JPWO2020116397A1 - Replica mold for imprint and its manufacturing method - Google Patents

Abstract

【Task】
We provide a new replica mold for imprinting.
SOLUTION:
An imprint replica mold having the following A layer and the following B layer adhered to the A layer.
Layer A: Structure composed of a cured product of the composition containing the following components (a1) and (a2) Component (a1): Compound (a2) having at least one radically polymerizable group in one molecule: The above (a2) a1) Photoradical polymerization initiator B layer of 0.01% by mass to 0.3% by mass with respect to 100% by mass of the component: A film composed of a cured product of the composition containing the following components (b1) and (b2). b1) Component: A compound composed of a linear or chain molecular chain containing a fluorine atom and having a radically polymerizable group at all ends of the molecular chain. Component (b2) Component: 100% by mass of the component (b1). On the other hand, there is no photoradical polymerization initiator of 0.05% by mass to 15% by mass [selection diagram].

Description

The present invention relates to an imprint replica mold having a pattern. More specifically, it is a replica mold that maintains high transparency in the ultraviolet region even if it is a thick film, and it does not require recoating of a release agent and can form a good pattern even when used for repeated optical imprinting. The present invention relates to a replica mold for imprinting and a method for manufacturing the replica mold.
As used herein, the term "thick film" refers to a film having a thickness of 0.01 mm or more and a maximum thickness of 2.0 mm.

Resin lenses are used in electronic devices such as mobile phones, digital cameras, and in-vehicle cameras, and are required to have excellent optical characteristics according to the purpose of the electronic devices. Further, the resin lens is required to have high durability, for example, heat resistance and weather resistance, and high productivity capable of molding with good yield according to the usage mode. As a material for a resin lens satisfying such a requirement, for example, a thermoplastic transparent resin such as a polycarbonate resin, a cycloolefin polymer, or a methacrylic resin has been used.

In manufacturing resin lenses, in order to improve yield and production efficiency, and to suppress optical axis deviation during lens lamination, from injection molding of thermoplastic resin to wafer by pressing molding using curable resin that is liquid at room temperature. The transition to level molding is being actively considered. In wafer level molding, a hybrid lens method in which a lens is formed on a support such as a glass substrate is common from the viewpoint of productivity.

In wafer level molding, the mold also needs to be molded at the wafer level. A general mold for manufacturing resin lenses is made by drilling and polishing metal, but at the wafer level, it has a large number of lens patterns in the plane, and its in-plane error and inter-pixel pitch are accurate. Need to be controlled. Therefore, it is very difficult to manufacture the mold and it becomes expensive. Further, when a metal mold is used, UV light used for curing the resin lens material is not transmitted, so that the material of the support on which the lens is molded is limited. Therefore, it is common to manufacture a replica mold using a master mold and a replica mold material, and perform wafer level molding using the replica mold. Among them, as described in Patent Document 1, a method of manufacturing a replica mold by step-and-repeat molding in a wafer using a relatively inexpensive master mold for one pixel and a replica molding material has been developed. ing.

Japanese Patent No. 4226061 (Japanese Unexamined Patent Publication No. 2009-172773)

The commonly used replica mold has a low transmittance of UV light used in the manufacturing process of a resin lens, particularly a wavelength of 365 nm. When molding a resin lens using such a replica mold, there is a method of applying a commercially available mold release agent in order to impart mold releasability. However, when the resin lens is repeatedly molded using the same replica mold, the release agent is peeled off from the surface of the replica mold. Therefore, it becomes difficult to repeatedly mold the resin lens using the same replica mold.

As described above, there is still no replica mold that can be used for molding a resin lens used for a camera module or the like, has high transparency, and can repeatedly mold a resin lens, and its development has been desired. .. The present invention has been made in view of such circumstances, and an object of the present invention is to provide a replica mold having high transparency and capable of repeatedly molding a resin lens.

As a result of diligent studies to solve the above problems, the present inventors have selected a compound having at least one radically polymerizable group in one molecule and a cured product of a composition containing a photoradical polymerization initiator. A film composed of a compound having a radically polymerizable group at all ends of a linear or chain molecular chain containing a fluorine atom and a cured product of a composition containing a photoradical polymerization initiator is adhered to the structure. This made the present invention. That is, the replica mold of the present invention has high transparency in the ultraviolet region and can repeatedly mold a resin lens.

That is, the first aspect of the present invention is an imprint replica mold provided with the following A layer and the following B layer adhered to the A layer.
Layer A: Structure composed of a cured product of the composition containing the following components (a1) and (a2) Component (a1): Compound (a2) having at least one radically polymerizable group in one molecule: The above (a2) a1) Photoradical polymerization initiator B layer of 0.01% by mass to 0.3% by mass with respect to 100% by mass of the component: A film composed of a cured product of the composition containing the following components (b1) and (b2). b1) Component: A compound composed of a linear or chain molecular chain containing a fluorine atom and having a radically polymerizable group at all ends of the molecular chain. Component (b2) Component: 100% by mass of the component (b1). On the other hand, 0.05% by mass to 15% by mass of a photoradical polymerization initiator

（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）で表される基の繰り返し数及び前記式（２ａ）で表される基の繰り返し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。）The compound of the component (b1) is all of the linear or chain molecular chains containing, for example, a group represented by the following formula (1) and a group represented by the following formula (2a) or the formula (2b). It is a polyfunctional (meth) acrylate compound having a group represented by the following formula (3) at the end via a urethane bond.

(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 hydrocarbon having 2 or 3 carbon atoms. Represents a hydrogen group, * represents a bond that bonds to the −O— group of the urethane bond, respectively, and p and q are represented by the number of repetitions of the group represented by the above formula (1) and the above formula (2a), respectively. It represents the number of repetitions of the group to be formed and independently represents an integer of 2 or more, and R ³ represents a methyl group or a hydrogen atom.)

Q representing the number of repetitions of the group represented by the above formula (2a) is, for example, an integer of 5 to 12.

The group represented by the formula (2a) is, for example, a poly (oxyethylene) group.

The group represented by the formula (1) is, for example, a group having both an oxyperfluoromethylene group and an oxyperfluoroethylene group.

The compound of the component (b1) is, for example, a macromonomer or a polymer having a weight average molecular weight of 1000 to 30,000.

The composition containing the component (b1) and the component (b2) may further contain a photosensitizer.

When the component (a1) contains at least two compounds, at least one of the two compounds is a compound having at least two (meth) acryloyloxy groups in one molecule.

（式中、Ｒ^４及びＲ^５はそれぞれ独立に水素原子又はメチル基を表し、Ｒ^６及びＲ^７はそれぞれ独立に炭素原子数１乃至４のアルキレン基を表し、Ｒ^８及びＲ^９はそれぞれ独立に水素原子又はメチル基を表し、ｒ^１及びｒ^２はそれぞれ独立に１乃至５の整数を表す。）The compound having at least two (meth) acryloyloxy groups in one molecule is, for example, a di (meth) acrylate compound represented by the following formula (4).

(In the formula, R ⁴ and R ⁵ independently represent a hydrogen atom or a methyl group, R ⁶ and R ⁷ independently represent an alkylene group having 1 to 4 carbon atoms, and R ⁸ and R ⁹ are independent, respectively. Represents a hydrogen atom or a methyl group, and r ¹ and r ² each independently represent an integer of 1 to 5).

The A layer has, for example, a lens-shaped inversion pattern. The maximum thickness of the A layer is, for example, 2.0 mm.

