JPWO2019031312A1 - Mold release agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel mold release agent. A mold release agent containing the following components (A), (B) and (C). (A): Via a urethane bond, at all terminals of a linear or chain molecular chain containing a group represented by the following formula (1) and a group represented by the following formula (2a) or formula (2b) A polyfunctional (meth)acrylate compound (B) having a polymerizable group containing a group represented by the following formula (3): 0.05 phr to 15 phr photopolymerization initiation based on the mass of the component (A). Agent (C): Solvent ##STR1## (wherein R1 represents a perfluoroalkylene group having 1 or 2 carbon atoms, R2a represents an alkylene group having 2 or 3 carbon atoms, and R2b represents 2 carbon atoms. Or 3 represents a trivalent hydrocarbon group, * represents a bond that bonds to the —O— group of the urethane bond, p and q represent the number of groups represented by the formula (1) and It represents the number of groups represented by formula (2a) and independently represents an integer of 2 or more, and R3 represents a methyl group or a hydrogen atom.) [Selection diagram] None

Description

The present invention relates to a release agent applied on a mold for use in imprinting. As the mold to which the release agent is applied, not only a resin mold but also a metal mold, a silicon (Si) mold, an alumina (Al ₂ O ₃ ) mold, and a quartz mold are used.

In 1995, Professor Chou and others at the current Princeton University proposed a new technique called nanoimprint lithography (Patent Document 1). In nanoimprint lithography, a mold having an arbitrary pattern is brought into contact with a substrate on which a resin film is formed, the resin film is pressed, and heat or light is used as an external stimulus to form a desired pattern of the cured resin film. It is a technology for forming. This nanoimprint lithography has an advantage that nanoscale processing can be performed easily and inexpensively as compared with conventional photolithography in semiconductor device manufacturing. Therefore, nanoimprint lithography is a technology that is expected to be applied to the production of semiconductor devices, optical devices, displays, storage media, biochips, etc., instead of photolithography technology. Various reports have been made on curable compositions (Patent Documents 2 and 3).

In nanoimprint lithography (hereinafter, abbreviated as “imprint” in the present specification), in order to improve releasability when releasing a cured resin film from a mold after imprinting, a release agent is preliminarily placed on the mold. A method of applying and releasing treatment is generally used, and various reports have been made on a releasing agent used for a mold made of silicon or the like. (Patent Document 4, Patent Document 5)

US Pat. No. 5,772,905 JP, 2008-105414, A JP, 2008-202022, A Patent No. 5274839 JP, 2011-148117, A

When imprinting is repeatedly performed using the same mold subjected to the mold release treatment, the coating film of the mold release agent (coating formed from the mold release agent) is gradually peeled off from the mold, and the mold releasability deteriorates. Therefore, the release agent used in the conventional mold is often used by holding a group that chemically reacts with the mold material and binding it to a functional group existing on the mold surface. Since the surface shape of the mold coated with the release agent has a great influence on the shape of the photocurable resin to be imprinted, it is desirable that the surface roughness of the coating film formed from the release agent be as small as possible. Be done. As described above, various reports have been made on the imprint release agent applied to the surface of a mold and used, but a release agent that can be used for resin molds as well as silicon molds and metal molds has been reported. Almost no specific studies or reports have been made on mold agents. In particular, almost no study or report has been made on the release agent used when repetitive imprinting is performed using a resin mold and the roughness of the surface of the coating film formed from the release agent.

The present invention has been made based on the above circumstances, and an object to be solved by the present invention is that the root mean square roughness of the mold-released surface of the mold is less than 1 nm, and the mold is used. An object of the present invention is to provide a mold release agent that enables repeated imprinting. Further, in the present specification, an optical nanoimprint technique that includes not only the case where the formed pattern size is on the order of nanometers but also the case of the order of micrometers and millimeters is referred to as optical imprint.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have adopted a specific polyfunctional (meth)acrylate compound, a photopolymerization initiator and a solvent as a component of a release agent, According to the knowledge obtained, the present invention was completed. That is, the mold release agent of the present invention can be applied to the surface of the mold to form a mold-treated surface on the mold. This makes it possible to perform imprint repeatedly using the mold, and further, the root mean square roughness of the release-treated surface becomes less than 1 nm.

（式中、Ｒ^１は炭素原子数１又は２のパーフルオロアルキレン基を表し、Ｒ^２ａは炭素原子数２又は３のアルキレン基を表し、Ｒ^２ｂは炭素原子数２又は３の３価の炭化水素基を表し、＊はそれぞれ前記ウレタン結合の−Ｏ−基と結合する結合手を表し、ｐ及びｑはそれぞれ前記式（１）で表される基の数及び前記式（２ａ）で表される基の数を表すと共に独立して２以上の整数を表し、Ｒ^３はメチル基又は水素原子を表す。）
第２観点として、前記ｑが、５乃至１２の整数である、第１観点に記載のモールド用離型剤。
第３観点として、前記式（２ａ）で表される基がポリ（オキシエチレン）基である、第１観点又は第２観点に記載のモールド用離型剤。
第４観点として、前記重合性基が前記式（３）で表される基を少なくとも２つ含む、第１観点乃至第３観点のいずれか一に記載のモールド用離型剤。
第５観点として、前記式（１）で表される基が、オキシパーフルオロメチレン基及びオキシパーフルオロエチレン基の双方を有する基である、第１観点乃至第４観点のいずれか一に記載のモールド用離型剤。
第６観点として、前記モールド用離型剤の総質量１００質量％に対し、前記（Ａ）成分の割合が０．０５質量％乃至１０質量％である、第１観点乃至第５観点のいずれか一に記載のモールド用離型剤。
第７観点として、（Ｄ）成分としてさらに光増感剤を含有する、第１観点乃至第６観点のいずれか一に記載のモールド用離型剤。
第８観点として、第１観点乃至第７観点のいずれか一に記載のモールド用離型剤から形成された被膜を備えた、離型処理された表面を有するモールド。
第９観点として、前記モールドは金属製モールド、シリコン製モールド、アルミナ製モールド、石英製モールド及び樹脂製モールドからなる群から選択される、第８観点に記載の離型処理された表面を有するモールド。
第１０観点として、第１観点乃至第７観点のいずれか一に記載のモールド用離型剤を樹脂製モールド上に塗布する工程、及び前記樹脂製モールド上に塗布されたモールド用離型剤をベークし、露光して前記樹脂製モールドの表面に被膜を形成する工程を有する、離型処理された樹脂製モールドの作製方法。
第１１観点として、第８観点又は第９観点に記載の離型処理された表面を有するモールドを光硬化性樹脂に圧着する工程、前記光硬化性樹脂を該モールドに圧着させたまま光硬化する工程、及び前記光硬化する工程の後、得られた光硬化物を前記離型処理された表面を有するモールドから離型する工程を有する、パターンが転写された最大膜厚が１．５ｍｍの硬化膜の作製方法。
第１２観点として、前記離型処理された表面の二乗平均粗さが１ｎｍ未満である、第８観点又は第９観点に記載の離型処理された表面を有するモールド。That is, the present invention, as a first aspect,
A mold release agent containing the following component (A), component (B) and component (C).
(A): Via a urethane bond at all terminals of a linear or chain molecular chain containing a group represented by the following formula (1) and a group represented by the following formula (2a) or formula (2b) A polyfunctional (meth)acrylate compound (B) having a polymerizable group containing a group represented by the following formula (3): 0.05 phr to 15 phr photopolymerization initiation based on the mass of the component (A). Agent (C): Solvent

