JP2008238502A - Manufacturing method of mold for imprinting - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method capable of manufacturing a mold for imprinting having only a small amount of an excess mold release agent remaining and only a small amount of a solvent at a low environmental load and low cost. <P>SOLUTION: The manufacturing method of the mold for imprinting has the steps of applying the mold release agent on the surface of a mold body 12, fixing the agent by chemical bonding to form a coating layer 14 to obtain a mold 10 and cleaning the mold 10 with supercritical carbon dioxide. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for manufacturing an imprint mold.

  As a method for manufacturing an article having a fine structure such as an optical element, a mold having a reverse structure corresponding to the fine structure formed on the surface is pressed against the resin material to form a fine structure on the surface of the resin material. A so-called imprint method (nanoimprint method) is known (Non-Patent Document 1).

  In a mold used for the imprinting method (hereinafter referred to as an imprinting mold), a coating layer made of a release agent is formed on the surface of the mold body in order to improve the releasability from the resin material. ing. As the mold release agent, a fluorine-containing organosilane compound having a good mold release property, excellent durability and heat resistance and having a hydrolyzable group bonded to a silicon atom is often used.

  In the imprint mold, since the size of the irregularities of the fine structure is nano-order, the thickness of the coating layer is also required to be nano-order, that is, a thickness of about a monomolecular film. Therefore, after forming the coating layer on the surface of the mold body, it is necessary to remove the excess release agent and leave only the release agent fixed to the mold body by chemical bonding on the surface of the mold body. .

As a method for removing the excess mold release agent, for example, the following method is known.
A method of cleaning a mold coated with a release agent with a fluorine-containing solvent (see Patent Document 1).

However, this method has the following problems.
(1) In order to separate the release agent from the fluorine-containing solvent in which the warming coefficient of the fluorine-containing solvent is high and the release agent is dissolved, it is necessary to perform distillation or the like.
(2) It is difficult to completely remove the excess release agent that has entered the nano-order concave portion of the fine structure.
(3) It is difficult to completely remove the residual solvent from the surface of the mold after cleaning, and defects on the surface of the mold due to the residual solvent are generated.
(4) The fluorine-containing solvent is expensive and the production cost of the mold is increased.
Applied Physics Letters, American Institute of Physics, 1994, Vol. 67, p. 3314 JP 2004-351893 A

  The present invention provides a method capable of producing an imprint mold with a small amount of remaining release agent and solvent with low environmental load and low cost.

The method for producing an imprint mold of the present invention includes a step of applying a release agent to the surface of a mold body, fixing by chemical bonding to form a coating layer, and obtaining the mold, and cleaning the mold with supercritical carbon dioxide. And a step of performing.
The release agent is preferably a fluorine-containing organosilane compound in which a hydrolyzable group is bonded to a silicon atom.

  According to the imprint mold manufacturing method of the present invention, it is possible to manufacture an imprint mold with less residual mold release agent and solvent with low environmental load and low cost.

  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. The repeating unit represented by the formula (u1) is referred to as a unit (u1). Repeating units represented by other formulas are also described in the same manner.

<Mold>
FIG. 1 is a cross-sectional view showing an example of an imprint mold (hereinafter referred to as a mold) obtained by the production method of the present invention. The mold 10 includes a mold body 12 and a coating layer 14 provided on the surface of the mold body 12.

(Mold body)
Examples of the shape of the mold body 12 include a sheet shape, a plate shape, a cylindrical shape, and a columnar shape.
Examples of the material of the mold body 12 include a material that can chemically react with the release agent. Examples of the material include quartz, silicon with a silicon carbide film formed by chemical vapor deposition, single crystal silicon carbide, tantalum, silicon, silicon with a silicon oxide film, silicon with a silicon nitride film, nickel , Copper, stainless steel, titanium, and the like, and nickel or copper is preferable because electroforming plating can be performed, that is, a mold body can be produced at low cost.

  The mold body 12 has a fine structure on the surface. The microstructure is an inverted structure corresponding to the microstructure of an article (such as an optical element) manufactured by an imprint method.

The fine structure means fine convex portions and / or concave portions.
As a convex part, the elongate protruding item | line extended on the surface of the mold main body 12, the processus | protrusion scattered on the surface, etc. are mentioned.
Examples of the recess include a long groove extending on the surface of the mold body 12 and holes scattered on the surface.

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 hole include a triangular prism, a quadrangular prism, a hexagonal prism, a cylinder, a triangular pyramid, a quadrangular pyramid, a hexagonal pyramid, a cone, a hemisphere, and a polyhedron.

