TW201005430A - Mold, process for producing the same, and process for producing substrate having transferred fine pattern - Google Patents

Abstract

A mold is provided which has high light transmission and high releasability and has a fine pattern having a relatively large maximum height. Also provided are: a process for producing the mold; and a process for producing a substrate with a transferred fine pattern using the mold. The mold (10) includes a transparent resin layer (A) (12) constituted of a transparent resin and having chemical bonds based on a functional group (x) in the surface thereof on the interlayer (C) side, an interlayer (C) (14) comprising a fluoropolymer (II) which has a backbone having a fluorinated alicyclic structure and has a reactive group (y) reactive with the functional group (x), and a surface layer (B) (16) comprising a fluoropolymer (I) which has a backbone having a fluorinated alicyclic structure and does not have the reactive group (y), the transparent resin having a glass transition temperature not higher than the glass transition temperatures of the fluoropolymer (I) and the fluoropolymer (II). The fine pattern has a maximum height exceeding the sum of the thickness of the surface layer (B) and the thickness of the interlayer (C).

Description

201005430 VI. Description of the Invention: [Technical Field] The present invention relates to a mold, a method of manufacturing the same, and a method of manufacturing a substrate having a transcriptional fine pattern using the mold, the substrate being photohardened The composition of the cured resin of the resin. [Drawing Chair; j Background] In recent years, a method in which a mold having a fine pattern on a surface is brought into contact with a substrate to form a reverse pattern of a fine pattern on a surface of a substrate, that is, a so-called nanoimprint method is attracting attention (refer to Patent Document and Patent Document 2). Among them, the photon imprinting method which performs the following steps in order, in particular, is a step of arranging a photocurable resin between the surface of the fine pattern of the i-die and the substrate; a step of performing light irradiation to cure the photocurable resin to form a cured product; and a step of separating the mold from the cured product. _ The nano-imprinting method is mainly used as a method of forming a micro-pattern of a fine wiring and a recording medium for a semiconductor element, which is based on a fine pattern of 1 〇〇 nm or less, but from the viewpoint of greatly improving productivity, Even in the method of forming a micro pattern having a maximum height of MEMS (Micro-Electro-Mechanical-Systems), biotechnology-related components, optical components, and the like from several to more than several tens of μm, the application thereof is expected. As a mold which can be used for the photo-nano imprint method, the following molds have been proposed. (1) Quartz mold. 3 201005430 (7) having: a transparent substrate (A); a surface layer (9) composed of a polymer having a fluorine-containing aliphatic ring structure in a main chain and having a fine pattern on the surface; and, present on the transparent substrate (A) and surface A mold of the intermediate layer (c) between the layers (B) (see Patent Document 3). The mold of ' ' (1) has a low mold release property, and the precision of the transcribed fine pattern of the hard resin is easily lowered when the mold is separated from the cured product. As a method of improving mold release property, a method of applying a release agent to the surface of a fine pattern of a mold has been proposed. However, due to the uneven thickness of the applied release agent, the fine pattern of the mold cannot be reproduced with high precision. Further, when the mold is continuously used, the release agent must be applied again, and the production efficiency is easily lowered. The mold of (2) is composed of a fluoropolymer because the surface layer (B) is formed, and the mold release property is high. However, in the mold (2) for the purpose of improving mechanical strength and dimensional stability, it is difficult to form the maximum height exceeding the thickness of the surface layer (B) because the hard material is used as the transparent substrate (A) for the following reason. A fine pattern of the total thickness of the intermediate layer (c) is applied to form an intermediate layer (the surface layer (B) on the surface of the transparent substrate (A), and the mother mold is pressed against the surface layer (B) to make the mother The mold inversion pattern is transcribed to the surface layer (B) to produce the mold of (2). However, since the thickness of the surface layer (B) formed by coating is thinner than the total thickness of the intermediate layer (C) ( 〇.1~i5gmj right) 'The maximum height of the flip pattern of the master mold (the maximum height difference of the concave-convex structure including the overall bending of the master mold) exceeds the total thickness described above, in order to correctly turn the flip pattern of the master mold, it exceeds In the above part of the total thickness, the flip pattern must also be transcribed on the transparent substrate (A). However, since the transparent substrate (A) is hard, the portion exceeding the total thickness is not able to transcribe the flip pattern 201005430 in transparency. On the base (Α). When the transfer pattern reaches the transparent substrate (A), the intermediate layer (c) and the surface layer (B) are broken, and the transparent substrate (A) is exposed to the surface. The transparent substrate (A) is exposed to the surface of the mold (2) due to the transparent substrate (A) ) Adhesive to hardened material, low release property.

[Patent Document 1] Japanese Patent Publication No. 2004-504718 (Patent Document 2) Japanese Patent Publication No. 2002-539604 (Patent Document 3) International Publication No. 2006/059580, the disclosure of the present invention; The present invention provides a mold having a high light transmittance and mold release property and having a fine pattern having a maximum height and a relatively large height; a method for producing the same; and a method for producing a substrate having a transcribed fine pattern, which can be high The fine pattern of the mold is transcribed with high precision and high productivity, and the maximum height of the transcribed fine pattern is relatively large. Means for Solving the Problem A mold according to the present invention is a mold having a fine pattern for molding a photocurable resin, comprising: a transparent resin layer (A); a surface layer (B) described below; The surface of the transparent thin layer (A), and the maximum height of the intermediate layer pattern existing between the transparent layer (A) and the surface layer (8), exceeding the surface layer (B) The total thickness of the thickness and the thickness of the intermediate layer (c); wherein, the layer of the moon is known as a layer composed of a transparent resin, and the glass transition temperature of the transparent tree 201005430 is in the following The (i) and the fluoropolymer (II) below are below the glass transition temperature, and the transparent resin layer (A) is formed before the intermediate layer (C) is formed, and the intermediate layer (c) is formed. The surface has a functional group (x)' and after the intermediate layer (c) is formed, has a chemical bond based on the aforementioned functional group (x) and the following reactive group (force-based) on the surface on which the intermediate layer (C) has been formed. Surface layer (B): a layer composed of a fluoropolymer (1) having a main chain a fluorine-containing aliphatic ring structure and having substantially no reactive group (y); an intermediate layer (C): a layer composed of a fluorine-containing polymer (II), the fluorine-containing polymer (II) The main chain has a fluorine-containing aliphatic ring structure and has a reactive group (y) reactive with the above functional group (X). The maximum height of the fine pattern is preferably from 1 to 500, which is 111. The aforementioned transparent resin layer (A) It is preferably supported by a transparent support (13). The aforementioned functional group (X) is preferably a hydroxyl group, an amine group or an epoxy group, and the aforementioned reactive group (y) is preferably a carboxyl group. (A) It is preferable to introduce a layer having a functional group (X) on the surface by surface treatment. The method for producing a mold of the present invention is a method for producing a mold having a fine pattern in which a photocurable resin is molded. The method has the following steps: forming the intermediate layer (C): on the surface of the transparent resin layer (A) having a functional group (X) on the surface of the transparent resin, the coating is dissolved a solution containing a solvent of a fluoropolymer (π) and dried by 201005430 to form a fluorine-containing material a step of preparing a mold precursor by forming an intermediate layer of the polymer (II): coating the surface of the intermediate layer (c) with the following (4) compound (1) dissolved in the fluorine-containing solution #1 The solution is dried and formed to form a surface layer (B) composed of the following fluoropolymer (1) to prepare a mold precursor; a step of preparing a mold: a surface having a fine pattern of a reverse pattern and The flip pattern of the master pattern of the total height of the flip pattern exceeding the thickness of the surface layer (B) and the thickness of the middle layer Pa1 layer (C) is at least one of the mold precursor 16 and the master mold described below. In a state where the fluorine-containing poly(I) (I) and the fluoropolymer (II) described below are at a glass transition temperature or higher, the surface layer (B) side of the mold precursor is pressed to cross the surface layer ( B), the intermediate layer (c) - and the transparent resin layer (A) form a fine pattern to prepare a mold; and a separating step: separating the master mold from the mold; wherein - the transparent resin: glass transition temperature is The following fluoropolymer (1) and the following fluoropolymer (II) have a glass transition temperature or lower Transparent resin; 含氟 Fluoropolymer (I): a fluoropolymer having a fluorinated aliphatic ring structure in the main chain and having substantially no reactive group (y): fluoropolymer (II): A fluoropolymer having a fluorinated aliphatic ring structure in the main chain and having a reactive group (y) reactive with the above functional group (X). The method for producing a substrate having a transcribed fine pattern of the present invention is characterized by the step of: arranging a photocurable resin on a surface of a substrate; and pressing the mold of the present invention against the photocurable resin a step of bringing the fine pattern of the mold into contact with the photocurable resin; and applying light to the photocurable resin 7 201005430 in a state where the mold is pressed against the photocurable resin, the light is irradiated a step of hardening the curable resin to form a cured product; and a step of separating the mold from the cured product. The method for producing a substrate having a transcribed fine pattern of the present invention is characterized by the step of disposing a photocurable resin on a surface of a fine pattern of a mold of the present invention; and pressing the substrate against the surface of the mold a step of the photocurable resin; the photocurable resin is irradiated with light, and the photocurable resin is cured to form a cured product in a state in which the substrate is pressed against the photocurable resin. a step; and a step of separating the mold from the hardened material. The method for producing a substrate having a transcription fine pattern of the present invention is characterized in that the substrate is brought into close contact with or in contact with the mold of the present invention such that the fine pattern of the mold becomes the substrate side; a step of filling a resin between the substrate and the mold; and irradiating the photocurable resin with light in a state in which the substrate is in close contact with or in contact with the mold, and curing the photocurable resin to form a cured product And a step of separating the mold from the hardened material. EFFECT OF THE INVENTION The method for producing a mold of the present invention can produce a mold having high light transmittance and mold release property and having a fine pattern having a maximum height and a relatively large height. Further, the present invention can manufacture a substrate by using the mold of the present invention, which can make the fine pattern of the mold high-precision and produce _ goodly transcribed, and has a transcribed fine pattern having a maximum height and a relatively large size. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an example of a mold of the present invention. 201005430 Fig. 2 is a cross-sectional view showing an example of a method of manufacturing a substrate having a transcribed fine pattern. Fig. 3 is a cross-sectional view showing another example of a method of producing a substrate having a transcribed fine pattern. Fig. 4 is a cross-sectional view showing another example of a method of producing a substrate having a transcribed fine pattern. Figure 5 is a laser microscope image of the mold of Example 7.

