TW201207034A - Photocurable composition and production method for formed body having fine pattern on surface - Google Patents

Abstract

The present invention provides a photocurable composition suitable to produce a cured product having excellent environmental characteristics, mold releasability and compatibility between one fluorine-containing surfactant and other components, and also provides a production method to produce a formed body whose surface has a uniform composition and a fine pattern that is an accurate transfer pattern of the mold. This invention relates to a photocurable composition for imprint, which contains a compound having at least one (meth)acryloyloxy group, and the following polymer (D): the polymer (D) comprises CH2=C(R11)-C(O)O-Q-Rf unit of 20-45 mass%, CH2=C(R21)-C(O)O-(CH2CH(R22)O) n-H unit (number average molecular weight is less than 350) of 20-65 mass%, and CH2=C(R31)-C(O)O-R32 unit of 5-40 mass% and has a mass average molecular weight of 1000-5000. Wherein, R11, R21 and R31 respectively represent a hydrogen atom or a methyl group; Q represents a divalent bonding group; Rf represents a C1-C6 polyfluoroalkyl group; R22 represents a hydrogen atom or the like; n represents a number of 3-6; and R32 represents a C2-C12 aliphatic group.

Description

201207034 * VI. Description of the Invention: [Technical Field] The present invention relates to a photocurable composition and a method for producing a molded body having a fine pattern on its surface. 2. Description of the Related Art In a method of forming a fine pattern by a bonding time in the manufacture of an optical member, a recording medium, a semiconductor device, or the like, it is known that a mold having a reverse pattern of the fine pattern on the surface is pressed to a photocurable composition disposed on a surface of the substrate. Then, the photocurable composition is irradiated with light to cure the photocurable composition, and a fine pattern is formed on the surface of the substrate (nanoimprint method) (see Patent Documents 1 and 2). However, in this method, since the cured product of the photocurable composition is in close contact with the mold, it is difficult to separate the cured product from the mold. Therefore, it is necessary to apply a release agent to the surface of the mold. However, it is difficult to precisely transfer the reverse pattern of the mold due to the film thickness of the release agent itself and uneven coating of the release agent. As a photocurable composition which can form a cured product excellent in mold release property, the following proposals have been made. ^ 0) Active energy ray-curable composition: a dry surfactant having a fluorinated group and a polar group in a molecule (Patent Document 3). Pine (2) photocurable composition: contains a fluorine-containing monomer, a fluorine-free monomer, a fluorine surfactant or a fluorine-containing polymer, and a polymerization initiator (Patent Document ^. However '(1), 2) The photocurable composition has the following problems: 201207034 (i) Fluoride surfactant is used to improve the mold release property, and it is often used as a raw material or a trace amount of a compound derived from perfluorooctyl lithospermic acid. However, compounds derived from PFOS are questioned by environmental residues or bioaccumulation, and their use is being limited. (H) When the fluorosurfactant has a terminal methyl group (oxyethylene) structure When the mold is a mold having a complicated fine pattern, a mold having a dense fine pattern, or a mold having a large area of a fine pattern, the mold release property of the mold and the cured product of the photocurable composition is insufficient. The Go light hardening composition cannot be completely filled in the fine pattern of the mold. (111) When the molecular weight or composition of the fluorine surfactant is not controlled, the composition of the surface of the cured material may be uneven, and the surface state of the cured product may be generate Irregularities, which are caused by a decrease in weather resistance when used as a permanent film, or an in-plane change in etching rate when used as a photoresist, and a part of a transfer body when used as a replica mold. Patent Document 1: Patent Document 1: Patent Document No. 6696220 Patent Document 2: Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. 2001-106710. Document 4: International Publication No. 2006/114958 [Invention Summary] SUMMARY OF THE INVENTION Problem to be Solved by the Invention The present invention provides a photocurable composition which is used as a raw material from 201207034 from a perfluorooctane sulfonic acid compound since it is not used. The fluorosurfactant can form a cured product excellent in mold release property, and is excellent in compatibility with a fluorine surfactant and other components; and a fine pattern which can be manufactured on a surface having a reverse pattern in which a mold is precisely transferred And a method of forming a molded body having a uniform surface. Means for Solving the Problem The photocurable composition for imprint of the present invention is the following pressure A photocurable composition for use as a photocurable composition for imprinting, which has a compound having one or more acryloxy groups or a mercapto acryloxy group (hereinafter, also referred to as a compound (X)) as a main component The photocurable composition for imprinting is a copolymer of the following compound (A) and the following compound (B) and the following compound (C), and the unit of the following compound (A) is as follows: The ratio of the unit of the compound (B) and the unit of the following compound (c), the ratio of the unit of the following compound (A) is 20 to 45% by mass, and the ratio of the unit of the following compound (B) is 2 〇~ 65% by mass, the ratio of the unit of the following person (C) is 5 to 40% by mass, and the photocurable composition for imprinting contains a polymer (D) having a mass average molecular weight of 1000 to 5000; ): a compound represented by the following formula (1), CH2=C(Rn)-C(0)0-Q.Rf (1) However, R11 is a hydrogen atom or a fluorenyl group 'Q system single bond or not a divalent bonded group of a fluorine-containing atom, a polyfluoroalkyl group in which the carbon number of the Rf-based main chain is 丨6 and an etheric oxygen atom may be present between the carbon atoms; and the compound (B): the following formula (2) represents 'and number a compound having a molecular weight of 35 Å or less, 201207034 CH2=C(R21)-C(0)0-(CH2CH(R22)0)nH (2) However, R is a hydrogen atom or a ruthenium group, and R22 is a hydrogen group. The atom or the alkyl group having a carbon number of 1 to 4 η is 3 to 6, and the η R22 in one molecule may be the same or different, respectively; Compound (C) · Compound represented by the following formula (3), CH 2 =C(R31)-C(0)0-R32 (3) However, R31 is a hydrogen atom or a methyl group, and r32 is a hydrazone aliphatic hydrocarbon group. The photocurable composition for imprint of the present invention is a composition containing the compound (X) as a main component, and usually contains a photopolymerization initiator (G). Further, the compound (X) is a compound selected from the group consisting of the following compounds: a compound having a propylene oxy group or a mercapto propylene oxide group (hereinafter, also referred to as a compound (7) And a compound (H) having two or more acryloxy or methacryloxy groups. In the present invention, the compound (Y) is classified into two types of a compound (E) having a fluorine atom and a compound (F) having no fluorine atom. When the compound (Y) of the present invention is composed of the compound (E), the compound (γ) is composed of at least one selected from the group consisting of the compound (E) and the compound (F). The photohardenable composition of the present invention preferably contains the compound (7). In other words, it is preferred that the compound (X) is at least one selected from the group consisting of the compound (Ε) and the compound (F). More preferably, both the compound (ε) and the compound (7) are contained. Further, the photocurable composition of the present invention preferably contains a compound (Η). In the photocurable composition of the present month, the content of the polymer (D) is preferably from 1 to 5% by mass based on the photocurable composition 201207034. Further, the photopolymerization initiator (G) is preferably contained in an amount of from 1 to 12% by mass based on the photocurable composition. The photocurable composition of the present invention contains at least any one of the compound (E), the compound (F) and the compound (H), and the content ratio of each compound to the photocurable composition, in the following ratio good. Compound (E): 5 to 40 mass 〇/〇 compound (F): 10 to 55 mass% Compound (H): 10 to 75 mass% In the present invention, the photocurable composition means a solvent-free composition . The composition subjected to photohardening is a composition containing no solvent. However, the composition before the hard A can also contain a solvent. In other words, the photocurable composition for imprint of the present invention can be subjected to a pre-curing operation in a state in which a solution containing a solvent is used for the treatment such as coating. The ratio of the above-mentioned respective components means the ratio of each component based on the photocurable composition containing no solvent (or the total amount of the component after removing the solvent when it is a composition containing a solvent). Further, in the same sense, the photocurable composition for imprint of the present invention preferably has a viscosity at 25 C of 3 to 200 mPa·s. A method for producing a molded body having a fine pattern on the surface of the present invention, comprising the steps of: contacting the compacted photohardenable composition of the present invention with a surface of a mold having a reverse pattern, the surface of the mold having the aforementioned fine pattern a pattern in which the photocurable composition is irradiated onto the surface of the mold, and the photocurable composition is cured to form a cured product; and the aforementioned 201207034 mold is used. The step of separating the molded body having a fine pattern on the surface from the hardened material. A method for producing a molded body having a fine pattern on the surface of the present invention, comprising the steps of: disposing the photocurable composition for imprinting of the present invention on a surface of a substrate; and forming a mold having a reverse pattern of the fine pattern on the surface thereof a step of pressing the photocurable composition to the inversion pattern of the mold and the photocurable composition; and irradiating the light to the photohardening state while pressing the mold to the photocurable composition The step of curing the photocurable composition to form a cured product, and the step of separating the mold or the substrate and the mold from the cured product to obtain a molded body having a fine pattern on the surface. A method for producing a molded body having a fine pattern on the surface of the present invention, comprising the step of disposing the photocurable composition for imprint of the present invention on a surface of a mold having a reverse pattern, the surface of the mold having the aforementioned fine a step of inverting the pattern; a step of pressing the substrate to the photocurable composition; and applying the light to the photocurable composition while pressing the substrate to the photocurable composition to cause the photocurability a step of curing the composition to form a cured product; and a step of separating the mold or the substrate and the mold from the cured product to obtain a molded body having a fine pattern on the surface. A method for producing a molded body having a fine pattern on a surface of the present invention, comprising the steps of: a mode in which a substrate and a surface have a pattern of reversal of a pattern of reversal, and an inversion pattern of X «Hail mold is located on the substrate side or a step of contacting; filling the photohardenable composition for imprinting of the present invention with a step between the substrate of the previous 201207034 and the mold; and irradiating the light to the photohardening in a state where the substrate is in close contact with or in contact with the mold The step of curing the photocurable composition to form a cured product, and the step of separating the mold or the substrate and the mold from the cured product to obtain a molded body having a fine pattern on the surface. The fine pattern may be a photoresist pattern, and the molded body having a fine pattern on the surface may be a replica mold for imprint or a replica mold for electroforming. Advantageous Effects of Invention The photocurable composition of the present invention does not require the use of a fluorosurfactant using a compound derived from perfluorooctane sulfonic acid as a raw material, and can form a cured product excellent in mold release property, and is compatible with a fluorine surfactant and other The composition is excellent in compatibility. According to the method for producing a molded body having a fine pattern on the surface of the present invention, it is possible to manufacture a molded body having a fine pattern on the surface of which the reverse pattern of the mold is precisely transferred and having a uniform surface composition. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an example of a method of producing a molded body having a fine pattern on its surface. Fig. 2 is a cross-sectional view showing another example of a method of producing a molded body having a fine pattern on its surface. Fig. 3 is a cross-sectional view showing an example of a molded body having a fine pattern on its surface. Fig. 4 is a cross-sectional view showing another example of a molded body having a fine pattern on its surface. [Embodiment j] Form for carrying out the invention In the present specification, a (meth)acryloxy group is a (tetra) ethionyl allysyloxy group. Further, in the present specification, (meth)acrylic acid = a methacrylate or a mercapto acrylate. ', heart s-acrylic light-curable composition> The pressure-sensitive (four) photocurable composition (hereinafter referred to as a photo-formed product) of the present invention is a compound having one or more acryloxy groups or a (tetra) ketone (i.e., the compound (X)) is a composition of a main component, and the 4-base hardening property usually includes a photopolymerization initiator (G, and the present invention = pre-light = the product contains the polymer (D) as an essential component. Also, the additive (1) and the like are as described above. As described above, the photohardening product of the present invention is intended to contain (4) the material L, and can be used in the case of photohardening in the field towel = = body fluid (ie, light) The soluble compound (X) of the sclerosing group has a "solid" (meth) propylene oxide oxygen, and in the present invention, it can be classified into (meth) propyl oxychloride & compound: That is, 'compound (7)) and (iv) _: number of compounds = compound (E) and compound (F). (9) (Y) is a compound which is divided into a thiopheneoxy group: more preferably: compound (Η): = 10 201207034 , 醯The oxy group is preferably an acryloxy group. Among the photocurable compositions (solvent-free compositions) of the present invention, the compound (X) is essential and mainly The photocurable composition of the present invention contains at least one selected from the group consisting of the compound (E), the compound (F), and the compound (H), and the total amount thereof becomes a photocurable composition. In the photocurable composition of the present invention, the content ratio of the compound (X) to the photocurable composition (the composition containing no solvent) is 60% by mass. The above is preferable, and it is more preferably 80 mass% / 〇 or more. The compound (X) contained in the photocurable composition of the present invention may be selected only from the compound (E), the compound (F) and the compound ( The compound (H) is preferably a compound (H). The compound (X) contained in the photocurable composition is more preferably a compound (E) or a compound (F). It is preferably composed of at least one of the compounds (H). The most preferred compound (X) is composed of the compound (E), the compound (F) and the compound (H) 3. Further, the photocurability of the present invention The composition may contain a photopolymerizable compound other than the compound (X) as needed. The photocurable composition of the present invention (without dissolution) The composition of the agent is at 25. The viscosity of the underarm is preferably 3 to 200 mPa.s, more preferably 5 to 100 mPa.s. When the viscosity of the photocurable composition is within this range, even if no special operation is performed (For example, the operation of heating the photocurable composition to a high temperature to make it low in viscosity, etc.), the contact of the photocurable composition with the surface of the mold having the reverse pattern can be easily performed. The photohardenability composition of the present invention. When the system is cured, the composition is substantially free of a solvent, and the photocurable composition 201207034, such as a coating before curing, is preferably a composition containing substantially no solvent. When the photocurable composition is used When the solvent is substantially not contained, the curing of the photocurable composition can be easily performed even if a special operation other than light irradiation (for example, 'heating of the photocurable composition to a high temperature to remove the solvent, etc.) is not performed. / gluten means a compound having the ability to dissolve any of polymer (D), compound (E), compound (F), light * & starter (g), compound (H) and additives And a compound having a boiling point of 16 (TC or less) under normal pressure. The photocurable composition which does not substantially contain a solvent means that the amount of the solvent contained in the photocurable composition is relative to the photocurable composition. In the present invention, the bath agent used in the preparation of the photocurable composition may be used as a residual solvent, but it is preferred that the residual solvent is removed as much as possible, and the solvent remains after the photocurable composition. The content of the solvent is preferably 7% by mass or less. «Polymer (D) >> The polymer (D) is a copolymer of the compound (A) and the compound (B) and the compound (c) and The polymer having a mass average molecular weight of 1000 to 5 mm, and the ratio of the unit of the compound (A) to the unit of the compound (B) and the unit of the compound (c), the ratio of the unit of the compound (A) is 2〇. ～45 mass%, the ratio of the compound (= unit to 2G to 65 mass% 'unit of compound (c) The ratio is 5 to 40% by mass. The compound (A) is a compound represented by the following formula (1): ch2 = c(r丨丨) - c(o)oQ-Rf · (1) R11 hydrogen atom Or a fluorenyl group. Q is a single bond or a divalent bond which does not contain a fluorine atom. The divalent bond may be 12 201207034 For example: a linear or branched alkyl group having a carbon number of 丨~1〇, a carbon number a straight-chain or branched alkenyl group of 2 to ι〇, an oxygen-exane 2 represented by the formula (CrHhMs (but an integer of the formula 2 to 6 in the formula, s is i~i 〇, and The oxygen-extension base; a linear structure, which may also be a branched structure), a 6-membered ring of a 6-membered ring, a saturated or unsaturated aliphatic group of 4 to 6 member rings, and a 2 price of 5: Class 2 And a heterocyclic group of the cockroach, or a divalent bond represented by the following formula (4). The divalent bond group may be used in combination of two or more kinds, and may be a condensed ring or a substituted mer. In addition, it is preferable that the Q-based combination of the atomic weight of 3 〇〇 or less is preferably -YZ- · · · (4) 〇Η However, the linear or branched extension of the lanthanoid carbon number W0 is two-valent. a saturated or unsaturated lipid of 4 to 6 membered rings of 2 squares a heterocyclic group of a 5 or 6-membered ring of a divalent group, or a ring having such a condensation, -〇-, -S...CO-, -C(0)〇_, _C(0)S-, _N (R)...s〇2 (6)=System-N(R)-C(0)0-, -N(R)-C(0)-, -N(R).S〇2_, ·' ~N( R)-P〇(〇r)_, r is a hydrogen atom or a carbon number i~3. The 〆Q system has a single bond, a linear or branched carbon number of 1 to 1 、, The group represented by the following formula (5), or a combination of the groups, is preferable, ' 彼 乙 ' Η 2) ρ · (however, ρ is an integer of 0 to 6, when Ρ is 〇 represents a single bond) good. -Υ -Ζ1 - · · · (5). However, the Υ1 series is a linear or branched shape having a carbon number of 1 to 10. 6-membered ring aromatic group, ζ1 series -N(R)-, -S〇2_, or 7 (1^8 or 2 R 虱 atom or a carbon number 1 to 3 alkyl group. R series primary bond carbon The number is 1 to 6 and the polyfluoroalkyl group of the carbon atom may also have a fluorocarbon group. The boundary between Q and Rf is such that the carbon number of Rf is the highest, and helium = 13 201207034. Polyfluoroalkyl The number of carbon atoms in the main chain (excluding the carbon number of the side chain) is 1 to 6 and the hydrogen atom of the base has two or more groups substituted with fluorine atoms. Further, the main chain means that when it is a straight bond The direct bond is the longest carbon bond in the branched form. The side bond means the carbon chain other than the main chain in the carbon chain constituting the branched polygas group. The side chain is composed of an alkyl group or a monofluoroalkyl group. Or a polyfluoroalkyl group. The polyfluoroalkyl group may, for example, be a partially fluorine-substituted alkane corresponding to a linear or branched alkyl group (methyl, ethyl, propyl, butyl, pentyl, hexyl). a polyfluoroalkyl group having an etheric oxygen atom between carbon atoms, preferably a polyfluoro(alkoxyalkyl) group or a polyfluoro(polyoxyalkylene alkyl ether) group. For example, polyfluoro(2-ethoxyethyl) group, polyfluoro(2-methoxypropyl) group Polyfluoro(polyoxyethylene methyl ether) group, polyfluoro(polyoxypropylene methyl ether) group, etc. R is preferably a linear one. When Rf is a branch, the branch portion exists as close as possible to 1^ The end portion is preferred.

