JP2007307752A - Mold and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a mold to which foreign matter such as dust or the like is hard to adhere, and a method for manufacturing the flawless mold. <P>SOLUTION: The mold 10 has a base material 12, a pattern layer 16 containing a fluorine-containing polymer and having a pattern 14 formed on its surface and the antistatic layer 18 provided between the base material 12 and the pattern layer 16 and is manufactured by a process for forming the antistatic layer 18 on the base material 12, a process for forming a film containing a fluorine-containing polymer on the antistatic layer 18, a process for pressing a heated original mold, which has the reversal pattern corresponding to the pattern 14 of the pattern layer 16, to the film containing the fluorine-containing polymer and a process for separating the original mold from the film containing the fluorine-containing polymer to form the pattern layer 16. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a mold and a manufacturing method thereof.

As a method of forming a fine pattern, a photocuring resin is irradiated with light in a state where a mold having a pattern obtained by inverting a desired fine pattern is pressed against a film made of a liquid photocurable resin, and photocuring is performed. A method of curing a functional resin to form a desired fine pattern, a so-called nanoimprint method is known (see Patent Documents 1 to 3).
Recently, a method for continuously forming a fine pattern using a cylindrical mold in which a resin mold having a pattern formed on a surface is wound around a cylinder has been proposed. (Patent Documents 4 and 5).

However, since resin molds are likely to adhere to foreign matters such as dust due to electrostatic action, defects due to foreign matters are produced in the mold itself when manufacturing resin molds, or fine patterns are formed using resin molds. When doing so, defects due to the adhesion of foreign matter may occur.
JP 2005-515617 A JP 2005-288803 A International Publication No. 2003/084727 Pamphlet JP 2006-037057 A US Patent Application Publication No. 2006/0021533

  The present invention provides a mold to which foreign matters such as dust are difficult to adhere, and a method capable of manufacturing the mold without defects.

  The mold of the present invention has a base material, a pattern layer containing a fluoropolymer, and having a pattern formed on the surface, and an antistatic layer provided between the base material and the pattern layer. Features.

The mold of the present invention may further include a first primer layer provided between the base material and the antistatic layer.
The mold of the present invention may further include a second primer layer provided between the antistatic layer and the pattern layer.

The fluorine-containing polymer preferably contains 35% by mass or more of fluorine atoms in 100% by mass of the fluorine-containing polymer, and the contact angle with respect to water of the film made of the fluorine-containing polymer is preferably 80 ° or more.
The fluorine-containing polymer preferably has a fluorine-containing aliphatic ring structure in the main chain.

  The mold production method of the present invention comprises a base material, a pattern layer containing a fluoropolymer, and having a pattern formed on the surface, and an antistatic layer provided between the base material and the pattern layer. A method of manufacturing a mold having a step of forming an antistatic layer on a substrate, a step of forming a film containing a fluoropolymer on the antistatic layer, and a film containing the fluoropolymer A step of pressing a heated original mold having a reversal pattern corresponding to the pattern of the pattern layer, and a step of separating the original mold from the film containing the fluoropolymer to form a pattern layer. It is characterized by having.

  The mold production method of the present invention comprises a base material, a pattern layer containing a fluoropolymer, and having a pattern formed on the surface, and an antistatic layer provided between the base material and the pattern layer. A process for forming an antistatic layer on a substrate to obtain a first intermediate, and an original mold having a reversal pattern corresponding to the pattern of the pattern layer. A step of forming a film including coalescence to obtain a second intermediate, and a step of bonding the first intermediate and the second intermediate so that the base material and the original mold are outside And a step of separating the original mold from the film containing the fluoropolymer and forming a pattern layer.

In the mold of the present invention, foreign matters such as dust are difficult to adhere.
According to the mold manufacturing method of the present invention, a mold to which foreign matters such as dust are difficult to adhere can be manufactured without defects.

In the present specification, a compound represented by the formula (1) is referred to as a compound (1). The same applies to compounds represented by other formulas.
In the present specification, (meth) acryloyl group means acryloyl group and / or methacryloyl group, (meth) acrylate means acrylate and / or methacrylate, (meth) acrylic acid means acrylic acid and / or Or methacrylic acid.

<Mold>
FIG. 1 is a cross-sectional view showing an example of the mold of the present invention. The mold 10 includes a base material 12, a pattern layer 16 containing a fluoropolymer and having a pattern 14 formed on the surface, and an antistatic layer 18 provided between the base material 12 and the pattern layer 16. .

  The mold of the present invention may have a first primer layer 20 provided between the base material 12 and the antistatic layer 18 as shown in FIG. 2, and as shown in FIG. The second primer layer 22 provided between the prevention layer 18 and the pattern layer 16 may be provided, and provided between the substrate 12 and the antistatic layer 18 as shown in FIG. You may have the 1st primer layer 20, and the 2nd primer layer 22 provided between the antistatic layer 18 and the pattern layer 16. FIG.

(Base material)
Examples of the shape of the substrate include a film or sheet shape, a plate shape, a cylindrical shape, and a columnar shape.
Examples of the base material include the following materials.
Glass: quartz glass, borosilicate glass, etc.
Carbon compound: silicon carbide, black glassy carbon compound, graphite.
Metal: Nickel, copper, etc.
Cellulose material: paper, etc.
Resin: Polyester (polyethylene terephthalate (PET), polyethylene naphthalate, etc.), polyvinyl alcohol, acrylic resin, polyamide, polyimide, cellophane, polycarbonate, soft vinyl chloride resin, hard vinyl chloride resin, fluororesin, silicone resin, etc.
Rubber: Fluoro rubber, etc.

The material of the base material is preferably a material that is 65% or more when the transmittance of ultraviolet rays in the vicinity of a wavelength of 365 nm is 100 μm, and examples thereof include glass, fluororesin, PET, silicone resin, and acrylic resin. When a base material that is opaque to ultraviolet rays is used, a support substrate on the side to be processed, which will be described later, is limited to a material that is transparent to ultraviolet rays.
As the material for the substrate, glass, PET, acrylic resin, and polyimide are particularly preferable from the viewpoint of good adhesion to the antistatic layer or primer layer.
20-5000 micrometers is preferable and, as for the thickness of a base material, 100-1000 micrometers is more preferable.

As the base material, a base material provided with an antistatic layer in advance may be used. Examples of the substrate include Cosmo Shine A7810, A6340, A8300 manufactured by Toyobo, and a high-performance antistatic PET film manufactured by Unitika.
Moreover, you may use the base material to which surface treatments, such as plasma processing, corona discharge, ultraviolet irradiation, vacuum ultraviolet irradiation, electron beam irradiation, ultraviolet ozone treatment, ion irradiation, were given beforehand. By using the base material, the first primer layer can be omitted.

(Pattern layer)
The pattern is preferably a fine pattern having a concavo-convex structure.
The convex portions in the concavo-convex structure are long ridges extending on the surface of the pattern layer, or protrusions scattered on the surface of the pattern layer.
The recesses in the concavo-convex structure are long grooves extending on the surface of the pattern layer or holes scattered on the surface of the pattern layer.
Examples of the shape of the ridge or groove include a straight line, a curved line, a bent shape, and the like. A plurality of ridges or grooves may exist in parallel and have a stripe shape.
Examples of the cross-sectional shape of the ridge or groove in the direction perpendicular to the longitudinal direction include a rectangle, a trapezoid, a triangle, and a semicircle.
Examples of the shape of the protrusion or the hole include a triangular prism, a quadrangular prism, a hexagonal prism, a cylinder, a triangular pyramid, a quadrangular pyramid, a hexagonal pyramid, a conical hemisphere, and a polyhedron.

The average width of the ridges or grooves is preferably 1 nm to 500 μm, more preferably 10 nm to 300 μm, and particularly preferably 50 nm to 400 nm. The width of the ridge means the length of the base in the cross section in the direction orthogonal to the longitudinal direction. The width of the groove means the length of the upper side in the cross section in the direction orthogonal to the longitudinal direction.
The average width of the protrusions or holes is preferably 1 nm to 500 μm, more preferably 10 nm to 300 μm, and particularly preferably 50 nm to 400 nm. The width of the protrusion means the length of the bottom side in a cross section perpendicular to the longitudinal direction when the bottom surface is elongated, and otherwise means the maximum length of the bottom surface of the protrusion. The width of the hole means the length of the upper side in the cross section perpendicular to the longitudinal direction when the opening is elongated, and otherwise means the maximum length of the opening of the hole.
The average height of the convex portions is preferably 1 nm to 500 μm, more preferably 10 nm to 300 μm, particularly preferably 10 nm to 10 μm, and most preferably 50 nm to 400 nm.
The average depth of the recesses is preferably 1 nm to 500 μm, more preferably 10 nm to 300 μm, particularly preferably 10 nm to 10 μm, and most preferably 50 nm to 400 nm.

