TW202027952A - Replica mold for imprint and manufacturing method thereof - Google Patents

Abstract

To provide a novel replica mold for imprinting. A replica mold for imprinting, which is provided with a layer A described below and a layer B described below, said layer B being bonded to the layer A. Layer A: a structure which is formed of a cured product of a composition that contains the following component (a1) and component (a2) Component (a1): a compound which has at least one radically polymerizable group in each molecule Component (a2): a radical photopolymerization initiator in an amount of from 0.01% by mass to 0.3% by mass relative to 100% by mass of the component (a1) Layer B: a film which is formed of a cured product of a composition that contains the following component (b1) and component (b2) Component (b1): a compound which is composed of a linear or chain-like molecular chain containing a fluorine atom, and which has a radically polymerizable group at all terminals of the molecular chain Component (b2): a radical photopolymerization initiator in an amount of from 0.05% by mass to 15% by mass relative to 100% by mass of the component (b1).

Description

Copy mold for imprinting and manufacturing method thereof

The present invention relates to a copy mold for imprinting with patterns. In more detail, the present invention relates to an imprint that maintains high transparency in the ultraviolet region even if it is a thick film, does not require re-coating of a release agent, and can achieve good pattern formation even when used for repeated light imprinting. Copy mold and manufacturing method of the copy mold. In this specification, the so-called "thick film" means a film with 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 that meet the purpose of the electronic devices. In addition, for the resin lens, it is required to have high durability, such as heat resistance and weather resistance, and high productivity that can be molded with a better yield when used in combination. As a material for resin lenses that meets such requirements, for example, thermoplastic transparent resins such as polycarbonate resins, cycloolefin polymers, and methacrylic resins are used.

In the manufacture of resin lenses, in order to improve the yield or production efficiency, and to suppress the deviation of the optical axis when the lens is laminated, we are actively researching from the injection molding of thermoplastic resins to the use of curable resins that are liquid at room temperature. The transformation of wafer-level forming performed by compression forming. Regarding wafer-level molding, from the viewpoint of productivity, it is usually a hybrid lens method in which lenses are formed on a support such as a glass substrate.

In wafer-level forming, the mold must also be formed at the wafer level. Generally, the mold used for resin lens manufacturing is made by digging and grinding metal. At the wafer level, it must have multiple lens patterns in the plane and accurately control the in-plane error or the pixel pitch. Therefore, the production of the mold is very difficult and becomes expensive. Furthermore, when a metal mold is used, the UV light used for the curing of the resin lens material cannot pass through, so there is a restriction on the material of the support for forming the lens. Therefore, a master mold and a replica mold material are usually used to make a replica mold, and the replica mold is used for wafer-level molding. Among them, as described in Patent Document 1, there has been developed a method of using relatively inexpensive master mold and replica mold materials of one pixel, and using step and repeat molding in the wafer to produce replica molds. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 4226061 (Japanese Patent Laid-Open No. 2009-172773)

[The problem to be solved by the invention]

In the commonly used copy molds, the UV light used in the manufacturing step of the resin lens, especially the transmittance at a wavelength of 365 nm, is low. 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 same replica mold is used to continuously mold the repeated resin lens, the release agent is peeled off from the surface of the replica mold. Therefore, it becomes difficult to mold repeated resin lenses using the same replica mold.

In this way, it can be used as a replica mold for the molding of resin lenses used in camera modules, etc., and has high transparency, and a replica mold capable of molding repeated resin lenses has not yet been discovered, and its development is expected. The present invention was made in view of this situation, and its object is to provide a replica mold with high transparency and capable of forming repeated resin lenses. [Technical means to solve the problem]

The inventors of the present invention conducted intensive research to solve the above-mentioned problems, and as a result, by including a compound having a radical polymerizable group at all ends of a linear or chain molecular chain containing a fluorine atom, and photoradical polymerization The film of the cured product of the composition of the initiator is then completed by the structure containing the cured product of the composition of the composition containing at least one radical polymerizable group in one molecule and the photoradical polymerization initiator this invention. That is, the replication mold of the present invention has high transparency in the ultraviolet region, and can mold repeating resin lenses.

That is, the first aspect of the present invention is a copy mold for imprint having the following A layer and the following B layer next to the A layer. Layer A: A structure containing a cured product of a composition containing the following (a1) and (a2) components (a1) Component: a compound having at least one radical polymerizable group in one molecule (a2) Component: 0.01% by mass to 0.3% by mass relative to 100% by mass of the above-mentioned component (a1) Layer B: A film containing a cured product of a composition containing the following components (b1) and (b2) (b1) Component: A compound containing a linear or chain molecular chain containing fluorine atoms and having radical polymerizable groups at all ends of the molecular chain (b2) Component: A photo-radical polymerization initiator of 0.05% to 15% by mass relative to 100% by mass of the above (b1) component

(式中，R¹ 表示碳原子數1或2之全氟伸烷基，R^2a 表示碳原子數2或3之伸烷基，R^2b 表示碳原子數2或3之3價之烴基，＊表示分別與上述胺基甲酸酯鍵之-O-基鍵結之鍵結鍵，p及q分別表示上述式(1)所表示之基之重複數及上述式(2a)所表示之基之重複數並且獨立地表示2以上之整數，R³ 表示甲基或氫原子)The compound of the component (b1) is, for example, a polyfunctional (meth)acrylate compound having a group represented by the following formula (3) via a urethane bond at all ends of the linear or chain molecular chain The linear or chain-shaped molecular chain includes a group represented by the following formula (1) and a group represented by the following formula (2a) or (2b). [化1]

(In the formula, R ¹ represents a perfluoroalkylene group with 1 or 2 carbon atoms, R ^2a represents an alkylene group with 2 or 3 carbon atoms, and R ^2b represents a trivalent hydrocarbon group with 2 or 3 carbon atoms, * Represents the bonding bond to the -O- group of the above urethane bond, p and q represent the repeating number of the group represented by the above formula (1) and the number of the group represented by the above formula (2a), respectively Repeat number and independently represent an integer of 2 or more, R ³ represents a methyl group or a hydrogen atom)

The q representing the number of repetitions of the base represented by the above formula (2a) is, for example, an integer of 5-12.

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

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

The compound of the component (b1) is, for example, a macromonomer or polymer having a weight average molecular weight of 1,000 to 30,000.

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

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

(式中，R⁴ 及R⁵ 分別獨立地表示氫原子或甲基，R⁶ 及R⁷ 分別獨立地表示碳原子數1至4之伸烷基，R⁸ 及R⁹ 分別獨立地表示氫原子或甲基，r¹ 及r² 分別獨立地表示1至5之整數)The compound having at least two (meth)acryloxy groups in one molecule is, for example, a di(meth)acrylate compound represented by the following formula (4). [化2]

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

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

Another aspect of the present invention is a method of making a replica mold for imprinting, which includes the step of applying a composition containing the following components (a1) and (a2) to a master mold through the steps including the following ( a1) The composition of component and (a2) The step of crimping the above-mentioned master mold to the substrate, passing the substrate pair in the state where the above-mentioned master mold is crimped to the substrate, contains the following (a1) components and (a2) ) The step of exposing the composition of the components to photocuring the composition, after the photocuring step, the step of releasing the cured product obtained on the substrate from the master mold to form the A layer, in the A layer The step of applying a composition containing the following components (b1) to (b3), and baking the composition containing the following components (b1) to (b3) at 40°C to 200°C and Then, exposure is performed to form the step of forming the layer B next to the layer A. (a1) Component: a compound having at least one radical polymerizable group in one molecule (a2) Component: 0.1% to 1% by mass of the photo-radical polymerization initiator relative to 100% by mass of the above (a1) component (b1) Component: A compound containing a linear or chain molecular chain containing fluorine atoms and having radical polymerizable groups at all ends of the molecular chain (b2) Component: A photo-radical polymerization initiator of 0.05% to 15% by mass relative to 100% by mass of the above (b1) component (b3) Ingredient: Solvent

Furthermore, another aspect of the present invention is a method of making a replica mold for imprinting, which includes the step of coating a composition containing the following components (a1) and (a2) on a substrate, and including The composition of the component (a1) and the component (a2) includes the step of crimping the base material to the master mold, and passing the base material in the state where the master mold is crimped to the base material, including the following component (a1) And the step of exposing the composition of component (a2) to photocuring the composition, after the photocuring step, the step of releasing the cured product obtained on the substrate from the master mold to form the A layer, in The step of applying a composition containing the following components (b1) to (b3) on the A layer, and baking the composition containing the following components (b1) to (b3) at 40°C to 200°C The step of baking and then exposing to form the layer B next to the layer A. (a1) Component: a compound having at least one radical polymerizable group in one molecule (a2) Component: 0.1% to 1% by mass of the photo-radical polymerization initiator relative to 100% by mass of the above (a1) component (b1) Component: A compound containing a linear or chain molecular chain containing fluorine atoms and having radical polymerizable groups at all ends of the molecular chain (b2) Component: A photo-radical polymerization initiator of 0.05% to 15% by mass relative to 100% by mass of the above (b1) component (b3) Ingredient: Solvent [Effects of Invention]

The replica mold for imprint of the present invention is cured by curing a film containing a cured product of a composition containing the above-mentioned (b1) component and (b2) component to a composition containing the above-mentioned (a1) component and (a2) component The structure of the object, even if it is a thick film, has high transparency and can be continuously transferred.