(In the formula, R ¹ represents a perfluoroalkylene group having 1 or 2 carbon atoms, R ^2a represents an alkylene group having 2 or 3 carbon atoms, and R ^2b is a trivalent carbon atom having 2 or 3 carbon atoms. Represents a hydrogen group, * represents a bond for bonding to the -O- group of the urethane bond, p and q are respectively represented by the number of groups represented by the formula (1) and the formula (2a). Represents an integer of 2 or more, and R ³ represents a methyl group or a hydrogen atom.)
As a second aspect, the mold release agent according to the first aspect, wherein the q is an integer of 5 to 12.
As a third aspect, the mold release agent according to the first aspect or the second aspect, wherein the group represented by the formula (2a) is a poly(oxyethylene) group.
As a fourth aspect, the mold release agent according to any one of the first to third aspects, wherein the polymerizable group includes at least two groups represented by the formula (3).
As a fifth aspect, according to any one of the first to fourth aspects, the group represented by the formula (1) is a group having both an oxyperfluoromethylene group and an oxyperfluoroethylene group. Mold release agent.
As a sixth aspect, any one of the first aspect to the fifth aspect, wherein the ratio of the component (A) is 0.05% by mass to 10% by mass relative to 100% by mass of the total amount of the mold release agent. The mold release agent according to 1.
As a seventh aspect, the mold release agent according to any one of the first to sixth aspects, which further contains a photosensitizer as the component (D).
As an eighth aspect, a mold having a release-treated surface, comprising a coating formed from the mold release agent according to any one of the first aspect to the seventh aspect.
As a ninth aspect, the mold having a release-treated surface according to the eighth aspect, wherein the mold is selected from the group consisting of a metal mold, a silicon mold, an alumina mold, a quartz mold and a resin mold. ..
As a tenth aspect, a step of applying the mold release agent according to any one of the first to seventh aspects onto a resin mold, and the mold release agent applied onto the resin mold. A method for producing a resin mold subjected to mold release treatment, which comprises the steps of baking and exposing to form a film on the surface of the resin mold.
As an eleventh aspect, a step of pressure-bonding a mold having a release-treated surface according to the eighth aspect or the ninth aspect to a photocurable resin, and photocuring while the photocurable resin is pressure-bonded to the mold. And a step of releasing the obtained photo-cured product from the mold having the release-treated surface after the step of photo-curing, and curing the pattern transferred maximum film thickness of 1.5 mm. Membrane fabrication method.
As a twelfth aspect, the mold having the release-treated surface according to the eighth aspect or the ninth aspect, wherein the root mean square roughness of the release-treated surface is less than 1 nm.

By adopting the mold releasing agent of the present invention, the root mean square roughness of the mold-released surface of the mold can be made less than 1 nm, and the coating film formed from the mold releasing agent is formed. It becomes difficult to peel off from the mold surface, and the resin mold, the quartz mold, the alumina (Al ₂ O ₃ ) mold, the silicon (Si) mold, and the metal mold to which the mold releasing agent is applied are repeatedly used. It becomes possible to print.
In particular, when the mold release agent of the present invention is applied to a resin mold, the surface of the resin mold and the coating formed from the mold release agent intermix (integrate), or the resin Since the polymerizable group existing on the surface of the mold for molding can react with the film, the film is less likely to be peeled off from the resin mold. When the mold release agent of the present invention is applied to a mold made of quartz, a mold made of alumina (Al ₂ O ₃ ), a mold made of silicon (Si), and a mold made of metal, the surface of these molds is preferably covered with a silane cup. By applying the mold release agent of the present invention to the surface after the treatment with the ring agent, the above-mentioned coating becomes difficult to peel from these molds.

Furthermore, the mold release agent of the present invention can control the curing rate, dynamic viscosity, film thickness, and coatability by changing the types and content ratios of the above-mentioned components (B) and (C). it can. Therefore, the mold release agent of the present invention can be designed according to the mold, the device type to be manufactured, the manufacturing process and the baking process.

[(A) component]
The polyfunctional (meth)acrylate compound of the component (A) is a linear or chain molecular chain containing a group represented by the formula (1) and a group represented by the formula (2a) or the formula (2b). Has a polymerizable group containing a (meth)acryloyloxy group via a urethane bond at all terminals. In addition, in this invention, a (meth)acrylate compound means both an acrylate compound and a methacrylate compound. Further, for example, a (meth)acroyloxy group means both an acryloyloxy group and a methacryloyloxy group.
Here, the polyfunctional (meth)acrylate compound is a bifunctional or higher functional acrylate compound or methacrylate compound excluding the monofunctional (meth)acrylate compound. The urethane bond means a structure represented by -NH-C(=O)-O-. The polyfunctional (meth)acrylate compound has at least two urethane bonds and at least two polymerizable groups containing a (meth)acryloyloxy group in one molecule.
The group represented by the formula (1) may be referred to as a poly(oxyperfluoroalkylene) group, and the group represented by the formula (2a) may be referred to as a poly(oxyalkylene) group. The (meth)acryloyloxy group is a group represented by the formula (3).

The number of carbon atoms of R ¹ of the oxyperfluoroalkylene group: —(O—R ¹ )— in the group represented by the above formula (1) is 1 or 2. That is, the group represented by the above formula (1) has a structure in which a divalent fluorocarbon group having 1 or 2 carbon atoms and an oxygen atom are alternately linked, and the oxyperfluoroalkylene group is the number of carbon atoms. It has a structure in which a monovalent or divalent divalent fluorocarbon group and an oxygen atom are linked. Specific examples the oxyperfluoroalkylene groups, - _(OCF 2) - (i.e., oxy perfluoromethylene group) and _{- (OCF 2 CF 2) -} ( i.e., oxy perfluoroethylene group). The oxyperfluoroalkylene groups, - (OCF ₂₎ - and - _{(OCF 2} CF 2) - may be used alone or one of a, it may be used in combination of two. When used in combination of two or, - (OCF ₂₎ - and - _{(OCF 2} CF 2) - the bond may be either a block bond and random bond.

From the viewpoint of enhancing the releasability of the mold, as the group represented by the formula _{(1), - (OCF 2} ) - ( i.e., oxy perfluoromethylene group) and _{- (OCF 2 CF 2) -} ( i.e., oxy It is preferable to use a group having both a perfluoroethylene group). As the group represented by the formula _{(1), - (OCF 2} ) - and - _{(OCF 2} CF 2) - and is, in a molar ratio _{[- (OCF 2) -]} : [- (OCF 2 CF 2) It is preferable that it is a group which is included in a ratio of −]=2:1 to 1:2, and more preferably a group that is included in a ratio of about 1:1. These bonds may be block bonds or random bonds. The number of groups <p> represented by the formula (1) is an integer of 2 or more, preferably in the range of 5 to 30, and more preferably in the range of 7 to 21.

The weight average molecular weight (Mw) of the group represented by the formula (1) measured by gel permeation chromatography in terms of polystyrene is 1,000 to 5,000, preferably 1,500 to 3,000. is there.

The number of carbon atoms of R ^2a of the oxyalkylene group: —(O—R ^2a )— in the group represented by the formula (2a) is 2 or 3. That is, the group represented by the formula (2a) has a structure in which an alkylene group having 2 or 3 carbon atoms and an oxygen atom are alternately linked, and an oxyalkylene group is an alkylene group having 2 or 3 carbon atoms. It has a structure in which oxygen atoms are linked. Examples of the oxyalkylene group include an oxyethylene group, an oxypropylene group, and an oxytrimethylene group. The oxyalkylene groups may be used alone or in combination of two or more, and in that case, the bond of the two or more oxyalkylene groups is either a block bond or a random bond. May be

The group represented by the formula (2a) is preferably a poly(oxyethylene) group. The number <q> of the groups represented by the formula (2a) is an integer of 2 or more, for example, in the range of 2 to 15, preferably in the range of 2 to 12, or in the range of 5 to 12, or 7 to The range is 12.