In the region where the concavo-convex structure is dense, the distance between adjacent convex portions (or concave portions) is preferably 1 nm to 500 μm on average, and particularly preferably 10 nm to 300 μm. The distance between adjacent convex parts means the distance from the end of the bottom of the cross section of the convex part to the beginning of the bottom of the cross section of the adjacent convex part. The distance between adjacent concave portions means the distance from the end of the upper side of the cross section of the concave portion to the start end of the upper side of the cross section of the adjacent concave portion.
The minimum dimension of the convex part is preferably 1 nm to 500 μm or less, and more preferably 50 nm to 500 nm. The minimum dimension means the minimum dimension among the width, length, and height of the convex portion.
The minimum dimension of the recess is preferably 1 nm to 500 μm or less, and more preferably 50 nm to 500 nm. The minimum dimension means the minimum dimension among the width, length and depth of the recess.
The thickness of the pattern layer is preferably equal to or higher than the height of the highest convex portion.

The pattern layer is a layer containing a fluoropolymer.
As the fluoropolymer, from the viewpoint of excellent releasability, the fluorine-containing resin contains 35 mass% or more of fluorine in 100 mass%, and the contact angle with respect to water of the film made of the fluoropolymer is 80 ° or more. Some polymers are preferred.
The contact angle of the film made of the fluoropolymer with respect to water is measured using a contact angle meter.

Examples of the fluorine-containing polymer include the following polymers.
Tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer,
Tetrafluoroethylene / ethylene copolymer,
Tetrafluoroethylene / hexafluoropropylene copolymer,
Vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer,
Fluorine-containing cyclic polymer,
Fluorine-containing alkylene-based polymer,
Fluorinated polyether polymer, etc.

  As the fluorine-containing polymer, a fluorine-containing cyclic polymer or a fluorine-containing polyether polymer is preferable, and a fluorine-containing cyclic polymer is more preferable from the viewpoint of excellent transmittance and durability with respect to light having a wavelength of 200 to 500 nm.

The fluorine-containing cyclic polymer is a fluorine-containing polymer having a fluorine-containing aliphatic ring structure in the main chain, and at least one carbon atom constituting the ring of the fluorine-containing aliphatic ring is the main chain of the fluorine-containing polymer. It is a polymer which is a carbon atom constituting The carbon atom of the main chain is derived from two carbon atoms of the polymerizable double bond of the cyclic monomer constituting the fluoropolymer, or a diene-based single atom having two polymerizable double bonds. In the case of a fluorine-containing polymer obtained by cyclopolymerizing a monomer, it is derived from four carbon atoms of two polymerizable double bonds. As atoms constituting the ring of the fluorinated aliphatic ring, oxygen atoms, nitrogen atoms and the like may be contained in addition to carbon atoms. The fluorine-containing aliphatic ring is preferably a fluorine-containing aliphatic ring having 1 to 2 oxygen atoms. The number of atoms constituting the fluorine-containing aliphatic ring is preferably 4-7.
As the polymerizable double bond, a vinyl group, an allyl group, and a (meth) acryloyl group are preferable.

Examples of the fluorinated cyclic polymer include homopolymers or copolymers of cyclic monomers, and homopolymers or copolymers obtained by cyclopolymerizing diene monomers.
The cyclic monomer is a monomer having a polymerizable double bond between carbon atoms constituting the fluorinated aliphatic ring, or a carbon atom constituting the fluorinated aliphatic ring and carbon outside the fluorinated aliphatic ring. A monomer having a polymerizable double bond with an atom.
The diene monomer is a monomer having two polymerizable double bonds.

  The cyclic monomer and the diene monomer are monomers having a fluorine atom, and the number of fluorine atoms bonded to the carbon atom relative to the total number of hydrogen atoms bonded to the carbon atom and fluorine atoms bonded to the carbon atom. A monomer having a ratio of 80% or more is preferable, and a perfluoro monomer having a ratio of 100% is more preferable.

The cyclic monomer and the diene monomer may be a perhalopolyfluoromonomer in which 1 to 4 fluorine atoms of the perfluoromonomer are substituted with chlorine.
The monomer to be copolymerized with the cyclic monomer or diene monomer is also preferably a perfluoromonomer or a perhalopolyfluoromonomer.

  As the cyclic monomer, compound (1) or compound (2) is preferable.

However, X < ¹¹ >, X <^12> , R < ¹¹ > and R < ¹² > show a fluorine atom, a C1-C4 perfluoroalkyl group, or a C1-C4 perfluoroalkoxy group each independently. X ¹¹ is preferably a fluorine atom. X ¹² is preferably a fluorine atom, a trifluoromethyl group, or a perfluoroalkoxy group having 1 to 4 carbon atoms.
X ²¹ and X ²² each independently represent a fluorine atom or a C 1-7 perfluoroalkyl group. X ²¹ and X ²² are preferably a fluorine atom or a trifluoromethyl group.

  Specific examples of compound (1) include compounds (1-1) to (1-3).

  Specific examples of compound (2) include compounds (2-1) to (2-2).

Examples of the monomer to be copolymerized with the cyclic monomer include CF ₂ = CF ₂ , CF ₂ = CFCl, CF ₂ = CFOCF _{3 and the} like.

As the diene monomer, the compound (3) is preferable.
_{CF 2 = CF-Q-CF} = CF 2 ··· (3).
However, Q shows the C1-C3 perfluoroalkylene group which may have an etheric oxygen atom. In the case of a perfluoroalkylene group having an etheric oxygen atom, the etheric oxygen atom in the perfluoroalkylene group may be present at one end of the group or may be present at both ends of the group. , May be present between the carbon atoms of the group. From the viewpoint of cyclopolymerizability, it is preferably present at one end of the group.

  A polymer having repeating units of the following formulas (3-1) to (3-3) is obtained by cyclopolymerization of the compound (3).

Examples of the diene monomer include the following compounds.
CF ₂ = CFOCF ₂ CF = CF ₂ ,
CF ₂ = CFOCF (CF ₃ ) CF = CF ₂ ,
CF ₂ = CFOCF ₂ CF ₂ CF = CF ₂ ,
CF ₂ = CFOCF ₂ CF (CF ₃ ) CF = CF ₂ ,
CF ₂ = CFOCF (CF ₃ ) CF ₂ CF = CF ₂ ,
CF ₂ = CFOCF ₂ OCF = CF ₂ ,
CF ₂ = CFOC (CF ₃ ) ₂ OCF = CF ₂ ,
CF ₂ = CFCF ₂ CF = CF ₂ ,
_{CF 2 = CFCF 2 CF 2 CF} = CF 2.

Examples of the monomer to be copolymerized with the diene monomer include CF ₂ = CF ₂ , CF ₂ = CFCl, CF ₂ = CFOCF _{3 and the} like.

  The fluorinated cyclic polymer preferably contains 20 mol% or more, more preferably 40 mol% or more of the repeating units having a fluorinated aliphatic ring structure, out of all the repeating units (100 mol%). It is particularly preferred that it consists only of repeating units having an aliphatic cyclic structure. The repeating unit having a fluorinated alicyclic structure is a repeating unit formed by polymerization of a cyclic monomer and a repeating unit formed by cyclopolymerization of a diene monomer.

The fluorine-containing alkylene-based polymer is a fluorine-containing polymer obtained by polymerizing a compound having a polyfluoroalkylene chain and a polymerizable group.
As the polyfluoroalkylene chain, a polyfluoroalkylene group having 2 to 24 carbon atoms is preferable. The polyfluoroalkylene group may contain a cycloalkylene group and may have a functional group.
As the polymerizable group, a vinyl group, an allyl group, a (meth) acryloyl group, an epoxy group, a dioxetane group, a cyano group, an isocyanate group, or a hydrolyzable silyl group represented by the following formula (4) is preferable.

_{- (CH 2) a Si (} M 1) 3-b (M 2) b ··· (4).
However, M < ¹ > is group converted into a hydroxyl group by a hydrolysis reaction. Examples of the group include a halogen atom, an alkoxy group, and an acyloxy group. As the halogen atom, a chlorine atom is preferable. As an alkoxy group, a methoxy group or an ethoxy group is preferable, and a methoxy group is more preferable. M ¹ is preferably an alkoxy group, more preferably a methoxy group.
M ² is a monovalent hydrocarbon group. Examples of M ² include an alkyl group, an alkyl group substituted with one or more aryl groups, an alkenyl group, an alkynyl group, a cycloalkyl group, and an aryl group, and an alkyl group or an alkenyl group is preferable.
a is an integer of 1 to 3, and 3 is preferable.
b is 0 or an integer of 1 to 3, and 0 is preferable.