[Embodiment] BEST MODE FOR CARRYING OUT THE INVENTION In the present specification, a compound represented by the formula (1) is referred to as a compound (1). Other compounds of the general formula are also described in the same manner. <Mold> The plate of the present invention is a mold having a fine pattern for molding a photocurable resin. The figure is a cross-sectional view showing an example of the mold of the present invention. The mold 10 has a transparent resin layer (A) 12; a surface layer (B) 16; an intermediate layer formed on the surface of the transparent resin layer (A) 12 and present between the transparent resin layer (A) 12 and the surface layer (8) i6 ( And a transparent support (D) 17 supporting the transparent resin layer (A) 12 from the inner side; and having a cross-surface layer (9) 16, an intermediate layer (C) 14, and a transparent resin layer (A) 12 Fine pattern 18. In addition, the transparent support (Ρ) 17 is not required to be set. (Micro pattern) The fine pattern is preferably a fine pattern composed of a concavo-convex structure. The convex structural portion in the uneven structure exists in a line shape or a dot shape on the surface of the mold. 9 201005430 The shape of the convex structure can be straight or curved, or it can be in a curved shape. In addition, the linear convex structure is parallelized and recorded in a stripe shape. The cross-sectional shape of P (relative to the long direction, Examples of the cross-sectional shape in the right-angle direction include a rectangular shape, a trapezoidal shape, a triangular shape, a semicircular shape, and the like. / (4) The shape of the convex structural portion may be, for example, a rectangular shape of a bottom surface, a square shape of a rhombus, a hexagon, a triangle, a circle, or the like. Columnar, tapered spherical shape, polyhedral shape, etc. Aspect ratio of the semi-convex structure (aspect ratio, convex structure height / convex

The width of the bottom edge of the part should be 5 or less. When the aspect ratio is 5 or less, the transcription master mold: when the pattern is rotated, the domain pores can be formed into fine pores (four). Vertical and horizontal: It is 3 or less, and more preferably 2 or less. The height of the convex structure portion and the width of the bottom edge can be obtained by measuring the conf〇fi(4) of a confocal laser micr〇sc〇pe.

However, the height of the convex structure portion and the width of the bottom edge are difficult to be used for the positive phase timing by the common laser microscope due to the fine pattern of the steep wall surface of the steep mountain, and the fine pattern can be cut off to reveal the microscope (laser, laser). Observe or electron microscope) Observe the cross section to find out. The cutting of the fine pattern is carried out by a conventional method. However, when the shape of the pattern is collapsed due to the cutting, the tree moon t embedding treatment and the liquid nitrogen cooling treatment are performed. The maximum height of the fine pattern exceeds the total thickness of the surface layer (B) and the intermediate layer. The maximum height of the fine pattern is preferably 5 μm or less. If the maximum height of the fine pattern is 5 〇〇 μηη or less, the flip pattern of the master pattern can be uniformly transcribed across a large area. The maximum height of the fine pattern is preferably 300 μm or less and more preferably ι〇〇μηι or less. 10 201005430 The maximum height lower limit of the fine pattern depends on the total thickness of the surface layer (B) and the thickness of the intermediate layer (C), but is usually Ιμηι. The maximum height in the present invention is the maximum height specified by JIS Β0601, that is, the maximum south-low difference between the highest peak line and the lowest bottom line of the uneven structure in the reference length L. The maximum height can be determined by the contour measurement of a conjugated focal laser microscope. • However, when the maximum height is difficult to measure by a conjugate focal point 0 laser microscope due to the fine pattern of a steep cliff surface, the fine pattern can be cut off and the cross section can be observed with a microscope (optical microscope, laser microscope, or electron microscope). Find out. The cutting of the fine pattern is carried out by a conventional method. However, when the shape of the pattern is collapsed due to the cutting, the resin embedding treatment, the liquid nitrogen, the cooling treatment, and the like are performed. - When the length of the reference length L is a periodic pattern of line-and-space, V-groove, dot-pattern, etc., let it be 5 to 20 cycles long. In the case of non-patterns, the length of the base red can be included in the design © which will be the highest point and the lowest point. When the length of the reference length is large (a few mm or more), it is necessary to use the rim measurement of the common focus and the observation of the cross section as the 丨: the maximum height is found to be very low. At this time, the measurement and the cross-sectional observation are divided into a plurality of face lines at each place, and then the data is connected to obtain the maximum height. • Further, the thickness of the surface layer (8) and the intermediate layer (9) is the thickness of the surface layer (B) and the intermediate layer (c) which form the fine pattern 刖 mold precursor. (Transparent Resin Layer (A)) The transparent resin layer (4) is a layer composed of a transparent resin whose transition temperature is lower than the glass transition temperature of the fluoropolymer (1) 11 201005430 and the fluoropolymer (ι 1); The system has a functional group (X) on the surface where the intermediate layer (c) will be formed before the intermediate layer (C) is formed, and an intermediate layer (C) is formed after the intermediate layer (C) is formed. The surface has a layer bonded chemically based on the functional group (x) and the reactive group (y). The glass transition temperature of the transparent resin is below the glass transition temperature of the fluoropolymer (I) and below the glass transition temperature of the fluoropolymer (η). The glass transition temperature of the transparent resin is below the glass transition temperature of the fluoropolymer (1) and the (tetra) compound (π), and the maximum height of the flip pattern of the master mold (including the maximum height difference of the concave-convex structure of the entire master mold) Even if the thickness of the surface layer (B) and the thickness of the intermediate layer (C) are exceeded, the transparent resin layer (A) is deformed to follow the concave-convex structure of the reverse pattern, the master mold, and the like, and the transcription can be accurately reproduced. Reverse the case. In addition, if the glass transition temperature of the transparent resin is below the glass transition temperature of the 3F core (I) and the fluoropolymer (9), when the master mold is pressed, even if the foreign matter is mixed with the master and the surface layer (Β) In the meantime, the transparent resin layer (Α) will be deformed to absorb the influence of foreign matter, so that it does not damage the high-priced master. The glass transition temperature of the transparent resin is preferably 5 or more lower than that of the oxygen-containing polymer (1) and the gas-containing polymer (Π), and is more preferably (10). c or more. The glass transition temperature of the transparent resin is preferably 20 t or more. When the glass transition temperature of the transparent resin is _1 or more, the transparent resin layer (A) is not deformed when the master mold is separated from the surface layer (B), and the dimensional accuracy of the fine pattern is improved. When the translucent resin (4) is transferred to the Wenxian County thief, the transcription of the mother pattern reversal pattern can be performed at (10) temperature to make the dimensional accuracy of the fine pattern good, and it is not advantageous from the viewpoint of workability and productivity in 12 201005430. The transfer temperature of the transparent resin is preferably 40 ° C or more. • The glass transition temperature of the transparent resin is preferably 200 ° C or less from the viewpoint of the fluoropolymer (1) and the fluoropolymer (Π) which are difficult to transfer the glass to a temperature exceeding 200 °C. The glass transition temperature in the present invention can be determined by using a differential scanning calorimeter (DSC) and in accordance with JIS K7121. Further, the glass transition temperature in the present invention means the intermediate point glass transition temperature. Examples of the transparent resin include acrylic resin, polystyrene, acrylonitrile butadiene styrene resin (ABS), amorphous polyester, cycloolefin resin (c〇p), polytetrafluoroethylene (PTFE), and polybutylene. Difluoroethylene (PVDF), ethylene-tetrafluoroethylene-copolymer (ETFE), fluoroolefin-alkyl vinyl ether copolymer (FEVE), and oxime oxy-resin. When the transparent support (D) is provided, the transparent resin is preferably an acrylic resin or an amorphous styrene WEVE from the viewpoints of light transmittance, moldability, and pattern formability. The acrylic resin may, for example, be polymethyl methacrylate (ΡΜΜA). FEVE can be cited as Lumifu (made by Asahi Glass Co., Ltd.). The amorphous polyester is exemplified by Bayon (manufactured by Toyobo Co., Ltd.). When the transparent support (D) is not provided, the transparent resin is preferably an acrylic resin, a polystyrene or a COP, from the viewpoints of light transmittance, moldability, (4) formability, and heat recovery. The acrylic resin may, for example, be PMMA. C〇p is exemplified by ZEONEX (manufactured by Nippon Kasei Co., Ltd.). The transparent tree moon layer (A) (when the transparent support (9) is provided, the layer of the transparent resin layer (A) and the transparent support (9) is preferably: in the light of the 3〇〇~ lion fine wavelength region 13 201005430 domain In at least a part of the wavelength region, the light transmittance is 75% or more; and more preferably 85% or more. When the light transmittance is (4) or more, the photocurable resin can be efficiently cured in the method for producing a substrate having a transcribed fine pattern which will be described later. In particular, it is preferable that the light transmittance of 436 (the g-wavelength of the high-pressure mercury lamp) or 365 nm (the wavelength of the high-pressure mercury lamp) is 75% or more, and more preferably 85% or more. When the light transmittance of the wavelength 365 is 5% or more, the base (4) manufacturing method towel having a transcribed fine pattern described later can be used to efficiently cure the photocurable resin using a high pressure water. When the transparent support (D) is provided, the transparent resin precursor or the transparent resin solution may be applied to the (4) domain _) fine, and the 彡 明 明 resin layer (8). Further, the film of the transparent resin layer (4) and the transparent support (9) may be laminated to be joined. The transparent support is not provided (joining, the transparent resin is formed by the forming method, and the shape of the transparent resin layer (A) is formed, and the shape of the transparent resin layer (A) is transmitted to form a cut product (clear = support layer (9) laminated body) The shape may be flat (four sides: cylindrical or heterogeneous (4) (transparent, cylindrical, (eight) *=Γ) (when transparent support (D) is provided, it is a transparent tree fat layer, (two (9) When the shape of the laminated body is flat, the transparent tree is .5 Γ: preferably. 4_ or more, and preferably 15mi« or less, more preferably 〇5 to μ transparent resin layer. 5 If the thickness of the brain above, 8mm «T.) is 0.4 or more, the mold is not easy to be bent and the thickness of the 201005430 transparent transparent wax layer (A) is added _ below, the waste of the material is more than It is better to change weight and use.