The trivalent hydrocarbon group R ^{2b in} the group represented by the formula (2b) has 2 or 3 carbon atoms. That is, the group represented by the formula (2b) is a trivalent group obtained by removing one hydrogen atom from an arbitrary carbon atom of an alkylene group having 2 or 3 carbon atoms (an alkylene group having 2 or 3 carbon atoms). (Group of) and one oxygen atom is linked to the structure.
Among the groups represented by the formula (2b), a group in which one oxygen atom is linked to the 1-position (or 3-position) of the 1,2,3-propanetriyl group is preferable.

The linear or chain molecular chain is not limited as long as it is a molecular chain containing a group represented by the above formula (1) and a group represented by the above formula (2a) or formula (2b).
In the above linear or chain molecular chain, the bonding order of the group represented by formula (1) and the group represented by formula (2a) or formula (2b) is not particularly limited, and the number of each group is It is not particularly limited.
In the above linear or chain molecular chain, the group represented by the formula (1) and the group represented by the formula (2a) or the formula (2b) may be bonded with a single bond (direct bond). Alternatively, they may be bonded via a structure (linking group) such as an alkylene group having 1 to 3 carbon atoms, a perfluoroalkylene group having 1 to 3 carbon atoms, or a combination thereof.

The polymerizable group is not limited to having one (meth)acryloyloxy group, and may have two or more. Examples of the polymerizable group include structures (terminal groups) represented by the formulas [X1] to [X5] shown below, and structures in which the acryloyloxy groups in these structures (terminal groups) are substituted with methacryloyloxy groups. Are listed.

The polyfunctional (meth)acrylate compound of the component (A) is represented by the compound represented by the structural formula (A-1) and (A-2) shown below from the viewpoint of easy industrial production. Preferred examples include the compound and the compound represented by (A-3), and the compound in which the acryloyloxy group in these compounds is substituted with a methacryloyloxy group. In the structural formula below, each terminal X represents one of the structures (terminal groups) represented by the formulas [X1] to [X5], and PFPE represents the poly(oxyperfluoroalkylene) group. And q ₁ and q ₂ each independently represent the number of oxyethylene groups, for example, an integer of 2 to 15, preferably an integer of 2 to 12, or an integer of 5 to 12, or 7 to Represents an integer of 12.

In the polyfunctional (meth)acrylate compound of the component (A), one polymerizable group has two or more (meth)acryloyloxy groups, for example, the structures represented by the above formulas [X3] to [X5]. (Terminal group) is preferable.

In the present invention, the component (A) is the total mass of the mold release agent, that is, the component (A) and the component (B), the component (C), and the optional component (D) and It is desirable to use it in a ratio of preferably 0.05% by mass to 10% by mass, more preferably 0.5% by mass to 8% by mass, based on the total mass of 100% by mass of other additives.

The component (A) of the mold release agent of the present invention has, for example, the above formula (2a) directly bonded to both ends of the group represented by the above formula (1) or bonded via the above linking group. Or a compound having at least two hydroxy groups via a group represented by the formula (2b), 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis( It is obtained by a method of subjecting an isocyanate compound having a (meth)acryloyloxy group such as (meth)acryloyloxymethyl)ethyl isocyanate to a urethane reaction. The weight average molecular weight (Mw) of the component (A) measured by gel permeation chromatography in terms of polystyrene is 1,500 to 7,000, preferably 2,000 to 6,000.

The mold releasing agent of the present invention has a linear or linear structure containing, in addition to the component (A), a group represented by the above formula (1) and a group represented by the above formula (2a) or formula (2b). Having a polymerizable group containing a (meth)acryloyloxy group through a urethane bond only at a part of the terminal of the chain-like molecular chain, and having a hydroxy group at the other end of the linear or chain-like molecular chain (I.e., a compound having no polymerizable group at the other end) may be included. The mold releasing agent of the present invention further comprises all linear or chain molecular chains containing a group represented by the above formula (1) and a group represented by the above formula (2a) or formula (2b). A compound having a hydroxy group at the terminal, that is, a compound having no polymerizable group may be contained.

[(B) component]
The photopolymerization initiator that is the component (B) is not particularly limited as long as it has absorption in the light source used during photocuring. Examples of the photopolymerization initiator include tert-butylperoxy-iso-butyrate, 2,5-dimethyl-2,5-bis(benzoyldioxy)hexane and 1,4-bis[α-(tert-butyldioxy)- iso-propoxy]benzene, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butyldioxy)hexene hydroperoxide, α-(iso-propylphenyl)-iso-propyl hydroperoxide, tert- Butyl hydroperoxide, 1,1-bis(tert-butyldioxy)-3,3,5-trimethylcyclohexane, butyl-4,4-bis(tert-butyldioxy)valerate, cyclohexanone peroxide, 2,2′,5,5′ -Tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-amylperoxycarbonyl)benzophenone , 3,3′,4,4′-tetra(tert-hexylperoxycarbonyl)benzophenone, 3,3′-bis(tert-butylperoxycarbonyl)-4,4′-dicarboxybenzophenone, tert-butylperoxybenzoate, Organic peroxides such as di-tert-butyldiperoxyisophthalate; quinones such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone and 1,2-benzanthraquinone; benzoinmethyl, Benzoin derivatives such as benzoin ethyl ether, α-methylbenzoin, α-phenylbenzoin; 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2. -Methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- [4-{4-(2-hydroxy-2-methyl-propionyl)benzyl}-phenyl]-2-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1-[4- (Methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1 -Butanone, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one and other alkylphenone compounds; bis(2,4,4 Acylphosphine oxide compounds such as 6-trimethylbenzoyl)-phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl] Examples include oxime ester compounds such as -1,2-octanedione and 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone. To be

The photopolymerization initiator is available as a commercial product, and specific examples thereof include IRGACURE (registered trademark) 651, 184, 500, 2959, 127, 754, 907, and 369. 379, 379EG, 819, 819DW, 1800, 1870, 784, OXE01, OXE02, 250, 1173, MBF, 4265, and TPO (above, manufactured by BASF Japan Ltd.). ), KAYACURE (registered trademark) DETX, MBP, DMBI, EPA, OA (above, manufactured by Nippon Kayaku Co., Ltd.), VICURE-10, 55 (above, manufactured by STAUFFER Co. LTD), ESACURE (above). (Registered trademark) KIP150, TZT, TZT100, KTO46, KB1, KL200, KS300, EB3, triazine-PMS, triazine A, triazine B (above, manufactured by Japan Siber Hegner Co., Ltd.), ADEKA OPTOMER N -1717, N-1414, and N-1606 (above, manufactured by ADEKA Corporation).

The above photopolymerization initiators may be used alone or in combination of two or more.

The content of the component (B) in the mold release agent of the present invention is, for example, 0.05 phr to 15 phr, preferably 0.1 phr to 15 phr, or 0 based on the mass of the component (A). 0.1 phr to 10 phr, more preferably 0.5 phr to 8 phr. When the content ratio of the component (B) is less than 0.05 phr, sufficient curability cannot be obtained, and the releasability tends to deteriorate during repeated imprinting. On the other hand, when the content ratio of the component (B) exceeds 15 phr, the transparency in the ultraviolet range is lowered. In the present specification, “phr” refers to the mass of the photopolymerization initiator, which is the component (B), for 100 g of the component (A).

[(C) component]
The solvent which is the component (C) plays a role of adjusting the viscosity of the components (A) and (B), and can adjust the viscosity of the components (A) and (B). It is not particularly limited. Further, the solvent used for the reaction system during the production of the above-mentioned component (A) can be used as it is as the solvent for the component (C).

