WO2020116397A1 - Replica mold for imprinting and method for producing same - Google Patents

Abstract

[Problem] To provide a novel replica mold for imprinting. [Solution] 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

Imprint replica mold and method of manufacturing the same

The present invention relates to a replica mold for imprint having a pattern. More specifically, it is a replica mold that retains high transparency in the ultraviolet region even if it is a thick film, and does not require recoating with a release agent and can form good patterns even when repeatedly used for optical imprinting. The present invention relates to an imprint replica mold 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 vehicle-mounted 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 being molded with a high yield, in accordance with the usage mode. As a material for a resin lens that meets such requirements, for example, a thermoplastic transparent resin such as a polycarbonate resin, a cycloolefin polymer, or a methacrylic resin has been used.

When manufacturing resin lenses, in order to improve yield and production efficiency, and also to suppress optical axis deviation when stacking lenses, wafers are manufactured from thermoplastic resin injection molding to pressing molding using a curable resin that is liquid at room temperature. The transition to level molding is being actively studied. In wafer level molding, a hybrid lens system in which a lens is formed on a support such as a glass substrate is generally used from the viewpoint of productivity.

In the wafer level molding, the mold also needs to be molded at the wafer level. A typical resin lens manufacturing mold is made by excavating 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 pitch between pixels are accurate. Need to control. Therefore, it is very difficult to manufacture the mold and it is expensive. Further, when a metal mold is used, UV light used for curing the resin lens material does not pass therethrough, 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 producing a replica mold by step-and-repeat molding in a wafer using a relatively inexpensive master mold for one pixel and a replica mold material has been developed. ing.

Japanese Patent No. 4226061 (Japanese Patent Laid-Open No. 2009-172773)

A 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 continuously molded using the same replica mold, the release agent peels 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 in a replica mold 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 thereof is to provide a replica mold having high transparency and capable of repeatedly molding a resin lens.

As a result of intensive studies to solve the above problems, the present inventors have found that a cured product of a composition containing a compound having at least one radically polymerizable group in one molecule and a photoradical polymerization initiator. A film comprising a cured product of a composition containing a compound having a radical polymerizable group at all terminals of a linear or chain molecular chain containing a fluorine atom and a photoradical polymerization initiator is adhered to the structure consisting of Thus, the present invention has been accomplished. That is, the replica mold of the present invention has high transparency in the ultraviolet region and can repeatedly mold resin lenses.

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

The compound of the component (b1) is, for example, all of the linear or chain molecular chains containing a group represented by the following formula (1) and a group represented by the following formula (2a) or formula (2b). It is a polyfunctional (meth)acrylate compound having a group represented by the following formula (3) at the terminal 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 carbon atom having 2 or 3 carbon atoms. Represents a hydrogen group, * represents a bond for bonding to the —O— group of the urethane bond, p and q represent the number of repeating groups of the formula (1) and the formula (2a), respectively. Represents a repeating number of a group represented by 2 and independently represents an integer of 2 or more, and R ³ represents a methyl group or a hydrogen atom.)

Q, which represents the repeating number of the group represented by the 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 as 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 component (b1) and the component (b2) may further contain a photosensitizer.

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

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 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 are each independently Represents a hydrogen atom or a methyl group, and r ¹ and r ² each independently represent an integer of 1 to 5.)

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

Another aspect of the present invention is the step of applying a composition containing a component (a1) and a component (a2) below onto a master mold, the master containing the composition containing a component (a1) and a component (a2) below. A step of pressure-bonding a mold to a substrate, exposing the composition containing the following component (a1) and component (a2) through the substrate while the master mold is pressure-bonded to the substrate, and photocuring the composition. Step, after the photo-curing step, a step of releasing the cured product obtained on the substrate from the master mold to form an A layer, and the following (b1) component to (b3) component on the A layer And a composition containing the following components (b1) to (b3) is baked at 40° C. to 200° C. and then exposed to form the B layer adhered to the A layer. A method for producing an imprint replica mold, which includes the steps of:
Component (a1): Compound having at least one radical-polymerizable group in one molecule (a2) Component: 0.1% by mass to 1% by mass of photoradical polymerization initiator based on 100% by mass of the component (a1). Component (b1): a compound composed of a linear or chain molecular chain containing a fluorine atom and having a radical polymerizable group at all terminals of the molecular chain (b2) component: 100 mass of the component (b1) % To 0.05% by mass to 15% by mass of the radical photopolymerization initiator (b3) component: solvent