Examples of the compound having a polyfluoroalkylene chain and a polymerizable group include the following compounds.
_{CH 2 = CHCOOCH 2 CH 2 (} CF 2) 8 F,
_{CH 2 = CHCOOCH 2 CH 2 (} CF 2) 6 F,
_{CH 2 = C (CH 3)} COOCH 2 CH 2 (CF 2) 8 F,
_{CH 2 = C (CH 3)} COOCH 2 CH 2 (CF 2) 6 F,
CH ₂ = CHCOOCH ₂ (CF ₂ ) ₆ F,
_{CH 2 = C (CH 3)} COOCH 2 (CF 2) 6 F,
CH ₂ = CHCOOCH ₂ CF ₂ CF ₂ H,
CH ₂ = CHCOOCH ₂ (CF ₂ CF ₂ ) ₂ H,
_{CH 2 = C (CH 3)} COOCH 2 (CF 2 CF 2) H,
_{CH 2 = C (CH 3)} COOCH 2 (CF 2 CF 2) 2 H,
_{CH 2 = CFCOOCH 2 CH (OH} ) CH 2 (CF 2) 6 CF (CF 3) 2,
_{CH 2 = CFCOOCH 2 CH (OH} ) CH 2 (CF 2) 6 CF (CF 3) 2,
_{CH 2 = CHCOOCH 2 CH 2 (} CF 2 CF 2) 3 CH 2 CH 2 COCOCH = CH 2,
_{CH 2 = C (CH 3)} COOCH 2 CH 2 (CF 2 CF 2) 3 CH 2 CH 2 COCOC (CH 3) = CH 2,
CH ₂ = CHCOOCH ₂ Cy ^F CH ₂ OCOCH = CH ₂ ,
_{CH 2 = C (CH 3)} COOCH 2 Cy F CH 2 OCOC (CH 3) = CH 2.
Cy ^F represents perfluoro (1,4-cyclohexylene group).

The fluorine-containing polyether polymer is a fluorine-containing polymer obtained by polymerizing a compound having a perfluoro (polyoxyalkylene) chain and a polymerizable group (hereinafter referred to as compound (f)).
The perfluoro (polyoxyalkylene) chain is a group consisting of (CF ₂ CF ₂ O) units, (CF ₂ CF (CF ₃ ) O) units, (CF ₂ CF ₂ CF ₂ O) units and (CF ₂ O) units. It is preferably composed of at least one perfluoro (oxyalkylene) unit selected from: (CF ₂ CF ₂ O) unit, (CF ₂ CF (CF ₃ ) O) unit or (CF ₂ CF ₂ CF ₂ O) unit It is more preferable that the fluorine-containing polymer is composed of (CF ₂ CF ₂ O) units from the viewpoint of excellent physical properties (heat resistance, acid resistance, etc.).
The number of perfluoro (oxyalkylene) units contained in the compound (f) is preferably an integer of 2 to 200, more preferably an integer of 5 to 50, from the viewpoint of high releasability and hardness of the fluoropolymer.

As the polymerizable group, a vinyl group, an allyl group, a (meth) acryloyl group, an epoxy group, a dioxetane group, a cyano group, an isocyanate group, or a hydrolyzable silyl group represented by the above formula (4) is preferable. An acryloyl group is more preferred.
The number of polymerizable groups contained in the compound (f) is preferably an integer of 1 to 4 from the viewpoint of excellent polymerizability, more preferably an integer of 2 to 4 from the viewpoint of excellent hardness of the fluoropolymer, etc. 3 or 4 is particularly preferred. When using 2 or more types of a compound (f) together, the average number of polymeric groups has 1-3.

As the compound (f), compounds (f1) to (f4) are preferable, and a compound (f1) is more preferable.
(Z ¹ —CH ₂ CF ₂ O (CF ₂ CF ₂ O) _y1 ) _a1 Y ¹ (f1),
(Z ² —CH ₂ CF ₂ O (CF ₂ CF ₂ O) _{y 2} · (CF ₂ O) _{g 2} ) a ₂ Y ² (f2),
_{^{(Z 3 -CH 2 CF 2 O}} (CF (CF 3) CF 2 O) y3 · (CF 2 O) g3) a3 Y 3 ··· (f3),
_{^{(Z 4 -CH 2 CF 2 O}} (CF 2 CF 2 CF 2 O) y4 · (CF 2 O) g4) a4 Y 4 ··· (f4).

However, the notation “·” means that the arrangement of the two units is not limited.
y1, y2, y3 and y4 each independently represent an integer of 1 to 100, preferably an integer of 5 to 50.
g2, g3 and g4 each independently represent an integer of 1 to 100.
a1, a2, a3 and a4 each independently represent an integer of 1 to 4, preferably an integer of 2 to 4, and particularly preferably 3 or 4.
Y ¹ represents an a1 valent linking group, Y ² represents an a2 valent linking group, Y ³ represents an a3 valent linking group, and Y ⁴ represents an a4 valent linking group. a1, a2, a3 and a4 have the same meaning as described above.
Examples of Y ¹ to Y ⁴ of the divalent linking group include —CF ₂ CF ₂ —.
Examples of Y ¹ to Y ⁴ of the trivalent linking group include the following linking groups.

Examples of the tetravalent linking group Y ¹ to Y ⁴ include the following linking groups.

Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a group represented by the following formula (5), and W is preferred.
_{W- (OCH 2 CH 2) c} · (OCH 2 CH (OW) CH 2) d - ··· (5).
However, c and d each independently represent 0 or an integer of 1 to 100, preferably 0.

W represents a group represented by the following formulas (5-1) to (5-5).
CH ₂ = CHCOO (CH ₂ ) _h1 -Q ^1- (5-1),
CH ₂ = CFCOO (CH ₂ ) _{h 2} -Q ^2- (5-2),
_{CH 2 = C (CH 3)} COO (CH 2) h3 -Q 3 - ··· (5-3),
_{CH 2 = C (CF 3)} COO (CH 2) h4 -Q 4 - ··· (5-4).

However, h1, h2, h3, h4 and h5 each independently represent 0 or an integer of 1 to 10.
Q ¹ , Q ² , Q ³ and Q ⁴ each independently represent a single bond, —COO— or —NHCOO—. If h1 is 0, Q ¹ is a single bond, if the h2 is 0, Q ² is a single bond, Q ³ where h3 is 0 is a single bond, when h4 is 0 Q ⁴ Is a single bond. Q ⁵ represents an etheric oxygen atom or —COO—.

  Moreover, as a fluoropolymer, the ratio of the number of fluorine atoms bonded to carbon atoms to the total number of hydrogen atoms bonded to carbon atoms and fluorine atoms bonded to carbon atoms is 100% because of excellent releasability. The perfluoropolymer (F) is preferable, and the amorphous or amorphous perfluoropolymer (F) is preferable from the viewpoint of excellent coating properties. The perfluoropolymer (F) can be produced, for example, by polymerizing a perfluoromonomer described later in the presence of a polymerization initiator.

In the case where the second primer layer is not provided, the fluorine-containing polymer includes a perfluoropolymer (F1) having a reactive functional group or the perfluoropolymer (F1) from the viewpoint of adhesion to the antistatic layer. A mixture with a perfluoro polymer (F2) described later is particularly preferred.
The contact angle of water of the perfluoropolymer (F1) or mixture is preferably 80 ° or more and less than 105 °.

  Examples of the reactive functional group include a carboxy group, a sulfonic acid group, a group having an ester bond, a hydroxyl group, an amino group, a cyano group, and an isocyanate group, and a carboxy group is preferable. For example, in the case of a perfluoropolymer (F1) having a carboxy group, the perfluoropolymer (F) having a functional group derived from a polymerization initiator or the like as a terminal group is heated in an oxygen atmosphere, and then immersed in water. It can be produced by converting the functional group into a carboxy group.

When the second primer layer is provided, the fluorine-containing polymer has substantially no reactive functional group obtained by treating the perfluoropolymer (F1) with fluorine gas from the viewpoint of excellent releasability. Perfluoropolymer (F2) is particularly preferred.
The water contact angle of the perfluoropolymer (F2) is preferably 105 ° or more.

(Antistatic layer)
The antistatic layer is a layer containing a conductive compound. When the antistatic layer has excellent adhesion to the substrate or the pattern layer, it may also serve as a primer layer.
The surface resistance of the conductive compound itself is preferably 10 ⁸ Ω / □ or less, and more preferably 10 ⁶ Ω / □ or less.
The surface resistance of the antistatic layer is preferably 10 ¹¹ Ω / □ or less, and more preferably 10 ^9.5 Ω / □ or less.
The surface resistance of the pattern layer provided on the antistatic layer is preferably 10 ¹⁶ Ω / □ or less, and more preferably 10 ¹³ Ω / □ or less.