Examples of the solvent include toluene, p-xylene, o-xylene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether. , Ethylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene Glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol, 1-octanol, ethylene glycol, hexylene glycol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, propylene glycol, Benzyl alcohol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, γ-butyrolactone, acetone, methyl ethyl ketone, methyl isopropyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone, cyclohexanone, 2-heptanone, ethyl acetate, isopropyl acetate, n-propyl acetate, isobutyl acetate, n-butyl acetate, ethyl lactate, ethyl pyruvate, methanol, ethanol, isopropanol, tert-butanol, allyl alcohol, n-propanol, 2-methyl. 2-butanol, isobutanol, n-butanol, 2-methyl-1-butanol, 1-pentanol, 2-methyl-1-pentanol, 2-ethylhexanol, trimethylene glycol, 1-methoxy-2-butanol , Isopropyl ether, 1,4-dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, N-cyclohexyl -2-pyrrolidine, methyl perfluoropropyl ether, methyl nona Fluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(tri Fluoromethyl)-pentane, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, 1,1,1,2,3,4,4,5,5,5-deca Fluoropentane, pentafluorononane, hexafluorobenzene, heptadecafluoro-n-octyl bromide, 1,1,1,3,3,3-hexafluoro-2-methoxypropane, octadecafluorooctane, octafluorocyclopentene, per Fluorotributylamine, perfluorodecalin, perfluorohexane, perfluoromethylcyclohexane, perfluoroheptane, octafluorotoluene, perfluorotripentylamine, perfluorotriethylamine, perfluoro(1,3-dimethylcyclohexane), perfluoroisohexane Are listed.

The above-mentioned solvent is available as a commercial product, and specific examples thereof include Novec (registered trademark) 7000, 7100, 7200, 7300 (above, manufactured by 3M Japan Co., Ltd.), Asahiclin (registered trademark). ) AE-3000, AE-3100E (above, manufactured by Asahi Glass Co., Ltd.), Vertrel (registered trademark) XF, XF-UP, XE-XP, X-E10, X-P10, X-D. , The same X-GY, the same MCA, the same SDG, the same SMT, the same SFR, the same DC, the same Cinera, the same supraion, and the same scion (above, manufactured by Mitsui DuPont Fluorochemical Co., Ltd.).

[(D) component]
The mold release agent of the present invention may contain a photosensitizer as the component (D), if necessary. Examples of the photosensitizer include thioxanthene-based, thioxanthone-based, xanthene-based, ketone-based, thiopyrylium salt-based, base styryl-based, merocyanine-based, 3-substituted coumarin-based, 3,4-substituted coumarin-based, cyanine-based , Acridine, thiazine, phenothiazine, anthracene, coronene, benzanthracene, perylene, ketocoumarin, coumarin, and borate. The photosensitizer is available as a commercial product, and specific examples thereof include Anthracure (registered trademark) UVS-581, UVS-1331 (above, manufactured by Kawasaki Kasei Co., Ltd.), KAYACURE ( Registered trademark) DETX-S (manufactured by Nippon Kayaku Co., Ltd.). This photosensitizer can be used alone or in combination of two or more. The absorption wavelength in the UV region can also be adjusted by using the above photosensitizer. When the mold releasing agent of the present invention contains the component (D), the content ratio is, for example, 0.01 phr to 10 phr, preferably 0.05 phr to 5 phr, based on the mass of the component (A). Is.

[Other additives]
The mold release agent of the present invention may contain a surfactant and a chain transfer agent, if necessary, as long as the effects of the present invention are not impaired.

Examples of the above-mentioned surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, and other polyoxyethylene alkyl ethers, polyoxyethylene octylphenyl ether, and polyoxyethylene. Polyoxyethylene alkylaryl ethers such as ethylene nonylphenyl ether, polyoxyethylene/polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan Sorbitan fatty acid esters such as tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc. Examples include nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters. The above-mentioned surfactant is available as a commercial product, and specific examples thereof include F Top (registered trademark) EF301, EF303, EF352 (above, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megafac ( (Registered trademark) F-171, F-173, F-477, F-486, F-554, F-556, R-08, R-30, R-30N, R-. 40, same R-40-LM, same RS-56, same RS-75, same RS-72-K, same RS-76-E, same RS-76-NS, same RS-78, same RS-90 ( As described above, manufactured by DIC Corporation, Florard FC430, FC431 (above, manufactured by 3M Japan Co., Ltd.), Asahi Guard (registered trademark) AG710, Surflon (registered trademark) S-382, SC101, SC102, SC103. , SC104, SC105, SC106 (all manufactured by Asahi Glass Co., Ltd.) and the like; and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-302, BYK-307, BYK. -322, BYK-323, BYK-330, BYK-333, BYK-370, BYK-375, BYK-378, BYK-UV 3500, BYK-UV 3570 (above, manufactured by Big Chemie Japan KK). .. You may use the said surfactant individually by 1 type or in mixture of 2 or more types.

Examples of the chain transfer agent include, as thiol compounds, methyl mercaptoacetate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, 3-methoxybutyl 3-mercaptopropionate, and n-mercaptopropionate. Octyl, stearyl 3-mercaptopropionate, 1,4-bis(3-mercaptopropionyloxy)butane, 1,4-bis(3-mercaptobutyryloxy)butane, trimethylolethane tris(3-mercaptopropionate) , Trimethylolethane tris(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptopropionate), Pentaerythritol tetrakis(3-mercaptobutyrate), Dipentaerythritol hexakis(3-mercaptopropionate), Dipentaerythritol hexakis(3-mercaptobutyrate), Tetraethylene glycol bis(3-mercaptopropionate) , Tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, tris[2-(3-mercaptobutyryloxy)ethyl]isocyanurate, 1,3,5-tris(3-mercaptobutyryloxyethyl) Mercaptocarboxylic acid esters such as -1,3,5-triazine-2,4,6-(1H,3H,5H)-trione; ethanethiol, 2-methylpropane-2-thiol, n-dodecanethiol, 2 , 3,3,4,5,5-hexamethylhexane-2-thiol (tert-dodecanethiol), ethane-1,2-dithiol, propane-1,3-dithiol, alkylthiols such as benzylthiol; benzene Aromatic thiols such as thiol, 3-methylbenzenethiol, 4-methylbenzenethiol, naphthalene-2-thiol, pyridine-2-thiol, benzimidazol-2-thiol, benzothiazole-2-thiol; 2-mercaptoethanol , Mercapto alcohols such as 4-mercapto-1-butanol; silane-containing thiols such as 3-(trimethoxysilyl)propane-1-thiol and 3-(triethoxysilyl)propane-1-thiol; bis(2- Mercaptoethyl) ether, and as a disulfide compound, Didisulfide, dipropyl disulfide, diisopropyl disulfide, dibutyl disulfide, di-tert-butyl disulfide, dipentyl disulfide, diisopentyl disulfide, dihexyl disulfide, dicyclohexyl disulfide, didecyl disulfide, bis (2,3,3,4,4,4) Alkyl disulfides such as 5-hexamethylhexane-2-yl)disulfide (di-tert-dodecyldisulfide), bis(2,2-diethoxyethyl)disulfide, bis(2-hydroxyethyl)disulfide, dibenzyldisulfide and the like; Aromatic disulfides such as diphenyl disulfide, di-p-tolyl disulfide, di(pyridin-2-yl)pyridyl disulfide, di(benzimidazol-2-yl)disulfide, di(benzothiazol-2-yl)disulfide; tetra Examples include thiuram disulfides such as methyl thiuram disulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, and bis(pentamethylene) thiuram disulfide; α-methylstyrene dimer. This chain transfer agent can be used alone or in combination of two or more.

[Preparation of mold release agent]
The method for preparing the mold release agent of the present invention is not particularly limited, and the components (A), (B), (C), and optionally the component (D) and the above-mentioned other additives are mixed to obtain a uniform mixture. It just has to be in such a state. The order of mixing the components (A) to (C), and optionally the component (D) and the above-mentioned other additives is not particularly limited as long as a uniform mold release agent can be obtained. For example, there may be mentioned a method in which the components (A), (B) and (C) are mixed in a predetermined ratio to prepare a uniform mold release agent. Furthermore, at a suitable stage of this preparation method, if necessary, the component (D) and the above-mentioned other additives may be further added and mixed.
The viscosity of the mold release agent of the present invention is not particularly limited as long as it is a viscosity suitable for being applied (applied) to a mold. For example, it can be used by adjusting the viscosity in the range of 0.5 mPa·s to 100 mPa·s.