»When the j-support (D) is again placed, the thickness of the transparent resin layer (4) should be within the range of 微 to ~1G times the maximum Π» degree of the micro pattern. - the thickness of the transparent resin layer (A) is smaller, the maximum height of the field pattern is smaller, and the transcription of the fine pattern may not be filled. The thickness of the resin layer (A) is 1 G times the maximum degree of the same pattern of the fine pattern. The glass transition temperature of the transparent resin layer (A) is low (10). When C is below), the dimensional stability of the 'fine graph # has deteriorated. The thickness of the transparent resin layer (4) can easily achieve both good transcription and good dimensional stability if it is within the range of 1 to 1 G times the maximum height of the fine pattern. The thickness of the transparent resin layer (8) is preferably in the range of 1, 5 times to 6 times the maximum height of the fine pattern. The functional group (8) is preferably a trans group, an epoxy group or an amine group. The functional group (X) may be a functional group derived from a transparent resin, or may be a functional group imparted to the surface of the transparent resin layer (A) by surface treatment for guiding the functional group (8). From the viewpoint of arbitrarily controlling the kind and amount of the functional group (X), it is preferable to be the latter's functional group. The surface treatment method for introducing the functional group (X) is preferably a method of surface-treating the transparent resin layer (A) with a silane coupling agent having a functional group (X); a method of surface treating a transparent resin layer (A); a method of surface treating the transparent resin layer (A) by graft polymerization; and a method of surface treating the transparent resin layer (A) by UV ozone treatment; A method of applying a primer having a functional group (X) to the transparent resin layer (A). The decane coupling agent having a functional group (X) is preferably the following compound. 15 201005430 Alkane-based decane coupling agent: aminopropyl triethoxy decane, aminopropyl decyl diethoxy oxalate, aminoethyl-aminopropyltrimethoxy oxetane, amine Ethylethyl-aminopropylmethyldimethoxydecane, and the like. A decane coupling agent having a cyclodecylethyl group: glycidoxypropyltrimethoxysilane, glycidoxypropylpropyldimethoxydecane, and the like. An intermediate layer (C) is formed on the surface of the transparent resin layer (A), whereby part or all of the functional group (X) forms a chemical bond with some or all of the reactive groups (y) of the fluoropolymer (II). . When a part of the functional group (χ) of the transparent resin layer (A) has formed a chemical bond, the transparent resin layer (Α) in the mold of the present invention has a functional group (X). On the other hand, when all the functional groups (8) of the transparent resin layer (?) have formed chemical bonding, the transparent resin layer (?) in the mold of the present invention does not have a fluorenyl group (X). In any case, the surface of the transparent resin layer (Α) after the formation of the intermediate layer (c) is chemically bonded by the official (8) and the reactive group (y)_red. The chemical bond may be, for example, a reactive group (y) which is a silk, and the functional group (8) is a sulfhydryl group via a sulfhydryl group; and a reactive field is a carboxyl group, and a guanamine bond at a functional amine group Wait. Therefore, in the mold of the present invention, the transparent resin layer () and the intermediate layer (C) are firmly adhered by chemical bonding. (surface layer (B)) surface layer (_^ main chain has a fluorinated fat ring structure does not have a lower ship base (like fluorinated shirt _ _ layer. or non:::: = family ring structure, polymer (1) is amorphous 16 201005430 The carbon skeleton which has a constituent ring of a fluorine-containing aliphatic cyclofluoroaliphatic ring in the main chain, and the carbon atom of the main chain in the polymer. One or more of the fluorine-containing lipids constitute a polymer. In addition to 'oxygen atoms and _ cut materials in addition to carbon atoms with two oxygen atoms of the fluorine-containing fat ring. Heart fluorine _ family ring should preferably have a number of 4~7. The atom of the aliphatic ring, the above-mentioned polymer is a ring-shaped single carbon atom ##ή ° when it is obtained, it constitutes the main chain

The above-mentioned polymer system is derived from a carbon atom of a polymerizable double bond, and the diuret is a single ring-breaking ring (four) material derived from four carbon atoms of two polymerizable double bonds. <Slave of the main chain of the main chain: a monomer having a fluorine-containing aliphatic ring and having a polymerizable double bond between the gas-containing lipid atoms and carbon atoms; or having a fluorine-containing aliphatic group The ring is a monomer having a polymerizable double bond between a carbon atom of the fluorine-containing aliphatic ring and a carbon atom other than the fluorine-containing aliphatic ring. The diene monosystem refers to a monomer having two polymerizable double bonds. In the cyclic monomer and the diene monomer, the ratio of the number of fluorine atoms bonded to the carbon atom is preferably relative to the total number of the SL atoms bonded to the carbon atom and the fluorine atom bonded to the carbon atom. It is 80% or more, and is preferably 1%. The cyclic monomer is preferably the compound (1) or the compound (2). 17 201005430 【化1】

3; x3 FC-CF 1 \ cf2 (2) 2 but 'X readings the atomic or carbon number (a) of the perfluorol group, Rl and R23 each independently represent a fluorine atom or a perfluorocarbon number of 1 to 6 carbon atoms The groups, X2 and X3 each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 9 carbon atoms. Specific examples of the compound (1) include, for example, the compounds (Μ) to (1_3). [Chemical 2]

OCF

Fp=CF FC=CF FC=C ' 〇V〇<>〇N; 0 F3 〇 Acf3 % Π-1) (1-2) (1-3) Specific examples of the compound (2) include, for example, a compound (2_i) ~ (2-2). [Chemical 3] cf3 f2C-CF2 f2c-cf v S; 0 CF2 cf2 (2-1) (2-2) 18 201005430 The diene monomer is preferably the compound (3). CF2 = CF-Q-CF = CF2 ---(3) However, Q represents a perfluoroalkylene group having 1 to 3 carbon atoms (which may also have an ether oxygen atom). In the case of a perfluoroalkylene group having an ether oxygen atom, an ether oxygen atom may be present at one terminal of the group, or may be present at both terminals of the group, or may be present between the carbon atoms of the group. From the viewpoint of cyclization polymerization, it is preferred to be present at one terminal of the group.

By the cyclization polymerization of the compound (3), a fluorine-containing polymer having one or more monomer units of the following formulas (r) can be obtained. 【化4】

Specific examples of the compound (3) include the compounds (3-1) to (3-9). Cf2 == CFOCF2CF = CF2 • • · (3_1); cf2 == cfocf(cf3)cf = cf2 • · · (3-2); cf2 == cfocf2cf2cf = cf2 • · · (3-3); 19 201005430 cf2 Cf2 cf2 cf2 cf2 2 . · · (3-4) CFOCF(CF3 )CF2 cf = CF CFOCF2CF(CF3)CF = CF2 . . . (3 5) CFOCF2 OCF = CF2 · · .(3-6); CFOC( CF3) 2OCF = CF2 . . . (3_7). CFCF2CF II CF2 · . . (3_8); CF2==CFCF2CF2CF = CF2 · · . (3-9).

From the viewpoint of the transparency of the fluoropolymer (I), in the fluorine-containing agglomerate (1), the ratio of the monomer unit having a money fat bicyclic structure to the all monomer unit (% by mole) It should be 2% or more of mol%, more preferably 4% by mole or more, and particularly preferably 100% by mole. The monomer unit having a fluorine-containing aliphatic ring structure means a monomer unit formed by polymerization of a cyclic monomer or a monomer unit formed by cyclization polymerization of a diene monomer.