Examples of the conductive compound include the following compounds.
Metal oxide: Tin oxide doped with niobium, tin oxide doped with phosphorus, tin oxide doped with antimony (ATO), indium oxide, indium oxide doped with tin (ITO), zinc oxide, zinc oxide doped with aluminum Indium-doped zinc oxide, zinc antimonate, antimony pentoxide, etc.
Conductive polymers: aliphatic conjugated polyacetylene, aromatic conjugated poly (paraphenylene), heterocyclic conjugated polypyrrole, polythiophene, heteroatom-containing polyaniline, mixed conjugated poly (phenylene vinylene) etc.
Conductive carbon materials: carbon powder (carbon nanotubes, carbon black, ketjen black, acetylene black, etc.), carbon fibers (polyacrylonitrile-based carbon fibers, pitch-based carbon fibers, etc.), carbon flakes of expanded graphite pulverized products, etc. .
Metal material: Metal (aluminum, copper, gold, silver, nickel, chromium, iron, molybdenum, titanium, tungsten, tantalum, etc.) or powder of alloy containing the metal, metal flake, metal fiber (iron, copper, stainless steel) , Silver-plated copper, brass, etc.).

As the conductive compound, a metal oxide or a conductive polymer is preferable from the viewpoint of adhesion to the pattern layer or the primer layer, and polythiophene or ITO is more preferable from the viewpoint of the transmittance of ultraviolet rays near a wavelength of 365 nm.
0.01-30 mol% is preferable among metal oxides (100 mol%), and, as for the content rate of the hetero atom doped by the metal oxide, 0.1-10 mol% is more preferable.
The content of the conductive compound is preferably 30 to 100% by mass in the antistatic layer (100% by mass), and more preferably 50 to 100% by mass from the viewpoint of antistatic properties.
What is necessary is just to determine the thickness of an antistatic layer suitably by a use. For example, when forming a highly transparent antistatic layer, the thickness is preferably 20 to 1000 nm, more preferably 30 to 300 nm, and particularly preferably 40 to 200 nm.

(First primer layer)
Examples of the material for the first primer layer include an adhesive, a silane coupling agent, and a resin material containing a silicon atom.
As the adhesive, a visible light curable resin, an epoxy adhesive, an acrylic adhesive, or a urethane adhesive is preferable. From the viewpoint of low curing shrinkage and high transparency, an adhesive containing a cyanoacrylate ester or an epoxy resin is used. Agents are preferred.

Examples of the silane coupling agent include the following silane coupling agents.
Silane coupling agents having amino groups: 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) ) -3-Aminopropylmethyldimethoxysilane and the like.
Silane coupling agents having an oxiranyl group: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and the like.
Silane coupling agent for trichlorosilane: vinyltrichlorosilane and the like.
Silane coupling agents having other functional groups (vinyl group, acryloyloxy group, methacryloyloxy group, epoxy group, styryl group, fluoroalkyl group, mercapto group, isocyanate group, ureido group, etc.).

As the silane coupling agent, a silane coupling agent having an amino group, a silane coupling agent having an oxiranyl group, and a silane coupling agent of trichlorosilane are preferable.
Examples of the resin material containing a silicon atom include a modified acrylic silicone resin and a resin containing a silsesquioxane skeleton.
The thickness of the first primer layer is preferably 0.02 to 25 μm, and more preferably 0.03 to 15 μm.

(Second primer layer)
Examples of the material for the second primer layer include a fluorine-containing polymer having a reactive functional group, a fluorine-containing cyclic polymer having a reactive functional group, a fluorine-containing alkylene polymer having a reactive functional group, or A fluorine-containing polyether polymer having a reactive functional group is preferred. Moreover, as this fluoropolymer, the perfluoro polymer (F1) which has the above-mentioned reactive functional group is especially preferable.
As the fluorine-containing polymer having a reactive functional group, a fluorine-containing polymer having units derived from the compounds (6-1) to (6-2); the terminal group derived from the polymerization initiator was changed to a carboxy group. Examples thereof include fluorine-containing polymers.
CH ₂ = CHCOOCH ₂ CH (OH) CH ₂ (CF ₂ ) ₂ CF (CH ₃ ) ₂ (6-1),
_{CF 2 = CFCF 2 C (CF} 3) (OH) CH 2 CH = CH 2 ··· (6-2).
The thickness of the second primer layer is preferably 0.03 to 5 μm, more preferably 0.06 to 1 μm.

<Mold manufacturing method>
The following method is mentioned as a manufacturing method of the mold of this invention.
(I) A method of forming a pattern layer by a hot embossing method.
(Ii) A method of forming the pattern layer by a casting method.
(iii) A method of forming the pattern layer by cutting, laser, radiation, etching or the like.
As the method for producing a mold of the present invention, the method (i) or the method (ii) is preferable because the pattern layer can be easily formed and the accuracy of the pattern to be formed is high.

(Method (i))
Examples of the method (i) include a method having the following steps (i-1) to (i-6).
(I-1) The process of forming a 1st primer layer on a base material as needed.
(I-2) A step of forming an antistatic layer on the substrate or the first primer layer.
(I-3) The process of forming a 2nd primer layer on an antistatic layer as needed.
(I-4) A step of forming a film containing a fluoropolymer on the antistatic layer or the second primer layer.
(I-5) The process of pressing the heated original mold which has the inversion pattern corresponding to the pattern of a pattern layer with the film | membrane containing a fluoropolymer.
(I-6) A step of separating the original mold from the film containing the fluoropolymer to form a pattern layer.

Hereinafter, a case where the first primer layer and the second primer layer are provided will be described.
(I-1) Step:
A first primer layer is formed by applying a solution containing the material of the first primer layer on the substrate and drying the coating film.
Examples of the coating method include a casting method, a spin coating method, a spray coating method, a potting method, and a bar coating method.
Examples of the drying method include a heat drying method, a warm air drying method, a vacuum drying method, and a method of drying by leaving in an air stream.

(I-2) Process:
An antistatic agent is apply | coated on a 1st primer layer, and an antistatic layer is formed by drying a coating film.
Examples of the coating method include the same method as in step (i-1).
Examples of the drying method include the same method as in step (i-1).
When the antistatic agent contains a curable resin, the curable resin is cured by heating or ultraviolet irradiation after the coating film is dried. For the ultraviolet irradiation, an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, or the like is used.

  Examples of the antistatic agent include those containing a conductive compound, a dispersant and a solvent. A commercially available antistatic agent may be used as the antistatic agent. Examples of commercially available antistatic agents include Conisol manufactured by Inscon Tech, MU-003 manufactured by Muromachi Technos, and the like.

  Examples of the conductive compound include the compounds described above. The concentration of the conductive compound is preferably 0.1 to 10% by mass in the antistatic agent (100% by mass), and preferably 0.4 to 5% by mass from the viewpoint of dispersibility and antistatic properties.

  As the dispersant, a dispersant having an anionic group is preferable. Examples of the anionic group include a group having an acidic proton such as a carboxy group, a sulfonic acid group (sulfo group), a phosphoric acid group (phosphono group), a sulfonamide group, or a salt thereof. A phosphoric acid group or a salt thereof is preferable, and a carboxy group and a phosphoric acid group are particularly preferable. The average number of anionic groups contained in the dispersant is 1 or more per molecule, and from the viewpoint of further improving the dispersibility of the conductive compound, the average is preferably 2 or more per molecule, and an average of 5 The above is more preferable, and an average of 10 or more is particularly preferable. Two or more types of anionic groups may be contained in one molecule.

  Examples of the dispersant having an anionic group include phosphanol (PE-510, PE-610, LB-400, EC-6103, RE-410, etc.) manufactured by Toho Chemical Industry Co., Ltd. and Disperbyk (- 110, −111, −116, −140, −161, −162, −163, −164, −164, −170, −171, etc.), Aronix M5300 manufactured by Toagosei Co., Ltd. KAYAMER (PM-21, PM-2 etc.) etc. are mentioned.

  It is preferable that the dispersant further has a crosslinkable or polymerizable functional group. Examples of the crosslinkable or polymerizable functional group include ethylenically unsaturated groups (acryloyl group, methacryloyl group, allyl group, styryl group, vinyloxy group, etc.) capable of crosslinking reaction or polymerization reaction by radicals, cationic polymerizable groups ( Epoxy group, oxacetanyl group, vinyloxy group, etc.), polycondensation reactive groups (hydrolyzable silyl group, N-methylol group, etc.) and the like, and ethylenically unsaturated groups are preferred.

As the dispersant, an oligomer or polymer having an anionic group and a crosslinkable or polymerizable functional group and having the crosslinkable or polymerizable functional group in the side chain is particularly preferable. 1000 or more are preferable, as for the mass average molecular weight (Mw) of this oligomer or polymer, 2000-1000000 are more preferable, 5000-200000 are further more preferable, and 10000-100,000 are especially preferable.
1-50 mass parts is preferable with respect to 100 mass parts of conductive compounds, and, as for the addition amount of a dispersing agent, 5-30 mass parts is more preferable, and 5-20 mass parts is especially preferable.
A dispersing agent may be used individually by 1 type, and may use 2 or more types together.