[Mold having a release-treated surface]
The mold release agent of the present invention can be applied to the surface of a mold and photocured by exposure to form a coating film on the surface of the mold. The mold on which the coating is formed has a release-treated surface. The present invention is also directed to a mold having a release-treated surface, which includes a coating formed from the mold release agent.

[Method of applying mold release agent]
The coating method is a known or known method, for example, a spin coating method, a dipping method, a flow coating method, an inkjet method, a spray method, a bar coating method, a gravure coating method, a slit coating method, a roll coating method, a transfer printing method. Brush coating, blade coating, and air knife coating.

The mold to which the mold release agent of the present invention is applied is obtained by photocuring a resin mold, for example, a resin composition containing a compound having at least two (meth)acryloyloxy groups in one molecule. Examples thereof include resin molds, quartz molds, alumina (Al ₂ O ₃ ) molds, silicon (Si) molds, and metal molds such as nickel and aluminum.

When the mold release agent of the present invention is applied to the above-mentioned various molds, in particular, a quartz mold, an alumina (Al ₂ O ₃ ) mold, a silicon (Si) mold and a metal mold, these are preferably used. After the surface of the mold is treated with a silane coupling agent (adhesion aid), it is desirable to apply the mold release agent of the present invention to the treated surface. By performing the pretreatment with the silane coupling agent, the adhesion between the mold formed by the mold release agent and the mold is improved, and the film can be made more difficult to peel from the mold.
Although the silane coupling agent is not particularly limited, for example, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane. , 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-acryloxypropyltriethoxysilane, methacryloxyoctyltrimethoxysilane, methacryloxyoctyltriethoxysilane Examples thereof include silane, octenyltrimethoxysilane, and octenyltriethoxysilane.

The light source for curing the mold release agent of the present invention is not particularly limited, and examples thereof include a high pressure mercury lamp, a low pressure mercury lamp, an electrodeless lamp, a metal halide lamp, a KrF excimer laser, an ArF excimer laser, an F ₂ excimer laser, An electron beam (EB), extreme ultraviolet (EUV), and ultraviolet LED (UV-LED) can be mentioned. As the wavelength, generally, a 436 nm G line, a 405 nm H line, a 365 nm I line, or a GHI mixed line can be used. Further exposure amount is preferably, 30 mJ / cm ² to 10000 mJ / cm ^2, more preferably at 100 mJ / cm ² to 8000 mJ / cm ^2.

For the purpose of evaporating the solvent which is the component (C) of the mold release agent of the present invention, a baking step may be added after the mold release agent is applied and before photocuring. The equipment used in the baking step is not particularly limited, and for example, using a hot plate, an oven, or a furnace, baking in a suitable atmosphere, that is, in the atmosphere, an inert gas such as nitrogen, or a vacuum is performed. Anything can be done. The baking temperature may be, for example, 40° C. to 200° C. at which the solvent can be evaporated.

The thickness of the coating film thus obtained is not particularly limited, but may be, for example, in the range of 0.01 μm to 1 μm.

Further, in the present invention, it is preferable that the coating formed from the mold release agent (the surface subjected to the mold release treatment) has a surface roughness of less than 1 nm.
In the present invention, "surface roughness" means root mean square roughness measured by an atomic force microscope (AFM): RMS (Root Mean Square: square root of a value obtained by averaging squares of deviations from a mean line to a measurement curve). Represents.
Preferably, the surface roughness (root mean square roughness: RMS) can be 0.8 nm or less, for example, 0.6 nm or less. The smaller the surface roughness (root mean square roughness: RMS), the better, but if the lower limit value is set, RMS>0 nm.

The present invention also includes a step of applying the mold release agent on a resin mold, and baking the mold release agent applied on the resin mold, exposing the resin to the surface of the resin mold. The present invention is also directed to a method for producing a resin mold that has been subjected to a mold release treatment and has a step of forming a coating film.

[Method of producing film on which optical imprint and pattern are transferred]
The present invention is also directed to a method for producing a pattern transfer film by photoimprinting using the mold having the release-treated surface.
That is, after the step of press-bonding the mold having the release-treated surface to the photo-curable resin, the step of photo-curing the photo-curable resin while being pressed to the mold, and the step of photo-curing The present invention is also directed to a method for producing a cured film having a maximum film thickness of 1.5 mm to which a pattern is transferred, which has a step of releasing the obtained photocured product from the mold having the release-treated surface. ..
The above-mentioned photocurable resin, the light source used for photocuring, and the device for performing photoimprint are not particularly limited, and the resin, light source, and device used in the conventional photoimprint method can be used.
The maximum film thickness of the pattern-transferred film obtained by the above method is preferably 1.5 mm, and the pattern size may be any of nanometer order, micrometer order and millimeter order.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, the apparatus and conditions used for the analysis of physical properties in the following synthesis examples and in the surface roughness evaluation of the coating film formed from the release agent are as follows.

(1) Gel permeation chromatography (GPC)
Device: Shimadzu Corporation GPC system GPC column: Shodex (registered trademark) GPC KF-804L and GPC KF-803L
Column temperature: 40°C
Solvent: Tetrahydrofuran Flow rate: 1 mL/min Standard sample: Polystyrene (2) Atomic force microscope (AFM)
Device: Nanoscope IV type Dimension 3100 manufactured by Digital Instruments

The abbreviations have the following meanings.
PFPE1: Perfluoropolyether having hydroxy groups at both ends via a poly(oxyethylene) group (the number of the groups is 8 to 9) [Fluorolink (registered trademark) 5147X manufactured by Solvay Specialty Polymers]
PFPE2: Perfluoropolyether having two hydroxy groups at each end via the group represented by the formula (2b) [Fomblin (registered trademark) T4 manufactured by Solvay Specialty Polymers]
BEI: 1,1-bis(acryloyloxymethyl)ethyl isocyanate [Karenzu (registered trademark) BEI manufactured by Showa Denko KK]
DBTDL: dibutyltin dilaurate [manufactured by Tokyo Chemical Industry Co., Ltd.]
DOTDD: Dioctyltin Dineodecanoate [Neostan (registered trademark) U-830 manufactured by Nitto Kasei Co., Ltd.]
AIBN: Azobisisobutyronitrile MEK: Methyl ethyl ketone MIBK: Methyl isobutyl ketone PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate

<Synthesis example 1>
An eggplant flask was charged with 10.5 g (5 mmol) of PFPE1, 2.39 g (10.0 mmol) of BEI, 0.129 g of DBTDL and 12.9 g of MEK. The mixture in the eggplant flask was stirred with a stirrer chip at room temperature (about 23° C.) for 24 hours to obtain a reaction product. To this reaction product, 30.37 g of PGMEA was added, and MEK was distilled off with an evaporator to obtain a PGMEA solution containing a polyfunctional acrylate compound SM1 as the component (A) with a solid content of 30% by mass. The weight average molecular weight Mw of the obtained SM1 measured by GPC in terms of polystyrene was 3,400, and the dispersity: Mw (weight average molecular weight)/Mn (number average molecular weight) was 1.1.

<Synthesis example 2>
An eggplant flask was charged with 10.5 g (5 mmol) of PFPE1, 2.39 g (10.0 mmol) of BEI, 0.0644 g of DOTDD and 12.9 g of PGMEA. The mixture in the eggplant flask was stirred with a stirrer chip at room temperature (about 23° C.) for 48 hours to obtain a reaction product. 38.9 g of PGMEA was added to this reaction product to obtain a PGMEA solution containing the polyfunctional acrylate compound SM2 as the component (A) at a solid content of 20% by mass. The weight average molecular weight Mw of the obtained SM2 measured by GPC in terms of polystyrene was 3,410, and the dispersity: Mw (weight average molecular weight)/Mn (number average molecular weight) was 1.1.