Another aspect of the present invention is a step of applying a composition containing the following components (a1) and (a2) onto a master mold, and the master via a composition containing the following components (a1) and (a2). In the step of crimping the mold to the base material, the composition containing the following components (a1) and (a2) is exposed through the base material while the master mold is being crimped to the base material, and the composition is photocured. After the step, the photocuring step, the cured product obtained on the substrate is released from the master mold to form the A layer, and the following components (b1) to (b3) are formed on the A layer. The step of applying the composition containing the above, and the composition containing the following components (b1) to (b3) are baked at 40 ° C. to 200 ° C., and then exposed to form the B layer adhered to the A layer. It is a method of manufacturing a replica mold for imprint including a step.
Component (a1): Compound having at least one radically polymerizable group in one molecule (a2) Component: 0.1% by mass to 1% by mass of a photoradical polymerization initiator with respect to 100% by mass of the (a1) component. Component (b1): A compound composed of a linear or chain molecular chain containing a fluorine atom and having a radically polymerizable group at all ends of the molecular chain. Component (b2) Component: 100 mass of the component (b1). 0.05% by mass to 15% by mass of photoradical polymerization initiator (b3) component: solvent

Further, another aspect of the present invention is the step of applying the composition containing the following components (a1) and (a2) onto the substrate, and the above via the composition containing the following components (a1) and (a2). In the step of crimping the base material to the master mold, the composition containing the following components (a1) and (a2) is exposed through the base material while the master mold is being crimped to the base material, and the composition is photocured. After the step of photo-curing, the step of releasing the cured product obtained on the substrate from the master mold to form the A layer, the following components (b1) to (b3) on the A layer. The step of applying the composition containing the components and the composition containing the following components (b1) to (b3) are baked at 40 ° C. to 200 ° C. and then exposed to form the B layer adhered to the A layer. It is a method of manufacturing a replica mold for imprint including the step of making.
Component (a1): Compound having at least one radically polymerizable group in one molecule (a2) Component: 0.1% by mass to 1% by mass of a photoradical polymerization initiator with respect to 100% by mass of the (a1) component. Component (b1): A compound composed of a linear or chain molecular chain containing a fluorine atom and having a radically polymerizable group at all ends of the molecular chain. Component (b2) Component: 100 mass of the component (b1). 0.05% by mass to 15% by mass of photoradical polymerization initiator (b3) component: solvent

The replica mold for imprint of the present invention is a cured product of the composition containing the components (b1) and (b2) in a structure composed of a cured product of the composition containing the components (a1) and (a2). Since the film made of the material is adhered, even a thick film has high transparency and continuous transfer is possible.

Further, the replica mold for imprinting of the present invention can be produced on an arbitrary base material, and the replica mold formed on the base material has high transparency even in a thick film in the ultraviolet region. Therefore, the replica mold for imprinting of the present invention can be suitably used for manufacturing optical members such as solid-state image sensors and sensor lenses, which require shape accuracy.

[(A1) component]
The component (a1) is a compound having at least one radically polymerizable group in one molecule. Examples of the radically polymerizable group include a (meth) acryloyloxy group. In the present invention, the (meth) acryloyloxy group means both an acryloyloxy group and a methacryloyloxy group. Further, (meth) acrylate means both acrylate and methacrylate.

Examples of the compound of the component (a1) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth). Acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, n-hexyl (meth) acrylate, isohexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl ( Meta) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, tetradecyl (meth) ) Acrylate, behenyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 1-adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, Dicyclopentenyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, cyclohexanespiro-2- (1,3-) Dioxolan-4-yl methyl (meth) acrylate, 3-ethyl-3-oxetanylmethyl (meth) acrylate, γ-butyrolactone (meth) acrylate, methoxydiethylene glycol di (meth) acrylate, methoxytriethylene glycol (meth) acrylate, Methoxytetraethylene glycol (meth) acrylate, methoxypolypropylene glycol # 400 (meth) acrylate, methoxypolyethylene glycol # 600 (meth) acrylate, methoxypolyethylene glycol # 1000 (meth) acrylate, methoxytripropylene glycol (meth) acrylate, 1, 4-Butandiol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, isononandiol di (meth) acrylate, 1,10-decanediol di ( Meta) acrylate, neopentyl glycol di (meth) acrylate, 2-hydroxy-3-methacrylpropylac Relate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol # 200 di (meth) acrylate, polyethylene glycol # 400 di (meth) acrylate, polyethylene glycol # 600 Di (meth) acrylate, polyethylene glycol # 1000 di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol # 400 diacrylate, polypropylene glycol # 700 diacrylate, polytetra Methylene glycol # 650 di (meth) acrylate, polyethylene polypropylene glycol di (meth) acrylate, dioxane glycol di (meth) acrylate, tricyclodecanol di (meth) acrylate, ethoxy-modified hydrogenated bisphenol A diacrylate, ethoxy-modified hydrogenated Bisphenol A dimethacrylate, propoxy-modified hydrogenated bisphenol A diacrylate, propoxy-modified hydrogenated bisphenol A dimethacrylate, butoxy-modified hydrogenated bisphenol A diacrylate, butoxy-modified hydrogenated bisphenol A dimethacrylate, ethoxypropoxy-modified hydrogenated bisphenol A diacrylate , Ethoxypropoxy-modified hydrogenated bisphenol A dimethacrylate, ethoxy-modified hydrogenated bisphenol F diacrylate, ethoxy-modified hydrogenated bisphenol F dimethacrylate, trimethylol propanetri (meth) acrylate, ethoxylated trimethylol propanetri (meth) acrylate, propoxy Trimethylol propantri (meth) acrylate, glycerin tri (meth) acrylate ethoxylated, glycerin tri (meth) acrylate propoxylated, tris- (2- (meth) acryloyloxyethyl) isocyanurate, caprolactone-modified tris- (2-) (Meta) acryloyloxyethyl) isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, propoxylated pentaerythritol Tri (meth) acrylate, propoxylated pentaerythritol tetra (meth) acrylic Rate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated ditrimethylolpropane tetra (meth) acrylate, propoxylated ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol poly (meth) acrylate , Eethoxylated dipentaerythritol poly (meth) acrylate, propoxylated dipentaerythritol poly (meth) acrylate, and ethoxylated polyglycerin poly (meth) acrylate.

The compound of the above component (a1) is available as a commercially available product, and specific examples thereof include light ester M, E, NB, IB, TB, EH, IB-X, and CH. Light Acrylate IB-XA, (Kyoeisha Chemical Co., Ltd.), NOAA, IOAA, INAA, LA, STA, ISTA, IBXA, Viscort # 155, 1-ADA, 1-ADMA, Viscort # 150, MEDOL-10 , CHDOL-10, OXE-10, OXE-30, GBLA, GBLMA, Viscort # 195, Viscort # 230, Viscote # 260, Viscote # 295, Viscote # 300, Viscote # 400, Viscote # 360 (above, Osaka Organic Chemistry) (Manufactured by Kogyo Co., Ltd.), LA, LMA, A-MS, AS, S-1800A, A-BH, AM-30G, AM-90G, AM-130G, AM-230G, AM-30PG, M-20G , M-30G, M-40G, M-90G, M-130G, M-230G, A-HD-N, A-NOD-N, A-IND, A-DOD-N, A-NPG, BD, HD -N, NOD-N, DOD-N, NPG, 701A, 701, A-200, A-400, A-600, A-1000, APG-100, APG-200, APG-400, APG-700, 1G , 2G, 3G, 4G, 9G, 14G, 23G, 3PG, 9PG, A-PTMG-65, A-1206PE, 1206PE, A-0612PE, A-0412PE, A-1000PER, 1000PER, A-3000PER, A-DOG , A-DCP, DCP, A-TMPT, A-TMPT-3EO, A-TMPT-9EO, AT-20E, AT-30E, A-TMPT-3PO, A-TMPT-6O, TMPT, TMPT-3EO, TMPT -9EO, TMPT-3PO, A-GLY-3E, A-GLY-6E, A-GLY-9E, A-GLY-20E, A-GLY-3P, A-GLY-6P, A-GLY-9P, GLY -3E, GLY-6E, GLY-9E, GLY-20E, A-9300, A-9200, A-9300-1CL, A-9300-3CL, A-TMM-3, A-TMM-3L, A-TMM -3LM-N, ATM-4EL, ATM-8EL, ATM-4PL, TM-4EL, TM-4PL, A-TMMT, ATM-4E, ATM-35E, ATM-4P, ATM-10P, TM-4E, TM -35E, TM-4P, TM -10P, AD-TMP-L, AD-TMP-4E, AD-TMP-4P, D-TMP, D-TMP-4E, D-TMP-4P, A-DPH, A-9550, A-DPH-6E , A-DPH-12E, A-DPH-6EL, A-DPH-12EL, A-DPH-6P, M-DPH-6E, M-DPH-12E, M-DPH-6P, A-PG5027E, A-PG5054E , M-PG5027E, M-PG5054E (above, Shin-Nakamura Chemical Industry Co., Ltd.), Funkrill (registered trademark) FA-513AS, FA-512AS, FA-511AS (above, Hitachi Kasei Co., Ltd.), New Frontier (registered trademark) HBPE-4, HBPEM-10 (above, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), KAYARAD (registered trademark) PET-30, DPHA, DPEA-12 (above, Nippon Kayaku Co., Ltd.) ) Made). The above component (a1) may be used alone or in combination of two or more.