As the solvent, a liquid having a boiling point of 60 to 170 ° C. is preferable.
As the solvent, ethanol, isopropanol, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and butanol are preferable, and ethanol, isopropanol, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and a mixed solvent of these with water are particularly preferable.

The antistatic agent may further contain a binder from the viewpoint of adhesion to the substrate and mechanical strength. Examples of the binder include a non-curable thermoplastic resin; a curable resin such as a thermosetting resin and a photocurable resin, and the like. A photocurable resin is particularly preferable from the viewpoint of adhesion.
The softening temperature or glass transition point of the binder is preferably 50 ° C or higher, more preferably 70 ° C or higher, and particularly preferably 100 ° C or higher.

As a photocurable resin, what contains the polyfunctional monomer which has 2 or more of photopolymerizable groups in 1 molecule is preferable, and the polyfunctional monomer which has 3 or more of photopolymerizable groups in 1 molecule More preferably, it contains
Examples of the photopolymerizable group include polymerizable groups such as an epoxy group, a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group, and a (meth) acryloyl group is preferable.

Examples of the photocurable resin include the following monomers.
Neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, propylene glycol di (meth) acrylate and the like.
Triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate and the like.
Pentaerythritol di (meth) acrylate and the like.
2,2-bis {4- (acryloxy-diethoxy) phenyl} propane and the like.

  Trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, 1,2,4-cyclohexanetetra (meth) acrylate, pentaglycerol triacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) Acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol triacrylate, tripentaerythritol hexatriacrylate and the like.

A polyfunctional monomer may be used individually by 1 type, and may use 2 or more types together.
The photocurable resin preferably contains a photopolymerization initiator. As the photopolymerization initiator, a photoradical polymerization initiator or a photocationic polymerization initiator is preferable, and a photoradical polymerization initiator is particularly preferable.

The antistatic agent is prepared by dispersing a conductive compound in a solvent in the presence of a dispersant.
When dispersing the conductive compound in the solvent, it is preferable to use a disperser. Examples of the dispersing machine include a sand grinder mill (bead mill with a pin), a dyno mill, a high-speed impeller mill, an Eiger mill, a pebble mill, a roller mill, an attritor, a colloid mill, and the like. Particularly preferred.
Prior to dispersing the conductive compound in the solvent, a preliminary dispersion treatment may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.

(I-3) Step:
On the antistatic layer, a solution obtained by dissolving a fluorine-containing polymer having a reactive functional group in a solvent is applied, and the coating film is dried to form a second primer layer.
Examples of the solvent include fluorine-containing solvents such as perfluorotributylamine, pentafluorobenzene, hexafluorometaxylene, and hydrofluoroether.
Examples of the coating method include the same method as in step (i-1).
Examples of the drying method include the same method as in step (i-1). The drying temperature is preferably 40 to 200 ° C.

(I-4) Process:
As shown in FIG. 5, a film 32 containing a fluoropolymer is formed on the second primer layer 22 by applying a solution obtained by dissolving a fluoropolymer in a solvent and drying the coating film. The precursor 30 is obtained.
Examples of the solvent include the solvents exemplified in the step (i-3).
Examples of the coating method include the same method as in step (i-1).
Examples of the drying method include the same method as in step (i-1). The drying temperature is the same temperature as in step (i-3).
Instead of a solution obtained by dissolving a fluorinated polymer in a solvent, a photocurable or thermosetting fluorinated monomer may be used.
In order to control the releasability of the film 32 containing the fluoropolymer, the surface of the film 32 containing the fluoropolymer is subjected to plasma treatment, corona discharge, ultraviolet irradiation, vacuum ultraviolet irradiation, electron beam irradiation, ultraviolet ozone treatment. Further, surface treatment such as ion irradiation may be performed.

(I-5) Step:
As shown in FIG. 6, a heated original mold 40 having a reversal pattern 42 corresponding to the pattern of the pattern layer is pressed against a film 32 containing a fluoropolymer of the mold precursor 30.
Examples of the material of the original mold 40 include silicon, glass, metal, and resin.
Examples of the method for forming the reversal pattern 42 on the original mold 40 include self-organization methods such as photolithography, electron beam lithography, X-ray lithography, cutting, laser beam processing, ultrasonic processing, and anodic oxidation.

The pressing pressure (gauge pressure) when the original mold 40 is pressed against the film 32 containing the fluoropolymer is preferably 0 to 10 MPa or less.
What is necessary is just to determine the temperature of the original mold 40 suitably according to the kind of fluoropolymer.

(I-6) Step:
The original mold 40 is separated from the film 32 containing the fluoropolymer, and the pattern layer 16 having the pattern 14 as shown in FIG. 4 is formed to obtain the mold 10.
When the substrate 12 is cylindrical or columnar, as shown in FIG. 7, the mold precursor 30 is rotated on the surface on which the reverse pattern (not shown) of the heated original mold 40 is formed. By doing this, the step (i-5) and the step (i-6) may be performed simultaneously to obtain a cylindrical or columnar mold having a pattern layer.

(Method (ii))
Examples of the method (ii) include a method having the following steps (ii-1) to (ii-6).
(Ii-1) The process of forming a 1st primer layer on a base material as needed.
(Ii-2) A step of forming an antistatic layer on the substrate or the first primer layer to obtain a first intermediate.
(Ii-3) A step of forming a second primer layer on the antistatic layer as necessary.
(Ii-4) The process of forming the film | membrane containing a fluoropolymer on the original mold which has the inversion pattern corresponding to the pattern of a pattern layer, and obtaining a 2nd intermediate body.
(Ii-5) The process of bonding a 1st intermediate body and a 2nd intermediate body so that a base material and an original mold may become an outer side.
(Ii-6) A step of separating the original mold from the film containing the fluoropolymer and forming a pattern layer.

Hereinafter, a case where the first primer layer and the second primer layer are provided will be described.
Steps (ii-1) to (ii-3):
(I-1)-(i-3) It carries out similarly to a process, the antistatic layer 18 is formed on the base material 12 via the 1st primer layer 20, and also the 2nd primer on the antistatic layer 18 A first intermediate 34 (see FIG. 9) in which the layer 22 is formed is obtained.

(Ii-4) Step:
As shown in FIG. 8, a solution obtained by dissolving a fluoropolymer in a solvent is applied on an original mold 40 having a reversal pattern 42 corresponding to the pattern of the pattern layer so that the solution and the reversal pattern 42 are in contact with each other. Then, the film 32 containing the fluoropolymer is formed by drying the coating film, and the second intermediate 36 is obtained.
Examples of the solvent include the solvents exemplified in the step (i-3).
Examples of the coating method include the same method as in step (i-1).
Examples of the drying method include the same method as in step (i-1). The drying temperature is the same temperature as in step (i-3).
Instead of a solution obtained by dissolving a fluorinated polymer in a solvent, a photocurable or thermosetting fluorinated monomer may be used.

(Ii-5) Step:
As shown in FIG. 9, the 1st intermediate body 34 and the 2nd intermediate body 36 are bonded together so that the base material 12 and the original mold 40 may become an outer side.
Examples of the bonding method include a method of bonding using an adhesive; a method of applying a solvent to the surfaces to be bonded, dissolving the surface, and then bonding the surfaces.

(Ii-6) Step:
After bonding the first intermediate 34 and the second intermediate 36, the original mold 40 is separated from the film 32 containing the fluoropolymer, and the pattern layer 16 having the pattern 14 as shown in FIG. Then, the mold 10 is obtained.

<Fine pattern formation method>
Examples of a method for forming a fine pattern using the mold of the present invention include the following methods.
(A) Photocurability in a state where the pattern layer of the mold of the present invention is pressed against a film made of a liquid photocurable resin formed on a support substrate, or after the mold is separated from the photocurable resin. A method of forming a desired fine pattern by irradiating a resin with light and curing the photocurable resin.
(B) A liquid photocurable resin is supplied to the surface of the pattern layer of the mold of the present invention, and the photocurable resin is irradiated with light simultaneously with or after the photocurable resin is transferred onto the support substrate. And curing the photocurable resin to form a desired fine pattern.

Examples of the method (a) include the following methods.
(I) When the mold of the present invention is a film or a sheet:
(I-1) As shown in FIG. 10, a film 52 made of a liquid photocurable resin formed on a belt-like support substrate 50 moving in a fixed direction and a film or sheet-like mold 10 are placed in a cylinder 62. The wound cylindrical mold 60 is continuously brought into contact with the cylindrical mold 60 while rotating the cylindrical mold 60 in synchronization with the moving speed of the support substrate 50, and the pattern layer 16 of the mold 10 is pressed against the film 52 made of a photocurable resin. In the applied state or after separating the mold 10 from the photocurable resin, the photocurable resin is irradiated with light from the light source 70 to cure the photocurable resin, and the pattern of the pattern layer 16 (not shown) is formed. A method for forming an inverted fine pattern (not shown).
Examples of the material of the cylinder 62 include glass, resin, metal, ceramics, wood, rubber, and the like. When the light source 70 is disposed in the cylindrical mold 60, glass, acrylic resin, fluororesin, fluororubber, or the like is used. Optical materials are preferred.