In addition, the copy mold for imprinting of the present invention can be made on any substrate, and the copy mold formed on the substrate has high transparency in the ultraviolet region even if it is a thick film. Therefore, the imprint replica mold of the present invention can be preferably used for the manufacture of optical components requiring shape accuracy, such as solid-state imaging devices and sensor lenses.

[(a1) Ingredients] (a1) The component is a compound having at least one radical polymerizable group in one molecule. As this radically polymerizable group, (meth)acryloxy group is mentioned, for example. In the present invention, the (meth)acryloyloxy group means both of the acryloyloxy group and the methacryloyloxy group. In addition, (meth)acrylate means both acrylate and methacrylate.

As the compound of the above-mentioned (a1) component, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (methyl) ) N-butyl acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate , Isohexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, (meth) Base) isononyl acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, tetradecyl (meth)acrylate, (meth)acrylic acid Behenyl ester, iso-(meth)acrylate, cyclohexyl (meth)acrylate, 1-adamantyl (meth)acrylate, dicyclopentyl (meth)acrylate, two (meth)acrylate Cyclopentenyloxyethyl, dicyclopentenyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-methyl-2-ethyl-1,3-diox (meth)acrylate Cyclopentane-4-yl)methyl, cyclohexanespiro-2-(1,3-dioxol-4-yl)methyl (meth)acrylate, 3-(meth)acrylic acid Ethyl-3-oxetanyl methyl ester, γ-butyrolactone (meth)acrylate, methoxydiethylene glycol di(meth)acrylate, methoxytriethylene glycol (meth)acrylic acid Ester, methoxy tetraethylene glycol (meth) acrylate, methoxy polyethylene glycol #400 (meth) acrylate, methoxy polyethylene glycol #600 (meth) acrylate, methoxy Base polyethylene glycol #1000 (meth)acrylate, methoxytripropylene glycol (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di( Meth) acrylate, 1,9-nonanediol di(meth)acrylate, isononanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl Glycol di(meth)acrylate, 2-hydroxy-3-methacryloyl propyl acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethyl Glycol di(meth)acrylate, polyethylene glycol #200 di(meth)acrylate, polyethylene glycol #400 di(meth)acrylate, polyethylene glycol #600 di(meth)acrylate Ester, polyethylene glycol #1000 di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol #400 diacrylate, polypropylene glycol #700 diacrylic acid Ester, polytetramethylene glycol #650 di(meth)acrylate, polyethylene polypropylene glycol di(meth)acrylate, diethylene 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 Base modified hydrogenated bisphenol A diacrylate, butoxy modified hydrogenated bisphenol A dimethacrylate, ethoxy propoxy modified hydrogenated bisphenol A diacrylate, ethoxy propoxy modified Hydrogenated bisphenol A dimethacrylate, ethoxy-modified hydrogenated bisphenol F diacrylate, ethoxy-modified hydrogenated bisphenol F dimethacrylate, trimethylolpropane tri(meth)acrylate , Ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, ethoxylated glycerol tri(meth)acrylate, propoxy Alkylated glycerol tri(meth)acrylate, isocyanurate tris-(2-(meth)acryloxyethyl) ester, caprolactone modified isocyanurate tris-(2-(meth)propene Ethoxylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate Ester, propoxylated pentaerythritol tris(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, ethoxylated di-tris Methylolpropane tetra(meth)acrylate, propoxylated di-trimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol poly(meth)acrylate , Ethoxylated dipentaerythritol poly(meth)acrylate, propoxylated dipentaerythritol poly(meth)acrylate, ethoxylated polyglycerol poly(meth)acrylate.

The compound of the above component (a1) can be obtained as a commercially available product, and specific examples thereof include: Lightester M, Lightester E, Lightester NB, Lightester IB, Lightester TB, Lightester EH, Lightester IB-X, Lightester CH, Light Acrylate IB-XA (manufactured by Kyoeisha Chemical Co., Ltd. above), NOAA, IOAA, INAA, LA, STA, ISTA, IBXA, Viscoat#155, 1-ADA, 1-ADMA, Viscoat#150, MEDOL-10 , CHDOL-10, OXE-10, OXE-30, GBLA, GBLMA, Viscoat#195, Viscoat#230, Viscoat#260, Viscoat#295, Viscoat#300, Viscoat#400, Viscoat#360 (The above are from Osaka Organic Chemical Industrial (Stock) Manufacturing), 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, AT M-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 (the above are manufactured by Shinnakamura Chemical Industry Co., Ltd.), Fancryl (registered trademark) FA-513AS, Fancryl FA-512AS, Fancryl FA-511AS (the above are manufactured by Hitachi Chemical Co., Ltd.) Manufacturing), New Frontier (registered trademark) HBPE-4, New Frontier HBPEM-10 (the above are manufactured by Daiichi Industrial Pharmaceutical Co., Ltd.), KAYARAD (registered trademark) PET-30, KAYARAD DPHA, KAYARAD DPEA-12 (the above are manufactured by Nippon Kayaku Co., Ltd.). The said (a1) component may be used individually by 1 type, or may mix and use 2 or more types.

[(a2) Ingredients] The photo-radical polymerization initiator of the component (a2) is not particularly limited as long as it absorbs the light source used in the light curing of the composition for forming the layer A of the imprint replica mold of the present invention. As the photoradical polymerization initiator of the component (a2), for example, t-butyl peroxyisobutyrate, 2,5-dimethyl-2,5-bis(benzyldioxy )Hexane, 1,4-bis[α-(tertiary butyldioxy)-isopropoxy]benzene, di-tertiary butyl peroxide, 2,5-dimethyl-2,5- Bis(tertiary butyldioxy)hexene hydroperoxide, α-(isopropylphenyl)-isopropyl hydroperoxide, tertiary butyl hydroperoxide, 1,1-bis(tertiary butyl) Dioxy)-3,3,5-trimethylcyclohexane, 4,4-bis(tert-butyldioxy)butyl valerate, cyclohexanone peroxide, 2,2',5 ,5'-Tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-Tetra(tert-butylperoxycarbonyl)benzophenone, 3,3' ,4,4'-Tetra (third pentylperoxycarbonyl) benzophenone, 3,3',4,4'-tetra(third hexylperoxycarbonyl) benzophenone, 3,3 '-Bis(tertiary butylperoxycarbonyl)-4,4'-dicarboxybenzophenone, tertiary butyl peroxybenzoate, di-tertiary butyl peroxyisophthalate, etc. Peroxide; 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone and other quinones; benzoin methyl, benzoin ethyl ether, α- Benzoin derivatives such as methylbenzoin and α-phenylbenzoin; 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy- 2-Methyl-1-phenylpropane-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-methylpropane-1-one, methyl phenylglyoxylate , 2-Methyl-1-[4-(methylthio)phenyl]-2-𠰌line propane-1-one, 2-benzyl-2-dimethylamino-1-(4-𠰌line) Phenyl)-1-butanone, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-𠰌olin-4-yl-phenyl)-butane-1- Benzophenone compounds such as ketones; bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide Isosinyl phosphine oxide compounds; 2-(O-benzyl oxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetyl oxime) Oxime)-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]ethanone and other oxime ester compounds.

The photoradical polymerization initiator of the component (a2) can be obtained as a commercially available product. Specific examples thereof include: IRGACURE (registered trademark) 651, IRGACURE 184, IRGACURE 500, IRGACURE 2959, IRGACURE 127, and IRGACURE 754 , IRGACURE 907, IRGACURE 369, IRGACURE 379, IRGACURE 379EG, IRGACURE 819, IRGACURE 819DW, IRGACURE 1800, IRGACURE 1870, IRGACURE 784, IRGACURE OXE01, IRGACURE OXE02, IRGACURE 4 MBF, IRGACURE 1 MBF, IRGACURE 1 Manufactured by BASF JAPAN (Stock)), KAYACURE (registered trademark) DETX, KAYACURE MBP, KAYACURE DMBI, KAYACURE EPA, KAYACURE OA (the above are manufactured by Nippon Kayaku Co., Ltd.), VICURE-10, VICURE-55 (the above are by STAUFFER Co. LTD), ESACURE (registered trademark) KIP150, ESACURE TZT, ESACURE 1001, ESACURE KTO46, ESACURE KB1, ESACURE KL200, ESACURE KS300, ESACURE EB3, Triazine-PMS, Triazine A, Triazine B (the above are provided by Nihon SiberHegner (shares) ) Manufacturing), Adeka Optomer N-1717, Adeka Optomer N-1414, Adeka Optomer N-1606 (manufactured by ADEKA Co., Ltd.). The said (a2) component may be used individually by 1 type, or may mix and use 2 or more types. The content ratio of the radical photopolymerization initiator of the component (a2) is 0.01% by mass to 0.3% by mass relative to 100% by mass of the component (a1).