[(A2) component]
The photoradical polymerization initiator of the component (a2) is particularly limited as long as it has absorption in the light source used during photocuring of the composition for forming the A layer of the replica mold for imprint of the present invention. It's not a thing. Examples of the photoradical polymerization initiator of the component (a2) include tert-butylperoxy-iso-butyrate, 2,5-dimethyl-2,5-bis (benzoyldioxy) hexane, and 1,4-bis [α-]. (Tart-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) -Amilperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (tert-hexylperoxycarbonyl) benzophenone, 3,3'-bis (tert-butylperoxycarbonyl) -4,4'-dicarboxybenzophenone, Organic peroxides such as tert-butylperoxybenzoate and di-tert-butyldiperoxyisophthalate; such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone and 1,2-benzanthraquinone. Kinones; benzoin derivatives such as benzoin methyl, benzoin ethyl ether, α-methylbenzoin, α-phenylbenzoin; 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenylketone, 2- Hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy- 1- [4- {4- (2-Hydroxy-2-methylpropionyl) benzyl} -phenyl] -2-methylpropan-1-one, phenylglioxylic acid methyl ester, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinofe) Alkylphenone compounds such as Nyl) -1-butanone, 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1-one; bis ( Acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; 2- (O-benzoyloxime) -1- [4- ( Phenylthio) Phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] oxime esters such as etanone Examples include system compounds.

The photoradical polymerization initiator of the component (a2) is available as a commercially available product, and specific examples thereof include IRGACURE (registered trademark) 651, 184, 500, 2959, 127, 754, and so on. 907, 369, 379, 379EG, 819, 819DW, 1800, 1870, 784, OXE01, OXE02, 250, 1173, MBF, 4265, TPO (above, BASF Japan Co., Ltd., KAYACURE (registered trademark) DETX, MBP, DMBI, EPA, OA (above, manufactured by Nippon Kayaku Co., Ltd.), VICURE-10, 55 (above, STAUFFER Co., Ltd.). Made by LTD), ESACURE (registered trademark) KIP150, TZT, 1001, KTO46, KB1, KL200, KS300, EB3, Triazine-PMS, Triazine A, Triazine B ), Adekaoptomer N-1717, N-1414, and N-1606 (manufactured by ADEKA Corporation). The above component (a2) may be used alone or in combination of two or more. The content ratio of the photoradical polymerization initiator of the component (a2) is 0.01% by mass to 0.3% by mass with respect to 100% by mass of the component (a1).

[(B1) component]
The component (b1) is a compound having a radically polymerizable group at all ends of a linear or chain molecular chain containing a fluorine atom. Examples of the radically polymerizable group include a (meth) acryloyloxy group.

Examples of the compound of the component (b1) include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, and 2- (perfluorobutyl). ) Ethyl (meth) acrylate, 3- (perfluorobutyl) -2-hydroxypropyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) Acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl (meth) acrylate, 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H-1- (trifluoromethyl) trifluoroethyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate, 1,2,2 , 2-Tetrafluoro-1- (trifluoromethyl) ethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,3,4,5,4-hepta Fluorobutyl (meth) acrylate, 1H, 1H-pentadecafluoro-n-octyl (meth) acrylate, 1H, 1H, 2H, 2H-tridecafluorooctyl acrylate, 1,6-bis ((meth) acryloyloxy)- Examples thereof include 2,2,3,3,4,5,5-octafluorohexane.

The above compounds are available as commercial products, and specific examples thereof include 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl methacrylate, and 2,2,3,3-. Pentafluoropropyl acrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2- (perfluorobutyl) ethyl acrylate, 2- (perfluorobutyl) ethyl methacrylate, 3- (perfluorobutyl)- 2-Hydroxypropyl acrylate, 3- (perfluorobutyl) -2-hydroxypropyl methacrylate, 2- (perfluorohexyl) ethyl acrylate, 2- (perfluorohexyl) ethyl methacrylate, 3-perfluorohexyl-2- Hydroxypropyl acrylate, 3-perfluorohexyl-2-hydroxypropyl methacrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropylmethacrylate Acrylate, 1H, 1H, 3H-tetrafluoropropyl acrylate, 1H, 1H, 3H-tetrafluoropropyl methacrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1H, 7H-dodecafluoroheptyl methacrylate, 1H, 1H, 7H-dodecafluoroheptyl acrylate, 1H-1- (trifluoromethyl) trifluoroethyl acrylate, 1H-1- (trifluoromethyl) trifluoroethyl methacrylate, 1H, 1H, 3H-hexafluorobutyl acrylate, 1H, 1H, 3H-hexafluorobutyl methacrylate, 1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethyl acrylate, Co., Ltd.), 2,2,3,3-tetrafluoropropyl acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,3,4,5,4-heptafluorobutylmethate Acrylate, 1H, 1H-pentadecafluoro-n-octyl acrylate, 1,6-bis (acryloyloxy) -2,2,3,3,4,5,5-octafluorohexane (above, Tokyo Kasei Kogyo) (Manufactured by Co., Ltd.), LINK-151EPA, LINK-152EPA, LINK-102A, LINK-2 A, LINK-5A, LINK-162A, LINK-3A (above, manufactured by Kyoeisha Chemical Co., Ltd.), FLOOLOLINK (registered trademark) MD500, MD700, MD40, MD1700, FOMBLIN (registered trademark) MT70 (above, Solvay) Includes (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and Viscort 13F (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

The component (b1) contains urethane at all ends of 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). It may be a polyfunctional (meth) acrylate compound having a group represented by the above formula (3), that is, a polymerizable group containing a (meth) acryloyloxy group via a bond. Here, the polyfunctional (meth) acrylate compound is a bifunctional or higher functional acrylate compound or a methacrylate compound excluding a monofunctional (meth) acrylate compound. The urethane bond refers to a structure represented by −NH—C (= O) −O−. The polyfunctional (meth) acrylate compound has two or four urethane bonds and two or four 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 linear or chain-like molecular chain is not particularly limited as long as it is a molecular chain containing a group represented by the formula (1) and a group represented by the formula (2a) or the formula (2b). In the linear or chain molecular chain, the bonding order of the group represented by the formula (1) and the group represented by the formula (2a) or the formula (2b) is not particularly limited, and the bonding order of each group is not particularly limited. The number is not particularly limited. Further, in the linear or chain molecular chain, even if the group represented by the formula (1) and the group represented by the formula (2a) or the formula (2b) are bonded (directly bonded) by a single bond. Alternatively, it 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 oxyperfluoroalkylene group in the group represented by the formula (1):-(OR ¹ )-R ¹ has 1 or 2 carbon atoms. That is, the group represented by the above formula (1) has a structure in which divalent fluorocarbon groups having 1 or 2 carbon atoms and oxygen atoms are alternately linked, and the oxyperfluoroalkylene group has the number of carbon atoms. It has a structure in which a 1 or 2 divalent carbon dioxide group and an oxygen atom are linked. Specific examples of the oxyperfluoroalkylene group include- (OCF ₂ )-(that is, oxyperfluoromethylene group) and-(OCF ₂ CF ₂ )-(that is, oxyperfluoroethylene group). As the oxyperfluoroalkylene group, any one of − (OCF ₂ ) − and − (OCF ₂ CF ₂ ) − may be used alone, or two types may be used in combination. When the two types are used in combination, the combination of-(OCF ₂ )-and-(OCF ₂ CF ₂ )-may be either a block bond or a random bond.

From the viewpoint of improving the mold releasability, the groups represented by the above formula (1) are-(OCF ₂ )-(that is, oxyperfluoromethylene group) and-(OCF ₂ CF ₂ )-(that is, oxyperfluoro). It is preferable to use a group having both of (ethylene group). As the group represented by the above formula (1),-(OCF ₂ )-and-(OCF ₂ CF ₂ )-are in molar ratio [-(OCF ₂ )-]: [-(OCF ₂ CF ₂ ). -] = It is preferable that the group contains a group having a ratio of 2: 1 to 1: 2, and it is more preferable that the group contains a group having a ratio of about 1: 1. These bonds may be either block bonds or random bonds. The number of repetitions p of the group 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) measured by gel permeation chromatography of the group represented by the formula (1) in terms of polystyrene is 1,000 to 5,000, preferably 1,500 to 3,000. be.