Rf is preferably a polyfluoroalkyl group, and a perfluoroalkyl group in which all hydrogen atoms are substantially substituted by a fluorine atom is more preferable, and a linear perfluoroalkyl group is particularly preferred, which is environmentally residual or biologically or biologically. In view of low accumulation and high mold release property, a linear perfluoroalkyl group having 4 to 6 carbon atoms is particularly preferred, and a linear perfluoroalkyl group having 6 carbon atoms is preferred. . The compound (A) is preferably a compound (A_1) represented by the following formula (6): CH2=C(R")-C(0)0-(CH2)p-RF . . . (6) 〇, R11 The hydrogen atom or the fluorenyl group 'p is an integer of 0 to 6, and the rF is a linear perfluoroalkyl group having a carbon number of 6. The specific compound of the compound (Al) is exemplified by the following compounds: CH2=CH -C(0)0-(CH2)2-(CF2)6F > ch2=ch-c(o)o-(ch2)2-(cf2)4f, ch2=ch-c(o)o-(ch2 )2-(cf2)2f, ch2=ch-c(o)o-(ch2)2-cf3, CH corpse C(CH3)-C(0)0-(CH2)2 -(CF2)6 F, CH2 =C(CH3 )-C(0)0-(CH2)2 -(CF2)4 F, ch2=c(ch3 )-c(o)o-(ch2)2 -(CF2)2 F, CH2=CH -C(0)0-CH2-(CF2)2F 'ch2=ch-c(o)o-ch2-cf3, etc. The compound (A) may be used singly or in combination of two or more. In other words, 'polymer (D) A unit having two or more kinds of the compound (A). The ratio of the unit of the compound (A) in the polymer (D) to the total amount of the unit to the compound (C) of the compound (A) is When the ratio of the unit of the compound (A) is 20% by mass or more, the mold release property of the cured product of the photocurable composition is good. When the ratio of the unit of the compound (A) is 45 When the amount is not more than 〇, the polymer (D) and the other components are uniformly dissolved. (Compound (B)) The compound (B) is a compound having a number average molecular weight of 350 or less represented by the following formula (2). =C(R21)-C(0)0-(CH2CH(R22)0)n -Η · · · (2) R21 is a hydrogen atom or a methyl group. R22 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, η R22 in one molecule may be the same or different, respectively. 15 201207034 η is the addition mole number of the alkylene oxide added to the compound (B). The average value indicates that the η system 3 to 6 ' is preferably 3.5 to 5.5. When n is in the range, the polymer (D) and the other components are uniformly dissolved. The number average molecular weight of the compound (B) is 350 or less. It is preferably 3 Å or less. When the number average molecular weight of the compound (B) is 350 or less, the polymer (D) and the other components are uniformly dissolved. The number average molecular weight of the compound (B) is based on n (average The compound (Β) has a hydroxyl group, and the fluorine component in the photocurable composition tends to be easily directed toward the surface to make the mold release property of the cured product of the composition good. Specifically, since the compound (Β) has a hydroxyl group of a polar group, it imparts polarity to the polymer (D). Thereby, the polymer (D) is amphiphilic and easily mixed with each component in the photocurable composition. Therefore, as the fluoroalkyl group derived from the unit of the compound (A) runs out of the surface, the fluorine-containing component in the photocurable composition becomes easy to escape to the surface, so that the cured product of the composition can be considered The release property will become good. Specific examples of the compound (B) include the following compounds. CH2=C(CH3)-C(0)0-(CH2CH20)nH, CH2=CH-C(0)0-(CH2CH20)nH, CH2=C(CH3)-C(0)0-(CH2CH(CH3) )0)nH, CH2=CH-C(0)0-(CH2CH(CH3)0)„-H, CH2=C(CH3)-C(0)0-(CH2CH20)nl-(CH2CH(CH3)0 n2-H 'CH2=CH-C(0)0-(CH2CH20)nl-(CH2CH(CH3)0)n2-H, etc. However, n is 3~6, nl+n2 is 3~6 ° 16 201207034 The compound (8) may be used alone or in combination of two or more. The resin polymer (D) may have two or more units of the compound (9), and the unit of the compound (4) to the unit (c). When the ratio of the unit of the compound (8) in the total composition (9) is 2Q to 65 mass%, and the ratio of the unit of the compound_ to 2% by mass or more, the composition of the polymer 1 will be uniformly soluble. When the ratio of (8) is 65% by mass or less, the mold release property of the cured product of the photocurable composition is good. (Compound (C)) The compound (C) is a compound represented by the following formula (3). CH2=C (R31)-C(0)0-R32 . . , (3) 〇R31 is a hydrogen atom or a fluorenyl group. R32 is a monovalent aliphatic hydrocarbon group having a carbon number of 2 to 15. When the carbon number of the fluorene aliphatic hydrocarbon group is In this range, polymer (D) and The other components are uniformly miscible. The valence aliphatic hydrocarbon group may, for example, be an alkyl 'alkenyl group or an alkynyl group. The aliphatic hydrocarbon group may be linear or branched or may be cyclic. The base is preferably 'the base having a carbon number of 4 to 12 is more preferred. Specific examples of the compound (C) include the following compounds: ch2 = c(ch3) - c(o)o - c4h9, CH2 = C (CH3)-C(0)0-CH2CH(CH3)2 'CH2=C(CH3)-C(0)0-C6H,3 'CH2=C(CH3)-C(0)0-Cy > ch2 =c(ch3)-c(o)o-ch(ch3)c2h5, ch2=c(ch3)-c(o)o-ch2ch(c2h5)C4H9, ch2=c(ch3)_c(o)o-c12h25 , 17 201207034 ch2=ch-c(o)o-c4h9, CH2=CH-C(0)0-CH2CH(CH3)2, CH2=CH-C(0)0-C6H|3 'CH2=CH-C (0)0-Cy, ch2=ch-c(o)o-ch(ch3)c2h5, ch2=ch-c(o)o-ch2ch(c2h5)c4h9, CH2=CH-C(0)0-C12H25 Wait. However, Cy is a cyclohexyl group. The compound (C) may be used alone or in combination of two or more. In other words, the polymer (D) may have two or more kinds of compounds (units of hydrazine. The total amount of units of the unit (A) to the compound (C), and the compound of the polymer (D) (unit of hydrazine) The ratio of the unit of the compound (C) is in this range, and the mold release property of the cured product of the photocurable composition is good. (Fourth component) in the polymer compound (A) When the unit is a compound (c), a fourth component which can be copolymerized with the unit to the compound (c) of the compound (A) may be added. The fourth component may have one or more carbon-carbon unsaturated double bonds. The compound (however, the compound (A) to the compound (except for hydrazine) is exemplified, and specific examples thereof include a (meth) acrylate containing a decyloxy group, maleic anhydride, and a thiol group. The acryl or the like. The fourth component may be used singly or in combination of two or more kinds thereof. The total amount of the unit to the unit of the compound (A) to the unit of the compound (c) and the unit of the fourth component (that is, the polymer) All units in (D), the unit of the fourth component of the polymer (9) 201207034 ( The ratio of the total amount of the unit of the fourth component to the total amount is preferably 20% by mass or less. When the unit of the fourth component is more than 20% by mass, the mold release property of the cured product having the photocurable composition is lowered. (Polymer (D)) The polymer (D) compound (A) and the compound are obtained by copolymerization with a compound and, if necessary, a fourth component. The photocurable composition of the present invention is contained. The polymer (D) as a nonionic surfactant can enhance the release property which is important at the time of imprinting. The mass average molecular weight of the polymer (D) is 1000 to 5000. When the mass average molecular weight of the polymer (9) is _ In the above, the release property of the cured product of the photocurable composition is good. When the mass average molecular weight of the polymer (D) is 5 or less, the polymer (D) and the other components are uniformly dissolved and hardened. The mass of the polymer (D) is preferably from 2,500 to 5,000. The polymerization form may be, for example, random polymerization, block polymerization, graft polymerization, etc., and random polymerization is preferred. The type of polymerization may be, for example, radical polymerization or cation. Ionic polymerization, cationic polymerization, etc. 4-combination method In the presence of a polymerization initiator, it is preferred to combine the compound (A) with the compound (B) in the presence of a polymerization initiator (4). The initiator, the compound (4) to the compound (C) are exemplified by water, an organic solvent, a fluorine-based solvent, and the like, and the organic solvent is preferably used as the solvent. The organic solvent may, for example, be propylene or methanol. 201207034 Ethanol, 2-propanol, stems and diced -. Dimethoate-butyl, ethyl acetate, decyl acetate, butyl hydrazine, methyl bromide, tetrahydrofuran, and others. The polymerization initiator can be oxidized. Examples of the azo compound, etc. From the point of view of the ease of polymerization, the polymerization temperature is preferably from G to 15 G ° C, and that from the point of decomposition of the activation energy of the poly-portion initiator is 3 〇 9 〇°C is preferred. The polybenzate (D) may be used alone or in combination of two or more. In other words, two or more kinds of polymers (D) may be used as the photocurable composition. The ratio of the poly σ (D) to the photocurable composition (the composition containing the polymer (D)) is preferably 〇〇1 to 5 mass%, more preferably 〇2 to 2 mass%. When the polymer (D) is G.G1 mass. /. In the above, the release property of the cured product of the photocurable composition is good. When the polymer (D) is 5% by mass or less, the polymer (D) and the other components will be uniformly dissolved, and the composition of the surface of the cured product will become uniform. «Compound (X)» compound (XM system has _ or more The (mercapto) acryloxy compound, in the present invention, may be classified into a compound having a (meth) propylene fluorenyloxy group (ie, a compound hydrazine) and a (meth) propylene fluorenyloxy group. The amount is two or more compounds (i.e., compound (H)). The compound (γ) is divided into the compound (E) and the compound (F). From the point of easy photopolymerization, the compound (χ) has The compound of the acryloxy group is more preferably. In other words, the compound (8) and the compound (f) are more preferably a compound having one propylene methoxy group, and the compound (H) is (meth) propylene oxy group. More preferably, it is a propylene oxime group. 1 20 201207034 - (Compound (E)) The compound (E) is a compound having M group and having a (10) (meth) acrylic acid gas group. When the photohardening of the present invention When the compound (6) is contained in the composition, the mold of the photocurable composition and the mold are easily released. The compound (6) is preferably a compound represented by the above formula (1). Further, in the compound, R" may be a fluorine atom. Further, from the viewpoint of compatibility and ring-shaped characteristics, the above chemical formula (6) The compound represented by the compound and wherein R11 is a hydrogen atom is more preferably used as the compound (Ε). The compound (Ε) may, for example, be a compound exemplified as a specific example of the compound (Α-1). For example, the following compound may be mentioned. CH2=CH -C(0)0-CH2CH(0H)CH2-CF2CF2CF(CF3)2, ch2=ch-c(o)o-ch(cf3)2, 'ch2=ch-c(o)o-ch2 -(CF2 6F, CH2=C(CH3)-C(0)0-CH2 -(CF2)6F, ch2=ch-c(o)o-ch2-cf2cf2h, CH2=CH-C(0)0-CH2-( CF2CF2)2H ' ch2=c(ch3)-c(o)o-ch2-cf2cf2h, ch2=c(ch3)-c(o)o-ch2-(cf2cf2)2h, CH2=CH-C(0)0 -CH2 -cf2ocf2cf2ocf3 > ch2=ch-c(o)o-ch2 -cf2o(cf2cf2o)3cf3, CH2=C(CH3)-C(0)0-CH2-CF2 OCF2 CF2 OCF3 '

Ch2=c(ch3)-c(o)o_ch2-cf2o(cf2cf2o)3cf3, ch2=ch-c(o)o-ch2-cf(cf3)ocf2cf(cf3)o(cf2)3F, ch2=ch-c (o)o-ch2-cf(cf3)o(cf2cf(cf3)o)2(cf2)3F 21 201207034 CH2=C(CH3)-C(〇)〇-CH2-CF(CF3)OCF2CF(CF3)〇 (CF2)3 F,