[(b1) Ingredients] (b1) The component is a compound having radical polymerizable groups at all ends of a linear or chain molecular chain containing fluorine atoms. As this radically polymerizable group, (meth)acryloxy group is mentioned, for example.

Examples of the compound of the component (b1) include: 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3,3-pentafluoropropyl (meth)acrylate, ( 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 (meth)acrylate ,3H-tetrafluoropropyl ester, (meth)acrylate 1H,1H,5H-octafluoropentyl ester, (meth)acrylate 1H,1H,7H-dodecafluoroheptyl ester, (meth)acrylate 1H-1- (Trifluoromethyl)trifluoroethyl, (meth)acrylate 1H,1H,3H-hexafluorobutyl, (meth)acrylate 1,2,2,2-tetrafluoro-1-(trifluoromethyl) ) Ethyl ester, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 2,2,3,3,4,4,4-heptafluorobutyl (meth)acrylate, (meth) Acrylic acid 1H,1H-pentadecafluoro-n-octyl ester, acrylic acid 1H,1H,2H,2H-tridecafluorooctyl ester, 1,6-bis((meth)acryloyloxy)-2,2,3, 3,4,4,5,5-octafluorohexane.

The above-mentioned compounds are available as commercially available products, and specific examples thereof include: 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3 acrylate ,3,3-pentafluoropropyl, 2,2,3,3,3-pentafluoropropyl methacrylate, 2-(perfluorobutyl) ethyl acrylate, 2-(perfluorobutyl methacrylate) ) Ethyl acrylate, 3-(perfluorobutyl)-2-hydroxypropyl acrylate, 3-(perfluorobutyl)-2-hydroxypropyl methacrylate, 2-(perfluorohexyl) ethyl acrylate, methyl 2-(perfluorohexyl) ethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 3-perfluorohexyl-2-hydroxypropyl methacrylate, 3-(perfluoro-3-methyl acrylate) Butyl)-2-hydroxypropyl, 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl methacrylate, 1H, 1H, 3H-tetrafluoropropyl methacrylate, 1H methacrylate ,1H,3H-Tetrafluoropropyl, 1H,1H,5H-octafluoropentyl acrylate, 1H,1H,5H-octafluoropentyl methacrylate, 1H,1H,7H-dodecafluoroheptyl methacrylate , Acrylic acid 1H, 1H, 7H-dodecafluoroheptyl ester, acrylic acid 1H-1-(trifluoromethyl) trifluoroethyl, methacrylic acid 1H-1-(trifluoromethyl) trifluoroethyl, acrylic acid 1H ,1H,3H-hexafluorobutyl, 1H,1H,3H-hexafluorobutyl methacrylate, 1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl acrylate, (above Daikin Industry Co., Ltd.), 2,2,3,3-tetrafluoropropyl acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,3 methacrylate, 4,4,4-Heptafluorobutyl, 1H,1H-pentadecafluoro-n-octyl acrylate, 1,6-bis(acryloyloxy)-2,2,3,3,4,4,5, 5-Octafluorohexane (the above are manufactured by Tokyo Chemical Industry Co., Ltd.), LINC-151EPA, LINC-152EPA, LINC-102A, LINC-2A, LINC-5A, LINC-162A, LINC-3A (the above are made by Kosei Soka Chemical Co., Ltd.), FLUOROLINK (registered trademark) MD500, FLUOROLINK MD700, FLUOROLINK MD40, FLUOROLINK MD1700, FOMBLIN (registered trademark) MT70 (manufactured by Solvay), Viscoat 13F (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

The above-mentioned (b1) component may be a linear or chain-like molecular chain containing the group represented by the above formula (1) and the group represented by the above formula (2a) or formula (2b) through carbamic acid at all ends The ester bond has a group represented by the above formula (3), that is, a polyfunctional (meth)acrylate compound containing a polymerizable group of (meth)acryloxy groups. Here, the polyfunctional (meth)acrylate compound is an acrylate compound or methacrylate compound having two or more functions other than the monofunctional (meth)acrylate compound. In addition, the aforementioned urethane bond refers to a structure represented by -NH-C(=O)-O-. The said polyfunctional (meth)acrylate compound has 2 or 4 urethane bonds, and 2 or 4 polymerizable groups containing a (meth)acryloxy group in 1 molecule. In addition, the group represented by the above formula (1) is sometimes referred to as poly(oxyperfluoroalkylene), and the group represented by the above formula (2a) is sometimes referred to as poly(oxyalkylene).

The linear or chain-shaped molecular chain is not particularly limited as long as it includes the group represented by the formula (1) and the group represented by the formula (2a) or (2b). In the linear or chain-like molecular chain, the bonding sequence of the group represented by the above formula (1) and the group represented by the above formula (2a) or formula (2b) is not particularly limited, and the order of the groups The number is not particularly limited. In addition, in the linear or chain molecular chain, the group represented by formula (1) and the group represented by formula (2a) or formula (2b) may be bonded by a single bond (direct bonding), or It is 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 oxygen perfluoroalkylene group in the group represented by the above formula (1): the number of carbon atoms of R ¹ in -(OR ¹ )- is 1 or 2. That is, the group represented by the above formula (1) has a structure in which a divalent carbon fluoride group with 1 or 2 carbon atoms is alternately connected with an oxygen atom, and an oxygen perfluoroalkylene group has a carbon atom number of 1 or 2 A structure formed by connecting a divalent fluorocarbon group and an oxygen atom. Specific examples of the oxyperfluoroalkylene group include -(OCF ₂ )- (that is, oxyperfluoromethylene) and -(OCF ₂ CF ₂ )- (that is, oxyperfluoromethylene). The above-mentioned oxyperfluoroalkylene group may be used alone or in combination of two of -(OCF ₂ )- and -(OCF ₂ CF ₂ )-. In the case of combining two kinds of use, the bonding of -(OCF ₂ )- and -(OCF ₂ CF ₂ )- can be any of block bonding and random bonding.

From the viewpoint of improving the mold release properties, as the base represented by the above formula (1), it is preferable to use -(OCF ₂ )- (ie, oxygen perfluoromethylene) and -(OCF ₂ CF ₂ )-(Ie, oxyperfluoroethylene group). The base represented by the above formula (1) is preferably [-(OCF ₂ )-]: [-(OCF ₂ CF ₂ )-] = 2:1 to 1:2 in molar ratio The base containing -(OCF ₂ )- and -(OCF ₂ CF ₂ )-, more preferably the base containing -(OCF ₂ )- and -(OCF ₂ CF ₂ )- at a ratio of approximately 1:1. These bonds can be any of block bonds and random bonds. The repeating number p of the group represented by the above formula (1) is an integer of 2 or more, preferably in the range of 5 to 30, more preferably in the range of 7 to 21.

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

The oxyalkylene group in the group represented by the above formula (2a): the number of carbon atoms of R ² in -(OR ² )- is 2 or 3. That is, the group represented by the above formula (2a) has a structure in which an alkylene group with 2 or 3 carbon atoms and an oxygen atom are alternately connected, and the oxyalkylene group has an alkylene group with 2 or 3 carbon atoms and an oxygen atom. Linked structure. Examples of the oxyethylene group include oxyethylene group, oxypropylene group, and oxytrimethylene group. The said oxyalkylene group may be used individually by 1 type, or may be used in combination of 2 or more types. When the oxyalkylene group is used in combination of two or more types, the bonding of the two or more oxyalkylene groups may be any of block bonding and random bonding.

The group represented by the above formula (2a) is, for example, poly(oxyethylene). The repeating number q of the group represented by the above 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 5 to 12, or 7 to 12.

The trivalent hydrocarbon group among the groups represented by the above formula (2b): R ^2b has 2 or 3 carbon atoms. That is, the group represented by the above formula (2b) has an alkane tolylene (alkane tolylene) with 2 or 3 carbon atoms (a hydrogen atom is removed from any carbon atom of an alkylene with 2 or 3 carbon atoms) The trivalent group formed) is a structure formed by connecting one oxygen atom. Among the groups represented by the above formula (2b), a group formed by connecting one oxygen atom to the 1-position (or 3-position) of the 1,2,3-propanetriyl group is preferred.