  (I-2) As shown in FIG. 11, a film 52 made of a liquid photocurable resin formed on a belt-like support substrate 50 moving in a fixed direction is connected to both ends of the belt-like mold 10. The endless belt-shaped mold 80 laid over the rolls 82 is continuously contacted while rotating the endless belt-shaped mold 80 in synchronization with the moving speed of the support substrate 50, so that the film 52 made of a photocurable resin is formed. The pattern layer 16 of the mold 10 is pressed or after the mold 10 is separated from the photocurable resin, the photocurable resin is irradiated with light from the light source 70 to cure the photocurable resin, and the pattern layer A method of forming a fine pattern (not shown) obtained by inverting 16 patterns (not shown).

  (I-3) A belt-shaped mold of the present invention and a film made of a liquid photocurable resin formed on a belt-shaped support substrate are continuously brought into contact with each other by overlapping while moving in the same direction. A method of forming a desired fine pattern by irradiating a photocurable resin with light from a light source while the mold pattern layer is pressed against a film made of a curable resin to cure the photocurable resin.

(II) When the mold of the present invention is cylindrical or columnar:
As shown in FIG. 12, a film 52 made of a liquid photocurable resin formed on a belt-like support substrate 50 that moves in a predetermined direction and a cylindrical or columnar mold 10 are moved by the support substrate 50. In synchronization with the speed, the mold 10 is continuously contacted while rotating, and the light from the light source 70 is applied to the photocurable resin with the pattern layer 16 of the mold 10 pressed against the film 52 made of photocurable resin. A method of forming a fine pattern (not shown) by irradiating or separating the mold 10 from the photocurable resin and then curing the photocurable resin to reverse the pattern (not shown) of the pattern layer 16.

(III) When the mold of the present invention is plate-shaped:
In a state where the plate-shaped mold is pressed against the film made of a liquid photocurable resin formed on the support substrate like a stamp, and the pattern layer of the mold is pressed against the film made of the photocurable resin, Alternatively, after separating the mold from the photocurable resin, the photocurable resin is irradiated with light from a light source to cure the photocurable resin, thereby forming a desired fine pattern.

Examples of the method (b) include the following methods.
(IV) When the mold of the present invention is a film or a sheet:
(IV-1) A liquid photocurable resin is supplied to the surface of the pattern layer of the cylindrical mold in which a film or sheet-shaped mold is wound around a cylinder, and the belt-shaped support substrate that moves in a certain direction and the surface of the cylindrical mold The photocurable resin is continuously contacted while rotating the cylindrical mold in synchronization with the moving speed of the support substrate, and the photocurable resin is transferred to the support substrate at the same time or after the photocurable resin is transferred. A method of forming a desired fine pattern by irradiating a resin with light from a light source and curing the photocurable resin.

  (IV-2) A liquid photocurable resin is supplied to the surface of the pattern layer of the endless belt-shaped mold in which both ends of the belt-shaped mold are connected, and the endless belt-shaped mold is moved on the belt-shaped support substrate that moves in a certain direction. The endless belt-shaped mold is continuously contacted while rotating in synchronization with the moving speed of the support substrate, and the photocurable resin is transferred to the photocurable resin from the light source simultaneously with or after the transfer onto the support substrate. A method of forming a desired fine pattern by irradiating light and curing a photocurable resin.

  (IV-3) A liquid photocurable resin is supplied to the surface of the pattern layer of the strip-shaped mold of the present invention, and the mold and the strip-shaped support substrate are overlapped while moving in the same direction. A method of forming a desired fine pattern by bringing the photocurable resin into contact with the photocurable resin and transferring the photocurable resin onto the support substrate, or after the transfer, irradiating the photocurable resin with light from the light source and curing the photocurable resin. .

(V) When the mold of the present invention is cylindrical or columnar:
Supply liquid photo-curing resin to the surface of the pattern layer of the cylindrical or columnar mold, and synchronize the belt-shaped support substrate that moves in a certain direction and the cylindrical or columnar mold with the moving speed of the support substrate The cylindrical or columnar mold is continuously contacted while rotating, and simultaneously or after transferring the photocurable resin onto the support substrate, the photocurable resin is irradiated with light from the light source, A method of curing a photocurable resin to form a desired fine pattern.

(VI) When the mold of the present invention is plate-shaped:
At the same time as supplying a liquid photocurable resin to the surface of the pattern layer of the plate-shaped mold and pressing the support substrate on the photocurable resin of the mold to transfer the photocurable resin onto the support substrate, or A method of forming a desired fine pattern by irradiating the photocurable resin with light from a light source after being transferred and curing the photocurable resin.

When the mold is made of a translucent material, the photocurable resin is cured by irradiating the photocurable resin with light from the mold side. When the support substrate is made of a light-transmitting material, the photocurable resin may be irradiated with light from the support substrate side. Moreover, you may use together hardening by a heating.
A high pressure mercury lamp or the like is used as a light source for light irradiation. As the light, ultraviolet light or visible light is used.
The light source may be provided inside the mold according to the translucency of the mold or the support substrate or the timing of light irradiation (light source 70 shown by a solid line in FIGS. 10 to 12), and the mold is sandwiched between the support substrates. You may provide in the other side (light source 70 shown with the dotted line in FIGS. 10-12), and you may provide downstream from a mold (light source 70 shown with the dashed-dotted line in FIGS. 10-12).

Examples of the shape of the support substrate include a film or sheet shape, a plate shape, a cylindrical shape, and a columnar shape.
Examples of the material for the support substrate include resin, glass, metal, and cellulose material.
Examples of the photocurable resin include known photocurable resins that can be cured by visible light or ultraviolet light.

Examples of the article on which a fine pattern is formed using the mold of the present invention include the following articles.
Optical element: Microlens array, optical waveguide, optical switching, Fresnel zone plate, wire grid, wavelength filter, polarizing plate, binary element, blazed element, photonic crystal, antireflection film, antireflection structure, etc.
Chips: Biochips, μ-TAS (Micro-Total Analysis Systems) chips, microreactor chips, and the like.
Recording media: optical disc, etc.
Display material: ribs, etc.
Energy related: Fuel cells, 3D batteries, capacitors, Peltier elements, solar cells, etc.
Semiconductor-related: MEMS (Micro-Electro-Mechanical-System), semiconductor devices, etc.
Others: catalyst carrier, filter, sensor member, super water-repellent material, etc.

Since the mold of the present invention described above has an antistatic layer between the base material and the pattern layer, defects due to adhesion of foreign matters occur when a fine pattern is formed using the mold of the present invention. There is no. As a result, the yield can be improved.
Further, in the mold manufacturing method of the present invention, the antistatic layer is formed on the substrate before the film containing the fluoropolymer (the layer to be the pattern layer later) is formed. Foreign matter such as dust does not adhere to the film containing the fluoropolymer, and defects derived from the foreign matter do not occur in the pattern layer.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited only to these Examples.
In the examples, the surface resistance was measured at an applied voltage of 1000 V using a surface resistance meter (Hiresta MCP-HTP16, manufactured by Mitsubishi Chemical Corporation).
The contact angle with respect to water was measured using a contact angle meter (CA-X150 type, manufactured by Kyowa Interface Science Co., Ltd.) by dropping about 20 μL of water droplets.

[Synthesis Example 1]
Glass autoclave, a diene is monomer _{CF 2 = CFOCF 2 CF 2 CF} = CF 2 of 100 g, 0.5 g and the polymerization initiator of methanol chain transfer agent ((CH _{3) 2} CHOCOO) 0.7 g of ₂ was added and cyclopolymerized by a suspension polymerization method to obtain a polymer A which is a fluorine-containing cyclic polymer and a perfluoropolymer (F). The intrinsic viscosity [η] of the polymer A was 0.34 dL / g in perfluoro (2-butyltetrahydrofuran) at 30 ° C.

  Polymer A was heated in a hot air circulation oven at 300 ° C. for 1 hour in an air atmosphere, then immersed in ultrapure water at 110 ° C. for 1 week to treat the functional group at the molecular end, and then vacuumed. The polymer A1 which is a perfluoro polymer (F1) was obtained by drying in a dryer at 100 ° C. for 24 hours. In the IR spectrum of the polymer A1, a peak attributed to the carboxy group was confirmed. The light transmittance at a wavelength of 400 to 2000 nm was 95% or more at a thickness of 100 μm. The fluorine content of the polymer A1 was 67% by mass in the polymer A1 (100% by mass). The contact angle of the film made of the polymer A1 with respect to water was 101 °.