CH2=C(CH3)-C(〇)〇-CH2-CF(CF3)0(CF2CF(CF3)〇)2(CF 2)3F. The photocurable composition of the present invention preferably contains the compound (E). In this case, the compound (E) contained in the photocurable composition may be in the form of two or more kinds. When the photocurable composition contains the compound (E), the ratio of the compound (£) to the photocurable composition (the composition containing the compound (E)) is preferably 5 to 40% by mass, preferably 1 〇. 25% by mass is more preferred. When the compound (E) is 5% by mass or more, a cured product excellent in mold release property can be obtained, and foaming of the photohardenable composition can be suppressed. Since the foaming of the photocurable composition can be suppressed, it becomes easy to be filtered at the time of preparation, and the defects of the pattern shape due to the incorporation of bubbles at the time of nanoimprinting can be avoided. When the compound (E) is 4% by mass or less, since it can be uniformly mixed, a cured product excellent in mechanical strength can be obtained. Further, by using the compound (E), the transparency of the cured product can be improved. Further, since the compound (E) contributes to a decrease in the viscosity of the photocurable composition or a decrease in the surface energy, it is useful for improving the resolution or reducing the residual layer when the cured product is used as a photoresist. . (Compound (F)) The compound (F) is a compound having one (fluorenyl) acryloxy group (except for the compound (E)). The compound (F) is a component which dissolves other components. When the photohardenable composition of the present invention contains the compound (F), the phase bath property of the polymer (D) and the compound (E) and the compound (Η) can be improved. When the compatibility of the polymer 1) with the compound (E) and the compound (H) 22 201207034 is good, it is possible to suppress the photocurable composition from being formed/packed during preparation, and it is easy to pass through a transition device or the like to harden the light. The current composition of the composition becomes easy, and a uniform photocurable composition can be obtained. Further, since a homogeneous cured product can be obtained, the mold release property and the mechanical strength can be sufficiently exhibited. Compound (F) is at 25. The viscosity of the sputum is better than the scorpion. When the viscosity of the human (F) is within this range, the viscosity of the photocurable composition can be easily lowered. Further, when the cured product is used as a photoresist, it is useful for improving the resolution or reducing the residual layer. The compound (F) may, for example, be a (meth) acrylate of a monohydroxy compound, a mono(meth) acrylate of a polyhydroxy compound, or the like, and a (meth) propyl group of a monohydroxy compound, particularly a mono-peripheral compound. The propylene is better. a monochemical compound, particularly an alkanol having 4 to 2 carbon atoms in the alkyl moiety, an alicyclic mono(tetra), poly (or mono) alkyl diol having a monocyclic condensed polycyclic or crosslinked ring (or aryl) scales are preferred. A particularly preferred single-pass compound is a municipal alcohol having a carbon number of 6 to 2 G and an alicyclic unit alcohol having a crosslinked ring. That is, when the cured product is used as a photoresist, the resistance is improved as it is, and it is preferred to use an alicyclic unit alcohol having a crosslinked ring. The compound (F) is exemplified by the following compounds. The presently-based ethyl (meth)propanoic acid @ HI phenoxypropyl (methyl) propylene W day oxy-ethylene glycol (meth) acrylate vinegar, (methyl) propylene glycol Benzyl methacrylate, methoxytriethylene glycol (meth) acrylate vinegar, methoxy polyethylene glycol (meth) acrylate S, 2 · (methyl) propyl oxyethyl hexahydro phthalate Dicarboxylic acid vinegar, (meth) acrylic acid, twenty H (methyl) propylene sulfonium oxyethyl sulphate 23 201207034 ethyl ester, octadecyl (meth) acrylate, (decyl) acrylate Ester, isodecyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 3-(trimethoxydecyl)propyl (meth)acrylate, butyl (meth)acrylate, Ethyl ethoxide, ethoxyethyl acrylate, methoxyethyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydroindenyl (mercapto) acrylate, 2-hydroxy (meth) acrylate Ethyl ester '2-hydroxypropyl (meth)acrylate, ν, Ν-diethylamine ethyl (meth)acrylate, ruthenium (decyl) ruthenium, ruthenium diamine, ethyl (meth) acrylate Methylaminoethyl, (mercapto) acrylic acid 2-mercapto-2-adamantate, 2-ethyl-2-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, ortho-(meth)acrylate, (A) Base) isobornyl acrylate, 2-carboxyethyl (meth)acrylate, octyl methacrylate, decyl methacrylate, 2-(tributylamine)ethyl (meth)acrylate, 1,2,2,6,6-pentamethyl-4-α-based D-(indene)-acrylic acid@-, (mercapto)-acrylic acid n-butyl vinegar, (mercapto)acrylic acid tert-butyl acrylate , 4-tertiary butylcyclohexyl (meth) acrylate, and the like. The photocurable composition of the present invention preferably contains the compound (F). In this case, the compound (F) contained in the photocurable composition may be one type or two or more types. When the photocurable composition contains the compound (F), the ratio of the compound (F) to the photocurable composition (including the composition of the compound (F)) is preferably 10 to 55 mass%, preferably 15 to 45. The mass % is better. When the compound (F) is at most 1% by mass, the viscosity of the low light curable composition can be adjusted, and the compatibility of the polymer (D) with the compound (E) and the compound (H) will be good. When the compound (F) is 55% by mass or less, the sensitivity is improved and the crosslinking density is also improved, whereby a cured product excellent in mechanical strength can be obtained. (Compound (H)) 24 201207034 The compound (Η) is a compound having two or more (fluorenyl) acryloxy groups. The compound (oxime) may also be a compound having a fluorine atom, but is usually a compound having no fluorine atom. The compound (Η) is a component which enhances the sensitivity of the photocurable composition. Further, according to the type of the compound (Η), the dry etching resistance, wet etching resistance, transparency, viscosity, refractive index, hardness, mechanical strength, flexibility, and adhesion to the substrate of the cured product of the photocurable composition can be adjusted. Physical properties such as sex. The amount of the (fluorenyl)propenyloxy group in the compound (Η) is preferably from 2 to 10, and is preferably from 2 to 6. When the amount of the (fluorenyl) acryloxy group is too large, there is a concern that the hardening becomes weak. However, as long as it is a small amount, a compound having a particularly large amount of (meth)acryloxy group can also be used. <The compound (Η) is a poly(meth)acrylic acid vinegar of a multi-permeate compound, as long as it is (meth) propylene! When the number of the oxy groups is two or more, it may have a mercapto group. The polyhydroxyl group can be, for example, a polyhydric alcohol of a polyhydric alcohol, a calcined base oxide of a polyhydric alcohol, or a polyamine, or a polyamine, which can be added to an alkylene oxide. Alkyl oxide adducts of functional group compounds, polycarbonate polyols, polyester polyols, and the like. Further, the compound (Η) is a compound having a poly (meth) acrylate structure of a compound of ruthenium, and may be an amine sulfonate S-methyl (meth) acrylate. Ethyl acetoacetate (mercapto) acrylic acid vinegar & E obtained by reacting isocyanate with methacrylic acid (meth) propyl vinegar in a compound of 4 in a poly-compound to make a polyisocyanate A group D having a urethane formate bond, such as a compound containing a group I, is a compound obtained by the reaction. A compound of urethane for the production of a raw material of a sulfonate, which is a thiol-based oxide adduct of a polyhydric alcohol, a condensed diol, and a polyphenol. Preferably, the polyether polyol is preferred, and the polyisocyanate compound is preferably a polyisocyanate compound having no yellowing property. The compound (H) is preferably selected from the group consisting of an alkylene oxide adduct of an alkyl polyol, an alkylene oxide adduct of an alkyl polyol, a polyalkylene glycol, and a polyhydric phenol. The poly(indenyl) acrylate of the polyhydroxy compound, and the ethyl phthalate (meth) acrylate obtained by using the polyether polyol. The compound (H) can be exemplified by the following compounds. Bis(A) bis(meth) acrylate, bisphenol A alkylene oxide adduct bis(indenyl) acrylate (ethoxylated bisphenol A di(methyl) acrylate, propoxy bisphenol A bis(indenyl) acrylate, ethoxylated ethoxylated bisphenol A di(meth) acrylate, bisphenol A glyceride di(indenyl) acrylate, bisphenol A propoxy glyceride di(indenyl) Acrylate, etc., ethoxylated bisphenol F di(methyl) acrylate, tricyclodecane dimethanol bis(indenyl) acrylate, decyl (decyl) acrylate, tricyclodecane dimethanol (fluorenyl) acrylate, ethylene glycol di(meth) acrylate, dipropylene glycol di(meth) acrylate, 1,3-butylene glycol di(meth) acrylate, 1,4-butanediol Di(meth) acrylate, glycerol 1,3-. diglyceride bis(indenyl) acrylate, 1,6-hexanediol ethoxy di(meth) acrylate, 1,6-hexanediol Propoxide di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, methyl 3-hydroxy-2,2-dipropionate di(indenyl)acrylate, 1,9 - decanediol II ( Mercapto) acrylate, 1,1 - decanediol di(meth) acrylate 'diethylene glycol di(meth) acrylate, neopentyl glycol bis(indenyl) acrylate, neopentyl glycol Propoxide bis(indenyl) acrylate, polyethylene glycol di(meth) acrylate, propylene glycol di(mercapto) acrylate, glycerol di(meth) propylene 26 201207034 acid ester, propylene glycol glyceride di(曱Acrylate, polypropylene glycol bis(indenyl) acrylate, polyethylene glycol di(meth) acrylate, tripropylene glycol di(meth) acrylate, triethylene glycol bis(indenyl) acrylate, four Ethylene glycol di(meth) acrylate, tripropylene glycol glyceride di(meth) acrylate, 2-hydroxy-3-propenyl methoxypropyl (meth) acrylate, 2-methyl-1,3 -propylene glycol diacrylate, trimethylolpropane benzoic acid bis(indenyl) acrylate, pentaerythritol bis(indenyl) acrylate monostearate, trimethylolpropane ethoxylated ether (Meth) acrylate, bis(indenyl) acrylate having two or more amine decanoate linkages UA-4200, ethyl urethane di(indenyl) acrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., bis(indenyl) acrylate with burial skeleton, 1,3-bis(3-methylpropene oxime) Oxypropyl)-1,1,3,3-tetramethyldioxane, trimethylolpropane tri(meth)acrylate, trishydroxypropylpropane ethoxytris(decyl)acrylate, Polyether triol tris(mercapto) acrylate, glycerol propoxy tri(meth) acrylate, neopentyl alcohol tris(decyl) acrylate, ethoxylated isomeric cyanuric acid triacrylate, ethoxylated three Hydroxymethylpropane triacrylate, trihydrocarbyl propane triacrylate, neopentyltetrakis(meth)acrylate, pentaerythritol ethoxytetrakis(meth)acrylate, ruthenium tris Propane tetra(indenyl) acrylate, propofol neopentyl tetraacrylate, dipentaerythritol hexa(meth) acrylate, ethyl citrate di(methyl) obtained using polyether diol Acrylate, ethyl citrate tri(meth) acrylate obtained by using polyether triol, amine hydrazine obtained by using polyether tetraol Ethyl tetra (meth) acrylate, the use of polyether alcohols obtained from six yuan Yue ethyl amine hexa (meth) acrylate. The photocurable composition of the present invention preferably contains the compound (H). In this case, the compound (H) contained in the photocurable composition may be one type or 2 27 201207034 or more. When the photocurable composition contains the compound (Η), the ratio of the compound (Η) is preferably 10 to 75 mass%, and 30 to 55, relative to the photocurable composition (the composition containing the compound). The mass % is better. When the compound (Η) is 10% by volume or more, the sensitivity of the photocurable composition can be improved. When the compound (Η) is 75% by mass or less, a light-hardening composition in which each component is uniformly dissolved can be obtained. (Photopolymerization initiator (G)) The photopolymerization initiator (G) may, for example, be an acetophenone photopolymerization initiator, a benzoin photopolymerization initiator, or a diphenyl ketone photopolymerization. Starting agent, thioxanthene photopolymerization initiator, α-amine ketone photopolymerization initiator, hydroxyketone photopolymerization initiator, α-mercaptopurine (acyl〇xhnester), benzyl _ (o-ethoxy ethoxy group)-α-single, acyl phosphine oxide (acryi ph〇Sphine oxide), ethyl vinegar, 3-ketolone (ketoc〇umarin), 2_ethyl hydrazine ( Ethyl anthraquinone), camphoroquinone, tetramethyl sulfonate, azobisisobutyronitrile, benzoquinone peroxide, dialkyl peroxide, secondary butyl peroxyisobutyrate, etc., by sensitivity and phase From the viewpoint of solubility, it is preferred to use a phenethyl photopolymerization initiator, a benzoin photopolymerization initiator, an α-amine ketone photopolymerization initiator or a ketone ketone photopolymerization initiator. . The acetophenone-based photopolymerization initiator can be exemplified by the following compounds. Benzene _, p-(tertiary butyl tri-o-acetophenone, chlorophenylethyl _, 2', 2'- acetophenone, hydroxyphenyl ethoxylate, 2,2 dioxin 2' _Phenyl acetophenone, 2-amine acetophenone, dialkylamine phenylethyl _, etc. The benzoin-based photopolymerization initiator may be exemplified by the following compounds: benzoin, benzoin, benzo Margin methyl ether, benzoin ethyl ether, benzoin 28 201207034 Cyclohexylbenzene remaining, 2_ -2-methyl-1-benzene

Isopropyl ether, benzoin, isobutyl, -2 methyl ketal, etc.