The polymerizable group containing the (meth)acryloxy group is not limited to one having one (meth)acryloxy group, and may have two or more. As the polymerizable group containing the (meth)acryloyloxy group, for example, the structure (terminal group) represented by the formula [X1] to the formula [X5] shown below, and these structures (terminal group) The acryloxy group is substituted with methacryloxy group.

[化3]

When the (b1) component is a polyfunctional (meth)acrylate compound having a polymerizable group containing the (meth)acryloyloxy group, in terms of ease of industrial production, the following can be listed The compound represented by the structural formula (A-1), the compound represented by (A-2) and the compound represented by (A-3), and the propyleneoxy group in these compounds is substituted with methpropylene A compound composed of an oxo group is a preferred example. Furthermore, in the following structural formula, 2 Xs or 4 Xs respectively represent one of the structures (terminal groups) represented by the above formula [X1] to formula [X5], and PFPE represents poly(oxyperfluoroextension) Alkyl), q ₁ and q ₂ each independently represent the number of oxyethylene groups, such as an integer of 2 to 15, preferably an integer of 2 to 12, or an integer of 5 to 12, or 7 to 12 Of integers. [化4]

When the above-mentioned (b1) component is a polyfunctional (meth)acrylate compound having the above-mentioned (meth)acryloxy group-containing polymerizable group, the (meth)acryloxy group-containing polymerizable group It is preferably a structure (terminal group) represented by the above-mentioned formula [X3] to formula [X5] having two or more (meth)acryloxy groups.

The said (b1) component may be used individually by 1 type, or may mix and use 2 or more types. The (b1) component is preferably 100% by mass relative to the total mass of the (b1) component, the following (b2) component, (b3) component, and other additives as optional components, preferably 0.1% by mass It is used at a rate of up to 10% by mass, more preferably 0.5% by mass to 8% by mass.

The above-mentioned (b1) component is obtained, for example, by the following method: the above-mentioned formula (2a) or formula (2b) which is directly bonded to or bonded to both ends of the group represented by the above-mentioned formula (1) via the above-mentioned linking group In a compound with at least 2 hydroxyl groups, the at least 2 hydroxyl groups are combined with 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis((meth)propylene isocyanate An isocyanate compound having a (meth)acryloxy group such as oxymethyl) ethyl ester undergoes a urethane 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.

The composition used to form the layer B of the imprinting replica mold of the present invention may contain only the base represented by the above formula (1) and the above formula (2a) or formula (2b) in addition to the above (b1) component. A part of the linear or chain-shaped molecular chain of the group represented by) has a polymerizable group containing (meth)acryloyloxy through a urethane bond, and the linear or chain-shaped molecule A compound having a hydroxyl group at the other end of the chain (ie, a compound having no polymerizable group at the other end). The composition for forming the above-mentioned layer B may be further included at all ends of the linear or chain-like molecular chain including the base represented by the above formula (1) and the base represented by the above formula (2a) or formula (2b) A compound having a hydroxyl group, that is, a compound that does not have the above-mentioned polymerizable group. The composition used to form the above-mentioned layer B is sometimes called a release agent.

[(b2) Ingredient] The photo-radical polymerization initiator of the component (b2) is not particularly limited as long as it absorbs the light source used in the light curing of the composition for forming the layer B of the imprint replica mold of the present invention. As this (b2) component, the same photoradical polymerization initiator as the said (a2) component is mentioned. The said (b2) component may be used individually by 1 type, or may mix and use 2 or more types. The content of the radical photopolymerization initiator of the component (b2) is 0.05 to 15% by mass relative to 100% by mass of the component (b1).

[(b3) Ingredients] The solvent as the component (b3) is not particularly limited as long as it exerts the effect of adjusting the viscosity of the component (b1) and (b2), and adjusts the viscosity of the component (b1) and (b2). The (b3) component is removed in the step of forming the B layer.

As the solvent, for example, 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 mono Butyl 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, hexanediol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, propylene glycol, benzyl alcohol, 1,3-butanediol, 1,4-butane Glycol, 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 , Tertiary 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-dimethyl Methamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethylsulfene, N-cyclohexyl -2-pyrrolidine, methyl perfluoropropyl ether, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1,2 ,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-pentane, 1,1,2,2-tetrafluoroethyl-2,2 ,2-Trifluoroethyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoropentane, pentafluorononane, hexafluorobenzene, heptafluoro-n-octyl bromide, 1,1,1,3,3,3-hexafluoro-2-methoxypropane, octafluorooctane, octafluorocyclopentene, perfluorotributylamine, perfluorodecalin, perfluorohexane Alkane, perfluoromethylcyclohexane, perfluoroheptane, octafluorotoluene, perfluorotripentylamine, perfluorotriethylamine, perfluoro(1,3-dimethylcyclohexane), perfluoro Isohexane.

The solvent as the above-mentioned (b3) component can be obtained as a commercially available product. Specific examples thereof include: Novec (registered trademark) 7000, Novec 7100, Novec 7200, Novec 7300 (the above are manufactured by 3M JAPAN (stock)), Asahiklin (registered trademark) AE-3000, Asahiklin AE-3100E (the above are manufactured by AGC (stock)), Vertrel (registered trademark) XF, Vertrel XF-UP, Vertrel XE-XP, Vertrel X-E10, Vertrel X-P10, Vertrel XD, Vertrel X-GY, Vertrel MCA, Vertrel SDG, Vertrel SMT, Vertrel SFR, Vertrel DC, Vertrel Sinera, Vertrel Suprion, Vertrel Sion (the above are manufactured by Dupont-Mitsui Fluorochemicals (stock)). The said (b3) component may be used individually by 1 type, or may mix and use 2 or more types.

[Other additives] The composition used to form the A layer of the replica mold for imprint of the present invention may contain a solvent if necessary. In addition, the composition for forming the A layer and the composition for forming the B layer may optionally contain a surfactant, a chain transfer agent, and a photosensitizer within a range that does not impair the effects of the present invention.

As the solvent, for example, 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 mono Butyl 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, hexanediol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, propylene glycol, benzyl alcohol, 1,3-butanediol, 1,4-butane Glycol, 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 , Tertiary 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-dimethyl Methamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethylsulfene, N-cyclohexyl -2-pyrrolidine, methyl perfluoropropyl ether, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoroisobutyl ether, 1,1,1,2 ,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-pentane, 1,1,2,2-tetrafluoroethyl-2,2 ,2-Trifluoroethyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoropentane, pentafluorononane, hexafluorobenzene, heptafluoro-n-octyl bromide, 1,1,1,3,3,3-hexafluoro-2-methoxypropane, octafluorooctane, octafluorocyclopentene, perfluorotributylamine, perfluorodecalin, perfluorohexane Alkane, perfluoromethylcyclohexane, perfluoroheptane, octafluorotoluene, perfluorotripentylamine, perfluorotriethylamine, perfluoro(1,3-dimethylcyclohexane), perfluoro Isohexane. These solvents may be used individually by 1 type, or may mix and use 2 or more types.

Examples of the above-mentioned surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, and polyoxyethylene octylbenzene. Ethers, polyoxyethylene alkyl aryl ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene/polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan Alcohol monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate and other sorbitan fatty acid esters, polyoxyethylene sorbitan monolaurate , Polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate and other polyoxyethylene Nonionic surfactants such as sorbitan fatty acid esters. The above-mentioned surfactants are available as commercially available products, and specific examples thereof include: Eftop (registered trademark) EF301, Eftop EF303, Eftop EF352 (the above are manufactured by Mitsubishi Materials Electronic Chemicals (stock)), Megafac (registered trademark) F-171, Megafac F-173, Megafac F-477, Megafac F-486, Megafac F-554, Megafac F-556, Megafac R-08, Megafac R-30, Megafac R-30N, Megafac R-40, Megafac R-40-LM, Megafac RS-56, Megafac RS-75, Megafac RS-72-K, Megafac RS-76-E, Megafac RS-76-NS, Megafac RS-78, Megafac RS-90 (Above by DIC (Stock) Manufacturing), Fluorad FC430, Fluorad FC431 (the above are manufactured by 3M JAPAN (Stock)), AsahiGuard (registered trademark) AG710, Surflon (registered trademark) S-382, Surflon SC101, Surflon SC102, Surflon SC103, Surflon SC104, Fluorine-based surfactants such as Surflon SC105 and Surflon SC106 (manufactured by AGC Co., Ltd.); 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 (the above are manufactured by BYK-Chemie JAPAN (stock)). These surfactants may be used alone or in combination of two or more kinds. When the composition for forming the layer A and the composition for forming the layer B contain the surfactant, the content ratio is preferably 0.01 mass% to 10% relative to 100% by mass of the component (a1) quality%.