The oxyalkylene group in the group represented by the formula (2a):-(OR ² )-R ² has 2 or 3 carbon atoms. 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 the 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 group may be used alone or in combination of two or more. When two or more kinds of the oxyalkylene groups are used in combination, the bond of the two or more kinds of oxyalkylene groups may be either a block bond or a random bond.

The group represented by the formula (2a) is, for example, a poly (oxyethylene) group. The number of repetitions q of the group 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 12. Is the range of.

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

The polymerizable group containing the (meth) acryloyloxy group is not limited to one having one (meth) acryloyloxy group, and may have two or more (meth) acryloyloxy groups. Examples of the polymerizable group containing the (meth) acryloyloxy group include structures (terminal groups) represented by the following formulas [X1] to [X5] and acryloyloxy groups in these structures (terminal groups). Can be mentioned as a structure in which is substituted with a methacryloyloxy group.

When the component (b1) is a polyfunctional (meth) acrylate compound having a polymerizable group containing the (meth) acryloyloxy group, industrial production is easy, and the structural formula (A-) shown below is shown below. Preferred examples are a compound represented by 1), a compound represented by (A-2), a compound represented by (A-3), and a compound in which the acryloyloxy group in these compounds is replaced with a methacryloyloxy group. Can be mentioned as. In the following structural formulas, two Xs or four Xs represent one of the structures (terminal groups) represented by the formulas [X1] to [X5], respectively, and PFPE is poly (oxyperfluoro). Represents an alkylene) group, where q ₁ and q ₂ independently represent the number of oxyethylene groups, eg, an integer of 2 to 15, preferably an integer of 2 to 12, or an integer of 5 to 12. Alternatively, it represents an integer of 7 to 12.

When the component (b1) is a polyfunctional (meth) acrylate compound having a polymerizable group containing the (meth) acryloyloxy group, the polymerizable group containing the (meth) acryloyloxy group is (meth) acryloyloxy. It is preferable that the structure (terminal group) has two or more groups, for example, represented by the above formulas [X3] to [X5].

The component (b1) may be used alone or in combination of two or more. The component (b1) is preferably 0.1% by mass with respect to 100% by mass of the total mass of the component (b1) and the components (b2), (b3) and other additives which are optional components described later. It is desirable to use in a proportion of 10% by mass, more preferably 0.5% by mass to 8% by mass.

The component (b1) is represented by the formula (2a) or the formula (2b), for example, which is directly bonded to both ends of the group represented by the formula (1) or bonded via the linking group. In a compound having at least two hydroxy groups via a group, 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis ((meth) acryloyloxymethyl) ethyl are used with respect to the at least two hydroxy groups. It is obtained by a method of subjecting an isocyanate compound having a (meth) acryloyloxy group, such as isocyanate, to a urethanization reaction.

The weight average molecular weight (Mw) of the component (b1) measured by gel permeation chromatography in terms of polystyrene is 1,500 to 7,000, preferably 2,000 to 6,000.

In addition to the component (b1), the composition for forming the B layer of the replica mold for imprint of the present invention includes a group represented by the formula (1) and the formula (2a) or the formula (2b). It has a polymerizable group containing a (meth) acryloyloxy group only at the end of a part of the linear or chain molecular chain containing the group represented by (meth) via a urethane bond, and the linear or chain form. A compound having a hydroxy group at the other end of the molecular chain of (that is, a compound having no polymerizable group at the other end) may be contained. The composition for forming the B layer further comprises 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). A compound having a hydroxy group at all terminals, that is, a compound having no polymerizable group may be contained. The composition for forming the B layer may be referred to as a release agent.

[(B2) component]
The photoradical polymerization initiator of the component (b2) is particularly limited as long as it has absorption in the light source used during photocuring of the composition for forming the B layer of the replica mold for imprint of the present invention. It's not a thing. Examples of the component (b2) include a photoradical polymerization initiator similar to that of the component (a2). The component (b2) may be used alone or in combination of two or more. The content ratio of the photoradical polymerization initiator of the component (b2) is 0.05% by mass to 15% by mass with respect to 100% by mass of the component (b1).

[(B3) component]
The solvent as the component (b3) plays a role of adjusting the viscosity of the component (b1) and the component (b2), and can adjust the viscosity of the component (b1) and the component (b2). It is not particularly limited. The component (b3) is removed in the step of forming the B layer.

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, and 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, dimethylsulfoxide, 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-decafluoroolo-3-methoxy-4- (tri) Fluoromethyl) -pentane, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, 1,1,1,2,3,4,5,5,5-deca Fluoropentane, pentafluorononane, hexafluorobenzene, heptadecafluoro-n-octylbromid, 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 Can be mentioned.

The solvent as the component (b3) is available as a commercially available product, and specific examples thereof include Novec (registered trademark) 7000, 7100, 7200, and 7300 (all manufactured by 3M Japan Co., Ltd.). , Asahi Clean (registered trademark) AE-3000, AE-3100E (all manufactured by AGC Inc.), Bartlell (registered trademark) XF, XF-UP, XE-XP, X-E10, X- P10, X-D, X-GY, MCA, SDG, SMT, SFR, DC, Cinella, Supreion, Psion (manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) Can be mentioned. The component (b3) may be used alone or in combination of two or more.

[Other additives]
The composition for forming the A layer of the replica mold for imprinting of the present invention can contain a solvent, if necessary. Further, the composition for forming the A layer and the composition for forming the B layer are, if necessary, a surfactant, a chain transfer agent, and a photosensitizer, as long as the effects of the present invention are not impaired. It can contain a sensitizer.

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, and 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, dimethylsulfoxide, 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-decafluoroolo-3-methoxy-4- (tri) Fluoromethyl) -pentane, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, 1,1,1,2,3,4,5,5,5-deca Fluoropentane, pentafluorononane, hexafluorobenzene, heptadecafluoro-n-octylbromid, 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 Can be mentioned. The above solvent may be used alone or in combination of two or more.

Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, and polyoxy. Polyoxyethylene alkylaryl ethers such as ethylene nonylphenyl ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan Solbitan fatty acid esters such as tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc. Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters can be mentioned. The above-mentioned surfactants are available as commercial products, and specific examples thereof include EF301 (registered trademark) EF301, EF303, EF352 (all manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.), and Megafuck (these are manufactured by Mitsubishi Materials Electronics Co., Ltd.). Registered Trademarks) F-171, F-173, F-477, F-486, F-554, F-556, R-08, R-30, R-30N, R- 40, R-40-LM, RS-56, RS-75, RS-72-K, RS-76-E, RS-76-NS, RS-78, RS-90 ( DIC Co., Ltd., Florard FC430, FC431 (3M Japan Co., Ltd.), Asahi Guard (registered trademark) AG710, Surfron (registered trademark) S-382, SC101, SC102, SC103 , SC104, SC105, SC106 (all manufactured by AGC Co., Ltd.) and other fluorine-based surfactants; 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 (all manufactured by Big Chemie Japan Co., Ltd.). .. The above-mentioned surfactant may be used alone or in combination of two or more. When the composition for forming the A layer and the composition for forming the B layer contain the above-mentioned surfactant, the content ratio thereof is 0.01 mass by mass with respect to 100% by mass of the component (a1). It is preferably% to 10% by mass.