The fluorine-containing compound (I) does not substantially have a reactive group (y). The fact that substantially no reactive group (y) means that the content of the reactive group (y) in the fluoropolymer (1) is below the detection limit. Further, the fluoropolymer (1) does not substantially have a reactive group other than the reactive group (y). The inherent viscosity of the fluoropolymer (I) is preferably ld.ldL/g to 1.0 dL/g. The intrinsic viscosity is related to the molecular weight of the fluoropolymer. If the intrinsic viscosity is 〇.ldL/g or more, it will become a fluoropolymer (I) having a high mechanical strength, so that the fine pattern is not easily damaged. When the intrinsic viscosity is 1. 〇dL/g or less, the fluidity of the fluoropolymer (I) becomes good when heated. Therefore, it becomes easy to form a fine pattern. The inherent viscosity of the fluoropolymer (1) is more preferably from 15 dL/g to 0.75 dL/g. The intrinsic viscosity in the present invention is the intrinsic viscosity measured in perfluoro(2-butyltetrahydrofuran) at 3 °C. The viscosity was measured using a Ubbel viscometer 20 201005430, (ubbelohde viscometer ‘capillary viscometer), and fine z was just performed. The fluoropolymer (1) is preferably a fluoropolymer having high transparency. The light transmittance of the fluorine-containing polymerization _ wavelength of 300 to 50 Å is preferably 9 (four) or more. The light penetration rate is the thickness of the light-containing compound (1). The glass transition temperature of the polymer (1) should be above the thief. If the glass-filling temperature of the polymer (1) is more than €, the master mold is removed from the surface layer (b). (4) The dimensional accuracy of the fine pattern is improved. The material is transcribed to the photohardening of the obtained mold. In the process of the resin (four), the shape of the fluoropolymer (1) is maintained to make the dimensional accuracy of the pattern become H. When the flaky temperature of the fluoropolymer (1) is not reached, the flipping pattern of the master mold can be performed at a low temperature. Transcription to make a fine map; #的尺寸 fine money is good, but in terms of workability and productivity, it is better than J Ke. The surface transfer temperature of the fluoropolymer (1) is more preferably a thief or more, and more preferably 70 ° C or more. From the difficulty of synthesis (four) transfer temperature exceeds ·. The fluoropolymer of c (1) ❹ The point of view of the gas-containing polymer (I) is preferably a glass transition temperature of S200T: below, and more preferably 150. (The following. The fluoropolymer (I) can be obtained by a conventional method. For example, a fluoropolymer (P) having a fluorinated aliphatic ring structure in the main chain or a reactive group can be obtained by the method described later ( After the fluoropolymer (II) of y), the fluoropolymer (P) ' or the fluoropolymer (II) is contacted with fluorine gas, whereby substantially no reactive group (y) can be obtained. Fluoropolymer (J) The thickness of the surface layer (B) is preferably 〇2μηη or more. If the thickness of the surface layer is 〇.2μηι or more 'in the flip pattern of the transcription master mold, 'pin holes do not occur, etc. 21 201005430 The surface layer (B) preferably has a thickness of 0_5 μm or more, and more preferably Ιμπι or more. The thickness of the surface layer (Β) is preferably ΐ5 μηι or less. The thickness of the surface layer (9) is 15 μm or less. The film having a uniform thickness can be formed by coating. The thickness of the surface layer (Β) is preferably 1 〇μΙη or less, and more preferably 5 μηη or less. The thickness of the surface layer (Β) is before the formation of the fine pattern. The thickness of the surface layer (Β) of the mold precursor. (Intermediate layer (C)). Intermediate layer (c) - a layer composed of a fluoropolymer (11), and the polymer (II) main chain has a fluorinated aliphatic ring structure, and the reactive group (y) which is reactive as the above (X) The fluoropolymer (11) having a primary structure having a ruin-containing aliphatic ring structure is an amorphous or amorphous polymer. The fluoropolymer (II) has a reactive fluoropolymer (II) in addition to the fluoropolymer ( I) is the same polymer.

From the viewpoint that the intermediate layer (C) and the surface layer (B) can be more firmly adhered to make the mold durable, the monomer unit having a fluorine-containing aliphatic ring Q structure in the fluorine-containing polymer (1) and the fluorine-containing polymerization are obtained. The monomer unit having a fluorinated aliphatic ring structure in _) is preferably the same monomer unit. From the viewpoint of the transparency of the fluoropolymer (I), in the fluoropolymer (II), the ratio of the monomer unit having the structure of the fraternal bribe is relative to the total monomer unit (%) Preferably, it is more than (%) ear% or more, and particularly preferably 100% by mole. The fluoropolymer (11) has a reactive group (y). The type of the reactive group (y) 22 201005430 can be appropriately selected depending on the type of the functional group (X). When the functional group (X) is a hydroxyl group, an epoxy group or an amine group, the reactive group (y) is preferably a carboxyl group, a hydroxyl group, a decyl group or a derivative thereof. The reactive group (y) is particularly preferably a carboxyl group from the viewpoint of high reactivity with an epoxy group or an amine group and easy formation of a stable bond. Further, when the functional group (X) is a trans-group, it is preferably a decyl group or an alkoxyalkyl group having 1 to 4 carbons from the viewpoint that a stable bond can be easily formed. It is preferable to confirm the presence or absence of a reactive group (y) by an infrared spectrum. In addition, it is necessary to quantify the average number of reactive groups of 1 to 6 carbon atoms using the method described in JP-A-60-240713. The inherent viscosity of the fluorine-containing polymer (II) is preferably from 0.1 dL/g to 1.0 dL/g. The intrinsic viscosity is related to the molecular weight of the fluoropolymer. Let the intrinsic viscosity be 0.ldL/g~l.〇dL/g, whereby the affinity with the fluoropolymer (I) can be improved, and between the surface layer (B) and the intermediate layer (C) Good adhesion can be obtained. The intrinsic viscosity of the polymer (II) is preferably from 0.15 dL/g to 0.75 dL/g. The fluoropolymer (II) is preferably a transparent fluoropolymer. The light transmittance of light having a wavelength of 300 to 500 nm of the fluorine-containing polymerization parameter (π) is preferably 90% or more. The light transmittance is the light transmittance of the fluoropolymer (π) having a thickness of ΙΟΟμηι. The fluoropolymer (II) can be obtained by a conventional method. For example, in the presence of a hydrocarbon-based radical polymerization initiator, a diene monomer or a cyclic monomer is polymerized to obtain a fluoropolymer (Ρ) having a fluorinated aliphatic ring structure in a main chain, followed by. The fluoropolymer (11) having a reactive group (y) as a carboxyl group can be obtained by subjecting the fluoropolymer (ρ) to heat treatment in a milky atmosphere and then impregnating it in water. The retinoyl group of the fluoropolymer (II) having a carboxyl group is made into a retinoic acid vinegar according to the method described in Japanese Patent Application Laid-Open No. Hei 4-226177, and the reductive methyl ester of 2010-0430 is provided. The amine group or the epoxy ethyl decane coupling agent reacts to form a brewing amine bond 'by thereby obtaining a fluoropolymer (1) having a reactive group (y) which is a sterol group. The carboxyl group of the fluoropolymer having a carboxyl group is reduced, whereby a fluoropolymer (11) having a reactive group (y) as a hydroxyl group can be obtained. The thickness of the intermediate layer (C) is preferably from 5 nm to 2000 nm. If the thickness of the intermediate layer (c) is 5 mn or more, a uniform film can be formed, and a high adhesion can be obtained. If the thickness of the intermediate layer (c) is 2000 nm or less, material waste is less. The intermediate layer (the thickness of the tantalum is more preferably from 10 nm to 100 nm, and more preferably from 20 to 500 nm. The thickness of the intermediate layer (C) is the thickness of the intermediate layer (C) of the mold precursor before the formation of the fine pattern. (Transparent Support (D)) The transparent resin layer (A) should be supported by the transparent support (D). The Mooncake layer (A) is supported by the transparent support (D), and the transcription pattern of the master mold is reversed. The bending of the transparent resin layer (4) is suppressed, and the option of a transparent resin as a material of the transparent resin layer (A) is increased.