The average width of the ridges or grooves is preferably 1 nm to 400 nm, particularly preferably 30 nm to 200 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 400 nm, particularly preferably 30 nm to 200 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 4 μm, more preferably 1 nm to 1 μm, further preferably 1 nm to 400 nm, further preferably 10 nm to 400 nm, and particularly preferably 30 nm to 200 nm.
The average depth of the recesses is preferably 1 nm to 4 μm, more preferably 1 nm to 1 μm, further preferably 1 nm to 400 nm, further preferably 10 nm to 400 nm, and particularly preferably 30 nm to 200 nm.

  In the region where the fine structure is dense, the interval between adjacent convex portions (or concave portions) is preferably 1 nm to 10 μm on average, more preferably 10 nm to 1 μm, and particularly preferably 30 nm to 200 nm. The interval between adjacent convex portions means the distance from the end of the base of the cross section of the convex portion to the start of the base of the cross section of the adjacent convex portion. The interval between adjacent recesses means the distance from the end of the upper side of the cross section of the recess to the start end of the upper side of the cross section of the adjacent recess.

The minimum dimension of the convex portion is preferably 1 nm to 400 nm or less, and more preferably 30 nm to 200 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 400 nm or less, and more preferably 30 nm to 200 nm. The minimum dimension means the minimum dimension among the width, length and depth of the recess.

  Examples of the fine structure forming method include a mechanical cutting method, a lithography method, an electroforming plating method, and the like. From the viewpoint that a nano-sized fine structure can be formed at low cost, the electroforming plating method is preferable.

(Coating layer)
The coating layer 14 is a layer made of a release agent.
As the release agent, a fluorine-containing organosilane compound in which a hydrolyzable group is bonded to a silicon atom is preferable from the viewpoints of releasability and adhesion to the mold body 12.

Examples of the fluorine-containing organic silane compound include compounds (1) to (6).
CF ₃ (CF ₂ ) _a (CH ₂ ) ₂ Si (OR ¹¹ ) ₃ (1),
CF ₃ (CF ₂ ) _b (CH ₂ ) ₂ Si (ONCO) ₃ (2),
CF ₃ (CF ₂ ) _c (CH ₂ ) ₂ SiCl ₃ (3),
_{CF 3 CF 2 CF 2 O- (} CF 2 CF 2 CF 2 O) d -CF 2 CF 2 (CH 2) 3 Si (OR 41) ··· (4),
^{_{(R 51 O) 3 Si-}} CH 2 CH 2 CH 2 -OCH 2 CF 2 - (OCF 2 CF 2) e - (OCF 2) f -OCF 2 CH 2 -O-CH 2 CH 2 CH 2 Si (OR ⁵² ) ₃ ... (5),

Compound (1):
R ¹¹ is an alkyl group (methyl group, ethyl group, propyl group, etc.) and the like, and a is an integer of 1 to 19. Examples of the compound (1) include 1H, 1H, 2H, 2H-perfluorodecyltrimethoxysilane. The compound can be purchased from Synquest Fluorochemicals.
Compound (2):
b is an integer of 1-19. Compound (2) can be produced, for example, by the method described in JP-A-9-286539.
Compound (3):
c is an integer of 1-19. Examples of the compound (3) include 1H, 1H, 2H, 2H-perfluorodecyltrichlorosilane. The compound can be purchased from Synquest Fluorochemicals.

Compound (4):
R ⁴¹ is an alkyl group (methyl group, ethyl group, propyl group, etc.) and the like, and d is an integer of 1 to 200. Compound (4) can be produced, for example, by the method described in JP-A No. 2002-283354. As a commercial item of compound (4), Daikin Industries, Ltd. OPTOOL DX etc. are mentioned.
Compound (5):
R ⁵¹ and R ⁵² are each an alkyl group (methyl group, ethyl group, propyl group, etc.), e is an integer of 1 to 200, and f is an integer of 1 to 200. Compound (5) can be produced, for example, by the method described in JP-A No. 2004-351493.

Compound (6):
R is Rf-X-.
Rf is a C 1-20 perfluoroalkyl group, preferably a C 1-10 perfluoroalkyl group. By having a perfluoroalkyl group, the mold releasability of the mold 10 is improved. If the carbon number of the perfluoroalkyl group is 20 or less, the solubility of the compound (6) in the diluting solvent is improved, so that the perfluoroalkyl group can be easily applied to the mold body 12. The perfluoroalkyl group may be linear or branched.