• Di-f-amine-1-(4-morpholinylbenzene)-butanone 丨, 2-methylmethylthio) benzene]·2_ 琳 基 丙 丙 丙 。 。 。. The diphenyl type photopolymerization initiator may be exemplified by the following compounds. Diphenyl _, benzamidine benzoic acid, benzyl phthalic acid methyl ester, methyl phthalic acid benzoate, 4-benzene benzene ketone, diphenyl ketone, diphenyl ketone, hydroxy two Phenyl ketone, hydroxypropyl diketone, 4,4,-bis(dimethylamine) diphenyl ketone, and the like. The photocurable composition of the present invention usually contains the compound (G). In this case, the compound (G) contained in the photocurable composition may be in the form of two or more kinds. The ratio of the photopolymerization initiator (the composition of the photopolymerization initiator) to the photopolymerization initiator ((3) is preferably 1 to 12% by mass, more preferably 4 to 10% by mass. When the photopolymerization initiator (G) is not more than 5% by mass, the cured product can be easily obtained. When the photopolymerization initiator (G) is 12% by mass or less, it can be uniformly mixed. Therefore, the photopolymerization initiator (〇) remaining in the hardened material is reduced, and the physical properties of the cured product are suppressed from being lowered. <<Other components" The photocurable composition may also contain the polymer (D) and the compound ( E), a compound (F), a photopolymerization initiator, and other components other than the compound (H), and other components may be, for example, a surfactant other than the polymer (D) (may be a fluorine-based surfactant), Light other than the compound (E), the compound (F) and the compound (H) 29 201207034 σ σ 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 The light hardening of the invention! · Health, and the product does not require special tasks other than the polymer (9) The active agent or the compound (F) and the compound (the photopolymerizable compound other than the imprinted surface, the photosensitizer, the resin, the metal oxide fine particles, the carbonized mouth, the metal straight, etc. (hereinafter, collectively referred to as the addition) The fine purpose is included in the photocurable composition of the present invention. The photosensitizer may, for example, be n-butylamine, di-n-butylamine, tri-n-butylphosphine, or dithio-s-phenylmethylisothiourea. Toluene sulphate, triethylamine, diethylamine methacrylate, oxime, oxime, tetraethylamine, 4,4,-bis(dialkylamine)diphenyl ketone oxime compound. For example, a resin, a polyacetate, a polyacetate oligomer, a polycarbonate, or a poly(meth)acrylate may be mentioned. Examples of the metal oxide fine particles include titanium oxide, oxidized oxide, and oxidization. Examples of the carbon compound include a carbon nanotube, a fullerene, etc. Examples of the metal fine particles include copper, platinum, and the like. Other organic compounds include, for example, 卟琳, metal inclusion 卟琳' ionic liquid (1 · hexyl _3_ decyl imidazole vapor, etc.), pigments, etc. when photocurability When the product contains the above-mentioned other components (particularly, the additive (I) is contained), the ratio of 'the photocurable composition (the composition containing the other components)' to the total amount of the other components is preferably 2% by mass or less. When the amount of the additive (1) is 20% by mass or less, the photocurable composition can be uniformly mixed to obtain a homogeneous photocurable composition. 30 201207034 The photocurable composition of the present invention described above is contained in a specific ratio. The lower molecular weight polymer (D)' obtained by copolymerizing the specific compounds (A) to (C) is used as a nonionic fluorosurfactant, so that a compound derived from perfluorooctyl acid is not required to be used as a raw material. It is possible to form a cured product excellent in mold release property and is excellent in compatibility with a fluorine surfactant and other components. <Manufacturing method of a molded article having a fine pattern on the surface> The method for producing a molded article having a fine pattern on the surface of the present invention has the following steps (1) to (3). (1) A step of bringing the photocurable composition of the present invention into contact with a surface of a mold having an inverted pattern. The surface of the mold has a reverse pattern of the aforementioned fine pattern. (2) A step of applying light to the photocurable composition and curing the photocurable composition to form a cured product in a state where the photocurable composition is brought into contact with the surface of the mold. (3) A step of separating the mold from the cured product to obtain a molded body having a fine pattern on the surface. The method for producing a molded body having a fine pattern on the surface of the present month is more specific. The following methods (4) to (4) can be exemplified. (4) The method of the following steps (a-1) to (a-4). The garden does not have a step of disposing the photocurable composition 20 on the surface of the substrate 30. (a2) As shown in Fig. 1, a step of pressing the mold 1〇 to the photocurable composition 2〇' to bring the inversion pattern 12 of the 4th mold 1G into contact with the photocurable composition 20 is 201207034. (a-3) A step of applying light to the photocurable composition 20 and curing the photocurable composition 2 to form a cured product in a state where the mold 10 is pressed against the photocurable composition 20. (a-4) A step of separating the mold 10, the substrate 30, and the mold 10 from the cured product to obtain a molded body having a fine pattern on the surface. (b) Method: A method having the following steps (b-Ι) to (b-4). (b-Ι) As shown in Fig. 2, the photocurable composition 20 is placed on the surface of the reverse pattern 12 of the mold 1〇. (b-2) The step of pressing the substrate 30 against the photo-curable composition 20 on the surface of the mold 1 as shown in Fig. 2 . (b-3) A step of applying light to the photocurable composition 20 in a state where the substrate 30 is pressed to the photocurable composition 2, and curing the photocurable composition 2 to be a cured product. (b-4) A step of separating the mold 10, the substrate 30, and the mold 1 from the cured product to obtain a molded body having a fine pattern on the surface. (c) Method: A method having the following steps (c_i) to (c_4). (c-1) As shown in Fig. 1, the substrate 3 is brought into close contact with or in contact with the mold 1 in such a manner that the reverse pattern 12 of the mold 1 is located on the side of the substrate 30. (c-2) The step of filling the photocurable composition 2〇 between the substrate 3〇 and the mold 10 as shown in Fig. 1 . (c-3) A step of curing the photocurable composition 20 and curing the photocurable composition 2 into a cured product in a state where the substrate 30 is in close contact with or in contact with the mold 1A. 32 201207034 (c_4) A step of separating the mold 〇 or 'the substrate 3' and the mold 1 from the cured product to obtain a molded body having a fine pattern on the surface. The substrate may be exemplified by a substrate made of an inorganic material or a substrate made of an organic material. Examples of the inorganic material include ruthenium wafer, glass, quartz glass, metal (aluminum, nickel, copper, etc.), metal oxide (alumina, etc.), tantalum nitride, nitriding, and lithium niobate. Wait. The organic material may, for example, be a fluororesin, a fluorinated resin, an acrylic resin, a polycarbonate, a polyacetate (poly(p-diphenyldicarboxylate), a polyimine, a polypropylene, a polyethylene 'nylon resin (nyl) 〇n resin), polyphenylene sulfide scale (p〇iyph mail_ sulfide), cyclic polyolefin, and the like. A surface-treated substrate can also be used as the substrate from the viewpoint of excellent adhesion to the photocurable composition. The surface treatment may, for example, be a primer coating treatment 'ozone treatment, electric (four) engraving treatment, or the like. The primer used in the primer coating treatment may be exemplified by poly(methyl)acrylic acid vinegar, money coupling agent, silazane or the like. The mold may be exemplified by a mold made of a non-transparent material or a mold made of a light-transmitting material. Examples of the non-translucent material include 11 wafers, nickel, copper, stainless steel, chin, SiC, mica, and the like. The light-transmitting material may, for example, be quartz, glass, cyclic polycarbonate or polycarbonate. At least one of polydimethylsiloxane, polyethylene terephthalate, transparent tree substrate and mold is made to pass light of a wavelength at which the photopolymerization initiator (G) acts. /. The above materials. The mold has a flip pattern on the surface. The flip pattern corresponds to the flip pattern of the fine pattern of the body surface of the forming 33 201207034. The flip pattern has fine protrusions and/or recesses. The convex portion may be, for example, a long strip extending from the surface of the mold, a protrusion scattered on the surface, or the like. The concave portion may be, for example, a long groove extending over the surface of the mold, a hole scattered on the surface, or the like. The shape of the ridge or groove may be, for example, a straight line, a curved line, a curved shape or the like. The ridges or grooves may also exist in parallel to form a stripe shape. The cross-sectional shape of the ridge or groove perpendicular to the longitudinal direction may be, for example, a rectangle, a trapezoid, a triangle, a semicircle or the like. The shape of the large rise or the hole may be, for example, a triangular prism, a quadrangular prism, a hexagonal column, a cylinder, a double pyramid, a quadrangular pyramid, a hexagonal cone, a cone, a hemisphere, a polyhedron, or the like. The width or width of the ridges or grooves is preferably from 1 nm to 500 μm, more preferably from 10 nm to ΙΟΟμηη, and even more preferably from 15 ηηη to 1 〇μπι. The width of the ridges means the length of the base in the section perpendicular to the longitudinal direction. The width of the groove means the length of the upper side in the section perpendicular to the longitudinal direction. The width of the protrusions or holes is preferably lmn~5〇〇μϊη, more preferably 10nm~ΙΟΟμηι, and 15ηιη~1〇μπι. The width of the protrusion means the length of the bottom side in the section perpendicular to the longitudinal direction when the bottom surface is elongated; otherwise, it 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 in the direction perpendicular to the longitudinal direction when the opening portion is elongated; otherwise, it means the maximum length in the opening portion of the hole. The height of the convex portion is preferably from 1 nm to 500 μm, and more preferably from 34 201207034 - l〇nm to l〇〇pm, and particularly preferably from 15 nm to ΙΟμηι. The depth of the recesses is preferably averaging from 1 nm to 5 〇〇μΓη, more preferably from 1 〇 nm to ΙΟΟμητ, and more preferably from 15 nm to 1 〇 Llm. In the region where the flip pattern is dense, the interval between the adjacent convex portions (or recesses) is preferably 1 nm to 50 〇 μηι, and more preferably 匕 刈 刈 刈. The interval between the adjacent convex portions means the distance from the bottom end of the cross section of the convex portion to the bottom end of the cross section of the adjacent convex portion. The interval between adjacent concave portions means the distance from the upper end of the carrying surface of the concave portion to the upper end of the wearing surface of the adjacent concave portion. The minimum size of the convex portion is preferably Inm 50 50 μm, more preferably 1 nm to 500 nm, and particularly preferably 1 nm to 50 nm. The minimum size means the smallest of the width, length and southness of the projection.