The heat distortion temperature of the transparent support (D) is preferably i 〇〇 ° c or more, more preferably j 12 〇 C or more. When the heat-resistant temperature of the transparent support (D) is 1 Torr (when the shape of the transparent resin layer (A) is maintained at rc or more, the workability is $, and when the transfer master mold is reversed, the dimensional stability is good. A. The transcriptional reversal pattern is not particularly limited. The heat distortion temperature of the transparent support (D) is not particularly limited. The thermal deformation temperature of inorganic materials such as sloping enamel may exceed 300. (: transparent support 〇)&gt;. The heat distortion temperature in the present invention is measured under the load condition according to ASTM D648 at 1.82 MPa 24 201005430. The material of the transparent support (D) may be, for example, an inorganic material (quartz, glass, light transmissive, etc.) and a transparent resin. (Polycarbonate (PC), polyethylene terephthalate-Sa (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), lanthanide polyester, C 〇P, polyarylate (__ pull, pAR), aromatic poly (tetra) lys (PEEK), aromatic (four) barrier (pES), (four) fragrant poly _, fluororesin, Wei resin, propylene riding resin, epoxy Resin and resin φ, etc.) From the viewpoints of light transmittance, formability and heat resistance, it is preferably quartz or glass. PC and COP. (Manufacturing method of the mold) The method for producing a mold according to the present invention includes the following steps: M1, the following step M2, the following step M3, and the following method of the elbow 4. ^Step M1 On the surface side of the transparent resin layer (A) having a functional group (X) on the surface, a solution in which a fluoropolymer (π) is dissolved in a fluorine-containing solvent is applied, followed by drying to remove the fluorine-containing solvent, Further, the inter-wicking layer (C) composed of the fluoropolymer (H) is formed on the surface side of the transparent resin layer (A) having the functional group (8) on the surface. Step M2·· on the surface of the intermediate layer (C) The side coating is a solution in which a fluorine-containing solvent is dissolved in the fluorine-containing polymer (I), followed by drying to remove the fluorine-containing solvent to form a surface layer composed of the fluorine-containing polymer (1) on the surface of the intermediate layer (C) ( B), made, the mold precursor. Step M3: the flip pattern of the surface having a fine pattern of the flip pattern and the flip pattern having a maximum height exceeding the thickness of the surface layer (B) and the total thickness of the intermediate layer (c) , at least one of the mold precursor and the master mold is 25 201005430 fluoropolymer (I) When the fluoropolymer (II) has a glass transition temperature or higher, it is pressed from the surface layer (B) side of the mold precursor, and across the surface layer (B), the intermediate layer (C), and the transparent resin layer ( A) A fine pattern is formed to obtain a mold of the present invention. Step M4: After cooling the mold and the master mold to a temperature below the glass transition temperature of the fluoropolymer (1) and the fluoropolymer (II), the mold is separated from the master mold. The dry dance in the step M1 is carried out at a temperature at which a part or all of the functional group (X) of the transparent resin layer (A) and a part or all of the reactive groups of the fluoropolymer (Π) form a chemical bond. The drying temperature is usually above 10 °C. The drying temperature in the step M2 is preferably at least the glass transition temperature of the fluoropolymer (II) and above the glass transition temperature of the fluoropolymer (I). The intermediate layer (C) and the surface layer (B) can be adhered with high strength by drying at this temperature. In the step M3, at least one of the mold precursor and the master mold is heated to a temperature higher than the glass transition temperature of the fluoropolymer (I) and the fluoropolymer (II). When the heating temperature is equal to or higher than the glass transition temperature of the fluoropolymer (1) and the fluoropolymer (II), the flip pattern of the master mold can be transcribed with high precision. The heating temperature is preferably higher than the glass transition temperature of the fluoropolymer (I) and the fluoropolymer (π) by 1 (rc or more. The heating temperature is preferably 250 ° C or less, more preferably 220 ° C or less. Above 250 ° C, the chemical bond based on the functional group (X) and the reactive group (y) is destroyed, and there is a peeling between the transparent resin layer (A) and the intermediate layer (C). In M3, even when the heating temperature of the mold such as the drive and the master mold does not reach the glass transition temperature of the fluoropolymer (1) and the fluoropolymer (π), as long as the heating temperature is the glass transition of the transparent resin layer (Α) Above the temperature, 26 201005430 can transcribe the pattern, but there will be a pattern shape that cannot be correctly transcribed, a region where the pattern is not transcribed, and a thick chain on the surface of the pattern. Step +3+ 'The temperature of the mold precursor and the master mold is higher than that of the transparent resin. When the glass transition temperature of f(A) is lower, the pattern will not be transcribed. The mold of the present invention described above is an intermediate layer composed of a transparent resin layer (Α) and a fluoropolymer (II). And the composition of (4) compound (1). Self-mixed) Laminate, having a height light penetration. Further, the mold of the present invention has the same degree of film release property as a layer of the fluoropolymer (I) because the surface layer (Β) is a layer of the fluoropolymer (I). In addition, 'there is no need to apply a release agent, and it has high precision, and the "pattern" is not easily contaminated by the release agent even if it is used repeatedly. η In addition, the transparent resin layer (Α) of the mold of the present invention is formed. The glass transition temperature of the transparent resin is below the glass transition temperature of the m-containing (1) and (tetra)-containing compound (II). Therefore, even the maximum height of the fine pattern (including the maximum height difference of the concave-convex structure of the mold ❹ (4) f curve) When the thickness of the surface layer (8) and the thickness of the intermediate layer (C) exceed the total thickness of the intermediate layer (C), the transparent resin layer (A) is deformed to follow the concave-convex structure of the inverted pattern and the overall bending of the master mold. The fine pattern is formed accurately across the surface layer (B), the intermediate layer (C), and the transparent resin layer (A). Further, when the master mold is pressed, even if the master mold is mixed with the 'surface layer (B) The foreign matter particles and the H transparent resin layer (A) are deformed without damaging the expensive master mold. <Method for Producing Substrate Having Transcribed Fine Pattern> The method for producing a substrate having a transcription fine pattern of the present invention can be List 27 201005430 as follows The method (a) to (c). The method (4): The method of the following steps (al) to (a-4): (a-Ι) The step of disposing the photocurable resin 20 on the surface of the substrate 30. -2) As shown in Fig. 2, the mold 10 is pressed against the photocurable resin 20 so that the fine pattern 18 of the mold 10 is in contact with the photocurable resin 20 (a-3). In the state in which the photocurable resin 20 is pressed against the photocurable resin 20, the photocurable resin 20 is irradiated with light to cure the photocurable resin 20 to produce a cured product. (a-4) Step of separating the mold 10 from the cured product Method: The method of the following steps (b-Ι) to (b-4): (b-Ι) The step of disposing the photocurable resin 20 on the surface of the fine pattern 18 of the mold 1 (b-2) As shown in Fig. 3, the substrate 30 is pressed against the photocurable resin 20 on the surface of the mold 10. (b-3) In the state where the substrate 30 is pressed to the photocurable resin 20, the light is applied. The curable resin 20 is irradiated with light to cure the photocurable resin 2 to produce a cured product. (b-4) A step of separating the mold 10 from the cured product. Method (c): has the following steps (c- 1) The method of (c-4) (c-1) the substrate 30 and The step of making the micro-28 201005430 fine pattern 18 of the mold 10 close to or in contact with the mold 10 is the step of the substrate 30. (c-2) As shown in Fig. 4, the photocurable resin 2 is filled on the substrate. (c-3) The photocurable resin 20 is irradiated with light to cure the photocurable resin 2 in a state in which the substrate 30 is in close contact with or in contact with the mold 10, and the photocurable resin is cured. Step of curing the cured material (c-4) Step of separating the mold 10 from the cured product. The photocurable resin is a resin which is cured by light irradiation to form a cured product. The photocurable resin is preferably a photocurable resin containing a polymerizable compound and a photopolymerization initiator. The polymerizable compound is a compound having a polymerizable group, and examples thereof include a polymerizable monomer, a polymerizable polymer, and a polymerizable polymer. The photopolymerization initiator refers to a photopolymerization initiator which causes a radical reaction or an ionic reaction due to light. Light irradiation is usually performed from the side of the mold 10. When the light transmittance of the substrate 30 is high, light irradiation can be performed from the side of the substrate 30. The wavelength of light in the light irradiation only needs to be a wavelength range in which the mold system of the present invention has high light transmittance. From the viewpoint of curing the general photocurable resin at a low temperature, the wavelength of light in the light irradiation is particularly preferably the g line (wavelength 436 nm) or the i line (wavelength 365 nm) of the high pressure mercury lamp. Since the transparent resin layer (A) is inferior in light resistance to quartz or glass, the light in the light irradiation should preferably not contain light having a wavelength of less than 300 nm, and preferably does not contain light of less than 350 nm. When the light of wavelength less than 3〇〇nm is not included, it is not easy to cause transparent tree. 29 201005430 The lipid layer (A) is yellow or embrittled, and the mold can be used for a longer period of time. In each of the steps (a) to (c), the system temperature is preferably below the glass transition temperature of the fluoropolymer (1). The substrate having a transcribed fine pattern produced by the production method of the present invention has a transcribed fine pattern composed of a cured product of a photocurable resin on the surface of the substrate. The transcribed fine pattern is a fine pattern in which the fine pattern of the mold of the present invention is inverted. The transcribed fine pattern is preferably a structure having a concavo-convex structure composed of a cured photocurable resin (hereinafter also referred to as a concavo-convex structure). The concavo-convex structure © may have a layer structure composed of a continuous object having a concavo-convex shape on the surface, and may have a structure composed of a collection of independent protrusions. The former is a structure in which a layer of a photocurable resin cured material covering the surface of the substrate is formed, and the surface of the layer of the photocurable resin cured product has a concavo-convex shape. The latter means that the projections composed of the cured film of the photocurable resin are mostly independently present on the surface of the substrate, and have a structure in which the concave portion formed by the surface of the substrate together exhibits a concavo-convex shape. In either case, the convex structure portion (protrusion) is composed of a photocurable resin cured product. Further, the concavo-convex structure may have a structure having the above two structures at different positions on the surface of the substrate. Examples of the substrate having a transcribed fine pattern include a semiconductor element, a recording medium, a MEMS, a biotechnology-related member, and an optical member. Specific examples of the MEMS, the biotechnological related component, and the optical component are as follows. Printing head, HDD head, high frequency switch, vibrator for vibrator, optical switch for optical communication, optical scanner, electronic paper, digital mirror device, microphone, 30 201005430 • Pressure sensor, tactile sensor, Inertial sensors, acceleration sensors, gyroscope sensors, biosensors, microvalve, microfluidics, DNA analysis wafers, protein analysis wafers, blood detection wafers, active catheters, drug delivery systems , chemical sensors, prism sheets, micro mirror arrays and optical waveguides. According to the method for producing a substrate having a transcribed fine pattern of the present invention described above, it is possible to transcribe a fine pattern φ of a mold with high precision and high productivity, and to form a transcribed fine pattern having a relatively large maximum height. EXAMPLES The following examples are given to illustrate the invention, but the invention is not limited to the examples. Examples 6 to 8, 12 to 14 are examples, and examples 4, 5, 9, 10, and 15 are comparative examples. ^ (Intrinsic Viscosity) The intrinsic viscosity of 3 fluoropolymers is the use of glass Ubbelite at 3 〇. The test is carried out in perfluoro(2-butyltetrahydrofuran). Ref. (Infrared Absorption Spectrum) The infrared absorption spectrum of the 3 fluoropolymer was measured using a Fourier transform infrared spectrometer (manufactured by Nikolet, 20DXC). (Glass transfer temperature) The glass transition temperature of the transparent resin and the fluoropolymer was measured using a differential sweeper - a seven-field pyrolyzer (manufactured by Bruker Axs, DSC31(R)) under the conditions of a heating rate of Cong/knife. Further, the glass transition temperature was measured in accordance with jis K7121: 1987, and the glass transition temperature between the towels was changed to the glass transition temperature. 31 201005430 (Heat Deformation Temperature) The heat distortion temperature of the transparent resin was measured under a load of 182 MPa using a heat distortion tester (Heat Distortion Tester, manufactured by Nishida Seiki Co., Ltd., HD_pc) according to ASTM D648'. - (Light transmittance) The film of the transparent resin layer (A), or the polar (10) transmittance of the laminate of the transparent resin layer (4) and the transparent support (D), and the 365 biliary penetration enthalpy and the gas-containing polymer film The light transmittance of the light of the wavelength of 3 GG to 5 GGnm was measured using a spectrophotometer (U-41 制, manufactured by Hitachi High-Technologies Corporation). © (thickness) The thickness of the surface layer (B) and the intermediate layer (C) was measured using an optical interference type film thickness measuring device (manufactured by Hamamatsu Hernix Co., Ltd., cl〇178). The refractive index of the fluoropolymer (1-1), the fluoropolymer (II-1) and the fluoropolymer (11_2) is respectively 1.34 〇 (maximum height). The height was obtained by a contour measurement using a conjugated-focus laser microscope (VK-9500, manufactured by Koshihiko Co., Ltd.). In the case of the ν groove 〇 pattern, the contour in the vertical direction with respect to the groove is measured, and in the case of the cylindrical pattern, the contour on the line passing through the center of the cylinder is measured. Specifically, the color ultra-depth observation is performed under the conditions of a lens magnification of 50 times, an optical zoom of 丨, and a measurement pitch of μ5 μm, and after the surface tilt correction (automatic) is performed, the contour in the range of 200 μm is obtained, and then The maximum height difference between the highest peak line and the lowest bottom line of the concave-convex structure. [Example 1] 32 201005430 Production of fluoropolymer (pi): 1 g of compound (3-3), 0.5 g of methanol, and 0.7 g of compound (4-1) were added to an autoclave (made of pressure-resistant glass). The polymerization of the compound (3-3) was carried out by a suspension polymerization method to obtain a fluoropolymer (P-1). The fluoropolymer (P-1) is a polymer composed of a monomer unit represented by the following formula (α-1). The intrinsic viscosity of the fluoropolymer (pq) was 0.34 dL/g. The glass transition temperature of the fluoropolymer (pq) is 1〇8. (:. ❹ CF2=CF〇CF2CF2CF = CF2 . . . (3-3); ((CH3)2CH〇CO〇) 2 · · .(4-1).