X is a group consisting of one or more of units (u1) to (u3).
_{- (OC 3 F 6) -} ··· (u1),
_{- (OC 2 F 4) -} ··· (u2),
_{- (OCF 2) - ··· (} u3).
However, C ₃ F ₆ and C ₂ F ₄ may be linear or branched.
The sum of the number of units (u1), the number of units (u2), and the number of units (u3) is 1 or more, preferably 2-50. If the sum of the units (u1) to (u3) is 1 or more, the mold releasability of the mold 10 is good. If the sum of the units (u1) to (u3) is 50 or less, the solubility of the compound (6) in the diluting solvent is improved, so that it is easy to apply to the mold body 12.
The order of existence of the units (u1) to (u3) in X is arbitrary.

R on the left and right are the same group. The same group means that Rf is the same, and the types, numbers, and order of units (u1) to (u3) constituting X are the same. For example, when R on the left side is C ₃ F ₇ — (OCF (CF ₃ ) CF ₂ ) — (OCF (CF ₃ ) —, R on the right side is — (CF (CF ₃ ) O) — (CF ₂ a _{CF (CF 3) O) -C} 3 F 7.

  Y is an organic group having 2 or more carbon atoms. The total number of carbon atoms in Y is preferably 50 or less. If the total number of carbon atoms exceeds 50, the molecular weight becomes too large and the solubility in a diluting solvent may be reduced, and the proportion of the fluorine moiety in the molecule will decrease and the releasability will decrease. There is a risk.

The average of n is 2 to 10, and 3 to 10 is preferable.
If the average of n is 2 or more, the adhesiveness between the mold body 12 and the coating layer 14 will be good. If the average of n is 10 or less, when a coating layer is formed on the mold body, high mold releasability can be imparted to the mold body.

The compound (6) is usually a mixture of plural kinds of compounds (6) having different numbers of n. Therefore, when the compound (6) is a mixture of two or more compounds (6) having different numbers of n, n is represented as an average. The mixture of two or more kinds of compounds (6) may contain the compound (6) in which n is 1 in the range where the average of n is 2 to 10, and the compound (6) in which n is more than 10. You may go out.
On the other hand, when the compound (6) is composed of only one compound (6) having the same number of n, the number of n is an average of n as it is.

The average of n is obtained by the following method.
(I) The number average molecular weight (polystyrene conversion) of the compound (6) is determined by gel permeation chromatography (GPC).
(Ii) The molecular weight of Rf-X is subtracted from the number average molecular weight to determine the molecular weight of (YZ) _n .
(Iii) the molecular weight of _{(Y-Z) n} is divided by the molecular weight of Y-Z, and calculates the average of n.

Z is —Si (R ¹ ) _m (R ² ) _3-m .
R ¹ is a hydrolyzable group. Since the hydrolyzable group reacts with the material of the mold body 12, the compound (6) contained in the coating layer 14 is chemically bonded to the surface of the mold body 12.
Examples of hydrolyzable groups include hydroxyl groups, alkoxy groups, ester groups (acetoxy groups, etc.), oxime groups, enoxy groups, amino groups, aminoxy groups, amide groups, halogen atoms, and the like. From the viewpoint of easy preparation of the agent solution, a methoxy group or an ethoxy group is preferable.
R ² is a hydrogen atom or a monovalent hydrocarbon group. Examples of the monovalent hydrocarbon group include an alkyl group having 1 to 3 carbon atoms.
m is an integer of 1 to 3, and 3 is preferable from the viewpoint of adhesion to the mold.

  As the compound (6), the compound (61) is preferable.

  Compound (61) can be produced, for example, by reacting compound (7) with compound (8) in a solvent under a nitrogen atmosphere.

As the solvent, a halogenated aliphatic solvent and a halogenated aromatic solvent are preferable.
Examples of halogenated aliphatic solvents include methylene chloride, chloroform, 2-chloro-1,2-dibromo-1,1,2-trifluoroethane, 1,2-dibromohexafluoropropane, 1,2-dibromotetrafluoroethane. 1,1-difluorotetrachloroethane, 1,2-difluorotetrachloroethane, fluorotrichloromethane, heptafluoro-2,3,3-trichlorobutane, 1,1,1,3-tetrachlorotetrafluoropropane, 1,1 , 1-trichloropentafluoropropane, 1,1,2-trichlorotrifluoroethane, 1,1,1,2,2-pentafluoro-3,3-dichloropropane, 1,1,2,2,3-penta Fluoro-1,3-dichloropropane, tridecafluorohexane, 1,1,1,2,2,3,4,5 5,5-decafluoropentane, nonafluorobutyl methyl ether, nonafluorobutyl ethyl ether, heptafluorocyclopentane, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, perfluoro And tributylamine, (1-trifluoromethyl) perfluorodecalin, and the like.