最小 The minimum size of the concave portion is preferably lnrn~50μηι, more preferably 1nm~5〇Onm, and particularly preferably 1nm~50nm. The minimum size means the width, length and depth of the four parts _ the smallest size. Step (a-Ι): The method of disposing the photocurable composition may, for example, be an inkjet method, a potting method, a spin coating method, a drum coating method, a cast coating method, a dip coating method, or a molding port. Coating method, Langmuir-Blodgett method, vacuum steaming method, and the like. The photocurable composition may be disposed on the entire surface of the substrate or may be disposed on a portion of the surface of the substrate. Step (a-2): Force 0 pressure (counting pressure) when the mold is pressed to the photocurable composition 35 201207034 It is preferable to be larger than G~1 GMPa or less, and Wei 1 to police a is better. The temperature at which the mold is pressed to the photocurable composition is preferably 〇~1〇〇〇c, and more preferably 丨〇~. Step (b-Ι): The method of disposing the photocurable composition may, for example, be an inkjet method, a filling method, a spin coating method, a roll coating method, a cast coating method, a dip coating method, a die coating method, or a blue screen Er-Broji method, vacuum distillation method, etc. The photocurable composition may be disposed on the entire surface of the inversion pattern of the mold, or may be disposed in one of the inversion patterns, and is preferably disposed on the entire surface of the inversion pattern. Step (b-2): The pressing force (counting pressure) at the time of pressing the substrate to the photocurable composition is preferably more than 0 to 10 MPa, more preferably 0.2 s MPa. The temperature at which the substrate is pressed to the photocurable composition is preferably 〇1 to 1 〇〇 ° C, and is 1 〇 to 6 〇.匚 Better. Step (c-2): A method of filling the photocurable composition between the substrate and the mold is exemplified by a method of attracting the photocurable composition to the void by a capillary phenomenon. The temperature at which the photocurable composition is filled is preferably 〇1 to 1 〇〇〇C, more preferably 10 to 60 °C. Steps (a-3), (b-3), and (c-3): The method of irradiating light may be, for example, a method of irradiating light from the mold side using a mold made of a light-transmitting material, or a substrate made of a light-transmitting material. A method of irradiating light on the substrate side. The wavelength of light is preferably 200 to 500 nm. When irradiated with light, also 36 201207034 - The photohardenable composition can be heated to promote hardening. The temperature at which the light is irradiated is preferably 〇1 to 1 〇〇 ° C, and more preferably 1 〇 to 6 〇 ° c. Steps (a-4), (b-4), and (c-4): The temperature at which the mold or the substrate and the mold are separated from the cured product is 〇1 to 1 Torr. (: Preferably, it is preferably 10 to 60 ° C. After the substrate and the mold are separated from the cured product, as shown in Fig. 3, the cured product 42 having only the surface on which the reverse pattern of the mold is transferred can be obtained. The molded body 40 having the fine pattern 44 on the surface thereof. When only the mold is separated from the cured product, as shown in Fig. 4, the cured product 42 and the substrate only having the surface on which the reverse pattern of the mold is transferred are obtained. 30 molded bodies 4 (layered body) having a fine pattern 44 on the surface thereof. Examples of the molded body having a fine pattern on the surface include the following items: Optical elements: microlens array, optical waveguide element, and optical switching element ( Grid 'polar polarizing element, wave plate, etc.), Fresenel zone plate element, binary element, blazed element, photonic crystal, etc. Anti-reflection member: AR (anti-reflection) coating Components, etc. Wafers: biochips, μ-TAS (micro total analysis system) wafers, microchips, etc. Others: recording media, display materials, catalyst carriers, filters, sensor components, semiconductor devices (including Photoresist used in the manufacture of MEMS.), a replica mold (mother mold) for electroforming, a replica mold for imprinting, a daughter mold, etc. When used as a photoresist, it can be Shaped molded body 37 201207034 As a mask, a substrate is formed into a fine pattern on a substrate. When used as a replica mold for an electric front, a conductive layer is formed on the surface of a molded body having the fine pattern by electroless plating or metal evaporation. Thereafter, nickel is deposited by electroplating on the surface of the conductive layer by nickel electroplating, whereby the nickel electroforming mold can be used. With the excellent mold release property of the surface of the molded body, it is easy to produce the nickel electroforming mold from the molded body. Further, since the molded body having the fine pattern has high transparency and high mold release property, it can also be used as a replica mold for imprinting. In particular, a light-transmitting material is used as a base of the molded body. In the case of a material, it can be used as a replica mold for photon imprinting. In the method for producing a molded body having a fine pattern on the surface of the present invention described above, the photocurable group of the present invention is used. The material can form a cured product excellent in release property, and is excellent in compatibility with a fluorine surfactant and other components, so that a fine pattern having a surface on which a reverse pattern of a mold is precisely transferred can be produced and a uniform surface composition can be formed. EXAMPLES Hereinafter, the present invention will be described by way of examples, but the present invention is not limited by the examples. Examples 1, 5 to 7, 10, 12, 13, 17 to 32, 37 to 46 are examples. Examples 2 to 4, 8, 9, U, 14 to 16, and 33 to 36 are comparative examples. (Mass average molecular weight) The mass average molecular weight of the polymer (D) is a GPC analyzer (Goldware Co., Ltd., GPC-101) For the measurement, specifically, use the column (KF801, KF802, KF803) of Showa Electric 38 201207034 Co., Ltd. to separate the eluate using tetrahydrofuran, and use polymethyl methacrylate as a standard substance. The mass average molecular weight is obtained. (Viscosity) The viscosity of the photocurable composition at 25 ° C was measured using a viscometer (manufactured by Toki Sangyo Co., Ltd., TV-20). The viscometer was calibrated with a standard solution (JS50 (33.17 mPa.s at 25 °C)). It is judged to be good for a viscosity of 300 mPa·s or less. (Sensitivity) The sensitivity of the photocurable composition was determined as follows. The photocurable composition was applied to the surface of the substrate by a spin coating method to have a thickness of about 1.5 μm, where the irradiation was carried out from a high-pressure mercury lamp (having a dominant wavelength at 255, 315, and 365 nm in 1.5 to 2.0 kHz). The light of the light source is obtained as the cumulative amount of light until it is completely hardened. Whether or not the photocurable composition is completely cured is determined by measuring the ruthenium spectrum based on the presence or absence of olefin absorption in the propylene group. It is judged to be good for those having a sensitivity of 5 〇〇 mJ/cm 2 or less. (Contact angle) The contact angle of the cured product with water was measured as follows. The photocurable composition was dropped to polyethylene terephthalate (T'gPETmm (trade name, manufactured by Toyobo Co., Ltd.)

The light of the main wavelength source is lighted for 15 seconds, and the carrier is covered thereon, and then irradiated with 〇 kHz, and 255, 315, and 365 nm have > seconds, clocks to obtain a cured product. 39 201207034 For the cured product, a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., model CA-X150) was used, and a water droplet of 4 μm was attached to the surface of the cured product to measure. When the contact angle is 80 degrees or more, it is judged to be good. The contact angle is the basis for the release property of the cured product. In addition, it is judged that it is good that the deviation σ when the contact angle is measured at a plurality of points is 2.5 or less. The deviation σ indicates the uniformity of the composition after the surface of the cured product. (Compound (Α)) Compound (Α1-1) : 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoromethyl acrylate S (Aldrich) Social system). CH2=C(CH3)-C(0)0-(CH2)2-(CF2)6F · · · (A1-1). (Compound (B)) Compound (B-1): polyethylene glycol monomethacrylate (manufactured by Nippon Oil & Fats Co., Ltd., number average molecular weight: 284). CH2=C(CH3)-C(0)0-(CH2CH20)4 5-H· · «(B-l). Compound (B-2): polyethylene glycol monodecyl acrylate (manufactured by Nippon Oil & Fats Co., Ltd., number average molecular weight: 438). CH2=C(CH3)-C(0)0-(CH2CH20)8-H · · · (B-2). Compound (B-3): polyethylene glycol monomethacrylate (manufactured by Nippon Oil & Fats Co., Ltd., number average molecular weight: 174). CH2=C(CH3)-C(0)0-(CH2CH20)2-H. (B-3). Compound (B-4): decyloxy polyethylene glycol monomethacrylate (manufactured by Sakai Oil Co., Ltd., number average molecular weight: 276). CH2=C(CH3)-C(0)0-(CH2CH20)4-CH3 · · · (B-4). 40 201207034 (Compound (c)) Compound (C-1): 2-ethylhexyl methacrylate (manufactured by Aldrich Co., Ltd.). CH2=C(CH3)-C(0)0-CH2CH(C2H5)C4H9. (C-1). Compound (C-2): hexyl methacrylate (manufactured by Aldrich Co., Ltd.). CH2=C(CH3)-C(0)0-C6Hl3 · · · (C-2). Compound (C-3): isobutyl methacrylate (manufactured by Aldrich Co., Ltd.). CH2=C(CH3)-C(0)0-CH(CH3)C2H5 . · · (C-3). Compound (C-4): dodecyl methacrylate (manufactured by Aldrich Co., Ltd.). CH2=C(CH3)-C(0)0-Cl2H25 · . . (C-4). Compound (C_5): mercaptoacrylic acid octagonal vinegar (manufactured by Aldrich Co., Ltd.). CH2=C(CH3)-C(0)0-C18H37 . · · (C-5). (Compound (E)) Compound (El-1) : 3,3,4,4,5,5,6,6,7,7,8,8,8-trifluorotrifluoroacrylate (manufactured by Aldrich) ). CH2=CH-C(0)0-(CH2)2-(CF2)6F · · · (EM). (Compound (F)) Compound (F-1): 2-methyl-2-endoic acid radix sin (manufactured by Idemitsu Kosan Co., Ltd.). [Chemical 1]