<Synthesis example 3>
61.2 g of PGMEA was put into a three-necked flask, and heated to 100° C. under a nitrogen atmosphere. Thereto, a solution of 30.00 g of 2-(perfluorohexyl)ethyl methacrylate, 16.59 g of cyclohexylmaleimide, 9.03 g of 2-hydroxyethyl methacrylate and 5.56 g of AIBN dissolved in 183.6 g of PGMEA for 1 hour. And added dropwise, and stirred at 100° C. for 24 hours to obtain a reaction solution. After cooling this reaction solution to room temperature, 0.44 g of DBTDL, 0.01 g of hydroquinone and 9.79 g of 2-acryloyloxyethyl isocyanate were added and heated to 60° C. and stirred for 24 hours. Then, the reaction solution was cooled to room temperature to obtain a PGMEA solution containing a copolymer CHM-A represented by the following formula (4) that does not correspond to the component (A) with a solid content of 22.6% by mass. The weight average molecular weight Mw of the obtained CHM-A measured by GPC in terms of polystyrene was 21,000, and the dispersity: Mw (weight average molecular weight)/Mn (number average molecular weight) was 2.1.

<Synthesis example 4>
An eggplant flask was charged with 11.45 g (5 mmol) of PFPE2, 4.79 g (20.0 mmol) of BEI, 0.162 g of DOTDD and 16.24 g of MEK. The mixture in the eggplant flask was stirred under a nitrogen atmosphere with a stirrer chip at room temperature (about 23° C.) for 72 hours to obtain a reaction product. 64.96 g of PGMEA was added to this reaction product, and MEK was distilled off by an evaporator to obtain a PGMEA solution containing the polyfunctional acrylate compound SM3 as the component (A) with a solid content of 20% by mass. The weight average molecular weight Mw of the obtained SM3 measured by GPC in terms of polystyrene was 2,750, and the dispersity: Mw (weight average molecular weight)/Mn (number average molecular weight) was 1.1.

<Synthesis example 5>
An eggplant flask was charged with 11.45 g (5 mmol) of PFPE2, 4.79 g (20.0 mmol) of BEI, 0.162 g of DOTDD and 16.24 g of PGMEA. The mixture in the eggplant flask was stirred under a nitrogen atmosphere with a stirrer chip at room temperature (about 23° C.) for 72 hours to obtain a reaction product. To this reaction product, 48.72 g of PGMEA was added to obtain a PGMEA solution containing the polyfunctional acrylate compound SM4 as the component (A) with a solid content of 20% by mass. The weight average molecular weight Mw of the obtained SM4 measured by GPC in terms of polystyrene was 2,760, and the dispersity: Mw (weight average molecular weight)/Mn (number average molecular weight) was 1.1.

<Example 1>
As component (A), 1.00 g of a PGMEA solution containing SM1 obtained in Synthesis Example 1, as component (B), IRGACURE (registered trademark) 127 (BASF Japan Ltd., 2-hydroxy-1-[4-{ 0.0060 g of 4-(2-hydroxy-2-methyl-propionyl)benzyl}-phenyl]-2-methyl-propan-1-one) (hereinafter, abbreviated as “IRGACURE 127” in this specification), and 7.67 g of PGMEA was mixed as the component (C) to prepare a mold release agent IP-A.

<Example 2>
A mixture of PGMEA solution containing SM2 obtained in Synthesis Example 2 as component (A), 1.00 g, IRGACURE 127 as component (B), 0.0040 g, and PGMEA as component (C), 4.80 g. Agent IP-B was prepared.

<Example 3>
1.00 g of a PGMEA solution containing SM2 obtained in Synthesis Example 2 as the component (A), IRGACURE (registered trademark) 819 (manufactured by BASF Japan Ltd., bis(2,4,6-trimethylbenzoyl) as the component (B)) )-Phenylphosphine oxide) (hereinafter abbreviated as “IRGACURE819” in the present specification), 0.0040 g, PGMEA as the component (C), 4.81 g, and Anthracure (registered trademark) UVS as the component (D). 0.0081 g of -581 (manufactured by Kawasaki Kasei Co., Ltd.) (hereinafter, abbreviated as "UVS-581" in this specification) was mixed to prepare a mold release agent IP-C.

<Example 4>
1.00 g of PGMEA solution containing SM2 obtained in Synthesis Example 2 as component (A), 0.0040 g of IRGACURE819 as component (B), 4.810 g of PGMEA as component (C), and KAYACURE as component (D). 0.0002 g of (registered trademark) DETX-S (manufactured by Nippon Kayaku Co., Ltd.) (hereinafter, abbreviated as "DETX-S") is mixed to prepare a mold release agent IP-D. did.

<Example 5>
1.00 g of a PGMEA solution containing SM2 obtained in Synthesis Example 2 as the component (A), IRGACURE (registered trademark) OXE-01 (BASF Japan Ltd., 2-(O-benzoyl oxime)) as the component (B) 0.0040 g of -1-[4-(phenylthio)phenyl]-1,2-octanedione), 4.81 g of PGMEA as the component (C), and 0.0002 g of UVS-581 as the component (D) were mixed. , A mold release agent IP-E was prepared.

<Example 6>
Mixing 1.00 g of the PGMEA solution containing SM1 obtained in Synthesis Example 1 as the component (A), 0.00030 g of IRGACURE 127 as the component (B), and 7.58 g of PGMEA as the component (C), and separating the mold. Molding agent IP-F was prepared.

<Example 7>
1.00 g of the PGMEA solution containing SM1 obtained in Synthesis Example 1 as the component (A), 0.030 g of IRGACURE 127 as the component (B), and 8.40 g of PGMEA as the component (C) were mixed, and the mold release Molding agent IP-G was prepared.

<Example 8>
As a component (A), 1.00 g of a PGMEA solution containing SM3 obtained in Synthesis Example 4, 0.0040 g of IRGACURE 127 as a component (B), and 4.82 g of PGMEA as a component (C) were mixed, and a mold release mold was prepared. Molding agent IP-H was prepared.

<Example 9>
As a component (A), 1.00 g of a PGMEA solution containing SM4 obtained in Synthesis Example 5, 0.0040 g of IRGACURE 127 as a component (B), and 4.82 g of PGMEA as a component (C) were mixed, and a mold release mold was prepared. Molding agent IP-I was prepared.

<Example 10>
1.00 g of the PGMEA solution containing SM3 obtained in Synthesis Example 4 as the component (A), 0.0040 g of IRGACURE819 as the component (B), 4.83 g of PGMEA as the component (C), and DETX as the component (D). 0.0002 g of -S was mixed to prepare a mold release agent IP-J.

<Example 11>
1.00 g of a PGMEA solution containing SM4 obtained in Synthesis Example 5 as the component (A), 0.0040 g of IRGACURE819 as the component (B), 4.83 g of PGMEA as the component (C), and DETX as the component (D). 0.0002 g of -S was mixed to prepare a mold release agent IP-K.

<Comparative Example 1>
Fluorolink (registered trademark) MD700 (manufactured by Solvay Specialty Polymers, Inc.) (hereinafter, abbreviated as "MD700" in the present specification) is 0.40 g, IRGACURE 127 is 0.0042 g as the component (B), and the component (C) is 5.66 g of PGMEA was mixed to prepare a mold release agent IP-a.
MD700 used in this Comparative Example and Comparative Example 2 described later is a perfluoropolyether (bifunctional methacrylate compound) modified with urethane methacrylate at both ends, and is a group represented by the formula (2a) or the formula (2b). Since it does not contain, it does not correspond to the component (A). Therefore, the mold release agent of this comparative example differs from the mold release agent of the examples of the present invention in that it does not contain the component (A).