Examples of the halogenated aromatic solvent include benzotrifluoride, hexafluoroxylene, pentafluorobenzene and the like.
A solvent may be used individually by 1 type and may use 2 or more types together.

As the solvent, from the point that the solubility of the compound (7) and the compound (8) is high, the availability is easy, and the reactivity with the compound (61) to be obtained is low. (9-6) is preferred.
CHFCClCF ₂ CF ₂ Cl (9-1),
CClF ₂ CCl ₂ F (9-2),
C ₆ F ₁₃ H (9-3),
CF ₂ HCF ₂ OCH ₂ CF ₃ (9-4),
(CF ₃ CF ₂ CF ₂ CF ₂ ) ₃ N (9-5),
_{c-C 10 F 17 CF 3} ··· (9-6).

The reaction temperature is preferably 5 to 80 ° C.
The reaction time is preferably 0.1 to 10 hours.
In order to adjust the average of n, the molar ratio between the compound (7) and the compound (8) may be adjusted.

  The thickness of the coating layer 14 is preferably 1 to 100 nm. If the thickness of the coating layer 14 is 1 nm or more, the releasability from the resin material is good. If the thickness of the coating layer 14 is 100 nm or less, the fine structure of the mold 10 can be sufficiently maintained.

The contact angle of the coating layer 14 with respect to water is preferably 90 degrees or more, and more preferably 95 to 130 degrees. If the contact angle with respect to the water of the coating layer 14 is 90 degree | times or more, the release property from a resin material will become favorable.
The contact angle of the coating layer 14 with respect to n-hexadecane is preferably 30 ° or more, and more preferably 35 to 90 °. If the contact angle with respect to n-hexadecane of the coating layer 14 is 30 degrees or more, the releasability from the resin material will be good.
The contact angle is measured according to JIS R3257.

<Mold manufacturing method>
The method for producing an imprint mold of the present invention includes a step of applying a release agent to the surface of a mold body, fixing by chemical bonding to form a coating layer, and obtaining the mold, and cleaning the mold with supercritical carbon dioxide. The method which has a process to do. It is preferable to clean the mold body before forming the coating layer on the surface of the mold body.

Specifically, the mold 10 is manufactured through the following steps (a) to (c).
(A) A step of cleaning the mold body 12 before forming the coating layer.
(B) A step of applying the mold release agent to the surface of the mold body 12 and fixing it by chemical bonding to form a coating layer to obtain the mold 10.
(C) A step of cleaning the mold 10 with supercritical carbon dioxide to remove excess mold release agent and leaving only the mold release agent fixed to the mold body 12 by chemical bonding on the surface of the mold 10.

(A) Process:
Examples of the method for cleaning the mold body 12 include the following methods.
(A-1) A method of ultrasonically cleaning the mold body 12 in an organic solvent.
(A-2) A method in which the mold body 12 is boiled and washed in an acid or peroxide solution.

Examples of the organic solvent include acetone, ethanol, 1,1,2,2,3-pentafluoro-1,3-dichloropropane, and the like.
Examples of the acid include sulfuric acid, hydrochloric acid, sulfamic acid, formic acid, citric acid, glycolic acid and the like.
Examples of the peroxide include an aqueous solution such as hydrogen peroxide.
After the washing, the surface of the mold body 12 may be cleaned by further washing with purified water and drying, followed by ozone irradiation.

(B) Process:
As a method for forming a coating layer by applying a release agent to the surface of the mold body 12 and fixing it by chemical bonding, the following methods may be mentioned.
(B-1) A method in which a release agent solution is applied to the surface of the mold body 12 and heated as necessary.
(B-2) A method in which the mold body 12 is immersed in a release agent solution and heated after the mold body 12 is pulled up as necessary.

The release agent solution can be prepared, for example, by diluting the release agent with a diluting solvent as necessary and adding an acid as a catalyst as necessary.
Diluting solvents include lower alcohols (1-butanol, isopropanol, ethanol, 1-propanol, t-butanol, etc.), fluorine inert solvents (perfluorohexane, perfluoromethylcyclohexane, perfluoro-1,3-dimethyl). Cyclohexane, dichloropentafluoropropane, etc.).
Examples of the acid include hydrochloric acid, sulfuric acid, nitric acid and the like.
Examples of the coating method include spin coating, casting, spray coating, and dip coating.