Examples of the chain transfer agent include methyl mercaptoacetate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, 3-methoxybutyl 3-mercaptopropionate, and n-mercaptopropionate as thiol compounds. Octyl, stearyl 3-mercaptopropionate, 1,4-bis (3-mercaptopropionyloxy) butane, 1,4-bis (3-mercaptobutyryloxy) butane, trimethylol ethanetris (3-mercaptopropionate) , Trimethylol ethanetris (3-mercaptobutyrate), trimetylol propanetris (3-mercaptopropionate), trimethylol propanetris (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-methylpropan-2-thiol, 1-dodecanethiol, 2 , 3,3,4,5-Hexamethylhexane-2-thiol (tert-dodecanethiol), ethane-1,2-dithiol, propane-1,3-dithiol, alkylthiols such as benzylthiol; benzene Aromatic thiols such as thiols, 3-methylbenzene thiols, 4-methylbenzene thiols, naphthalene-2-thiols, pyridine-2-thiols, benzoimidazol-2-thiols, benzothiazole-2-thiols; 2-mercaptoethanol , 4-Mercapto alcohols such as 4-mercapto-1-butanol; silane-containing thiols such as 3- (trimethoxysilyl) propan-1-thiol, 3- (triethoxysilyl) propan-1-thiol; bis (2- A mercaptoethyl) ether is mentioned, and as a disulfide compound, a dieti Ludisulfide, dipropyl disulfide, diisopropyl disulfide, dibutyl disulfide, di-tert-butyl disulfide, dipentyl disulfide, diisopentyl disulfide, dihexyl disulfide, dicyclohexyl disulfide, didecyl disulfide, bis (2,3,3,4,5,4) Alkyl disulfides such as 5-hexamethylhexane-2-yl) disulfide (di-tert-dodecyl disulfide), bis (2,2-diethoxyethyl) disulfide, bis (2-hydroxyethyl) disulfide, dibenzyldisulfide; Aromatic disulfides such as diphenyl disulfide, di-p-tolyl disulfide, di (pyridin-2-yl) pyridyl disulfide, di (benzoimidazol-2-yl) disulfide, di (benzothiazole-2-yl) disulfide; tetra Thiuram disulfides such as methyl thiuram disulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, bis (pentamethylene) thiuram disulfide; α-methylstyrene disulfide can be mentioned. This chain transfer agent can be used alone or in combination of two or more. When the composition for forming the A layer and the composition for forming the B layer contain the chain transfer agent, the content ratio thereof is 0.01 mass by mass with respect to 100% by mass of the component (a1). It is preferably% to 20% by mass.

Examples of the photosensitizer include thioxanthene-based, thioxanthone-based, xanthene-based, ketone-based, thiopyrilium salt-based, basestyryl-based, merocyanine-based, 3-substituted coumarin-based, 3,4-substituted coumarin-based, and cyanine-based. , Acridine-based, thiazine-based, phenothiazine-based, anthracene-based, coronene-based, benzanthracene-based, perylene-based, ketocoumarin-based, coumarin-based, and borate-based. The photosensitizer is available as a commercially available product, and specific examples thereof include Antracure (registered trademark) UVS-581, UVS-1331 (all manufactured by Kawasaki Kasei Chemicals Co., Ltd.), and KAYACURE (above, manufactured by Kawasaki Kasei Chemicals Co., Ltd.). Registered trademark) DETX-S (manufactured by Nippon Kayaku Co., Ltd.) can be mentioned. This photosensitizer can be used alone or in combination of two or more. By using the above photosensitizer, the absorption wavelength in the UV region can also be adjusted. When the composition for forming the A layer and the composition for forming the B layer contain the photosensitizer, the content ratio thereof is 100 mass by mass of the component (a1) or the component (b1). %, For example, 0.01% by mass to 10% by mass, preferably 0.05% by mass to 5% by mass.

[Preparation of replica mold material for imprint]
The method for preparing the composition for forming the A layer and the composition for forming the B layer of the replica mold for imprinting of the present invention is not particularly limited. In the case of the composition for forming the A layer, for example, the component (a1), the component (a2), and other additives may be mixed as necessary so that the composition is in a uniform state. .. Further, in the case of the composition for forming the B layer, for example, the component (b1), the component (b2), the component (b3), and other additives as necessary are mixed to bring the composition into a uniform state. It should be. The order in which each component of the composition for forming the A layer and the composition for forming the B layer is mixed is not particularly limited as long as a uniform composition can be obtained.

The replica mold for imprint of the present invention can be obtained by forming the A layer by optical imprint and then forming the B layer on the A layer by photocuring.

In the A layer of the replica mold for imprinting of the present invention, the composition containing the components (a1) and (a2) is applied onto a base material or a master mold, and the base material and the master mold are bonded together. The desired structure can be obtained by photo-curing and releasing the mold. As a method for applying the composition containing the component (a1) and the component (a2), known or well-known methods such as a potting method, a spin coating method, a dip method, a flow coating method, an inkjet method, a spray method, and a bar coating method are used. Examples thereof include a method, a gravure coating method, a slit coating method, a roll coating method, a transfer printing method, a brush coating method, a blade coating method, and an air knife coating method.

Examples of the base material on which the A layer of the replica mold for imprint of the present invention is formed include silicon, glass (ITO substrate) on which indium tin oxide (ITO) is formed, and silicon nitride (SiN). Base material made of filmed glass (SiN substrate), glass with indium tin oxide (IZO) film formed, polyethylene terephthalate (PET), triacetyl cellulose (TAC), acrylic, plastic, glass, quartz, ceramics, etc. Can be mentioned. Also, flexible substrates with flexibility, such as triacetyl cellulose, polyethylene terephthalate, polymethyl methacrylate, cycloolefin (co) polymer, polyvinyl alcohol, polycarbonate, polystyrene, polyimide, polyamide, polyolefin, polypropylene, polyethylene, polyethylene. It is also possible to use a substrate composed of naphthalate, polyether sulphon, and a copolymer obtained by combining these polymers.

The light source to be photocured to form the A layer of the replica mold for imprint of the present invention is not particularly limited, but for example, a high-pressure mercury lamp, a low-pressure mercury lamp, an electrodeless lamp, a metal halide lamp, a KrF excimer laser, and ArF. excimer laser, _{F 2} excimer laser, electron beam (EB), extreme ultraviolet (EUV), may be mentioned ultraviolet LED (UV-LED). Further, as the wavelength of the light source, generally, a G line of 436 nm, an H line of 405 nm, an I line of 365 nm, or a GHI mixed line can be used. Furthermore, the 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.

When the composition for forming the layer A contains a solvent, the solvent is evaporated to at least one of the coating film before light irradiation and the photocured product obtained after light irradiation. A baking step may be added. The equipment used in the baking process is not particularly limited, and for example, a hot plate, an oven, or a furnace is used to bake in an appropriate atmosphere, that is, in an atmosphere, an inert gas such as nitrogen, or a vacuum. Anything that can be done is sufficient. The baking temperature is not particularly limited as long as the purpose of evaporating the solvent can be achieved, but can be, for example, 40 ° C. to 200 ° C.

The device for performing optical imprinting is not particularly limited as long as the desired pattern can be obtained. For example, ST50 manufactured by Toshiba Machine Co., Ltd., Sindre (registered trademark) 60 manufactured by Obducat Co., Ltd., and NM manufactured by Meisho Kiko Co., Ltd. A method of crimping the base material and the master mold with a commercially available device such as −0801HB and removing the cured product from the master mold after photocuring can be used.

Examples of the master mold material used for the optical imprint used in the present invention include quartz, silicon (Si), nickel, alumina (Al ₂ O ₃ ), carbonylsilane, and glassy carbon. As long as the desired pattern can be obtained, there is no particular limitation. Further, the master mold may be subjected to a mold release treatment for forming a thin film such as a fluorine-based compound on the surface thereof in order to improve the mold releasability. Examples of the mold release agent used for the mold release treatment include Optool (registered trademark) HD and DSX manufactured by Daikin Industries, Ltd., but are not particularly limited as long as the desired pattern can be obtained.

The A layer of the replica mold for imprinting of the present invention can be heated after being released from the master mold to improve the transparency in the ultraviolet region. Examples of the method for heating the layer A include a method using a heating means such as a hot plate and an oven.

In the B layer of the replica mold for imprinting of the present invention, a composition containing the (b1) component, the (b2) component and the (b3) component is applied onto the A layer and photocured to form a desired film. Obtainable. As a method for applying the composition containing the component (b1), the component (b2) and the component (b3), a known or well-known method, for example, a potting method, a spin coating method, a dip method, a flow coating method, an inkjet method, etc. Examples thereof include a spray method, a bar coating method, a gravure coating method, a slit coating method, a roll coating method, a transfer printing method, a brush coating method, a blade coating method, and an air knife coating method.