[Synthesis Example 2]
5 g of the polymer A1 was added to a 1 L stainless steel autoclave, the inside of the autoclave was purged with nitrogen three times, and then the pressure was reduced to 4 KPa. Thereafter, fluorine gas diluted to 14% by volume with nitrogen was introduced into the autoclave up to 101 KPa, and fluorination treatment was performed at 230 ° C. for 6 hours to obtain 5 g of polymer A2 as a perfluoropolymer (F2). In the IR spectrum of the polymer A2, no peak indicating a hydrocarbon group, a carboxy group or the like at the molecular terminal derived from the polymerization initiator was confirmed. The fluorine content of the polymer A2 was 68% by mass in the polymer A2 (100% by mass). The contact angle of the film made of the polymer A2 with respect to water was 116 °.

[Example 1]
An antistatic agent (Inscon Tech Co., Ltd., Conisol F-205) is diluted 5 times with a mixed solvent of water / isopropanol (1/7 mass ratio) to prepare an antistatic agent for coating. The antistatic agent is applied to an acrylic resin pipe (thickness 1.8 mm, diameter 30 mm, length 150 mm) by spray coating for 1 minute while rotating the pipe at a speed of 120 rpm, and dried with a dryer. To form an antistatic layer. The surface resistance of the antistatic layer is 10 ⁹ Ω / □.

  The polymer A1 is dissolved in perfluorotributylamine to prepare a 1% by mass solution of the polymer A1, and the solution is filtered through a polytetrafluoroethylene (PTFE) membrane filter having a pore size of 0.2 μm. The solution is applied onto the antistatic layer by spray coating for 1 minute while rotating the pipe at a speed of 120 rpm, and dried with a dryer to form a second primer layer.

  The polymer A2 is dissolved in perfluorotributylamine to prepare a 5% by mass solution of the polymer A2, and the solution is filtered through a PTFE membrane filter having a pore size of 0.2 μm. The solution is applied on the second primer layer by spray coating for 2 minutes while rotating the pipe at a speed of 120 rpm, and dried with a drier. When the surface of the film made of the polymer A2 stops flowing, the pipe is put into a dryer and dried at 140 ° C. for 2 hours to obtain a cylindrical mold precursor. The total thickness of the film composed of the antistatic layer, the second primer layer and the polymer A2 is about 1 μm.

An original mold made of nickel of 5 cm × 10 cm is prepared. On the surface of the original mold, as shown in FIG. 13, a plurality of ridges (reversal patterns 42) extending in the longitudinal direction of the original mold 40 are formed in parallel. The width w of the ridge is 100 μm, the distance p between adjacent ridges is 50 μm, and the height of the ridge is 50 μm.
After the original mold is heated to 150 ° C., the mold precursor is rotated about 1 in the original mold while rotating the mold precursor in the longitudinal direction of the original mold at a rotation speed of 1 rpm on the surface on which the ridges are formed. A pattern in which the protrusions of the original mold are inverted is formed on the film made of the polymer A2 of the mold precursor by pressing at a pressure of 0.0 MPa, and a cylindrical mold M1 having a pattern layer is obtained. The surface resistance of the pattern layer is 10 ¹³ Ω / □.

In a clean room where ultraviolet light is cut, 1.31 g of CF ₂ ═CFCF ₂ C (CF ₃ ) (OCH ₂ OCH ₃ ) CH ₂ CH═CH ₂ , CF ₂ ═CFCF ₂ C (CF ₃ ) Add 0.14 g of (OH) CH ₂ CH═CH ₂ and 0.06 g of photo radical polymerization initiator (Ciba Specialty Chemicals, Irgacure 651) and mix well to prepare a photocurable resin. To do.

The photocurable resin is supplied to an easy-adhesive surface of a PET film (Toyobo Co., Ltd., A4100, thickness 100 μm) having a length of 25 cm and a width of 12 cm by a die coater to form a film made of the photocurable resin.
While the mold M1 is rotated at a rotational speed of 1 rpm, the UV light from the light source (from the PET film side to the photocurable resin is applied to the photocurable resin film at room temperature with a pressure of about 0.1 MPa. Irradiation at a wavelength of 365 nm: 252 mW / cm ² ) is applied to cure the photocurable resin, and a fine pattern in which the pattern of the pattern layer is reversed is formed on the PET film.

[Example 2]
An antistatic agent (manufactured by Inscon Tech, Conisol F-205) was diluted 5 times with a mixed solvent of water / isopropanol (1/7 mass ratio) to prepare an antistatic agent for coating. The antistatic agent was applied to the easy adhesion surface of an A4 size PET film (Toyobo Co., Ltd., A4100, thickness 100 μm) with No. It was applied by a bar coating method using 5 bars. The PET film was put into a dryer and dried at 100 ° C. for 30 minutes to form an antistatic layer. The surface resistance of the antistatic layer was 10 ⁹ Ω / □.

  The polymer A1 was dissolved in perfluorotributylamine to prepare a 5% by mass solution of the polymer A1, and the solution was filtered with a PTFE membrane filter having a pore size of 0.2 μm. The solution was applied on the antistatic layer with No. The coating was performed by a bar coating method using 7 bars. The PET film was put into a dryer and dried at 140 ° C. for 2 hours to form a second primer layer.

  The polymer A2 was dissolved in perfluorotributylamine to prepare a 9% by mass solution of the polymer A2, and the solution was filtered through a PTFE membrane filter having a pore size of 0.2 μm. The solution was applied to the second primer layer with No. The coating was performed by a bar coating method using 7 bars. The PET film was put in a dryer and dried at 140 ° C. for 2 hours to form a film made of the polymer A2 to obtain a film-like mold precursor. The total thickness of the film composed of the antistatic layer, the second primer layer, and the polymer A2 was about 5 μm. The mold precursor was cut into 2 cm × 2 cm.

An original mold made of silicon of 1 cm × 1 cm was prepared. A groove having a width of 400 nm, a depth of 100 nm, and a length of 5 μm is formed on the surface of the original mold.
After the mold precursor of 2 cm × 2 cm is overlaid on the original mold so that the groove of the original mold and the film made of the polymer A2 of the mold precursor are in contact with each other, the original mold and the mold precursor are heated to 130 ° C. Pressing at a pressure of 2.0 MPa. Thereafter, the original mold and the mold precursor are cooled to 30 ° C., the original mold is slowly separated from the film made of the polymer A2, a pattern layer having a pattern in which the grooves of the original mold are inverted is formed, and the film-like mold M2 Got. The surface resistance of the pattern layer was 10 ¹³ Ω / □.

The photocurable resin prepared in Example 1 was dropped on the easy-adhesion surface of a 3 cm × 3 cm PET film (Toyobo, A4100, thickness 100 μm), and the mold M2 was placed on the photocurable resin at room temperature. In a state of pressing at a pressure of 0.5 MPa, UV light from a light source (illuminance at a wavelength of 365 nm: 63 mW / cm ² ) is irradiated from the mold M2 side to the photocurable resin for 10 seconds to cure the photocurable resin. It was. The mold M2 was slowly separated from the cured film, and a fine pattern in which the pattern of the pattern layer was reversed was formed on the PET film.

The following evaluation was performed about the fine pattern. The results are shown in Table 1.
(Mold defect)
The pattern of the mold was observed with a laser microscope (manufactured by Keyence Corporation, VK-9500) to confirm the presence or absence of defects due to adhesion of foreign matters such as dust.
(Fine pattern defects)
The fine pattern formed on the PET film was observed with a laser microscope (manufactured by Keyence Corporation, VK-9500) to confirm the presence or absence of defects due to adhesion of foreign matters such as dust.

(Groove size)
The fine pattern (groove) formed on the PET film was observed with a laser microscope (VK-9500, manufactured by Keyence Corporation), and the width and height of the groove were measured.
(Releasability)
When separating the mold M2 from the cured film, the case where it could be easily separated was evaluated as ◯, the case where it could be separated by an operation such as ultrasonic waves was evaluated as Δ, and the case where it was not closely separated was evaluated as ×.

Example 3
A4 size PET film (AT-38, manufactured by Kaneka Corp., thickness 38 μm) having an antistatic layer formed on the surface was prepared. The surface resistance of the antistatic layer was 10 ⁸ Ω / □.
The polymer A1 was dissolved in perfluorotributylamine to prepare a 2% by mass solution of the polymer A1, and the solution was filtered with a PTFE membrane filter having a pore size of 0.2 μm. The solution was applied on the antistatic layer with No. The coating was performed by a bar coating method using 7 bars. The PET film was put into a dryer and dried at 140 ° C. for 2 hours to form a second primer layer.