The concentration of the release agent in the release agent solution is preferably 0.01 to 10% by mass. If the density | concentration of a mold release agent is 0.01 mass% or more, generation | occurrence | production of unpainted will be suppressed. When the concentration of the release agent is 10% by mass or less, there is little coating unevenness.
The heating temperature is preferably 50 to 180 ° C.
The heating time is preferably 0.1 to 24 hours.
The atmosphere during heating is preferably in the air.

(C) Process:
Supercritical carbon dioxide means carbon dioxide in a supercritical state that exceeds the critical point (critical temperature and pressure) of carbon dioxide, and the properties of gas and liquid, that is, gas diffusivity and liquid dissolving power Have both. Supercritical carbon dioxide is a good solvent for a release agent (such as a fluorine-containing organosilane compound in which a hydrolyzable group is bonded to a silicon atom).

FIG. 2 is a schematic configuration diagram showing an example of an imprint mold cleaning apparatus.
The cleaning apparatus includes a carbon dioxide storage container 21 that stores carbon dioxide, a booster pump 22 that boosts carbon dioxide to a critical pressure, a heater 23 that heats carbon dioxide to a critical temperature, and a supplied supercritical fluid. A pressure vessel 24 for cleaning the mold 10 with carbon dioxide, a pressure adjustment valve 25 for reducing the pressure in the pressure vessel 24 to atmospheric pressure, and vaporizing the reduced supercritical carbon dioxide discharged from the pressure adjustment valve 25 It comprises a vaporization vessel 26, a filter 27 that filters the vaporized carbon dioxide, and a recycle pump 28 that returns the filtered carbon dioxide to the carbon dioxide storage vessel 21.

Cleaning of the mold 10 using the cleaning device is performed as follows.
The carbon dioxide supplied from the carbon dioxide storage container 21 is increased in pressure to a pressure exceeding the critical pressure by the pressure increasing pump 22, and then heated to a temperature exceeding the critical temperature by the heater 23 to obtain supercritical carbon dioxide.
Supercritical carbon dioxide is supplied to the pressure vessel 24 and the mold 10 is cleaned with supercritical carbon dioxide. When the supercritical carbon dioxide comes into contact with the mold 10, contaminants, excess mold release agent, and the like attached to the surface of the mold 10 are dissolved in the supercritical carbon dioxide and removed from the surface of the mold 10.

After completion of the cleaning, the pressure in the pressure vessel 24 is reduced to atmospheric pressure by the pressure adjustment valve 25. The depressurized supercritical carbon dioxide is vaporized in the vaporization vessel 26 to be converted into normal carbon dioxide.
After removing contaminants, mold release agent and the like mixed in the carbon dioxide with the filter 27, the filtered carbon dioxide is returned to the carbon dioxide storage container 21 with the recycle pump 28 and stored.
The cleaned mold 10 is removed from the pressure vessel 24 at atmospheric pressure.

The pressure in the pressure vessel 24 is preferably 7.3 MPa to 30.0 MPa. If this pressure is 7.3 MPa or more, the critical pressure of carbon dioxide is exceeded, and carbon dioxide enters a supercritical state. If the pressure is 30.0 MPa or less, the cost of the booster pump 22 and the like can be suppressed.
The temperature in the pressure vessel 24 is preferably 31 to 120 ° C. If the temperature is 31 ° C. or higher, the critical temperature of carbon dioxide is exceeded, and carbon dioxide becomes a supercritical state. If this temperature is 120 degrees C or less, the density of supercritical carbon dioxide will become high and compatibility with a mold release agent will improve.

In the method of manufacturing the mold 10 described above, the mold 10 is washed with supercritical carbon dioxide, which has a smaller environmental load than conventional fluorine-containing solvents, and the supercritical carbon dioxide can be recycled. The mold 10 can be manufactured.
Moreover, since the mold 10 is washed with supercritical carbon dioxide, which is easier to remove the solvent than the conventional fluorine-containing solvent, the mold 10 with less residual solvent can be manufactured.
In addition, since the mold 10 is washed with supercritical carbon dioxide, a mold with a small excess of the remaining release agent can be manufactured. That is, supercritical carbon dioxide is a good solvent for the release agent, and has low viscosity and high diffusivity compared to conventional fluorine-containing solvents, and therefore has good permeability to the recesses of the mold 10. Therefore, the excess mold release agent that has entered the recess can be sufficiently removed.
In addition, since supercritical carbon dioxide can be recycled, the mold 10 can be manufactured at a lower cost than when a conventional fluorine-containing solvent is used.

