. . Next, the same silicon mold as in Example 4 was heated to 120° C., and then pressure-bonded to the thin film side of the quartz substrate at a pressure of 2.0 MPa (absolute pressure) for 10 minutes.

Then, after cooling the temperature of the mold and the quartz substrate to 30° C. or lower, the mold was detached from the quartz substrate to obtain a quartz substrate on which a thin film made of polymer (21) was formed with the concavo-convex structure transferred from the mold. On the surface of the film, a concavo-convex structure in which convex structures of 100 nm in height and 0.7 μm in width were arranged at intervals of 9.3 μm was formed.

[Example 6] Manufacturing method of treated substrate with fine pattern formed on the surface

1.31g of CF ₂ =CFCF ₂ C(CF ₃ )(OCH ₂ OCH ₃ )CH ₂ CH=CH ₂ and 0.14g of CF ₂ =CFCF ₂ C(CF ₃ )(OH ) CH ₂ CH=CH ₂ , 0.03 g of Photocuring Initiator 1 (manufactured by Chiba Specialty Chemicals Co., Ltd.: Irugakiyua 651), and 0.03 g of Photocuring Initiator 2 (manufactured by Chiba Specialty Chemicals Co., Ltd.: Irugakiyua 907 ) to obtain a photocurable resin.

Two drops of the photocurable resin were applied on the silicon wafer to obtain a silicon wafer in which a thin film (film thickness: 2.5 μm) of the photocurable resin was formed. The film side was pressed against the fine pattern surface of the mold obtained in Example 5. Ultraviolet rays (wavelength: 365 nm, illuminance: 63 mW/cm ² ) were irradiated from the mold side for 10 seconds to cure the photocurable resin. Then, the mold is released to obtain a fine pattern (concave-convex structure with a depth of 99 nm and a width of 0.7 μm arranged at intervals of 9.3 μm) formed by inversion of the convex structure of the mold made of a cured product of the photocurable resin. ) silicon wafer.

Possibility of industrial use

The mold of the present invention can be used as a mold for nanoimprint using a photocurable resin. The treated substrate obtained by using the mold of the present invention can be used for various purposes because of its fine pattern on the surface. The treated substrate can be exemplified by optical elements (microlens arrays, optical waveguides, optical switches, Fresnel zone plates, binary elements, blazed grating elements, photonic crystals, etc.), anti-reflection filters, biochips, micro Reactor chips, recording media, display materials, catalyst carriers, etc.

In addition, all contents of the specification, claims and abstract of Japanese Patent Application No. 2004-346029 filed on November 30, 2004 and Japanese Patent Application No. 2005-247722 filed on August 29, 2005 are incorporated herein as Disclosure of the specification of the present invention.

Claims (5)

1. mould, it is the mould that possesses fluoropolymer layer and transparent base that is used for the light-cured resin shaping, above-mentioned fluoropolymer layer has fine pattern in the surface, it is characterized in that, possess by following intermediate layer A and be formed at the fluoropolymer layer that the following superficial layer B on the surface of this intermediate layer A constitutes

Intermediate layer A: be formed at transparent base the surface by fluoropolymer 1 form the layer, this transparent base has the x of functional group on the surface that forms this intermediate layer A, this fluoropolymer 1 has and the reactive reactive group y of aforementioned functional groups x tool as the fluoropolymer that has fluorine-containing aliphatic ring structure on the main chain

Superficial layer B: by the layer that has fine pattern in the surface that fluoropolymer 2 forms, this fluoropolymer 2 does not have previous reaction group y in fact as the fluoropolymer that has fluorine-containing aliphatic ring structure on the main chain,

The fluoropolymer that has fluorine-containing aliphatic ring structure on the above-mentioned main chain is to make the cyclic monomer polymerization and the polymer that obtains or make the cyclopolymerization of dienes monomer and the polymer that obtains,

Above-mentioned cyclic monomer is following compound 1 or following compound 2,

Wherein, X ¹The perfluoro alkoxy of expression fluorine atom or carbon number 1～3, R ¹And R ²The perfluoroalkyl of representing fluorine atom or carbon number 1～6 respectively, X ²And X ³The perfluoroalkyl of representing fluorine atom or carbon number 1～9 respectively,

Above-mentioned dienes monomer is with formula CF ₂=CF-Q-CF=CF ₂The monomer of expression, wherein Q represents the perfluorinated alkylidene that can have etheric oxygen atom of carbon number 1～3,

The above-mentioned x of functional group is hydroxyl, Oxyranyle or amino,

Above-mentioned reactive group y is the carboxyl or derivatives thereof.

2. the described mould of claim 1 is characterized in that, the fine pattern of mould is made of concaveconvex structure, and the average height of male structure portion is 1nm～500 μ m.

3. mould as claimed in claim 1 is characterized in that, reactive group y is a carboxyl.

4. mould as claimed in claim 1 is characterized in that, the transparent base that has the x of functional group on the surface is for having introduced the glass basis of the x of functional group by surface treatment.

5. the manufacture method that has the base material of the transfer printing fine pattern that the solidfied material by light-cured resin forms, it is characterized in that, use each described mould in base material, light-cured resin and the claim 1～4, carry out following operation successively: light-cured resin is clipped in the operation of pressurizeing between the fine pattern face of mould and the substrate surface; Carry out illumination from die side, make light-cured resin solidify to form the operation of solidfied material; And the operation that mould is peeled off from this solidfied material.