As the chain transfer agent, for example, the thiol compound includes methyl thioglycolate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, and 3-methoxy 3-mercaptopropionate. Butyl ester, n-octyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, 1,4-bis(3-mercaptopropionoxy) butane, 1,4-bis(3-mercaptobutyroxy) Yl)butane, trimethylolethane tris(3-mercaptopropionate), trimethylolethane tris(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptopropionate) ), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate), dipentaerythritol hexa(3-mercaptopropionate) , Dipentaerythritol hexa(3-mercaptobutyrate), tetraethylene glycol bis(3-mercaptopropionate), tris[2-(3-mercaptopropoxy)ethyl]isocyanurate, isocyanurate Tris[2-(3-mercaptobutanoyloxy)ethyl] urate, 1,3,5-tris(3-mercaptobutanoyloxyethyl)-1,3,5-tris𠯤-2,4 ,6-(1H,3H,5H)-triketone and other mercapto carboxylic acid esters; ethyl mercaptan, 2-methylpropane-2-mercaptan, 1-dodecyl mercaptan, 2,3,3,4 ,4,5-hexamethylhexane-2-thiol (third-dodecyl mercaptan), ethane-1,2-dithiol, propane-1,3-dithiol, benzyl sulfide Alkyl mercaptans such as alcohols; benzene mercaptan, 3-methylbenzene mercaptan, 4-methylbenzene mercaptan, naphthalene-2-mercaptan, pyridine-2-mercaptan, benzimidazole-2-mercaptan , Benzothiazole-2-thiol and other aromatic mercaptans; 2-mercaptoethanol, 4-mercapto-1-butanol and other mercapto alcohols; 3-(trimethoxysilyl)propane-1-thiol, Silane-containing mercaptans such as 3-(triethoxysilyl)propane-1-thiol; bis(2-mercaptoethyl)ether; as the disulfide compound, diethyl disulfide, Dipropyl disulfide, diisopropyl disulfide, dibutyl disulfide, di-tertiary butyl disulfide, dipentyl disulfide, diisopentyl disulfide, dihexyl disulfide Sulfide, dicyclohexyl disulfide, didecyl disulfide, bis(2,3,3,4,4,5-hexamethylhexane-2-yl) disulfide (di-third- Dodecyl disulfide), bis(2,2-diethoxyethyl) disulfide, bis(2-hydroxyethyl) disulfide, dibenzyl disulfide and other alkyl disulfides Class; diphenyl disulfide, two-p-tolyl disulfide, two (pyridin-2-yl) pyridyl disulfide, two (benzimidazol-2-yl) disulfide, two (benzo Thiazol-2-yl) disulfide and other aromatic disulfides; tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, bis(five Methylene) thiuram disulfide and other thiuram disulfides; α-methylstyrene dimer. This chain transfer agent can be used individually by 1 type, and can be used in combination of 2 or more types. When the composition for forming the layer A and the composition for forming the layer B contain the chain transfer agent, the content ratio is preferably 0.01% by mass to 20% relative to 100% by mass of the component (a1) quality%.

系、9-氧硫𠮿

系、𠮿

系、酮系、噻喃鎓鹽系、基礎苯乙烯基(base styryl)系、部花青系、3-取代香豆素系、3,4-取代香豆素系、花青系、吖啶系、噻𠯤系、啡噻𠯤系、蒽系、蔻系、苯并蒽系、苝系、酮基香豆素系、香豆素系、硼酸酯系。該光增感劑可作為市售品而獲得，作為其具體例，可列舉：ANTHRACURE(註冊商標)UVS-581、ANTHRACURE UVS-1331(以上由川崎化成工業(股)製造)、KAYACURE(註冊商標)DETX-S(日本化藥(股)製造)。該光增感劑可單獨使用1種，可組合2種以上使用。藉由使用上述光增感劑，亦可調整UV區域之吸收波長。於用以形成上述A層之組合物及用以形成上述B層之組合物含有上述光增感劑之情形時，其含有比率相對於上述(a1)成分或上述(b1)成分100質量%，例如為0.01質量%至10質量%，較佳為0.05質量%至5質量%。As the above photosensitizer, for example, sulfur 𠮿

Department, 9-oxysulfur𠮿

Department, 𠮿

Series, ketone series, thiopyrylium salt series, base styryl series, merocyanine series, 3-substituted coumarin series, 3,4-substituted coumarin series, cyanine series, acridine Series, thiophene series, phenanthrene series, anthracene series, coronene series, benzanthracene series, perylene series, ketocoumarin series, coumarin series, borate series. The photosensitizer is available as a commercially available product, and specific examples thereof include: ANTHRACURE (registered trademark) UVS-581, ANTHRACURE UVS-1331 (manufactured by Kawasaki Chemical Industry Co., Ltd.), KAYACURE (registered trademark) ) DETX-S (manufactured by Nippon Kayaku Co., Ltd.). This photosensitizer can be used individually by 1 type, and can be used in combination of 2 or more types. By using the aforementioned photosensitizer, the absorption wavelength in the UV region can also be adjusted. When the composition for forming the layer A and the composition for forming the layer B contain the photosensitizer, the content ratio is relative to 100% by mass of the component (a1) or the component (b1), For example, it is 0.01% by mass to 10% by mass, preferably 0.05% by mass to 5% by mass.

[Preparation of copy mold material for imprinting] The preparation method of the composition for forming the A layer of the imprint replica mold of the present invention and the composition for forming the B layer is not particularly limited. In the case of the composition for forming the layer A, for example, the component (a1), the component (a2), and other additives as necessary are mixed to make the composition uniform. In addition, in the case of forming the composition of the above-mentioned B layer, for example, only the (b1) component, (b2) component, (b3) component, and other additives as necessary are mixed to make the composition uniform OK. In addition, the order of mixing the components of the composition for forming the A layer and the composition for forming the B layer is not a problem as long as a uniform composition can be obtained, and is not particularly limited.

The replica mold for imprinting of the present invention can be obtained by forming the A layer by light imprinting, and then forming the B layer on the A layer by light curing.

The layer A of the replica mold for imprinting of the present invention can be applied to a substrate or a master mold by applying a composition containing the above-mentioned (a1) component and (a2) component to the master mold. Light harden and demold to obtain the desired structure. As the coating method of the composition containing the above-mentioned (a1) component and (a2) component, known or well-known methods such as pouring method, spin coating method, dipping method, flow coating method, inkjet method, spray method can be cited , Bar coating method, gravure coating method, slit coating method, roll coating method, transfer printing method, brush coating, knife coating method, air knife coating method.

As the substrate for forming the A layer of the imprinting replica mold of the present invention, for example, glass (ITO substrate) containing silicon, indium tin oxide (ITO) formed into a film, and silicon nitride (SiN) made Film made of glass (SiN substrate), glass made of indium zinc oxide (IZO) film, polyethylene terephthalate (PET), triacetyl cellulose (TAC), acrylic resin , Plastic, glass, quartz, ceramics, etc. In addition, flexible substrates with flexibility, such as triacetyl cellulose, polyethylene terephthalate, polymethyl methacrylate, cycloolefin (co)polymer, poly Vinyl alcohol, polycarbonate, polystyrene, polyimide, polyamide, polyolefin, polypropylene, polyethylene, polyethylene naphthalate, polyether turpentine, and copolymers combining these polymers The base material of things.

The light source for photocuring to form the A layer of the imprinting replica mold of the present invention is not particularly limited. Examples include high-pressure mercury lamps, low-pressure mercury lamps, electrodeless lamps, metal halide lamps, and KrF excimer lasers. , ArF excimer laser, F ₂ excimer laser, electron beam (EB), extreme ultraviolet (EUV), ultraviolet LED (UV-LED). In addition, with regard to the wavelength of the above-mentioned light source, G-rays of 436 nm, H-rays of 405 nm, I-rays of 365 nm, or GHI mixed rays can usually be used. Furthermore, the exposure amount is preferably 30 mJ/cm ² to 10000 mJ/cm ² , more preferably 100 mJ/cm ² to 8000 mJ/cm ² .

Furthermore, when the composition for forming the A layer contains a solvent, at least one of the coating film before light irradiation and the photocured product obtained after light irradiation can be added with a baking step for the purpose of evaporating the solvent. The equipment used in the baking step is not particularly limited. For example, it may be capable of using a hot plate, oven, or furnace, and baking in an appropriate environment, that is, air, inert gas such as nitrogen, or vacuum. The baking temperature is not particularly limited as long as it can achieve the purpose of evaporating the solvent. For example, it can be performed at 40°C to 200°C.