(α-1) Manufacture of a polymer composed of a monomer unit represented by the above formula (α -1) and having a terminal of _cF3 (hereinafter referred to as fluoropolymer (1-1)): 3 gas polymer (P·1) 襄人热压蚤 (nickel, internal volume 1L), and then replaced with H/ 礼乳 3 times in hot pressure dad, decompression to 4.0kPa (absolute pressure) will After the industry and money are diluted to 14% by volume, the pressure of the person is reduced to 101.3 kPa, and the internal temperature of the I is maintained at 230 ° C for 6 hours. The fluoropolymer (1-1) was obtained by recovering the grain in the autoclave. When the fluoropolymer (1-1) ^ line absorption spectrum was measured, the peak due to the carboxyl group was not confirmed. The chaotic polymer *' was processed into a thickness of ΙΟΟμπι, and the light transmittance of light having a wavelength of 33 201005430 300 to 500 nm was measured, and as a result, it was 95% or more. The glass transition temperature of the fluorine-containing polymer (μ) was 108 〇c. The inherent degree of the fluoropolymer (11) was 0.33 dL/g. Preparation of a fluoropolymer (solution composition of Ι-D (hereinafter referred to as a solution composition): A perfluorotributylamine solution containing 9 mass% of a fluoropolymer (1_1} was prepared as a membrane filter ( The pore size: 0·2 μΓη, manufactured by PTFE) was filtered to obtain a solution composition 1. [Example 3] A polymer composed of a monomer unit represented by the above formula (α-l) and terminally a reactive group (y) (Fluorinated) fluoropolymer (hereinafter referred to as fluoropolymer (11_1}): The fluoropolymer (P-1) is placed in a hot air circulating furnace at atmospheric pressure and heat treated at 300 ° C After 1 hour, it was immersed in ultrapure water for 1 week at ll 〇 °c and then dried in a vacuum dryer for 24 hours under a loot: to obtain a polymer II-containing (II-1). The infrared absorption spectrum of the substance (II-1) was confirmed to be a peak derived from a ruthenium at 1810 cm-1. The fluoropolymer (II-1) was processed into a film having a thickness of ΙΟΟμηι, and light having a wavelength of 300 to 500 nm was measured. The light transmittance is 93% or more. The glass transition temperature of the fluoropolymer (Π-1) is 108 ° C. The solid content of the fluoropolymer (Π-1) The viscosity is 〇.34 dL/g. Preparation of a solution composition containing a fluoropolymer (II-1) (hereinafter referred to as solution composition 2): A fluoropolymer (II-1) containing 1% by mass is prepared. Perfluorotributylamine 201005430 Solution 'The solution was filtered with a membrane filter (pore size: 〇·2μηι, PTFE) to obtain a solution composition 2. [Example 4] . Mold manufacturing: Preparation of a PC sheet (longitudinal 40 mm x horizontal 40 mm x thick) 0.5 mm) as the transparent resin layer (A). The physical properties of the transparent resin layer are shown in Table 1. 'A mixed solvent of ethyl acetate/2-propanol (5/9 by mass) will have an oxirane The primer (manufactured by Shin-Etsu Chemical Co., Ltd., FS-10) was diluted to 20 times to prepare a primer coating liquid. The primer coating liquid was applied onto the surface of the transparent resin layer (A) by spin coating. The film was heated and dried at 100 Torr for 3 minutes in a nitrogen stream to carry out a surface treatment for introducing an epoxy group onto the surface of the transparent resin layer (A). Next, the solution composition 2 was applied to the transparent resin layer by spin coating ( A) The surface-treated surface was heated and dried at 11 °C for 2 hours to volatilize perfluorotributylamine in solution composition 2. The epoxy ethyl group on the surface of the transparent resin layer (A) is chemically bonded to the rebel group of the disordered polymer (II-1) to form an intermediate layer (c) composed of the fluorine-containing cerium polymer (II-1). (thickness: 〇_1μιη). Next, the solution composition 1 was applied to the surface of the intermediate layer (c) by spin coating, and dried by heating at 110 ° C for 4 hours to make the solution composition fluorinated. The butylamine volatilizes to form the surface layer (B) to obtain a mold precursor. The total thickness of the surface layer (B) and the thickness of the intermediate layer (C) is ι.3 μηι. Prepare a nickel master mold having a depth (maximum height of 1 〇μπι, pitch: 2 screaming, bevel angle: 45 degrees, and a fine pattern of V grooves) as a wedge. ',,, and heat the master mold to Pressing at 160 ° C from the side of the mold precursor surface (B) for 35 minutes at 35 201005430 3 MPa (absolute pressure). After the temperature of the master mold and the mold precursor is less than 5 ° C, the master mold is driven from the mold. The object is separated to obtain a mold in which a transparent resin layer (A), an intermediate layer (C), and a surface layer (B) are formed and a fine pattern is formed across the surface layer (B) and the intermediate layer (C). The maximum height of the pattern is 9·8 μm. It is observed that the mold has a certain curvature. Further, the transparent resin layer is exposed at the bottom of the fine pattern of the mold. Fabrication of a substrate having a transcribed fine pattern: a photocurable resin ( Nippon Glass Co., Ltd., NIF-A-1) is applied to the surface of the fine pattern of the mold, and the wafer is pressed from above to bond with the photocurable resin. The ultraviolet light is irradiated from the mold side (wavelength: 365 nm, illumination: 50 mW) /cm2) 30 seconds' hardens the photocurable resin. Then, In order to separate the mold, the mold cannot be separated from the wafer. [Example 5] r Mold manufacturing: ~ A PMMA sheet (4 mm mm x 40 mm x thickness 1.8 mm) was prepared as the transparent resin layer (A). The physical properties of the transparent resin layer (A) are shown in Table 1. The same procedure as in Example 4 was carried out except that the transparent resin layer (A) was replaced with a PC sheet using a PMMA sheet and the heating temperature of the master mold was 130 °C. A mold comprising a transparent resin layer (A), an intermediate layer (C) and a surface layer (B), and having a fine pattern formed across the surface layer (B) and the intermediate layer (C). The maximum height of the fine pattern is In addition, the transparent resin layer (A) is exposed to the bottom of the fine pattern of the mold. - Fabrication of a substrate having a transcribed fine pattern: Photocurable resin (made by Asahi Glass Co., Ltd., MF- Ai) Applying on the mold 36 201005430 Fine pattern surface, pressing the wafer from above to contact the photocurable resin. Irradiation from the mold side (wavelength · · 3 6 5 nm, illuminance: 50 mW / cm 2 ) 3 〇. Second, the photocurable resin is hardened. Then, although the mold is to be divided However, the mold cannot be separated from the tantalum wafer. [Example 6] Mold manufacturing: Prepare PMMA sheet (vertical 40 mm x horizontal 40 mm x thickness 1.8 mm) with a lower glass transition temperature than the PMMA sheet used in Example 5 as a transparent Resin layer (A) The physical properties of the transparent resin layer (A) are shown in Table 2. In addition to the transparent resin layer (A), a PMMA sheet was used instead of the PC sheet, and the master mold heating temperature was 120. In the same manner as in Example 4, the transparent resin layer (A), the intermediate layer (C), and the surface layer (B) were formed, and the surface layer (B) and the intermediate layer (the ruthenium and the transparent resin layer were formed finely). The mold of the pattern. The maximum height of the fine pattern is 1 〇.Qpm. A number of bends were observed in the mold. Production of a substrate having a transcribed fine pattern: A photocurable resin (Asahi Glass, manufactured by Asahi Glass Co., Ltd.) is applied to the surface of the fine pattern of the mold, and the wafer is directly pressed from above to form a photocurable resin. Pick up. Ultraviolet rays (wavelength: 365 nm, illuminance: 50 mW/cm 2 ) were irradiated from the mold side for 30 seconds to cure the photocurable resin. Next, the mold was separated from the Shishi wafer, and the tantalum wafer having the transcribed fine pattern composed of the photocurable _cured material was formed on the surface. The result of observing the fine pattern of transcription was observed by a laser microscope (manufactured by Kwai Kasei Co., Ltd.), and the fine pattern of the master mold was reproduced. 37 201005430 [Example 7] Manufacture of a mold: FEVE (manufactured by Asahi Glass Co., Ltd., amil. LF71 〇F) was dissolved in toluene to obtain 30 mass. /. , made into a coating liquid. Using a applicator, the coating liquid was applied to a transparent support (D) (soda lime glass plate 'thickness: 1.30 mm 'heat distortion temperature: 3 〇〇 ° c or more') and dried under (10) force 2 The transparent resin layer (A) was formed in an hour. The thickness of the transparent resin layer (A) was measured by a micrometer and found to be 3 μm. The physical properties of the transparent resin layer (A) and the transparent support (D) are shown in Table 2. © In addition to using a glass plate on which a transparent resin layer (F) composed of FEVE is formed, in place of the pc sheet, and the heating temperature of the master mold is 12 (except for rc, the transparent support is produced in the same manner as in Example 4) D), the transparent resin layer (a), the intermediate layer (C), and the surface layer (B) are formed, and finely formed across the surface layer (B), the intermediate layer (c), and the 'transparent resin layer (A) The mold of the pattern. The maximum height of the fine pattern is 9·9 μηι. The laser microscope image of the mold is shown in Fig. 5. No bending is observed in the mold. Fabrication of substrate with transcriptional fine pattern: Except for use example 7 The surface was made to have a surface hardened by a photocurable resin in the same manner as in Example 6 except that the mold was replaced with the mold of Example 6. A fine wafer in which a fine pattern is transcribed. The fine pattern of the master mold is reproduced by a laser microscope. _ [Example 8] Manufacture of a mold: 38 201005430 FEVE of transparent resin (Asako Glass Co., Ltd. The product was prepared by dissolving in toluene to 30% by mass to prepare a coating liquid. The coating liquid was applied to a transparent support (d) (soda lime glass using an applicator' Plate, thickness: 1.3 〇 mm, heat distortion temperature: 3 〇〇 t or more), dried at ι〇η:τ for 2 hours to form a transparent resin layer (A). The transparent resin layer (4) was measured by a micrometer (micr_ter) The thickness was 3 () handsome. The physical properties of the New Zealand layer (8) and the transparent support (D) are shown in Table 2. The surface of the transparent resin layer (A) was hydrophilized (nitrogen plasma treatment) in advance. Hydrophilization The treatment was carried out under the conditions of a nitrogen flow rate: 2 〇 sccm, a pressure: he, an output of 8 〇 W, and a treatment time of 1 minute using a reactive ion etching apparatus ("RIE-10NR" manufactured by Saku Co., Ltd.). Coating method, containing 0.5% by mass of an amine-based stone kiwi noodle mixture (Shinoshi Chemical Industry Co., Ltd., &amp; 8匕903) and a 5 mass% water ethanol solution were applied to the surface of the transparent resin layer (A). After the transparent resin layer (A) was washed with water, it was dried by heating at 3 GGC in a nitrogen stream. The surface treatment of introducing the amine group derived from the kiln-baked dough mixture into the surface of the transparent resin layer (A) is carried out. Next, the solution composition 2 is applied onto the surface-treated surface of the transparent resin layer (A) by spin coating. The mixture was dried by heating at 11 G C for 2 hours to volatilize perfluorodibutylamine in the solution composition 2. At the same time, the amine group on the surface of the transparent resin layer was chemically bonded to the carboxyl group of the fluoropolymer (II-1). An intermediate layer (C) (thickness: 〇10 μmη) composed of the fluoropolymer (II-1) was formed. Next, the solution composition is applied onto the surface of the intermediate layer (c) by spin coating, and dried by heating at ll ° C for 4 hours to volatilize perfluorotributylamine in the solution composition to form a surface layer. (B), a mold precursor is produced. The thickness of the surface layer 39 201005430 and the thickness of the intermediate layer (C) are! 25 years old. A fine pattern was formed in the same manner as in Example 4 except that the mold precursor was used, and the resultant was composed of a transparent resin layer (8), an intermediate layer (c), and a surface layer (9), and straddle the surface layer (B) and the intermediate layer ( C) and the (10) lipid layer (4) are formed with a fine pattern of the mold. The maximum height of the fine pattern is qing. No bending was observed in the mold. Fabrication of a substrate having a transcribed fine pattern: A ruthenium wafer having a pdf-structured fine pattern embossed by a hardened enamel cured material was produced in the same manner as in Example 6 except that the mold of Example 8 was used instead of the mold of Example 6. . As a result of observing the transcribed fine pattern by a laser microscope, the fine pattern of the mother chess has been reproduced. [Example 9] Production of a mold: The same procedure as in Example 7 was carried out except that the epoxy group was not introduced into the surface of the transparent resin layer (A), and when the master mold was separated from the mold, the permeation layer (A) was Peeling occurred between the intermediate layers (C). [Example 10] Production of a mold: When the intermediate layer (C) was formed, the same procedure as in Example 8 was carried out except that the solution composition 1 was used instead of the solution composition 2. As a result, when the master mold was separated from the mold, the transparent resin was used. Peeling occurs between layer (A) and the intermediate layer. [Example 11] A polymer composed of a monomer unit of the above formula (α-1) and terminally a fluoropolymer of a reactivity 40 201005430 (y) (nonanol (alkoxyalkyl)) Hereinafter, the production of the gas-containing polymer (II-2)) is as follows: • The carboxyl group of the fluoropolymer (II-1) obtained in Example 3 is esterified to form -COOCH3. O.lg 7*-aminopropyltrimethoxy decane was added to a solution in which 3.5 g of the polymer was dissolved in 46_5 g of perfluoro(2-butyltetrahydrofuran). It was replaced with nitrogen in the system and stirred at room temperature for 3 hours to obtain a gas-containing polymer (Π-2). The infrared absorption spectrum of the fluoropolymer (II-2) was measured, and the φ was not present in the ISOOcm.1 absorption of -COOCH3 of the original polymer, and the absorption of -CONH- was confirmed to be 1730 cm·1. The fluoropolymer (11_2) was processed into a film having a thickness of 100 μm. The light transmittance of light having a wavelength of 300 to 5 nm was measured and found to be 92% or more. The glass transition temperature of the fluoropolymer (Π-2) was 108 °C. The intrinsic viscosity of the fluoropolymer (II-2) was 〇32 dL/g. • Preparation of a solution composition containing fluoropolymer (II-2) (hereinafter referred to as solution composition • 3): Preparation of perfluorotributylamine containing 1% by mass of fluoropolymer (II-2) The solution was filtered through a membrane filter (pore size: 〇·2 μm, PTFE) to obtain a solution composition 3. [Example 12] Manufacture of a mold: 'Amorphous polyester of a transparent resin (manufactured by Toyobo Co., Ltd., Benelux) was dissolved in cyclohexanone to 30% by mass to prepare a coating liquid. The coating liquid was applied to a transparent support (D) (soda lime glass plate, thickness: 1.30 mm 'heat distortion temperature: 300 ° C or more) using an applicator to dry at 150 ° C for 2 hours to form a transparent Resin layer (A). The thickness of the transparent resin layer was measured by a micrometer 41 201005430 degrees, and the result was 30 μm. The physical properties of the transparent resin layer (A) and the transparent support (D) are shown in Table 2. The surface of the transparent resin layer (A) was previously subjected to a hydrophilization treatment (nitrogen plasma treatment). The hydrophilization treatment was carried out under the conditions of a flow rate of oxygen: 50 sccm, a pressure: i〇pa, an output of 100 W, and a treatment time of 10 seconds using a reactive ion remanufacturing device (manufactured by Sasaki Co., Ltd., RIE-10NR). By this treatment, the surface of the transparent resin layer (A) has been introduced into the warp group. Next, the solution composition 3 was applied onto the surface-treated surface of the transparent resin layer (a) by spin coating, and dried by heating under litre for 2 hours to volatilize perfluorotributylamine in the solution composition 3. At the same time, the hydroxyl group on the surface of the transparent resin layer (A) is chemically bonded to the ground alcohol group of the compound (II-1) to form an intermediate layer composed of the fluoropolymer (II-2) (C). ) (thickness: 〇1μηι). Next, the solution composition was applied to the surface of the intermediate layer (c) by spin coating, and dried by heating at 11 (TC for 4 hours) to volatilize perfluorotributylamine in the solution composition to form a surface.模具), a mold precursor was prepared. The thickness of the surface layer (8) and the total thickness of the intermediate layer (c) were 丨2 μm. A fine pattern was formed in the same manner as in Example 4 except that the mold precursor was used, and the system was made transparent. a mold in which a resin layer (4), an intermediate layer (c), and a surface layer (β) are formed and a fine pattern is formed across the surface layer (中间) and the intermediate layer (〇 and the transparent resin layer (。). The maximum height of the fine pattern 9: The mold was not observed to be bent. Fabrication of a substrate having a transcribed fine pattern: The surface was made to be hardened by a photocurable resin in the same manner as in Example 6 except that the mold of Example U was used instead of the mold of Example 6. Transcription micro-structured by the object 42 201005430 Fine-patterned enamel wafer. The micro-pattern of the mother mold was reproduced as a result of observing the transcribed fine pattern by a laser microscope. [Example 13] Manufacture of the mold: Amorphous of the transparent resin Polyester (Toyobo Co., Ltd. The solution was prepared by dissolving it in cyclohexanone to 30% by mass to prepare a coating liquid. The coating liquid was applied to a transparent support (D) (soda lime glass plate) using an applicator. , thickness: 1.30 mm, heat distortion temperature: 300 ° C or more), dried at 15 ° for 2 hours to form a transparent resin layer (A). The thickness of the transparent resin layer (a) was measured by a micrometer, and the result was 30 μm. The physical properties of the transparent resin layer (A) and the transparent support are shown in Table 2. • Instead of using a glass plate which has been opened with a transparent resin layer (A) made of amorphous polyester, replace the PC sheet. And a transparent support (D), a transparent resin layer (A), an intermediate layer (C), and a surface layer (B) were obtained in the same manner as in Example 4 except that the heating temperature of the master was 12 〇tw. A mold having a fine pattern formed across the surface layer (b), the intermediate layer (C), and the transparent resin layer (A). The maximum height of the fine pattern is ιο. ίμη». No bending is observed in the mold. Production of substrate of fine pattern: A table was produced in the same manner as in Example 6 except that the mold of Example 13 was used instead of the mold of Example 6. A ruthenium wafer having a transcribed micropattern of a cured film of a photocurable resin. The transcribed fine pattern was observed by a laser microscope, and although the fine pattern was reproduced, the tilting and collapse of the fine pattern were partially observed* 43 201005430 m Η] Mold manufacturing: In place of the master mold of Example 1, except that a tantalum mold having a fine pattern of a lattice shape of a diameter of 5 μm and a depth of 5 μm is arranged in a lattice shape at intervals of ΙΟμηι, In the same manner as in Example 7, a transparent support (D), a transparent resin layer (Α), an intermediate layer (C), and a surface layer (Β) were formed, and the surface layer (Β) and the intermediate layer (C) were formed. And the transparent resin layer (4) is formed with a mold having a fine pattern. The maximum height of the fine pattern is 5·1 μηι. No bending was observed in the mold. © Manufacture of a substrate having a transcribed fine pattern: A ruthenium wafer having a pattern of a thin film having a surface of a light-curable resin and a fine pattern of Example 6 was produced in the same manner as in the mold of Example 14 except that the mold of Example 14 was used. The micro-pattern of the sister model of the transcribed micropattern was observed by a laser microscope. 'The mother has been reproduced [Example 15] 进 The pattern is entered in the same manner as in Example 7. Mold manufacturing: In addition to the heating temperature of the master mold is 4 〇. (Besides:, the result is that the surface of the mold is not transcribed with the fineness of the master mold. 44 201005430 Table 1 Example 4 Example 5 Example 9 Example 10 Fluoropolymer 0) Glass transition temperature rc) 108 108 108 108 Fluoropolymer on Glass transition temperature rc) 108 108 108 • Fluorinated polymer on reactive group (y) Carboxycarboxycarboxylate transparent resin drawer Α) Functional group on the surface (X) Xenon ethyl epoxide ethyl • Amino transparent resin PC PMMA FEVE FEVE Transparent resin glass transition temperature rc) 145 115 55 55 Transparent resin heat distortion temperature rc) 124 105 _ Transparent support (D) - Glass transparent support (DH transparent resin layer (A) Thickness (mm) 0.5 1.8 1.33 1.33 Transparent support (D) + transparent resin layer (A) 436 nm transmittance (%) 89 92 93 93 Transparent support (D) + transparent resin layer (A) 365 nm penetration Rate (%) 87 36 89 89 Total thickness of surface layer (B) + intermediate layer (C) (μηι) 1.3 1.3 1.3 1.3 Maximum height of the reverse pattern of the mother film (Mm) 10 10 10 10 Fine pattern of the film Maximum height (nm) 9.8 9.8 The manufacture of chess pieces is not (peeling), not (division) with fine transcription The manufacture of the substrate of the pattern is not acceptable.