Compound (F-2): isobornyl acrylate (manufactured by Aldrich Co., Ltd.). 41 201207034 Compound (F-3): 2-ethylhexyl acrylate (manufactured by Aldrich Co., Ltd.). (Photopolymerization initiator (G)) Photopolymerization initiator (G-1): manufactured by Ciba. Geigy. Specialty, trade name: IRGACURE 651. Photopolymerization initiator (G-2): manufactured by Ciba. Geigy. Specialty, trade name: IRGACURE 184. Photopolymerization initiator (G-3): manufactured by Ciba. Geigy. Specialty, trade name: IRGACURE 907. (Compound (H)) Compound (H-1): tetraethylene glycol diacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.). The compound (H-2): a compound represented by the following formula (however, a mixture of a compound of the hydrogen atom and a compound of the R-methyl group) (a compound of Aldrich). CH2=C(CH3)-COO-CH2CH2OCONHCH2-(C(CH3)R-CH2)2-CH2NHCOO-CH2CH2-OCO-C(CH3)=CH2 Compound (H-3): Polyether type amine citrate Acrylate (trade name: UA-4200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)). Compound (H-4): neopentyl glycol dimethacrylate (manufactured by Aldrich Co., Ltd.). Compound (H-5): tricyclic tert-doped diacrylic acid g (manufactured by Aldrich Co., Ltd.). Compound (H-6): bisphenol A propoxy diacrylate (manufactured by Aldrich Co., Ltd.). Compound (H-7): trihydroxymercaptopropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.). Compound (H-8): neodymethylene tetraacetate (manufactured by Aldrich Co., Ltd.). [Synthesis Example 1] 42 201207034 Into a 100 mL financial pressure reaction vessel, 16.00 g of a compound (Al-1), 16.68 g of a compound (Bl), 7.32 g of a compound (Cl), and 3.88 g of a molecular weight modifier were added. Ethyl mercaptan (manufactured by Wako Pure Chemical Industries, Ltd.), 40.00 g of ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) as a solvent, and 0.60 g of dimethyl 2,2'-azo as a polymerization initiator Bis(2-propionate) (manufactured by Wako Pure Chemical Industries, Ltd.), after replacing the inside of the reaction vessel with nitrogen, the mixture was stirred at 70 ° (for 16 hours). After the polymerization was completed, the mixture was distilled under reduced pressure. The ethyl acetate was removed to obtain a polymer (D-1). [Synthesis Examples 2 to 11] The same as the synthesis example 1 except that the types (A) to (C) of the compounds and the addition ratio were changed as shown in Table 1. The polymer (D-2) to (D-11) were obtained. [Synthesis Example 12] The types and addition ratios of the compounds (A) to (C) were used as shown in Table 1, and they were used as molecular weight regulators. The polymer (D-12) was obtained in the same manner as in Synthesis Example 1 except that the octyl mercaptan was 5.04 g. [Synthesis Example 13] The compound was used as shown in Table 1. The polymer (D-13) was obtained in the same manner as in Synthesis Example 1 except that the octyl mercaptan as the molecular weight modifier was 5.82 g, and the polymer (D-13) was obtained. In the same manner as in Synthesis Example 1, except that the types and addition ratios of the compounds (A) to (C) were used as shown in Table 1, and the octyl mercaptan as the molecular weight modifier was 6.25 g, a polymer was obtained. (D-14) [Synthesis Example 15] 43 201207034 In addition to the types and addition ratios of the compounds (A) to (C) as shown in Table 1, the octyl mercaptan as a molecular weight modifier was 1.94 g. The polymer (D-15) was obtained in the same manner as in Synthesis Example 1. [Synthesis Example 16] 14.20 g of the compound (Al-1) and 9-94 g of the compound (Bl) were added to the reaction vessel under 100 mL. 4.26 g of the compound (C-1), 2.76 g of octyl mercaptan (manufactured by Wako Pure Chemical Industries, Ltd.) as a molecular weight regulator, and 28.41 g of ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.43 g as a solvent. Dimethyl 2,2'-azobis(2-propionic acid methyl ester) (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator, replacing the reaction volume with nitrogen After the inside of the apparatus, the mixture was polymerized at 70 ° C for 16 hours while stirring. After the completion of the polymerization, ethyl acetate was distilled off under reduced pressure to obtain a polymer (D-16). [Synthesis Examples 17 to 19] The polymer (D-17) to (D-19) were obtained in the same manner as in Synthesis Example 16 except that the addition ratio of the compounds (A) to (C) was changed as shown in Table 1. 44 201207034 [Table 1] Polymer (D) Compound (A) (mass ° /.) Compound (B) (% by mass) Compound (C) (% by mass) Mass average molecular weight D-1 A1-1 40 B-1 42 C-1 18 4520 D-2 A1-1 40 B-2 42 C-1 18 4950~ D-3 A1-1 40 B-3 42 C-1 18 4950 D-4 A1-1 40 B-4 42 C-1 18 2600 D-5 A1-1 40 B-1 42 C-2 18 3880~~ D-6 A1-1 40 B-1 42 C-3 18 4020~ D-7 A1-1 40 B-1 42 C-4 18 4020 D-8 A1-1 40 B-1 42 C-5 18 4180 D-9 A1-1 60 B-1 28 C-1 12 3220~~ D-10 A1-1 25 B-1 52 C-1 23 4200 D-11 A1-1 10 B-1 60 C-1 30 3120~~ D-12 A1-1 40 B-1 42 C-1 18 2560 D-13 A1-1 40 B-1 42 C-1 18 1060 D-14 A1-1 40 B-1 42 C-1 18 850 D-15 A1-1 40 B-1 42 C-1 18 7540 D-16 A1-1 50 B-1 35 C -1 15 3500 D-17 A1-1 20 B-1 75 C-1 5 5010 ~ D-18 A1-1 40 B-1 Bu 60 C-1 ~~0~~ 4680 D-19 A1-1 25 B -1 30 C-1 45 3370 [Example 1] In a small glass bottle container (internal volume 13 mL), 4 g of a polymer (Dl), 2.00 g of a compound (El-l), 4. a compound of g (jr)), 3 36 g of a compound (H-1), followed by a photopolymerization initiator of 〇.6〇§ 〖), filtered with a polyethylene terephthalate to obtain a photocurable composition. The composition of the composition is shown in Table 2, and the evaluation results are shown in Table 3. [Examples 2 to 43] ° As shown in Table 2, except that the composition was changed, a photocurable composition was prepared in the same manner as in the above. The evaluation results are shown in Table 3. 45 201207034 [Table 2-1] Example polymer (D) (% by mass) Compound (E) (% by mass) Compound (F) (% by mass) Photopolymerization initiator (G) (% by mass) Compound (H) (% by mass) 1 D-1 0.4 E1-1 20 F-1 40 G-1 6 H-1 33.6 2 D-2 0.4 E1-1 20 F-1 40 G-1 6 H-1 33.6 3 D-3 0.4 E1-1 20 F-1 40 G-1 6 H-1 33.6 4 D-4 0.4 E1-1 20 F-1 40 G-1 6 H-1 33.6 5 D-5 0.4 E1-1 20 F-1 40 G-1 6 H-1 33.6 6 D-6 0.4 E1-1 20 F-1 40 G-1 6 H-1 33.6 7 D-7 0.4 E1-1 20 F-1 40 G-1 6 H-1 33.6 8 D-8 0.4 E1-1 20 F-1 40 G-1 6 H-1 33.6 9 D-9 0.4 E1-1 20 F-1 40 G-1 6 H-1 33.6 10 D-10 0.4 E1- 1 20 F-1 40 G-1 6 H-1 33.6 11 D-11 0.4 E1-1 20 F-1 40 G-1 6 H-1 33.6 12 D-12 0.4 E1-1 20 F-1 40 G- 1 6 H-1 33.6 13 D-13 0.4 E1-1 20 F-1 40 G-1 6 H-1 33.6 14 D-14 0.4 E1-1 20 F-1 40 G-1 6 H-1 33.6 15 D -15 0.4 E1-1 20 F-1 40 G-1 6 H-1 33.6 16 - - E1-1 20 F-1 40 G-1 6 H-1 34.0 17 D-1 0.4 E1-1 20 F-2 40 G-1 6 H-1 33.6 18 D-1 0.4 E1-1 20 F-3 40 G-1 6 H-1 33.6 19 D-1 0.4 E1-1 20 F-1 40 G-2 6 H-1 33.6 20 D-1 0.4 E1-1 20 F-1 40 G-3 6 H-1 33 .6 21 D-1 0.4 E1-1 20 F-1 40 G-1 6 H-2 33.6 22 D-1 0.4 E1-1 20 F-1 40 G-1 6 H-3 33.6 23 D-1 0.4 E1 -1 20 F-1 40 G-1 6 H-4 33.6 24 D-1 0.4 E1-1 20 F-1 40 G-1 6 H-5 33.6 25 D-1 0.4 E1-1 20 F-1 40 G -1 6 H-6 33.6 [Table 2-2] Example polymer (D) (% by mass) Compound (E) (% by mass) Compound (F) (% by mass) Light-driven Μ (C (quality 1 L combined) Ø0 Ϊ%) Compound (Η) (% by mass) 26 D-1 0.4 E1-1 20 F-1 40 G-1 6 Η-1+Η-2 23.6+10 27 D-1 0.4 E1-1 20 F-1 40 G-1 6 Η-1+Η-5 23.6+10 28 D-1 0.4 E1-1 20 F-1 40 G-1 6 Η-1+Η-7 23.6+10 29 D-1 0.4 E1-1 20 F-1 40 G-1 6 Η-1+Η-8 23.6+10 30 D-1 0.4 E1-1 20 F-1 40 G-1 6 Η-4+Η-7 23.6+10 31 D-1 0.4 E1-1 20 F-1 40 G-1 6 Η-5+Η-8 23.6+10 32 D-1 0.4 E1-1 11 F-1 12 G-1 6 Η-5+Η-8 30.6+40 33 D-16 0.4 E1-1 20 F-1 40 G-1 6 Η-1 33.6 34 D-17 0.4 E1-1 20 F-1 40 G-1 6 Η-1 33.6 35 D-18 0.4 E1-1 20 F-1 40 G-1 6 Η-1 33.6 36 D-19 0.4 E1-1 20 F-1 40 G-1 6 Η-1 33.6 46 201207034 37 Dl 3.1 El-1 19.5 Fl 38.9 Gl 5.8 H-5+H-8 23+9.7 38 Dl 0.05 El-1 20 Fl 40 Gl 6 H-5+H-8 23.95+10 39 Dl 0.4 El-1 8 Fl 19 Gl 6 H-5+H-8 42+24.6 40 Dl 0.4 El-1 30 F-3 30.6 Gl 6 H-4 33 41 Dl 0.4 El-1 15 Fl 50 Gl 8 Hl 26.6 42 Dl 0.4 El-l 20 Fl 35 Gl 3 Hl 41.6 43 Dl 3 El-1 30 Fl 40 Gl 9 Hl 18 [Table 3] Example Viscosity (mPa*s) Sensitivity (mJ/cm2) Contact angle (degrees) Deviation of contact angle σ 1 16 441 84 1.2 2 16 441 82 2.9 3 16 441 82 4.6 4 16 441 81 2.8 5 16 441 85 2.1 6 16 441 85 1.7 7 16 441 87 2.1 8 16 441 85 4.4 9 16 441 78 2.7 10 16 441 90 2.3 11 16 441 77 2.1 12 16 441 85 2.5 13 16 441 86 0.8 14 16 441 87 3.1 15 16 441 82 4.6 16 16 441 75 1.6 17 12 441 84 1.3 18 10 441 84 1.4 19 16 441 83 1.2 20 16 441 84 1.1 21 56 441 86 1.3 22 85 441 88 1.3 23 14 441 88 1.4 24 35 441 89 1.2 25 23 441 87 1.3 26 54 441 84 1.3 27 25 441 86 1.4 28 22 441 83 1.2 29 33 441 84 1.3 30 29 441 85 1.3 31 41 441 86 1.5 32 78 441 84 1.4 33 16 441 71 5.2 34 16 441 75 3.0 35 16 441 75 4.1 36 16 441 79 2.9 47 201207034

[Example 44] The photocurable composition of Example 1 was dropped onto the surface of a tantalum wafer at 25 ° C to obtain a tantalum wafer uniformly coated with the composition. A quartz mold having a surface having a width of 800 nm, a height of 180 nm, and a length of 10 mm is pressed against a photocurable composition on a Shi Xi wafer, and is directly added at 0.5 MPa (measured pressure) in this state. Pressure. Next, the photocurable composition was irradiated with light from a high pressure mercury lamp (a light source having a dominant wavelength of 255, 315, and secret (10) at 1.5 to 2.0 kHz) from the mold side at 25 ° C for 15 seconds. 'A cured product of a photocurable composition is obtained. In the hunger, the mold was separated from the Shixi wafer, and the surface of the Shixi wafer was formed to form a cured product. The cured product was attached to the concave portion of the surface of the mold with the convex portion of the mold turned over. The depth of the recess is 178~18 〇. Then, 'the molded body is used as a photomask, and the dry type engraving device manufactured by SAMC Co., Ltd.' is used, and the mixed gas of the oxygen (4) and the oxygen of the (4) is used at 5 Pa, 7 GW to perform dry engraving. . It can be engraved on the :: 805nm, deep: 3〇nm, long: (1) 哗 pattern. [Example 45], at 25 C, the photocurable composition of Example 3 was dropped onto the pET film (Toyo, Miscellaneous 'trade name: c〇sm〇sh_dip (9)), the easy side, surface (4) The ρΕτ film of the composition was uniformly applied. A surface mold having a surface of 48 201207034 - a quartz mold having a width of 800 nm, a height of 180 nm, and a length of 1 〇 is pressed against the photocurable composition on the Ρ Ε film, and is directly 0.5 MPa in this state (in this state). The gauge pressure is pressurized. Next, the photocurable composition was irradiated with light from a high pressure mercury lamp (a light source having a dominant wavelength at 255, 315, and 365 nm at 1.5 to 2.0 kHz) from the mold side at 25 ° C for 15 seconds to obtain light. A hardened substance of a hardening composition. The mold was separated from the PET film at 25 ° C to obtain a molded body having a cured product formed on the surface of the PET film, which had a concave portion on the surface of which the convex portion of the mold was inverted. The depth of the recess is 178 to 18 〇 nm. Next, the molded body was used as a replica mold for nanoimprinting. Specifically, 1 of the photocurable composition of Example 1 was dropped on the surface of the PET film (trade name: COSMOSHINE A4100, manufactured by Toyobo Co., Ltd.), and a PET film uniformly coated with the composition was obtained. The replica mold was pressed to the photocurable composition on the PET film, one side at 25. (: A light having a pressure of 5 MPa is applied, and the photocurable composition is irradiated with light from a high-pressure mercury lamp (a light source having a dominant wavelength at 255, 315, and 365 nm in I·5 to 2 〇 kHz) from the replica mold side. After 15 seconds, a cured product of the photocurable composition of Example 1 was obtained. The replica mold was separated from the pet film at 25 ° C to obtain a molded body having a cured product formed on the surface of the PET film, and the cured product was attached thereto. The surface has a convex portion in which the concave portion of the replica mold is inverted. The height of the convex portion is 175 to 177 nm. [Example 46] A photocurable composition of Example 30 is dropped onto a PET film at 25 ° C (Toyo Spinning Co., Ltd.) Co., Ltd., trade name: COSMOSHINE A4100) The surface of the easy-to-contact side 49 201207034, a PET film uniformly coated with the composition was obtained. The surface was made of quartz having a width of 800 nm, a height of 180 nm, and a length of ΙΟμπι. The mold is pressed against the photocurable composition on the PET film, and is directly pressurized at 〇-5 MPa (measured pressure) in this state. Next, the photocurable composition is irradiated from the mold side at a temperature of 25 ° C from a high pressure. Mercury lamp (in 1.5~2.0kHz, at 255 , 315, and 365πιη light having a dominant wavelength of light source for 15 seconds to obtain a cured product of the photocurable composition. At 25 C, the mold is separated from the PET film to form a cured film having a surface formed with a cured product. The hardened body has a mold convex surface on the surface thereof, and the recessed portion is turned over. The depth of the concave portion is 178 to 18 〇 plus, and the money body is used as a enamel electroformed replica mold. Co., Ltd.) The medium scale replica mold is impregnated in the electroless plating solution (high-purity chemistry, the formula 'with a nickel layer on the surface. Next, the copying mold with the brocade layer attached to the brocade 1: deplating m night towel circulation When the current is recorded with a fresh film thickness of about 2°, the electric ore operation is stopped, and the copying of the nickel electrolysis liquid is taken out, and the height of the convex portion of the gold mold which is peeled off from the nickel mold is 178~ 18. Fine. Applicable body on the skin, the molded body obtained by the manufacturing method has a fine pattern as an optical element, an antireflection member, a recording medium, a Japanese film, a microreaction|§, a system, a touch Media carrier, semiconductor package, complex M clothing, 1 It is useful to use a mold, a embossing tool, a material copying mold, etc. In addition, the patent specification, patent application scope, and drawing of Japanese Patent Application No. 50 201207034 - 2009-025083, filed on Feb. 5, 2009. The entire disclosure of the invention and the summary of the invention is incorporated in the specification of the present invention. I: BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view showing an example of a method of producing a molded body having a fine pattern on its surface. 2 is a cross-sectional view showing another example of a method of producing a molded body having a fine pattern on its surface. Fig. 3 is a cross-sectional view showing an example of a molded body having a fine pattern on its surface. Fig. 4 is a cross-sectional view showing another example of a molded body having a fine pattern on its surface. ' [Main component symbol description] • 1〇...Mold 40...Formed body 12.··Flip pattern 42...cured material 20.. Photocurable composition 44...fine pattern 30.. .substrate 51

Claims (1)

201207034 VII. Patent application scope: L A photocurable composition for imprinting, which is a main component of a compound having one or more acryloxy or methacryloxy groups, and the photocuring property for imprinting The composition is a copolymer of the following compound (4) and the following compound (B) and the following compound (c), and the unit of the following compound (a) and the following compound (B) and the following compounds The total amount of the unit of (6), the ratio of the unit of the following compound (VIII) is 20 to 45% by mass, and the ratio of the unit of the following compound (B) is 2 () to 65 % by volume, and the following compound (C) is early το. The ratio of the photocurable composition for imprinting contains a polymer (D) having a mass average molecular weight of ～5 GGG; Compound (A): a compound represented by the following formula (1), , CH2=C(R")-C(〇)〇-Q.Rf (1) But 'R11 is a hydrogen atom or a methyl group, (10) a single bond or a divalent bond containing no gas atom, Rf is The number of carbon atoms in the main chain is a polyfluoroalkyl group having an etheric oxygen atom between carbon atoms; 'The compound order is represented by T formula (2), and the number average molecular weight is 35 The following compound, CH2=C(R2,)-C(0)0-(CH2CH(R22)〇)nH .. (2) However, R21 is a hydrogen atom or a methyl group, and R22 is a hydrogen atom or a carbon number ^ The alkyl group, the η system is 3 to 6, and the "solid scales 22 in one molecule may be the same or different, respectively; Compound (C): a compound represented by the following formula (3), CH2=C(R3,) -C(0)0-R32 (3) However, R31 is a hydrogen atom or a methyl group, and R32 is a carbon number of 丨 脂肪 脂肪 52 52 201207034 a family hydrocarbon group. 2. The light of the first item of the patent application The curable composition, wherein the ratio of the polymer (D) in the photocurable composition is 0.01 to 5 mass% with respect to the photocurable composition. 3_ Photocuring property according to the scope of the patent application or the item a composition in which at least a part of a compound having one or more acryloxy or decyl propylene methoxy groups is a compound having one propylene methoxy group or a fluorenyl propylene group. a photocurable composition of 3, wherein at least a part of a compound having 1 propylene decyloxy group or methacryloxycarbonyl group is a compound (E) having a fluorine atom and is relative to light The ratio of the compound (E) in the photocurable composition is 5 to 4 〇 mass 〇 / 〇. 5. The photocurable composition of claim 3, which has i propylene. At least a part of the compound of a decyloxy group or a methacryloxy group is a fluorine-free compound (F), and the ratio of the compound (F) in the photocurable composition to the photocurable composition is 1〇~55质量%. 6) The photocurable composition according to claim 1 or 2, wherein at least a part of the compound having a ruthenium oxy group or a decyl propylene oxime group having two or more oxime has two or more propylene oxime groups Or a methacryloxy group-containing compound (Η), and the ratio of the compound (Η) in the photocurable composition is from 1% to 75% by mass based on the photocurable composition. 7. The photocurable composition according to any one of claims 1 to 6, wherein the photocurable composition contains 12% by mass of a photopolymerization initiator (for the photocurable composition) G). 8. The photocurable composition of the __ item of claim 1 to 7 wherein the photocurable composition has a viscosity of 3 to 2 mpa.s at 25 ° C. A method of producing a molded body having a fine pattern on a surface, comprising the steps of: contacting a photocurable composition for imprinting according to any one of claim 8 to the surface of the mold having a reverse pattern; The surface of the mold has an inverted pattern of the fine pattern; and the light curable composition is irradiated to the photocurable composition in a state where the photocurable composition is in contact with the surface of the mold to harden the photocurable composition. And a step of forming a cured product; and separating the mold from the cured product to obtain a molded body having a fine pattern on the surface. A method of producing a molded article having a fine pattern on a surface thereof, comprising the steps of: arranging the photocurable composition for imprinting according to any one of claims 1 to 8 on a surface of a substrate a step of pressing a mold having an inverted pattern of the fine pattern on the surface to the photocurable composition, and bringing the reverse pattern of the mold into contact with the photocurable composition; and pressing the mold to the photocurable composition a step of irradiating light to the photocurable composition to cure the photocurable composition to form a cured product; and 54 201207034 separating the mold or the substrate and the mold from the cured product. A step of obtaining a molded body having a fine pattern on the surface is obtained. A method for producing a molded body having a fine pattern on the surface, comprising the step of: arranging the photocurable composition for imprinting according to any one of claims 1 to 8 in a mold a step of the surface of the mold having the reverse pattern of the fine pattern; a step of pressing the substrate to the photocurable composition; and irradiating the light to the state of pressing the substrate to the photocurable composition The photocurable composition is a step of curing the photocurable composition to form a cured product, and a step of separating the mold or the substrate and the mold from the cured product to obtain a molded body having a fine pattern on its surface. 12. A method of producing a molded body having a fine pattern on its surface, comprising the steps of: approaching or contacting a mold having a reverse pattern of the fine pattern on a substrate and a surface thereof in such a manner that an inverted pattern of the mold is located on the substrate side; a step of filling a photocurable composition for imprinting according to any one of claims 1 to 8 between the substrate and the mold; and in a state where the substrate is in close contact with or in contact with the mold, a step of irradiating the photocurable composition to the photocurable composition to cure the photocurable composition to form a cured product; and separating the mold or the substrate and the mold from the cured product 55 201207034 to obtain f, l I ^ n A step of forming a molded body of a fine pattern. • D Patent Application No. 9 to 2, the surface of the item has a fine pattern, which is an open/body mounting method, wherein the fine pattern is a photoresist pattern. For example, in the scope of application No. 9 to 12 A method of producing a molded body having a fine pattern on a surface thereof, wherein the surface has a fine pattern of a replica mold for embossing a molding system. 15. The molded article having a fine pattern on the surface of any one of the claims (4) The manufacturing method of the present invention, wherein the surface having the fine pattern has a replica mold for electroforming of a forming system.