The light source to be photocured to form the B layer of the replica mold for imprint of the present invention is not particularly limited, but for example, a high-pressure mercury lamp, a low-pressure mercury lamp, an electrodeless lamp, a metal halide lamp, a KrF excimer laser, and ArF. excimer laser, _{F 2} excimer laser, electron beam (EB), extreme ultraviolet (EUV), may be mentioned ultraviolet LED (UV-LED). Further, as the wavelength of the light source, generally, a G line of 436 nm, an H line of 405 nm, an I line of 365 nm, or a GHI mixed line can be used. Furthermore, the exposure amount is preferably, 30 mJ / cm ² to 2000 mJ / cm ^2, more preferably from 30 mJ / cm ² to 1000 mJ / cm ^2.

In the step of forming the B layer of the imprint replica mold of the present invention, for the purpose of evaporating the solvent which is the component (b3), after applying the composition for forming the B layer, before photocuring or photocuring. A baking step may be added later. The equipment used in the baking process is not particularly limited, and is, for example, using a hot plate, an oven, or a furnace in an appropriate atmosphere, that is, in an atmosphere, an inert gas such as nitrogen, or a vacuum. Anything that can be baked will do. The baking temperature in the baking step can be, for example, 40 ° C. to 200 ° C., which allows the solvent to evaporate.

The pattern size of the replica mold for imprint obtained by the present invention is not particularly limited, and it is possible to obtain a good pattern even on the order of nanometer, micrometer, or millimeter, for example.

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 the following Examples. The apparatus and conditions used for the analysis of the physical properties of the compounds obtained in the following synthetic examples are as follows.

(1) Gel Permeation Chromatography (GPC)
Equipment: GPC system manufactured by Shimadzu Corporation 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

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

<Synthesis example 1>
178.84 g of PGMEA was placed in a 2 L four-necked flask, and the mixture was stirred under a nitrogen atmosphere at an internal temperature of 80 ° C. Here, methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 120 g, isobornyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 249.66 g, AIBN (manufactured by Kanto Chemical Industry Co., Ltd.) 5.904 g, and PGMEA 679. The solution in which 48 g was mixed was added dropwise over 2 hours, and the reaction was carried out for 17 hours after the addition. The reaction solution was added dropwise to 6.3 kg of methanol (manufactured by Junsei Chemical Co., Ltd.), and the precipitated polymer was dried at 80 ° C. under a reduced pressure of 133.3 Pa to obtain 330.4 g of a non-crosslinkable copolymer MI55. .. When the weight average molecular weight of the obtained MI55 was measured by GPC, it was 20,100 in terms of standard polystyrene.

<Synthesis example 2>
The 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 at room temperature (approximately 23 ° C.) for 24 hours using a stirrer tip to obtain a reaction product. 30.37 g of PGMEA was added to this reaction product, MEK was distilled off by an evaporator, and a PGMEA solution containing SM1 as the component (b1) was obtained 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 3>
The 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 at room temperature (approximately 23 ° C.) for 48 hours using a stirrer tip to obtain a reaction product. 38.9 g of PGMEA was added to this reaction product to obtain a PGMEA solution containing SM2 as a component (b1) having 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 4>
The 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 at room temperature (about 23 ° C.) for 72 hours using a stirrer tip under a nitrogen atmosphere to obtain a reaction product. 64.96 g of PGMEA was added to this reaction product, MEK was distilled off by an evaporator, and a PGMEA solution containing SM3 as a component (b1) was obtained 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>
The 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 at room temperature (about 23 ° C.) for 72 hours using a stirrer tip under a nitrogen atmosphere to obtain a reaction product. 48.72 g of PGMEA was added to this reaction product to obtain a PGMEA solution containing SM4 as a component (b1) 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.

[Preparation of composition for forming layer A]
<Preparation Example 1>
New Frontier (registered trademark) HBPE-4 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) (hereinafter abbreviated as "HBPE-4" in the present specification) 7 g, KAYARAD (registered trademark) PET-30 (Nippon Kayaku) 3 g of (hereinafter abbreviated as "PET-30" in the present specification) and IRGACURE (registered trademark) 184 (manufactured by BASF Japan Co., Ltd.) (hereinafter, "IRGACURE 184" in the present specification). The composition A1 was prepared by adding 0.01 g (0.1% by mass based on the total mass of HBPE-4 and PET-30).

<Preparation example 2>
Composition A2 was prepared by adding 9 g of HBPE-4, 1 g of MI55 obtained in Synthesis Example 1, and 0.01 g of IRGACURE 184 (0.1% by mass based on the total mass of HBPE-4 and MI55).

<Preparation example 3>
9.5 g of HBPE-4, 0.5 g of MI55 obtained in Synthesis Example 1, and 0.01 g of IRGACURE 184 (0.1% by mass based on the total mass of HBPE-4 and MI55) were added to the composition A3. Was prepared.

<Preparation Example 4>
9.75 g of HBPE-4, 0.25 g of MI55 obtained in Synthesis Example 1, and 0.01 g of IRGACURE 184 (0.1% by mass based on the total mass of HBPE-4 and MI55) were added to the composition A4. Was prepared.

<Preparation Example 5>
5 g of HBPE-4, 5 g of NK ester A-DOG (hereinafter abbreviated as "A-DOG" in the present specification) (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and 0.01 g of IRGACURE 184 (HBPE). -4, 0.1% by mass based on the total mass of A-DOG) was added to prepare the composition A5.

<Preparation Example 6>
7 g of PET-30, 1.5 g of NK ester A-200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 1.5 g of A-DOG, and 0.01 g of IRGACURE 184 (PET-30, A-200, Composition A6 was prepared by adding 0.1% by mass based on the total mass of A-DOG.

<Preparation Example 7>
5 g of HBPE-4, 5 g of NK ester A-DCP (hereinafter abbreviated as "A-DCP" in the present specification) (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and 0.01 g of IRGACURE 184 (HBPE). -4, 0.1% by mass based on the total mass of A-DCP) was added to prepare the composition A7.

<Preparation Example 8>
Add 5 g of A-DCP, 5 g of 1-ADMA (manufactured by Osaka Organic Chemical Industry Co., Ltd.), and 0.01 g of IRGACURE 184 (0.1% by mass based on the total mass of A-DCP, 1-ADMA). Composition A8 was prepared.

<Preparation Example 9>
5 g of A-DCP, 5 g of 1-ADMA (manufactured by Osaka Organic Chemical Industry Co., Ltd.), and 0.5 g of IRGACURE 184 (5% by mass based on the total mass of A-DCP, 1-ADMA) were added to the composition. A9 was prepared.

[Preparation of composition (release agent) for forming layer B]
<Preparation Example 10>
0.285 g of LINK-5A (manufactured by Kyoeisha Chemical Co., Ltd.), 0.015 g of 2,2,2-trifluoroethyl acrylate (manufactured by Daikin Industries, Ltd.), IRGACURE (registered trademark) 819 (BASF Japan Ltd.) ), Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide) (hereinafter abbreviated as "IRGACURE 819") is mixed with 0.006 g and PGMEA (8.44 g) to form a composition. A product (release agent) B1 was prepared.

<Preparation Example 11>
The composition (release agent) B2 was prepared by mixing 0.3 g of LINK-162A (manufactured by Kyoeisha Chemical Co., Ltd.), 0.006 g of IRGACURE 819, and 8.44 g of PGMEA.

<Preparation Example 12>
The composition (release agent) B3 was prepared by mixing 0.3 g of LINK-102A (manufactured by Kyoeisha Chemical Co., Ltd.), 0.006 g of IRGACURE 819, and 8.44 g of PGMEA.

<Preparation Example 13>
A composition (release agent) B4 was prepared by mixing 0.3 g of LINK-5A (manufactured by Kyoeisha Chemical Co., Ltd.), 0.006 g of IRGACURE 819, and 8.44 g of PGMEA.

<Preparation Example 14>
The composition (release agent) B5 was prepared by mixing 1.0 g of DAC-HP (manufactured by Daikin Industries, Ltd.), 0.004 g of IRGACURE 819, and 4.82 g of PGMEA.

<Preparation Example 15>
1.00 g of PGMEA solution containing SM1 obtained in Synthesis Example 2, IRGACURE (registered trademark) 127 (manufactured by BASF Japan Ltd., 2-hydroxy-1- [4- {4- (2-hydroxy-2-methyl) 0.0060 g of propionyl) benzyl} -phenyl] -2-methylpropan-1-one) and 7.67 g of PGMEA as the component (C) were mixed to prepare a composition (release agent) B6.