Table 2 Example 6 Example 7 Example 8 Example 12 Example 13 Example 14 Fluoropolymer 0) Glass transition temperature rc) 108 108 108 108 108 108 Fluoropolymer 01) Glass transition temperature rc) 108 108 108 108 108 108 Reactive group of fluoropolymer (II) fv) Carboxylcarboxycarboxycarboxy-reactive transparent resin layer (a) Functionality of the surface ω Ethylene oxime Ethyl Ethyl Ethyl Ethoxy Epoxy Epoxy. Transparent resin PMMA FEVE FEVE Polyester polyester FEVE Transparent resin glass transition temperature (°c) 105 55 55 67 7 55 Transparent resin heat distortion temperature (°c) 95 - - Transparent support iDI - Glass glass _ glass glass The total thickness of the transparent support (D) + transparent resin layer (A) is 1.8 1.33 1.33 1.33 1.33 1.33 Transparent support (D) + transparent resin layer (A) 436 nm transmittance (%) 92 93 93 91 92 93 Transparent support (D) + transparent resin layer (A) 365nm transmittance (%) 36 89 89 90 89 89 Surface layer (B) + intermediate layer (total thickness C of Cum) 1.3 1.3 1.25 1.2 1 , 3 13 The maximum height of the mother film flipping case (Qing) 10 10 10 10 is called 10 1 5 The maximum height and width of the fine pattern of the film is 10.0 9.9 10.0 9.7 10.1 5.1 IHis of Mold Cocoa Cocoa Cocoa with transcripts of micro-patterns Cocoa Cocoa Cocoa---- Industrial Applicability