The device for light imprinting is not particularly limited as long as the target pattern can be obtained. For example, ST50 manufactured by Toshiba Machine Co., Ltd., Sindre (registered trademark) 60 manufactured by Obducat Co., Ltd., and Mingchang Machinery Co., Ltd. can be used. NM-0801HB and other commercially available devices are a method of crimping the base material and the master mold and curing the hardened product from the master mold.

In addition, as the material of the master mold used for photoimprinting used in the present invention, for example, quartz, silicon (Si), nickel, alumina (Al ₂ O ₃ ), carbonyl silane, glassy carbon, as long as available The pattern of the target is not particularly limited. In addition, in order to improve the mold releasability, the master mold may be subjected to a mold release treatment to form a thin film of a fluorine-based compound or the like on its surface. As the mold release agent used for the mold release treatment, for example, OPTOOL (registered trademark) HD and OPTOOL DSX manufactured by Daikin Industry Co., Ltd. are listed, and there is no particular limitation as long as the target pattern can be obtained.

The A layer of the copy mold for imprinting of the present invention is heated after being released from the master mold, so that the transparency in the ultraviolet region can be improved. The heating method of the A layer may be a method using a heating mechanism such as a hot plate and an oven.

The layer B of the replica mold for imprinting of the present invention can be obtained by applying a composition containing the above-mentioned (b1) component, (b2) component and (b3) component on the above-mentioned layer A and photocuring. Laminated. As the coating method of the composition containing the above-mentioned (b1) component, (b2) component and (b3) component, known or well-known methods such as pouring method, spin coating method, dipping method, flow coating method, spray Ink method, spray method, bar coating method, gravure coating method, slit coating method, roll coating method, transfer printing method, brush coating, knife coating method, air knife coating method .

The light source for photocuring to form the B layer of the imprinting replica mold of the present invention is not particularly limited. Examples include high-pressure mercury lamps, low-pressure mercury lamps, electrodeless lamps, metal halide lamps, and KrF excimer lasers. , ArF excimer laser, F ₂ excimer laser, electron beam (EB), extreme ultraviolet (EUV), ultraviolet LED (UV-LED). In addition, with regard to the wavelength of the above-mentioned light source, G-rays of 436 nm, H-rays of 405 nm, I-rays of 365 nm, or GHI mixed rays can usually be used. Furthermore, the exposure amount is preferably 30 mJ/cm ² to 2000 mJ/cm ² , more preferably 30 mJ/cm ² to 1000 mJ/cm ² .

In the step of forming the B layer of the imprinting replica mold of the present invention, the solvent as the component (b3) can be evaporated for the purpose of coating, before photocuring, or photocuring of the composition for forming the B layer Add baking step later. The equipment used in this baking step is not particularly limited. For example, as long as it can be baked in a suitable environment, that is, in the atmosphere, inert gas such as nitrogen, or in a vacuum, a hot plate, oven, or furnace can be used. can. Regarding the baking temperature in the above baking step, it can be carried out at a temperature of 40°C to 200°C that can evaporate the solvent.

The pattern size of the imprint replica mold obtained by the present invention is not particularly limited, and good patterns can be obtained, for example, at the nanometer, micrometer, and millimeter levels. [Example]

Hereinafter, examples and comparative examples are given to further describe the present invention in detail, but the present invention is not limited to the following examples. In addition, the equipment and conditions used in the analysis of the physical properties of the compounds obtained in the following synthesis examples are as follows.

(1) Gel permeation chromatography (GPC) Device: GPC system manufactured by Shimadzu Corporation GPC column: Shodex (registered trademark) GPC KF-804L and GPC KF-803L Column temperature: 40℃ Solvent: Tetrahydrofuran Flow rate: 1 mL/min Standard sample: polystyrene

In addition, the following abbreviated symbols indicate the following meanings. PFPE1: Perfluoropolyether with hydroxyl groups at both ends via poly(oxyethylene) (number of repeating units 8-9) [manufactured by Solvay Specialty Polymers, Fluorolink (registered trademark) 5147X] PFPE2: A perfluoropolyether having 2 hydroxyl groups at each end via the group represented by the above formula (2b) [manufactured by Solvay Specialty Polymers, Fomblin (registered trademark) T4] BEI: 1,1-bis(acryloxymethyl)ethyl isocyanate [manufactured by Showa Denko Corporation, Karenz (registered trademark) BEI] DBTDL: Dibutyltin dilaurate [manufactured by Tokyo Chemical Industry Co., Ltd.] DOTDD: Dioctyltin dineodecanoate [manufactured by Nitto 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＞ PGMEA 178.84 g was added to a 2 L four-necked flask, and stirred at an internal temperature of 80°C under a nitrogen atmosphere. Methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 120 g, isopropyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 249.66 g, and AIBN (manufactured by Kanto Chemical Co., Ltd.) were added dropwise over 2 hours. ) A solution of 5.904 g and 697.48 g of PGMEA was added dropwise and reacted for 17 hours. The reaction solution was dropped into 6.3 kg of methanol (manufactured by Junsei Chemical Co., Ltd.), and the precipitated polymer was dried under a reduced pressure of 133.3 Pa at 80°C to obtain a non-crosslinkable copolymer MI55 330.4 g . The weight average molecular weight of MI55 measured by GPC was 20,100 in terms of standard polystyrene.

＜Synthesis example 2＞ Add 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 to the eggplant-shaped flask. Using a stirrer chip, the mixture in the eggplant-shaped flask was stirred at room temperature (approximately 23° C.) for 24 hours to obtain a reactant. 30.37 g of PGMEA was added to the reactant, MEK was distilled off using an evaporator, and a PGMEA solution containing SM1 as a component (b1) was obtained at 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 degree of dispersion: Mw (weight average molecular weight)/Mn (number average molecular weight) was 1.1.

＜Synthesis example 3＞ Into the eggplant-shaped flask were added PFPE1 10.5 g (5 mmol), BEI 2.39 g (10.0 mmol), DOTDD 0.0644 g, and PGMEA 12.9 g. Using a stir bar, the mixture in the eggplant-shaped flask was stirred at room temperature (approximately 23° C.) for 48 hours to obtain a reactant. 38.9 g of PGMEA was added to the reactant, and a PGMEA solution containing SM2 as a component (b1) was obtained 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 dispersion degree: Mw (weight average molecular weight)/Mn (number average molecular weight) was 1.1.

＜Synthesis example 4＞ 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 were added to the eggplant-shaped flask. Under a nitrogen atmosphere, using a stir bar, the mixture in the eggplant-shaped flask was stirred at room temperature (approximately 23° C.) for 72 hours to obtain a reactant. 64.96 g of PGMEA was added to the reactant, MEK was distilled off using an evaporator, and a PGMEA solution containing SM3 as a component (b1) was obtained at a solid content of 20% by mass. The weight average molecular weight Mw of the obtained SM3 measured in terms of polystyrene by GPC was 2,750, and the dispersion degree: Mw (weight average molecular weight)/Mn (number average molecular weight) was 1.1.

＜Synthesis example 5＞ Into the eggplant-shaped flask were added 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. Under a nitrogen atmosphere, using a stir bar, the mixture in the eggplant-shaped flask was stirred at room temperature (approximately 23° C.) for 72 hours to obtain a reactant. 48.72 g of PGMEA was added to the reactant to obtain a PGMEA solution containing SM4 as a component (b1) at 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 dispersion degree: Mw (weight average molecular weight)/Mn (number average molecular weight) was 1.1.

[Preparation of composition for forming A layer] <Preparation Example 1> Added New Frontier (registered trademark) HBPE-4 (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) (hereinafter, referred to as "HBPE-4" in this manual) 7 g, KAYARAD (registered trademark) PET-30 (Nippon Kayaku (Stock) Manufacturing) (hereinafter referred to as "PET-30" in this manual) 3 g, and IRGACURE (registered trademark) 184 (made by BASF JAPAN (stock)) (hereinafter, referred to as "IRGACURE 184" in this manual ") 0.01 g (0.1% by mass relative to the total mass of HBPE-4 and PET-30) to prepare composition A1.

<Preparation Example 2> 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 relative to the total mass of HBPE-4 and MI55) were added to prepare composition A2.

<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 relative to the total mass of HBPE-4 and MI55) were added to prepare composition A3.

<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 relative to the total mass of HBPE-4 and MI55) were added to prepare composition A4.

<Preparation Example 5> Added HBPE-4 5 g, NK ESTER A-DOG (hereinafter, referred to as "A-DOG" in this manual) (manufactured by Shinnakamura Chemical Co., Ltd.) 5 g, and IRGACURE 184 0.01 g (relative to HBPE- 4. The total mass of A-DOG is 0.1% by mass) to prepare composition A5.