<Preparation Example 16>
1.00 g of PGMEA solution containing SM2 obtained in Synthesis Example 3, 0.0040 g of IRGACURE 819, KAYACURE (registered trademark) DETX-S (manufactured by Nippon Kayaku Co., Ltd.) (hereinafter, "DETX-" in the present specification. 0.0002 g of (abbreviated as "S") and 4.80 g of PGMEA were mixed to prepare a composition (release agent) B7.

<Preparation Example 17>
The composition (release agent) B8 was prepared by mixing 1.00 g of the PGMEA solution containing SM3 obtained in Synthesis Example 4, 0.0040 g of IRGACURE 819, 0.0002 g of DETX-S and 4.83 g of PGMEA. ..

<Preparation Example 18>
The composition (release agent) B9 was prepared by mixing 1.00 g of the PGMEA solution containing SM4 obtained in Synthesis Example 5, 0.0040 g of IRGACURE 819, 0.0002 g of DETX-S and 4.83 g of PGMEA. ..

[Making a replica mold for imprint]
<Example 1>
The composition A1 obtained in Preparation Example 1 is previously subjected to a mold release treatment using NOVEC (registered trademark) 1720 (manufactured by 3M Japan Ltd.) (hereinafter, abbreviated as "NOVEC 1720" in the present specification). Potted into a mold (2 mm diameter x 300 μm depth concave lens mold arranged in 15 rows of 3 rows x 5 rows), covered with a quartz glass substrate, and nanoimprint device NM-0801HB (manufactured by Meisho Kiko Co., Ltd.) ) Was used for optical imprinting. Optical imprint is always performed under the condition of 23 ° C., a) pressurizing to 500 N over 10 seconds, b) ^{exposing to 5000 mJ / cm 2} using a high-pressure mercury lamp, c) depressurizing over 10 seconds, d) nickel. The molding and the quartz glass substrate were separated and separated, and a convex lens pattern having a diameter of 2 mm and a height of 300 μm was obtained on the quartz glass substrate. The convex lens pattern obtained on the quartz glass substrate was heated on a hot plate at 150 ° C. for 5 minutes to form a layer A. The quartz glass substrate used was spin-coated with KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) in advance and heated on a hot plate at 150 ° C. for 5 minutes to perform an adhesion treatment. The composition (release agent) B1 obtained in Preparation Example 10 was formed on the obtained layer A with a spin coater, and baked at 80 ° C. for 5 minutes using a hot plate. Then, in 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 through an i-ray transmission filter and UV-exposed at ^{40 mW / cm 2 for 125 seconds.} , A A layer B was formed on the layer to prepare a replica mold RM-1 for imprinting.

<Example 2>
Replica mold for imprinting in the same manner as in Example 1 except that the composition (release agent) B1 obtained in Preparation Example 10 was changed to the composition (release agent) B2 obtained in Preparation Example 11. RM-2 was prepared.

<Example 3>
Replica mold for imprinting in the same manner as in Example 1 except that the composition (release agent) B1 obtained in Preparation Example 10 was changed to the composition (release agent) B3 obtained in Preparation Example 12. RM-3 was prepared.

<Example 4>
Replica mold for imprinting in the same manner as in Example 1 except that the composition (release agent) B1 obtained in Preparation Example 10 was changed to the composition (release agent) B4 obtained in Preparation Example 13. RM-4 was prepared.

<Example 5>
Replica mold for imprinting in the same manner as in Example 1 except that the composition (release agent) B1 obtained in Preparation Example 10 was changed to the composition (release agent) B5 obtained in Preparation Example 14. RM-5 was prepared.

<Example 6>
Replica mold for imprinting in the same manner as in Example 1 except that the composition (release agent) B1 obtained in Preparation Example 10 was changed to the composition (release agent) B7 obtained in Preparation Example 16. RM-6 was prepared.

<Example 7>
The composition A1 obtained in Preparation Example 1 was changed to the composition A2 obtained in Preparation Example 2, and the composition (release agent) B1 obtained in Preparation Example 10 was changed to the composition obtained in Preparation Example 16. was changed to (release agent) B7, it was prepared imprint replica mold RM-7 in the same manner as in example 1.

<Example 8>
The composition A1 obtained in Preparation Example 1 was changed to the composition A3 obtained in Preparation Example 3, and the composition (release agent) B1 obtained in Preparation Example 10 was changed to the composition obtained in Preparation Example 16. was changed to (release agent) B7, it was prepared imprint replica mold RM-8 in the same manner as in example 1.

<Example 9>
The composition A1 obtained in Preparation Example 1 was changed to the composition A4 obtained in Preparation Example 4, and the composition (release agent) B1 obtained in Preparation Example 10 was changed to the composition obtained in Preparation Example 15. was changed to (release agent) B6, it was prepared imprint replica mold RM-9 in the same manner as in example 1.

<Example 10>
The composition A1 obtained in Preparation Example 1 was changed to the composition A4 obtained in Preparation Example 4, and the composition (release agent) B1 obtained in Preparation Example 10 was changed to the composition obtained in Preparation Example 16. was changed to (release agent) B7, were prepared imprint replica mold RM-10 in the same manner as in example 1.

<Example 11>
The composition A1 obtained in Preparation Example 1 was changed to the composition A4 obtained in Preparation Example 4, and the composition (release agent) B1 obtained in Preparation Example 10 was changed to the composition obtained in Preparation Example 17. was changed to (release agent) B8, were prepared imprint replica mold RM-11 in the same manner as in example 1.

<Example 12>
The composition A1 obtained in Preparation Example 1 was changed to the composition A4 obtained in Preparation Example 4, and the composition (release agent) B1 obtained in Preparation Example 10 was changed to the composition obtained in Preparation Example 18. was changed to (release agent) B9, were prepared imprint replica mold RM-12 in the same manner as in example 1.

<Example 13>
The composition A1 obtained in Preparation Example 1 was changed to the composition A5 obtained in Preparation Example 5, and the composition (release agent) B1 obtained in Preparation Example 10 was changed to the composition obtained in Preparation Example 16. was changed to (release agent) B7, were prepared imprint replica mold RM-13 in the same manner as in example 1.

<Example 14>
The composition A1 obtained in Preparation Example 1 was changed to the composition A6 obtained in Preparation Example 6, and the composition (release agent) B1 obtained in Preparation Example 10 was changed to the composition obtained in Preparation Example 16. was changed to (release agent) B7, were prepared imprint replica mold RM-14 in the same manner as in example 1.

<Example 15>
The composition A1 obtained in Preparation Example 1 was changed to the composition A7 obtained in Preparation Example 7, and the composition (release agent) B1 obtained in Preparation Example 10 was changed to the composition obtained in Preparation Example 16. was changed to (release agent) B7, were prepared imprint replica mold RM-15 in the same manner as in example 1.

<Example 16>
The composition A1 obtained in Preparation Example 1 was changed to the composition A8 obtained in Preparation Example 8, and the composition (release agent) B1 obtained in Preparation Example 10 was changed to the composition obtained in Preparation Example 16. was changed to (release agent) B7, were prepared imprint replica mold RM-16 in the same manner as in example 1.

<Comparative example 1>
The layer A was formed in the same manner as in Example 1 except that the composition A1 obtained in Preparation Example 1 was changed to the composition A8 obtained in Preparation Example 8. NOVEC1720 was spin-coated on the obtained layer A and heated on a hot plate at 150 ° C. for 5 minutes to prepare a replica mold RM-19 for imprinting.

<Comparative example 2>
The layer A was formed in the same manner as in Example 1 except that the composition A1 obtained in Preparation Example 1 was changed to the composition A8 obtained in Preparation Example 8. PFPE1 was spin-coated on the obtained layer A and heated on a hot plate at 150 ° C. for 5 minutes to prepare a replica mold RM-20 for imprinting.

<Comparative example 3>
The composition A1 obtained in Preparation Example 1 was changed to the composition A9 obtained in Preparation Example 9, and the composition (release agent) B1 obtained in Preparation Example 10 was changed to the composition obtained in Preparation Example 11. A replica mold RM-21 for imprinting was produced in the same manner as in Example 1 except that the mold release agent was changed to B2.

[Preparation of imprint material]
Mix 5 g of NK ester A-DOG (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and 5 g of radically polymerizable group-containing polycarbonate ETERNCOLL (registered trademark) UM-90 (1/3) DA (manufactured by Ube Industries, Ltd.). , 0.2 g of IRGACURE184 was added to the mixture to prepare an imprint material.