<Manufacturing method of article having fine structure>
Examples of a method for producing an article having a fine structure using the mold 10 include the following methods.
(I) As shown in FIG. 3, the mold 10 was pressed against the resin material layer 32 made of a liquid photocurable resin formed on the substrate 30, and then the mold 10 was pressed against the resin material layer 32. In the state or after separating the mold 10 from the resin material layer 32, the resin material layer 32 is irradiated with light to cure the photocurable resin, and an article having a desired microstructure on the surface of the resin material layer 32 is obtained. Method.

  (II) As shown in FIG. 3, in a state where the resin material layer 32 is heated to the glass transition temperature or higher of the thermoplastic resin, the mold 10 is applied to the resin material layer 32 made of the thermoplastic resin formed on the substrate 30. Then, in a state where the mold 10 is pressed against the resin material layer 32 or after the mold 10 is separated from the resin material layer 32, the resin material layer 32 is cooled to make the thermoplastic resin into a solid state. A method for obtaining an article having a desired microstructure on the surface of the material layer 32.

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 material for the 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 having a fine structure 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.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited only to these Examples.
Example 1 is an example.

(Contact angle)
The contact angle of the coating layer with respect to water or n-hexadecane was measured according to JIS R3257, and 4 μL of water or n-hexadecane was applied to the surface of the coating layer using a contact angle meter (CA-X150 type, manufactured by Kyowa Interface Science Co., Ltd.). It was dropped and measured.

[Example 1]
Into a 100 mL round bottom flask equipped with a condenser tube, 0.74 g (5.0 mmol) of the compound (7-1) was added, and further 4 of the compound (8-1) was added to the compound (9-1). 45.71 g of a solution containing .97 g (5.0 mmol) was added, and the reaction was performed at 50 ° C. for 2 hours in a nitrogen atmosphere.

  After completion of the reaction, the reaction crude liquid was filtered with a filter to obtain 27.2 g of a solution containing the compound (61-1) in the compound (9-1).

The concentration of the compound (61-1) in the solution was 10.2% by mass. When the number average molecular weight (polystyrene conversion) of the compound (61-1) was measured by GPC and the average of n was calculated, the average of n was 2.8.
1 g of the solution was added to 9.18 g of 1-butanol, and 0.081 g of hydrochloric acid was further added to prepare a release agent solution (release agent concentration: 1% by mass).

As the mold body, a nickel substrate having a fine structure (line and space in which a plurality of grooves having a width of 80 nm are formed at intervals of 3000 nm and the depth of the grooves is 200 nm) is prepared. Is ultrasonically washed in acetone.
The surface of the nickel substrate is spin-coated with a release agent solution at a rotation speed of 500 rpm for 10 seconds, and then spin-coated at 2000 rpm for 20 seconds to form a release agent film.
The release agent film is heated at 150 ° C. for 1 hour together with the nickel substrate to form a coating layer on the surface of the nickel substrate to obtain a mold.

The mold is placed in the pressure vessel 24 of the cleaning apparatus shown in FIG. 2 and cleaned with supercritical carbon dioxide at 30 MPa and 80 ° C. for 10 minutes.
The surface of the mold is observed with a scanning electron microscope, and it is confirmed that the microstructure of the mold is not changed and that the original microstructure of the nickel substrate is maintained after the coating layer is formed.
Moreover, the contact angle with respect to the water or n-hexadecane of a coating layer is measured. The contact angle is much higher than the contact angle of the nickel substrate (water: 76 degrees, n-hexadecane: less than 10 degrees), and it is confirmed that the coating layer is formed uniformly.

  The mold for imprinting of the present invention is useful as a mold used in imprinting methods, particularly nanoimprinting methods.

It is sectional drawing which shows an example of the mold of this invention. It is a schematic block diagram which shows an example of the washing | cleaning apparatus of the mold for imprints. It is sectional drawing which shows one of the manufacturing processes of the articles | goods which have a microstructure.

Explanation of symbols

10 Mold 12 Mold body 14 Coating layer

Claims (2)

Applying a release agent to the surface of the mold body, fixing by chemical bonding to form a coating layer, and obtaining a mold;
And a step of cleaning the mold with supercritical carbon dioxide.   The method for producing an imprint mold according to claim 1, wherein the release agent is a fluorine-containing organosilane compound in which a hydrolyzable group is bonded to a silicon atom.

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