<Preparation Example 6> Added PET-30 7 g, NK ESTER A-200 (manufactured by Shinnakamura Chemical Industry Co., Ltd.) 1.5 g, A-DOG 1.5 g, and IRGACURE 184 0.01 g (relative to PET-30, A-200, A-DOG The total mass is 0.1% by mass) to prepare composition A6.

<Preparation Example 7> Add HBPE-4 5 g, NK ESTER A-DCP (hereinafter, referred to as "A-DCP" in this manual) (manufactured by Shinnakamura Chemical Co., Ltd.) 5 g, and IRGACURE 184 0.01 g (relative to HBPE- 4. The total mass of A-DCP is 0.1% by mass) to prepare composition A7.

<Preparation Example 8> A-DCP 5 g, 1-ADMA (manufactured by Osaka Organic Chemical Industry Co., Ltd.) 5 g, and IRGACURE 184 0.01 g (0.1% by mass relative to the total mass of A-DCP and 1-ADMA) were added to prepare a composition A8.

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

[Preparation of the composition (release agent) used to form layer B] <Preparation Example 10> Mixed LINC-5A (manufactured by Kyoeisha Chemical Co., Ltd.) 0.285 g, 2,2,2-trifluoroethyl acrylate (manufactured by Daikin Industry Co., Ltd.) 0.015 g, IRGACURE (registered trademark) 819 (BASF JAPAN ( Stock), bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide) (hereinafter, referred to as "IRGACURE 819" in this manual) 0.006 g, and PGMEA 8.44 g, preparation combination物 (release agent) B1.

<Preparation Example 11> 0.3 g of LINC-162A (manufactured by Kyoeisha Chemical Co., Ltd.), IRGACURE 819 0.006 g, and PGMEA 8.44 g were mixed to prepare composition (release agent) B2.

<Preparation Example 12> 0.3 g of LINC-102A (manufactured by Kyoeisha Chemical Co., Ltd.), IRGACURE 819 0.006 g, and PGMEA 8.44 g were mixed to prepare composition (release agent) B3.

<Preparation Example 13> 0.3 g of LINC-5A (manufactured by Kyoeisha Chemical Co., Ltd.), IRGACURE 819 0.006 g, and PGMEA 8.44 g were mixed to prepare a composition (release agent) B4.

<Preparation Example 14> 1.0 g of DAC-HP (manufactured by Daikin Industry Co., Ltd.), IRGACURE 819 0.004 g, and PGMEA 4.82 g were mixed to prepare a composition (release agent) B5.

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

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

<Preparation Example 17> The PGMEA solution containing SM3 1.00 g, IRGACURE 819 0.0040 g, DETX-S 0.0002 g and PGMEA 4.83 g obtained in Synthesis Example 4 were mixed to prepare composition (release agent) B8.

<Preparation Example 18> The PGMEA solution containing SM4, 1.00 g, IRGACURE 819 0.0040 g, DETX-S 0.0002 g, and PGMEA 4.83 g obtained in Synthesis Example 5 were mixed to prepare composition (release agent) B9.

[Preparation of a replica mold for imprinting] <Example 1> The composition A1 obtained in Preparation Example 1 was poured in advance using NOVEC (registered trademark) 1720 (manufactured by 3M JAPAN (stock)) (hereinafter referred to as abbreviated in this manual) It is "NOVEC1720") in a nickel mold (with 3 rows of vertical × 5 rows of horizontal, 15 concave lenses of 2 mm diameter × 300 μm depth), on which a quartz glass substrate is placed, using nano Imprinting device NM-0801HB (manufactured by Mingchang Machinery Co., Ltd.) performs light imprinting. Light imprinting is always performed at 23°C in the following order: a) Pressurization to 500 N in 10 seconds, b) Exposure to 5000 mJ/cm ² using a high-pressure mercury lamp, c) 10 seconds Perform pressure relief and d) Separate the nickel mold from the quartz glass substrate and demold, and obtain a convex lens pattern of 2 mm diameter × 300 μm height on the quartz glass substrate. The convex lens pattern obtained on the quartz glass substrate was heated for 5 minutes using a heating plate at 150°C to form a layer A. The above-mentioned quartz glass substrate used has been subjected to a close bonding process by spin-coating KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) in advance and heating it with a hot plate at 150°C for 5 minutes. Using a spin coater, the composition (release agent) B1 obtained in Preparation Example 10 was formed into a film on the obtained layer A, and baked at 80° C. for 5 minutes using a hot plate. After that, in a nitrogen environment, a batch-type UV irradiation device (high-pressure mercury lamp 2 kW×1 lamp) (manufactured by EYE GRAPHICS Co., Ltd.) was used to pass the i-ray filter through a 40 mW/cm ² UV exposure for 2 seconds to form layer B on the above layer A to make a replica RM-1 for imprinting.

<Example 2> 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, a replica mold for imprint was produced in the same manner as in Example 1 RM-2.

<Example 3> The composition (release agent) B1 obtained in Preparation Example 10 was changed to the composition (release agent) B3 obtained in Preparation Example 12, except that the same method as Example 1 was used to produce a replica mold for imprint RM-3.

<Example 4> 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, the replica mold for imprint was produced in the same manner as in Example 1 RM-4.

<Example 5> The composition (release agent) B1 obtained in Preparation Example 10 was changed to the composition (release agent) B5 obtained in Preparation Example 14, except that the same method as Example 1 was used to produce a replica mold for imprint RM-5.

<Example 6> The composition (release agent) B1 obtained in Preparation Example 10 was changed to the composition (release agent) B7 obtained in Preparation Example 16, except that the same method as Example 1 was used to produce a replica mold for imprint RM-6.

<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 (release Agent) B7, except for this, in the same manner as in Example 1, a replica RM-7 for imprinting was produced.

<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 (release Agent) B7, except for this, in the same manner as in Example 1, a replica RM-8 for imprinting was produced.

<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 (release Agent) B6, except for this, in the same manner as in Example 1, a replica RM-9 for imprinting was produced.

<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 (release Agent) B7, except for this, in the same manner as in Example 1, a replica RM-10 for imprinting was produced.

<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 (release Agent) B8, except for this, in the same manner as in Example 1, a replica RM-11 for imprinting was produced.

<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 (release Agent) B9, except for this, in the same manner as in Example 1, a replica RM-12 for imprinting was produced.

<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 (release Agent) B7, except for this, in the same manner as in Example 1, a replica RM-13 for imprint was produced.

<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 (release Agent) B7, except for this, in the same manner as in Example 1, a replica RM-14 for imprinting was produced.

<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 (release Agent) B7, except for this, in the same manner as in Example 1, a replica RM-15 for imprinting was produced.

<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 (release Agent) B7, except for this, in the same manner as in Example 1, a replica RM-16 for imprinting was produced.

<Comparative example 1> Except for changing the composition A1 obtained in Preparation Example 1 to the composition A8 obtained in Preparation Example 8, the A layer was formed in the same manner as in Example 1. NOVEC 1720 was spin-coated on the A layer obtained, and heated with a hot plate at 150° C. for 5 minutes, thereby making a replica RM-19 for imprinting.

＜Comparative example 2＞ Except for changing the composition A1 obtained in Preparation Example 1 to the composition A8 obtained in Preparation Example 8, the A layer was formed in the same manner as in Example 1. PFPE1 was spin-coated on the obtained layer A, and heated with a hot plate at 150°C for 5 minutes, thereby making a replica 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 (release Agent) B2, except that, in the same manner as in Example 1, a replica RM-21 for imprinting was produced.

[Preparation of imprinting material] Mixed NK ESTER A-DOG (manufactured by Shinnakamura Chemical Industry Co., Ltd.) 5 g and polycarbonate ETERNACOLL (registered trademark) containing radical polymerizable groups ΜM-90(1/3)DA (Ube Industries Co., Ltd.) Manufacturing) 5 g, 0.2 g of IRGACURE184 was added to the mixture to prepare an imprinting material.

[Production of concave lens pattern using copy mold for imprinting] The prepared imprinting material was poured onto a quartz glass substrate that had been closely bonded by the method described in Example 1, and the examples 1 to were placed thereon 16 and each of the imprinting replica molds obtained in Comparative Example 1 to Comparative Example 3 was subjected to light imprinting using a nanoimprinting device NM-0801HB (manufactured by Mingchang Machinery Co., Ltd.). Light imprinting is always performed at 23°C in the following order: a) Pressurization to 500 N in 10 seconds, b) Exposure to 5000 mJ/cm ² using a high-pressure mercury lamp, c) 10 seconds Perform pressure relief and d) separate the replication mold from the quartz glass substrate and demold, and obtain a concave lens pattern on the quartz glass substrate. Using an industrial microscope ECLIPSE L150 (manufactured by Nikon Co., Ltd.), observe whether the resulting concave lens pattern is peeled off or cracked. The results are shown in Table 1 and Table 2.