<Comparative example 2>
MD700 (0.40 g), IRGACURE819 (B) component 0.0042 g, UVS-581 (0.002 g) as component (D), and PGMEA (5.66 g) as component (C) are mixed, and a mold release agent IP for molding is mixed. -B was prepared.
As described above, the mold releasing agent of this comparative example differs from the mold releasing agent of the examples of the present invention in that it does not contain the component (A).

<Comparative example 3>
0.21 g of 1,6-bis(acryloyloxy)-2,2,3,3,4,4,5,5-octafluorohexane (manufactured by Tokyo Chemical Industry Co., Ltd.), and IRGACURE 127 as the component (B) 0.0042 g and 5.91 g of PGMEA as the component (C) were mixed to prepare a mold release agent IP-c.
The 1,6-bis(acryloyloxy)-2,2,3,3,4,4,5,5-octafluorohexane used in this comparative example is a bifunctional methacrylate compound having a fluoroalkyl group. However, it does not correspond to the component (A) because it does not contain the group represented by the formula (1) and the group represented by the formula (2a) or the formula (2b) and does not contain a urethane bond.
Therefore, the mold release agent of this comparative example differs from the mold release agent of the examples of the present invention in that it does not contain the component (A).

<Comparative example 4>
A PGMEA solution containing CHM-A obtained in Synthesis Example 1.00 g, 0.0045 g of IRGACURE 127 as the component (B), and 5.55 g of PGMEA as the component (C) were mixed, and a mold releasing agent IP- d was prepared.
The CHM-A used in this comparative example is a copolymer represented by the formula (4) as described above and does not correspond to the component (A), and the mold release agent for this comparative example is (A) 3) is different from the mold release agent of the embodiment of the present invention in that it does not contain a component.

<Comparative Example 5>
0.21 g of PFPE1 and 5.79 g of PGMEA as the component (C) were mixed to prepare a mold release agent IP-e.
PFPE1 used in this comparative example is a perfluoropolyether having a hydroxy group at both ends via a poly(oxyethylene) group as described above, and is polymerizable at both ends of the compound through urethane bonds. It does not have a group and does not correspond to the component (A).
That is, the mold release agent of this comparative example differs from the mold release agent of the examples of the present invention in that it does not contain the component (B) in addition to the component (A).

<Comparative example 6>
Novec (registered trademark) 1720 (manufactured by 3M Japan Co., Ltd.) was prepared and used as a mold release agent IP-f.
Novec 1720 used in this comparative example is a conventionally known fluorine-based compound that is also used as a mold release agent used in photoimprinting, and is a perfluoroether group-containing silane compound.
That is, the mold release agent of this comparative example differs from the mold release agent of the examples of the present invention in that it does not contain the components (A), (B) and (C).

<Comparative Example 7>
As a component (A), 1.00 g of a PGMEA solution containing SM1 obtained in Synthesis Example 1, as a component (B), IRGACURE 127 (0.06 g), and as a component (C), 9.15 g of PGMEA, and mold-releasing. Agent IP-g was prepared.
That is, in the mold release agent of this comparative example, the content ratio of the component (B) exceeds the upper limit of 0.05 phr to 15 phr based on the mass of the component (A). Different from the mold release agent.

<Comparative Example 8>
10.00 g of the PGMEA solution containing SM1 obtained in Synthesis Example 1 as the component (A), 0.00030 g of IRGACURE 127 as the component (B), and 75.12 g of PGMEA as the component (C) were mixed, and a mold release mold was prepared. Agent IP-h was prepared.
That is, the mold release agent of this comparative example is that the content ratio of the component (B) is less than the lower limit value of 0.05 phr to 15 phr based on the mass of the component (A), that is, the embodiment of the present invention. Different from the mold release agent.

<Production of photocurable resin (imprint material)>
5 g of NK ester A-DOG (hereinafter abbreviated as "A-DOG" in the present specification) (manufactured by Shin-Nakamura Chemical Co., Ltd.) and UM-90 (1/3) DA (Ube Industries, Ltd.) (Manufactured by Mfg. Co., Ltd.) is mixed with 5 g, and IRGACURE (registered trademark) 184 (manufactured by BASF Japan Ltd.) is added to the mixture in an amount of 0.2 g (2 phr based on the total mass of A-DOG and UM-90 (1/3) DA). , 0.05 g (0.5 phr with respect to the total mass of A-DOG and UM-90 (1/3)DA) of thiocalcol (registered trademark) 20 (manufactured by Kao Corporation) was added, and the imprint material PNI-A was added. Was prepared.

[Preparation of resin mold 1 subjected to release treatment]
Obtained in Examples 1 to 11 and Comparative Examples 1 to 4, Comparative Examples 7 and 8 onto a resin mold having a convex lens shape with a diameter of 9.5 mm and a maximum height of 0.25 mm. Mold release agent IP-A, IP-B, IP-C, IP-D, IP-E, IP-F, IP-G, IP-H, IP-I, IP-J, IP-K, IP Each of -a, IP-b, IP-c, IP-d, IP-g, and IP-h was formed into a film by a spin coater, and baked at 80°C for 5 minutes using a hot plate. Then, under a nitrogen atmosphere, UV irradiation was performed at 40 mW/cm ² for 125 seconds using a batch type UV irradiation device (high pressure mercury lamp 2 kW×1 lamp) (manufactured by Eye Graphics Co., Ltd.), and the resin was subjected to mold release treatment. A mold was produced.
In this example and the following examples, a resin mold obtained by photocuring a resin composition containing a compound having at least two (meth)acryloyloxy groups in one molecule was used as the resin mold.

[Preparation of resin mold 2 subjected to mold release treatment]
On the resin mold having a convex lens shape with a diameter of 9.5 mm and a maximum height of 0.25 mm, the mold releasing agent IP-C obtained in Examples 3 to 5, Example 10 and Example 11, IP-D, IP-E, IP-J, and IP-K were each formed into a film with a spin coater, and baked at 80° C. for 5 minutes using a hot plate. Then, under a nitrogen atmosphere, a batch type UV irradiation device (high pressure mercury lamp 2 kW x 1 lamp) (manufactured by Eye Graphics Co., Ltd.) was used to pass an i-line transmission filter, and UV exposure was performed at 40 mW/cm ² for 125 seconds. A resin mold that has been subjected to a mold release treatment was produced.

[Preparation of resin mold 3 subjected to mold release treatment]
The mold release agents IP-e and IP-f obtained in Comparative Example 5 and Comparative Example 6 were respectively placed on a resin mold having a convex lens shape having a diameter of 9.5 mm and a maximum height of 0.25 mm using a spin coater. A film was formed and baked at 80° C. for 5 minutes using a hot plate to prepare a mold made of resin.

[Optical imprint using a resin mold that has undergone mold release processing]
A silica glass substrate was spin-coated with 3-acryloxypropyltrimethoxysilane, baked at 150° C. for 5 minutes using a hot plate, and the silica glass substrate was subjected to silane coupling treatment. After that, the imprint material PNI-A was potted on the silane coupling-treated surface of the quartz glass substrate, and sandwiched by the resin molds subjected to mold release treatment according to the above-mentioned Preparation 1, Preparation 2 and Preparation 3, and the nanoimprint apparatus NM was used. Optical imprinting was performed with -0801HB (manufactured by Meisho Kiko Co., Ltd.). The optical imprinting is always 23° C. under conditions of a) pressurizing to 500 N for 10 seconds, b) exposing at 6000 mJ/cm ² using a high-pressure mercury lamp, c) depressurizing for 10 seconds, and d) releasing. By performing a sequence of separating the mold-treated resin mold and the quartz glass substrate and releasing the mold, a concave lens-shaped pattern having a diameter of 9.5 mm and a maximum depth of 0.25 mm was formed on the quartz glass substrate.