[Making a concave lens pattern using a replica mold for imprinting]
The prepared imprint material was potted on a quartz glass substrate that had been adhered by the method described in Example 1, and the imprints obtained in Examples 1 to 16 and Comparative Examples 1 to 3 were placed on the same imprint material. It was covered with a replica mold for printing, and optical imprinting was performed using a nanoimprint apparatus NM-0801HB (manufactured by Meisho Kiko Co., Ltd.). Optical imprint is always performed under the condition of 23 ° C., a) pressurizing to 500 N over 10 seconds, b) ^{exposing to 5000 mJ / cm 2} using a high-pressure mercury lamp, c) depressurizing over 10 seconds, d) replica. The mold and the quartz glass substrate were separated and separated, and a concave lens pattern was obtained on the quartz glass substrate. Using an industrial microscope ECLIPSE L150 (manufactured by Nikon Corporation), the presence or absence of peeling / cracking of the obtained concave lens pattern was observed. The results are shown in Tables 1 and 2.

[Evaluation of optical characteristics]
The transmittance of each imprint replica mold obtained in Examples 1 to 16 and Comparative Examples 1 to 3 at a wavelength of 365 nm was measured using a spectrophotometer UV2600 (manufactured by Shimadzu Corporation) as a reference. It was measured in the state of quartz glass. The results are shown in Tables 1 and 2. The replica mold for imprint whose transmittance is measured has a convex lens pattern having a diameter of 2 mm and a height of 300 μm.

[Measurement of the number of times that can be repeatedly imprinted]
Using the replica molds for imprints obtained in Examples 1 to 16 and Comparative Examples 1 to 3 as they are, the same optical imprinting as described above was repeated up to 10 times, and the diameter was 2 mm × 300 μm. The number of optical imprints was measured until the concave lens shape pattern of the depth was no longer formed. The results obtained are shown in Tables 1 and 2.

From the results shown in Tables 1 and 2, no cracking or peeling was observed in the concave lens patterns produced by using the replica molds for imprint produced in Examples 1 to 16. The imprint replica molds produced in Examples 1 to 16 were all capable of repeated imprinting 8 times or more. Further, the replica molds for imprints produced in Examples 1 to 16 had a transmittance of 80% or more at 365 nm, and high transparency in the ultraviolet region was confirmed. On the other hand, peeling was observed in the concave lens pattern produced by using the replica mold for imprint produced in Comparative Example 2 and Comparative Example 3. The imprint replica molds produced in Comparative Example 1 and Comparative Example 2 could be repeatedly imprinted once or 0 times. Further, the replica mold for imprint produced in Comparative Example 3 resulted in a transmittance of less than 80% at a wavelength of 365 nm.

From the above results, the replica mold for imprinting of the present invention has high transparency in the ultraviolet region and can be repeatedly imprinted. Further, the pattern produced by using the replica mold for imprint is free from cracking and peeling.

Claims (13)

An imprint replica mold having the following A layer and the following B layer adhered to the A layer.
Layer A: Structure composed of a cured product of the composition containing the following components (a1) and (a2) Component (a1): Compound (a2) having at least one radically polymerizable group in one molecule: The above (a2) a1) Photoradical polymerization initiator B layer of 0.01% by mass to 0.3% by mass with respect to 100% by mass of the component: A film composed of a cured product of the composition containing the following components (b1) and (b2). b1) Component: A compound composed of a linear or chain molecular chain containing a fluorine atom and having a radically polymerizable group at all ends of the molecular chain. Component (b2) Component: 100% by mass of the component (b1). On the other hand, 0.05% by mass to 15% by mass of a photoradical polymerization initiator The compound of the component (b1) is all the ends of the linear or chain molecular chain containing the group represented by the following formula (1) and the group represented by the following formula (2a) or formula (2b). The imprint replica mold according to claim 1, which is a polyfunctional (meth) acrylate compound having a group represented by the following formula (3) via a urethane bond.

(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 hydrocarbon having 2 or 3 carbon atoms. Represents a hydrogen group, * represents a bond that bonds to the −O— group of the urethane bond, respectively, and p and q are represented by the number of repetitions of the group represented by the above formula (1) and the above formula (2a), respectively. It represents the number of repetitions of the group to be formed and independently represents an integer of 2 or more, and R ³ represents a methyl group or a hydrogen atom.) The replica mold for imprint according to claim 2, wherein q representing the number of repetitions of the group represented by the formula (2a) is an integer of 5 to 12. The replica mold for imprint according to claim 2 or 3, wherein the group represented by the formula (2a) is a poly (oxyethylene) group. The imprint replica according to any one of claims 2 to 4, wherein the group represented by the formula (1) is a group having both an oxyperfluoromethylene group and an oxyperfluoroethylene group. mold. The replica mold for imprint according to any one of claims 1 to 5, wherein the compound of the component (b1) is a macromonomer or polymer having a weight average molecular weight of 1000 to 30000. The replica mold for imprint according to any one of claims 1 to 6, wherein the composition containing the component (b1) and the component (b2) further contains a photosensitizer. Claim 1 that the component (a1) contains at least two compounds, and at least one of the two compounds is a compound having at least two (meth) acryloyloxy groups in one molecule. Replica mold for imprint described in. The replica mold for imprint according to claim 8, wherein the compound having at least two (meth) acryloyloxy groups in one molecule is a di (meth) acrylate compound represented by the following formula (4).

(In the formula, R ⁴ and R ⁵ independently represent a hydrogen atom or a methyl group, R ⁶ and R ⁷ independently represent an alkylene group having 1 to 4 carbon atoms, and R ⁸ and R ⁹ are independent, respectively. Represents a hydrogen atom or a methyl group, and r ¹ and r ² each independently represent an integer of 1 to 5). The replica mold for imprint according to any one of claims 1 to 9, wherein the layer A has a lens-shaped inversion pattern. The replica mold for imprint according to any one of claims 1 to 10, wherein the maximum thickness of the A layer is 2.0 mm. A step of applying a composition containing the following components (a1) and (a2) onto a master mold.
A step of crimping the master mold to a base material via a composition containing the following components (a1) and (a2).
A step of exposing a composition containing the following components (a1) and (a2) through the base material while the master mold is pressure-bonded to the base material, and photocuring the composition.
After the photocuring step, a step of releasing the cured product obtained on the substrate from the master mold to form the A layer.
A step of applying the composition containing the following components (b1) to (b3) onto the layer A, and baking the composition containing the following components (b1) to (b3) at 40 ° C. to 200 ° C., and then baking. A method for producing a replica mold for imprint, which comprises a step of forming the B layer adhered to the A layer by exposure.
Component (a1): Compound having at least one radically polymerizable group in one molecule (a2) Component: 0.1% by mass to 1% by mass of a photoradical polymerization initiator with respect to 100% by mass of the (a1) component. Component (b1): A compound composed of a linear or chain molecular chain containing a fluorine atom and having a radically polymerizable group at all ends of the molecular chain. Component (b2) Component: 100 mass of the component (b1). 0.05% by mass to 15% by mass of photoradical polymerization initiator (b3) component: solvent A step of applying a composition containing the following components (a1) and (a2) onto a substrate,
A step of crimping the base material to the master mold via a composition containing the following components (a1) and (a2).
A step of exposing a composition containing the following components (a1) and (a2) through the base material while the master mold is pressure-bonded to the base material, and photocuring the composition.
After the photocuring step, a step of releasing the cured product obtained on the substrate from the master mold to form the A layer.
A step of applying the composition containing the following components (b1) to (b3) onto the layer A, and baking the composition containing the following components (b1) to (b3) at 40 ° C. to 200 ° C., and then baking. A method for producing a replica mold for imprint, which comprises a step of forming the B layer adhered to the A layer by exposure.
Component (a1): Compound having at least one radically polymerizable group in one molecule (a2) Component: 0.1% by mass to 1% by mass of a photoradical polymerization initiator with respect to 100% by mass of the (a1) component. Component (b1): A compound composed of a linear or chain molecular chain containing a fluorine atom and having a radically polymerizable group at all ends of the molecular chain. Component (b2) Component: 100 mass of the component (b1). 0.05% by mass to 15% by mass of photoradical polymerization initiator (b3) component: solvent