  The polymer A2 was dissolved in perfluorotributylamine to prepare a 5% by mass solution of the polymer A2, and the solution was filtered through a PTFE membrane filter having a pore size of 0.2 μm. The solution was applied to the second primer layer with No. The coating was performed by a bar coating method using 7 bars. The PET film was put in a dryer and dried at 140 ° C. for 2 hours to form a film made of the polymer A2 to obtain a film-like mold precursor. The total thickness of the film made of the antistatic layer, the second primer layer and the polymer A2 was about 0.7 μm. The mold precursor was cut into 2 cm × 2 cm.

The same original mold as in Example 2 was prepared, and a pattern layer having a pattern in which the grooves of the original mold were inverted was formed in the same manner as in Example 2 to obtain a film-like mold M3. The surface resistance of the pattern layer was 10 ¹¹ Ω / □.
A fine pattern in which the pattern of the pattern layer was inverted was formed on the PET film in the same manner as in Example 2 except that the mold M3 was used.
The same evaluation as Example 2 was performed about the fine pattern. The results are shown in Table 1.

Example 4
An antistatic agent (manufactured by Inscon Tech, Conisol F-205) was diluted 5 times with a mixed solvent of water / isopropanol (1/7 mass ratio) to prepare an antistatic agent for coating. The antistatic agent was applied to the easy adhesion surface of an A4 size PET film (Toyobo Co., Ltd., A4100, thickness 100 μm) with No. The coating was performed by a bar coating method using 5 bars. The PET film was put into a dryer and dried at 100 ° C. for 30 minutes to form an antistatic layer. The surface resistance of the antistatic layer was 10 ⁹ Ω / □.

  The polymer A1 was dissolved in perfluorotributylamine to prepare a 5% by mass solution of the polymer A1, and the solution was filtered with a PTFE membrane filter having a pore size of 0.2 μm. The solution was applied on the antistatic layer with No. The coating was performed by a bar coating method using 7 bars. The PET film was put into a drier and dried at 140 ° C. for 2 hours to form a second primer layer to obtain a first intermediate. The first intermediate was cut to 2 cm × 2 cm.

An original mold made of silicon of 1 cm × 1 cm was prepared. A groove having a width of 400 nm, a depth of 100 nm, and a length of 5 μm is formed on the surface of the original mold.
The polymer A2 was dissolved in perfluorotributylamine to prepare a 9% by mass solution of the polymer A2, and the solution was filtered through a PTFE membrane filter having a pore size of 0.2 μm. The solution was applied onto the original mold using a casting method in an atmosphere reduced to about 40 kPa. Thereafter, the film was dried at 180 ° C. for 3 hours to form a film (thickness: 3.0 μm) made of the polymer A2 on the original mold to obtain a second intermediate.

Next, after dropping a few drops of the 5% by mass solution of the polymer A1 on the surface of the film composed of the second intermediate polymer A2, the film is bonded to the second intermediate layer side of the first intermediate, It was made to adhere by heating at 140 ° C. and pressing at a pressure of 0.5 MPa. Then, the first and second intermediates including the original mold are cooled to 30 ° C., and the original mold is slowly separated from the film made of the polymer A2, and the grooves of the original mold are inverted. A pattern layer having the above pattern was formed to obtain a film-like mold M4. The surface resistance of the pattern layer was 10 ¹³ Ω / □.
A fine pattern in which the pattern of the pattern layer was reversed was formed on the PET film in the same manner as in Example 2 except that the mold M4 was used.
The same evaluation as Example 2 was performed about the fine pattern. The results are shown in Table 1.

[Comparative Example 1]
The same original mold as in Example 2 was prepared.
A 2 cm x 2 cm PET film (Toyobo Co., Ltd .: A4100, film thickness: 100 μm) is stacked on the original mold so that the groove of the original mold and the highly smooth surface of the PET film are in contact with each other, and the original mold is heated to 150 ° C. After that, it was pressed at a pressure of 2.0 MPa. Thereafter, the original mold and the PET film were cooled to 30 ° C., and the original mold was slowly separated from the PET film to obtain a film-like mold M5 having a pattern in which the grooves of the original mold were inverted. The surface resistance of the pattern layer was 10 ¹⁶ Ω / □ or more (unmeasurable).
A fine pattern in which the pattern of the pattern layer was reversed was formed on the PET film in the same manner as in Example 2 except that the mold M5 was used.

[Comparative Example 2]
An ethanol solution containing 0.5% by mass of an amino group-containing silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903) and 5% by mass of water was prepared. The ethanol solution was applied to the easy-adhesion surface of an A4 size PET film (Toyobo Co., Ltd., A4100, thickness 100 μm) with No. It was applied by a bar coating method using 5 bars. The PET film was put into a dryer and dried at 100 ° C. for 30 minutes to form a first primer layer.

  On the 1st primer layer, it carried out similarly to Example 2, the 2nd primer layer and polymer A2 were formed, and the film-form mold precursor was obtained. The total thickness of the film composed of the first primer layer, the second primer layer, and the polymer A2 was about 5 μm. The mold precursor was cut into 2 cm × 2 cm.

The same original mold as in Example 2 was prepared, and a pattern layer having a pattern in which the grooves of the original mold were inverted was formed in the same manner as in Example 2 to obtain a film-like mold M6. The surface resistance of the pattern layer was 10 ¹⁶ Ω / □ or more (unmeasurable).
A fine pattern in which the pattern of the pattern layer was reversed was formed on the PET film in the same manner as in Example 2 except that the mold M6 was used.
The same evaluation as Example 2 was performed about the fine pattern. The results are shown in Table 1. Due to the adhesion of dust, defects occurred in the mold M5, and many defects were observed in the fine pattern. As for the part having no defect in the mold M6, the mold surface itself was excellent in releasability, so that the result was inferior in the width and height of the groove.

  The mold of the present invention is useful as a mold used in the nanoimprint method. Further, it can also be used as a mold used for molding a photocurable resin, a mold used for printing such as screen printing, gravure printing, and a mold for 2P molding.

It is sectional drawing which shows an example of the mold of this invention. It is sectional drawing which shows the other example of the mold of this invention. It is sectional drawing which shows the other example of the mold of this invention. It is sectional drawing which shows the other example of the mold of this invention. It is sectional drawing which shows an example of the mold precursor obtained in the middle of manufacture of a mold. It is sectional drawing which shows 1 process in manufacture of a mold. It is sectional drawing which shows one process in manufacture of a cylindrical mold. It is sectional drawing which shows 1 process in manufacture of a mold. It is sectional drawing which shows 1 process in manufacture of a mold. It is sectional drawing which shows an example of the formation method of a fine pattern. It is sectional drawing which shows an example of the formation method of a fine pattern. It is sectional drawing which shows an example of the formation method of a fine pattern. It is a front view which shows the original mold used in an Example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Mold 12 Base material 14 Pattern 16 Pattern layer 18 Antistatic layer 20 1st primer layer 22 2nd primer layer 30 Mold precursor 32 Film | membrane containing a fluoropolymer 34 1st intermediate body 36 2nd intermediate body 40 Original mold 42 Reverse pattern 60 Cylindrical mold 80 Endless belt mold

Claims (7)

A substrate;
A pattern layer containing a fluoropolymer and having a pattern formed on the surface;
A mold comprising: an antistatic layer provided between the substrate and the pattern layer.   The mold according to claim 1, further comprising a first primer layer provided between the base material and the antistatic layer.   Furthermore, the mold of Claim 1 or 2 which has a 2nd primer layer provided between the said antistatic layer and the said pattern layer.   The fluorine-containing polymer contains 35% by mass or more of fluorine atoms in 100% by mass of the fluorine-containing polymer, and the contact angle with respect to water of the film made of the fluorine-containing polymer is 80 ° or more. 4. The mold according to any one of 3.   The mold according to any one of claims 1 to 4, wherein the fluoropolymer has a fluorinated aliphatic ring structure in the main chain. A method for producing a mold comprising a base material, a pattern layer containing a fluoropolymer and having a pattern formed on the surface, and an antistatic layer provided between the base material and the pattern layer. ,
Forming an antistatic layer on the substrate;
Forming a film containing a fluoropolymer on the antistatic layer;
Pressing a heated original mold having a reversal pattern corresponding to the pattern of the pattern layer onto the film containing the fluoropolymer; and
Separating the original mold from the film containing the fluoropolymer, and forming a pattern layer. A method for producing a mold comprising a base material, a pattern layer containing a fluoropolymer and having a pattern formed on the surface, and an antistatic layer provided between the base material and the pattern layer. ,
Forming an antistatic layer on a substrate to obtain a first intermediate;
Forming a film containing a fluoropolymer on an original mold having a reverse pattern corresponding to the pattern of the pattern layer to obtain a second intermediate;
Bonding the first intermediate and the second intermediate so that the base material and the original mold are on the outside;
Separating the original mold from the film containing the fluoropolymer, and forming a pattern layer.

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