[Evaluation of Optical Properties] Using a spectrophotometer UV2600 (manufactured by Shimadzu Corporation), measuring the values of the replica molds obtained in Examples 1 to 16 and Comparative Examples 1 to 3 in a state where the reference is set to quartz glass The transmittance at a wavelength of 365 nm. The results are shown in Table 1 and Table 2. The above-mentioned replica mold for imprint, whose transmittance was measured, has a convex lens pattern of 2 mm diameter × 300 μm height.

[Determination of the number of times that can be repeatedly imprinted] Using the copy molds for imprinting obtained in Example 1 to Example 16 and Comparative Example 1 to Comparative Example 3 directly, repeat the same light imprinting as above, up to 10 times, and measure the number of light imprinting until it fails. Until the formation of a concave lens shape pattern of 2 mm diameter × 300 μm depth. The results obtained are shown in Table 1 and Table 2.

[Table 1] Table 1 Whether the concave lens pattern is broken Whether the concave lens pattern is peeled off Transmittance under 365 nm (%) The number of times that can be repeated Example 1 no no 83.7 8 times Example 2 no no 83.5 8 times Example 3 no no 84.0 9 times Example 4 no no 84.1 8 times Example 5 no no 83.8 9 times Example 6 no no 82.1 10 times Example 7 no no 84.3 10 times Example 8 no no 85.2 10 times Example 9 no no 84.9 10 times Example 10 no no 84.7 10 times Example 11 no no 85.2 10 times Example 12 no no 85.7 10 times Example 13 no no 84.9 10 times Example 14 no no 84.3 10 times Example 15 no no 84.5 10 times Example 16 no no 84.2 10 times

[Table 2] Table 2 Whether the concave lens pattern is broken Whether the concave lens pattern is peeled off Transmittance under 365 nm (%) The number of times that can be repeated Comparative example 1 no no 82.1 1 time Comparative example 2 no Have 82.1 0 times Comparative example 3 no Have 75.2 10 times

According to the results shown in Table 1 and Table 2, no cracking or peeling was observed in the concave lens pattern produced using the replica mold for imprint produced in Example 1 to Example 16. In addition, the imprint replica molds produced in Example 1 to Example 16 were able to perform repeated imprinting more than 8 times. Furthermore, the transmittance at 365 nm of the replica molds for imprints produced in Example 1 to Example 16 were all 80% or more, and it was confirmed that they had high transparency in the ultraviolet region. On the other hand, peeling was observed in the concave lens pattern produced using the replica mold for imprint produced in Comparative Example 2 and Comparative Example 3. In addition, the copy mold for imprint produced in Comparative Example 1 and Comparative Example 2 can be repeatedly imprinted once or 0 times. Furthermore, the transmittance of the replica mold for imprint produced in Comparative Example 3 at a wavelength of 365 nm was lower than 80%.

Based on the above results, the copy mold for imprinting of the present invention has high transparency in the ultraviolet region and can perform repeated imprinting. Furthermore, the pattern produced using this imprinting replica mold has no cracking or peeling.

Claims (13)

A copy mold for imprinting, comprising the following A layer and the following B layer next to the A layer, Layer A: A structure containing a cured product of a composition containing the following (a1) and (a2) components (a1) Component: a compound having at least one radical polymerizable group in one molecule (a2) Component: 0.01% by mass to 0.3% by mass relative to 100% by mass of the above-mentioned component (a1) Layer B: A film containing a cured product of a composition containing the following components (b1) and (b2) (b1) Component: A compound containing a linear or chain molecular chain containing fluorine atoms and having radical polymerizable groups at all ends of the molecular chain (b2) Component: A photo-radical polymerization initiator of 0.05% by mass to 15% by mass relative to 100% by mass of the aforementioned (b1) component. The copy mold for imprinting according to claim 1, wherein the compound of the component (b1) is represented by the following formula (3) at all ends of the linear or chain molecular chain via urethane bonds The multifunctional (meth)acrylate compound of a group, the linear or chain-shaped molecular chain includes a group represented by the following formula (1) and a group represented by the following formula (2a) or (2b), [化1]

(In the formula, R ¹ represents a perfluoroalkylene group with 1 or 2 carbon atoms, R ^2a represents an alkylene group with 2 or 3 carbon atoms, and R ^2b represents a trivalent hydrocarbon group with 2 or 3 carbon atoms, * Represents the bonding bond to the -O- group of the above urethane bond, p and q represent the repeating number of the group represented by the above formula (1) and the number of the group represented by the above formula (2a), respectively The repeating number independently represents an integer of 2 or more, and R ³ represents a methyl group or a hydrogen atom). For example, the copy mold for imprinting of claim 2, wherein q representing the number of repetitions of the base represented by the above formula (2a) is an integer from 5 to 12. Such as claim 2 or 3 of the copy mold for imprint, wherein the group represented by the above formula (2a) is poly(oxyethylene). The copy mold for imprinting according to any one of claims 2 to 4, wherein the group represented by the above formula (1) is a group having both of oxyperfluoromethylene and oxyperfluoroethylene. The replica mold for imprinting according to any one of claims 1 to 5, wherein the compound of the component (b1) is a macromonomer or polymer with a weight average molecular weight of 1,000 to 30,000. The copy mold for imprint according to any one of claims 1 to 6, wherein the composition containing the above-mentioned (b1) component and (b2) component further contains a photosensitizer. For example, the copy mold for imprint of claim 1, wherein the component (a1) contains at least two compounds, and at least one of the two compounds has at least two (meth)acryloyloxy groups in one molecule The compound. The copy mold for imprinting according to claim 8, wherein the compound having at least two (meth)acryloxy groups in one molecule is a di(meth)acrylate compound represented by the following formula (4), [化2]

(In the formula, R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group, R ⁶ and R ⁷ each independently represent an alkylene group having 1 to 4 carbon atoms, and R ⁸ and R ⁹ each independently represent a hydrogen atom Or methyl, r ¹ and r ² each independently represent an integer of 1 to 5). The copy mold for imprinting according to any one of claims 1 to 9, wherein the layer A has a lens-shaped reverse pattern. Such as the copy mold for imprinting in any one of Claims 1 to 10, wherein the maximum thickness of the A layer is 2.0 mm. A method for making a copy mold for imprinting, which includes: The step of coating the composition containing the following (a1) components and (a2) components on the master mold, The step of crimping the above-mentioned master mold to the substrate through a composition containing the following (a1) components and (a2) components, The step of exposing a composition containing the following components (a1) and (a2) through the substrate in a state where the master mold is pressure-bonded to the substrate, and the composition is photocured, The step of releasing the cured product obtained on the substrate from the master mold to form the A layer after the light curing step, The step of applying a composition containing the following components (b1) to (b3) on the A layer, and A step of baking a composition containing the following components (b1) to (b3) at 40°C to 200°C and then performing exposure to form the layer B next to the layer A, (a1) Component: a compound having at least one radical polymerizable group in one molecule (a2) Component: 0.1% to 1% by mass of the photo-radical polymerization initiator relative to 100% by mass of the above (a1) component (b1) Component: A compound containing a linear or chain molecular chain containing fluorine atoms and having radical polymerizable groups at all ends of the molecular chain (b2) Component: A photo-radical polymerization initiator of 0.05% to 15% by mass relative to 100% by mass of the above (b1) component (b3) Ingredient: solvent. A method for making a copy mold for imprinting, which includes: The step of coating a composition containing the following (a1) components and (a2) components on a substrate, The step of crimping the above-mentioned base material to the master mold through a composition containing the following (a1) components and (a2) components, The step of exposing a composition containing the following components (a1) and (a2) through the substrate in a state where the master mold is pressure-bonded to the substrate, and the composition is photocured, The step of releasing the cured product obtained on the substrate from the master mold to form the A layer after the light curing step, The step of applying a composition containing the following components (b1) to (b3) on the A layer, and A step of baking a composition containing the following components (b1) to (b3) at 40°C to 200°C and then performing exposure to form the layer B next to the layer A, (a1) Component: a compound having at least one radical polymerizable group in one molecule (a2) Component: 0.1% to 1% by mass of the photo-radical polymerization initiator relative to 100% by mass of the above (a1) component (b1) Component: A compound containing a linear or chain molecular chain containing fluorine atoms and having radical polymerizable groups at all ends of the molecular chain (b2) Component: A photo-radical polymerization initiator of 0.05% to 15% by mass relative to 100% by mass of the above (b1) component (b3) Ingredient: solvent.