[Measurement of the number of times imprint can be repeated]
Using the resin mold used in the above-mentioned optical imprint and subjected to the mold release treatment according to the production 1, the production 2, and the production 3 as it is, the same optical imprint as described above is repeated to obtain a diameter on the quartz glass substrate. The number of optical imprints was measured until the concave lens-shaped pattern of 9.5 mm and the maximum depth of 0.25 mm was not formed. The results obtained are shown in Table 1.

[Evaluation of Surface Roughness of Coating Formed from Mold Release Agent]
Mold release agents IP-A, IP-B, IP-C, IP-D, IP- obtained in Examples 1 to 11 and Comparative Examples 1 to 8 on a 4-inch silicon wafer. E, IP-F, IP-G, IP-H, IP-I, IP-J, IP-K, IP-a, IP-b, IP-c, IP-d, IP-e, IP-f, Each of IP-g and IP-h was spin-coated and baked at 80° C. for 5 minutes using a hot plate. Then, under a nitrogen atmosphere, UV irradiation was performed at 40 mW/cm ² for 125 seconds using a batch type UV irradiation device (high pressure mercury lamp 2 kW×1 lamp) (manufactured by Eye Graphics Co., Ltd.) to form a mold release agent film. Was produced. Then, the root mean square roughness (RMS) of the coating was measured using an atomic force microscope (AFM). The obtained results are shown in Table 2.

[Transparency evaluation]
The mold release agents IP-A and IP-g obtained in Example 1 and Comparative Example 7 were formed on a resin mold having a concave lens shape with a diameter of 9.5 mm and a maximum depth of 0.25 mm by a spin coater. Membranes were baked for 5 minutes at 80° C. using a hot plate. Then, under a nitrogen atmosphere, UV irradiation was performed at 40 mW/cm ² for 125 seconds using a batch type UV irradiation device (high pressure mercury lamp 2 kW×1 lamp) (manufactured by Eye Graphics Co., Ltd.), and the resin was subjected to mold release treatment. A mold was produced. Then, the transmittance of the resin mold subjected to the mold release treatment at 365 nm was measured using a spectrophotometer UV2600 (manufactured by Shimadzu Corporation) with the reference being air. The obtained results are shown in Table 2.

From the results shown in Table 1, repeated imprints were made possible by using the resin molds that were mold-release treated with the mold release agent prepared in Examples 1 to 11. On the other hand, in the case of using the resin mold which has been subjected to the mold release treatment with the mold release agent prepared in Comparative Examples 1 to 6 and Comparative Example 8, repeated imprinting is impossible, or Example 1 As a result, the number of repeated imprints was smaller than that in Example 11. Further, from the results shown in Table 2, the RMS of the coating films obtained from the mold release agents prepared in Examples 1 to 11 was less than 1 nm. In addition, the resin mold prepared by the mold release agent prepared in Comparative Example 7 had a lower transparency than that of Example 1 as a result. As described above, by subjecting a resin mold to a mold release treatment using the mold release agent of the present invention, repeated imprinting can be performed using the resin mold, and a film of the obtained mold release agent is obtained. RMS will be very small.

[Preparation of release-treated metal mold]
3-acryloxypropyltrimethoxysilane was spin-coated on a moth-eye pattern mold (manufactured by Inox Co., Ltd.) having a pitch of 250 nm and a height of 250 nm made of nickel, baked at 150° C. for 5 minutes using a hot plate, and then a silane cup. Ring processing was performed. Then, the mold release agent IP-A obtained in Example 1 was formed into a film on the silane coupling treated surface of the mold with a spin coater, and baked at 80° C. for 5 minutes using a hot plate. Then, under a nitrogen atmosphere, UV exposure was performed at 40 mW/cm ² for 125 seconds using a batch type UV irradiation device (high pressure mercury lamp 2 kW×1 lamp) (manufactured by Eye Graphics Co., Ltd.), and the mold-treated nickel product was used. A mold was produced.

[Optical imprinting using a metal mold that has been subjected to mold release processing]
A silica glass substrate was spin-coated with 3-acryloxypropyltrimethoxysilane, baked at 150° C. for 5 minutes using a hot plate, and the silica glass substrate was subjected to silane coupling treatment. After that, the imprint material PNI-A was potted to the silane coupling treated surface of the quartz glass substrate, and sandwiched by the metal mold subjected to the mold release treatment, and the nanoimprint apparatus NM-0801HB (manufactured by Meisho Kiko Co., Ltd.). I did optical imprint in. The optical imprinting is always 23° C. under conditions of a) pressurizing to 500 N for 10 seconds, b) exposing at 6000 mJ/cm ² using a high-pressure mercury lamp, c) depressurizing for 10 seconds, and d) releasing. By performing a sequence of separating the mold-treated metal mold and the quartz glass substrate and releasing the mold, a moth-eye pattern having a pitch of 250 nm and a height of 250 nm was formed on the quartz glass substrate. When the obtained shape was confirmed by using a scanning electron microscope S-4800 (manufactured by Hitachi High-Technologies Corporation), all were good pattern shapes without cracking or peeling.

Claims (12)

A mold release agent containing the following component (A), component (B) and component (C).
(A): Via a urethane bond at all terminals of a linear or chain molecular chain containing a group represented by the following formula (1) and a group represented by the following formula (2a) or formula (2b) A polyfunctional (meth)acrylate compound (B) having a polymerizable group containing a group represented by the following formula (3): 0.05 phr to 15 phr photopolymerization initiation based on the mass of the component (A). Agent (C): Solvent

(In the formula, R ¹ represents a perfluoroalkylene group having 1 or 2 carbon atoms, R ^2a represents an alkylene group having 2 or 3 carbon atoms, and R ^2b is a trivalent carbon atom having 2 or 3 carbon atoms. Represents a hydrogen group, * represents a bond for bonding to the -O- group of the urethane bond, p and q are respectively represented by the number of groups represented by the formula (1) and the formula (2a). Represents an integer of 2 or more, and R ³ represents a methyl group or a hydrogen atom.) The mold release agent according to claim 1, wherein the q is an integer of 5 to 12. The mold release agent according to claim 1 or 2, wherein the group represented by the formula (2a) is a poly(oxyethylene) group. The mold release agent according to any one of claims 1 to 3, wherein the polymerizable group contains at least two groups represented by the formula (3). The mold release according to any one of claims 1 to 4, wherein the group represented by the formula (1) is a group having both an oxyperfluoromethylene group and an oxyperfluoroethylene group. Agent. The ratio of the component (A) is 0.05% by mass to 10% by mass, relative to 100% by mass of the total mass of the mold release agent. Mold release agent. The mold releasing agent according to any one of claims 1 to 6, further comprising a photosensitizer as the component (D). A mold having a release-treated surface, comprising a coating formed from the mold release agent according to any one of claims 1 to 7. The mold having a release treated surface according to claim 8, wherein the mold is selected from the group consisting of a metal mold, a silicon mold, an alumina mold, a quartz mold, and a resin mold. The process of apply|coating the mold release agent for molds as described in any one of Claim 1 thru|or 7 on a resin mold, and baking the mold release agent applied on the said resin mold, and exposing. And a step of forming a coating film on the surface of the resin mold, and a method for producing a resin mold subjected to mold release treatment. A step of press-bonding a mold having a release-treated surface according to claim 8 or 9 to a photo-curable resin, a step of photo-curing the photo-curable resin while being press-bonded to the mold, and the light. A method for producing a cured film having a maximum film thickness of 1.5 mm to which a pattern is transferred, including a step of releasing the obtained photo-cured product from the mold having the release-treated surface after the step of curing. A mold having a release treated surface according to claim 8 or claim 9, wherein the root mean square roughness of the release treated surface is less than 1 nm.