The mold of the present invention is useful as a light nanoimprinting tool using a photocurable resin. The substrate having the transferred fine pattern which can be obtained by using the mold of the present invention is used as a semiconductor element 'fourth body, mems, biotechnology related parts, optical parts, and the like. 45 201005430 In addition, the entire contents of the specification, the scope of the application, the drawings and the abstract of the Japanese Patent Application No. 2008-100552, filed on Apr. 8, 2008, the disclosure of which is incorporated herein by reference. Add. Inclusion. *I: Brief description of the drawings 3 Fig. 1 is a cross-sectional view showing an example of the mold of the present invention. Fig. 2 is a cross-sectional view showing an example of a method of producing a substrate having a transcribed fine pattern. Fig. 3 is a cross-sectional view showing another example of a method of producing a substrate having a transcribed fine pattern. Fig. 4 is a cross-sectional view showing another example of a method of producing a substrate having a transcribed fine pattern. Figure 5 is a laser microscope image of the mold of Example 7. &gt; I: Description of main component symbols] 10.. Mold 17... Transparent support (D) .. Fine pattern: Photocurable resin: Substrate 12: Transparent resin layer (A) 18 14.. . Middle layer (C) 16.. Surface layer (B) 20. 30. 46

Claims (1)

201005430 VII. Patent application scope: 1. A mold having a fine pattern for forming a photocurable resin, characterized in that it has: 'the following transparent resin layer (A); the following surface layer (B); And an intermediate layer (C) formed on the surface of the transparent resin layer and present between the transparent resin layer (A) and the surface layer (B); Q and 'the maximum height of the aforementioned fine pattern The thickness of the surface layer (B) and the total thickness of the intermediate layer (C) are exceeded; wherein the transparent resin layer (A) is a layer composed of a transparent resin, and the glass transition temperature of the transparent resin is as follows. The fluoropolymer (1) and the following fluoropolymer (π) have a glass transition temperature below, and the transparent resin layer (the 树脂) is formed before the intermediate layer (C) is formed, and an intermediate layer (C) is formed. The surface of the surface has a functional group (x)' and after the intermediate layer (C) is formed, the surface having the intermediate layer (C) has the functional group (X) and the following reactive group (y) a chemically bonded layer; a surface layer (B): consisting of a fluoropolymer (1) In the layer, the fluoropolymer (I) has a fluorinated aliphatic ring structure in the main chain and does not substantially have the following reactive group (y); the intermediate layer (C): is composed of a fluoropolymer (II) In the layer formed, the fluoropolymer (II) has a fluorine-containing aliphatic ring structure in the main chain and has a reactive group (y) reactive with the functional group (X). 2. The mold of claim 1, wherein the finest pattern has a maximum south degree of from 1 to 500 μm. 47 201005430 3. The mold of claim No. 2 or 2, wherein the transparent resin layer (Α) is supported by a transparent support (D). 4. The mold according to any one of claims 1-3, wherein the aforementioned b-base (X) is a trans group, an amine group or an epoxy ethyl group, and the aforementioned anti-reagent group (y) is a carboxyl group. 5. The mold according to any one of the above-mentioned claims, wherein the transparent resin layer (A) is a layer obtained by surface treatment with a functional group introduced on the surface. A manufacturing method of a mold having a fine pattern for forming a photocurable tree, and the method for manufacturing the mold described above is characterized by the following steps: I forming an intermediate layer (C) a step of coating a fluorine-containing solvent having the following fluoropolymer (Π) dissolved on the surface of the transparent resin layer (4) having a functional group (χ) on the surface: Forming a liquid mixture and drying it to form an intermediate layer (C) composed of the following gas-containing polymer (9); a step of preparing a mold precursor: coating on the surface of the intermediate layer (C) The cloth has been prepared by dissolving the following fluoropolymer (1) in a solution containing a gas solvent and drying it to form a surface layer (Β) composed of the following fluoropolymer (1), thereby preparing a mold precursor. ▲Step of making a mold: a flip pattern having a fine pattern on the surface ▲ The maximum height of the X flip pattern is the flip pattern of the master mold exceeding the thickness of the surface layer (9) and the thickness of the intermediate layer (C) In the foregoing mold, at least one of the drive and the master mold is When the following gas-containing polymerization 48 201005430 (I) and the following fluoropolymer (II) have a glass transition temperature or higher, the surface layer (B) side of the mold precursor is pressed, and the product is produced. The surface layer (B), the intermediate layer (C) and the transparent resin layer (A) form a micro-pattern and prepare a mold; and @ separation step: separating the master mold from the mold; wherein, the transparent resin: glass transition temperature system The transparent fluorene polymer (I) having a fluoropolymer (1) or less and a glass transition temperature of the following fluoropolymer (II): a fluorinated aliphatic ring structure in the main chain, and substantially a fluorine-containing polymer having no reactive group (y) described below; a fluorine-containing polymer (II) having a fluorine-containing aliphatic ring structure in a main chain and having a reactivity with respect to the aforementioned functional group (X) a fluoropolymer of the group (y). 7. A method of producing a substrate having a transcribed fine pattern, comprising the steps of: disposing a photocurable resin on a surface of a substrate; and as in any one of claims 1 to 5 of the patent application; a step of pressing the mold on the s-light-curable resin to bring the fine pattern of the mold into contact with the photo-curable resin; and pressing the mold against the photo-curable resin The step of irradiating light to the curable resin, curing the photocurable resin to form a cured product, and separating the mold from the cured product. 8. A method of producing a substrate having a transcribed fine pattern, characterized in that: 49 201005430 has the following steps: arranging the photocurable resin in a fine mold of any one of the patents a step of patterning the surface; the photocurable resin that presses the substrate against the surface of the mold; step; in the state where the substrate is pressed against the photocurable resin, the photohardenability depends on (4) a step of hardening the photocurable resin to form a cured product; and a step of separating the mold from the cured product. 〇9. A method for producing a substrate having a transcribed fine pattern, comprising: the step of: contacting or contacting a substrate with a mold according to any one of claims 1 to 5, a fine pattern of the mold is made to be the substrate side; a step of filling the photocurable resin between the substrate and the mold; and the punching material is in close proximity to or in contact with the mold The step of irradiating the photocurable resin with light, curing the photocurable resin to form a cured product, and separating the mold from the cured product. 50