Still another embodiment of the present invention is the step of applying a composition containing the following component (a1) and the component (a2) onto a substrate, the above-mentioned composition comprising the component (a1) and the component (a2). A step of press-bonding the base material to the master mold, exposing the composition containing the following component (a1) and component (a2) through the base material while pressing the master mold to the base material, and photocuring the composition. And the step of photo-curing, the step of releasing the cured product obtained on the base material from the master mold to form an A layer, and the following components (b1) to (b3) on the A layer. A step of applying a composition containing the components, and a composition containing the components (b1) to (b3) below is baked at 40° C. to 200° C. and then exposed to form the B layer adhered to the A layer. The method for producing an imprint replica mold including the step of:
Component (a1): Compound having at least one radical-polymerizable group in one molecule (a2) Component: 0.1% by mass to 1% by mass of photoradical polymerization initiator based on 100% by mass of the component (a1). Component (b1): a compound composed of a linear or chain molecular chain containing a fluorine atom and having a radical polymerizable group at all terminals of the molecular chain (b2) component: 100 mass of the component (b1) % To 0.05% by mass to 15% by mass of the radical photopolymerization initiator (b3) component: solvent

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

The imprint replica mold of the present invention can be produced on any 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 an optical member such as a solid-state imaging device and a lens for a sensor, which is required to have a high shape accuracy.

[Component (a1)]
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 as 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( (Meth)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, methoxypolyethylene glycol #400 (meth)acrylate, methoxypolyethylene glycol #600 (meth)acrylate, methoxypolyethylene 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-methacrylpropyl acrylate 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, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxy Trimethylolpropane tri(meth)acrylate, ethoxylated glycerin tri(meth)acrylate, propoxylated glycerin tri(meth)acrylate, tris-(2-(meth)acryloyloxyethyl)isocyanurate, caprolactone modified tris-(2- (Meth)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)acrylate Rate, ditrimethylolpropane tetra(meth)acrylate, ethoxylated ditrimethylolpropane tetra(meth)acrylate, propoxylated ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol poly(meth)acrylate , Ethoxylated dipentaerythritol poly(meth)acrylate, propoxylated dipentaerythritol poly(meth)acrylate, ethoxylated polyglycerin poly(meth)acrylate.

The compound of the component (a1) is available as a commercial product, and specific examples thereof include light ester M, the same E, the same NB, the same IB, the same TB, the same EH, the same IB-X and the same CH, Light acrylate IB-XA (manufactured by Kyoeisha Chemical Co., Ltd.), 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 (above, Osaka Organic Chemistry) Industrial, 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 Co., Ltd.), Fancryl (registered trademark) FA-513AS, FA-512AS, FA-511AS (above, Hitachi Chemical Co., Ltd.), New Frontier (registered trademark) HBPE-4, HBPEM-10 (above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), KAYARAD (registered trademark) PET-30, DPHA, DPEA-12 (above, Nippon Kayaku Co., Ltd. ) Made). The component (a1) may be used alone or in combination of two or more.

[Component (a2)]
The photoradical polymerization initiator of the component (a2) is not particularly limited as long as it has absorption in the light source used during photocuring of the composition for forming the layer A of the replica mold for imprint of the present invention. Not a thing. Examples of the radical photopolymerization initiator of the component (a2) include tert-butylperoxy-iso-butyrate, 2,5-dimethyl-2,5-bis(benzoyldioxy)hexane and 1,4-bis[α- (Tert-Butyldioxy)-iso-propoxy]benzene, di-tert-butylperoxide, 2,5-dimethyl-2,5-bis(tert-butyldioxy)hexene hydroperoxide, α-(iso-propylphenyl)-iso- Propyl hydroperoxide, tert-butyl hydroperoxide, 1,1-bis(tert-butyldioxy)-3,3,5-trimethylcyclohexane, butyl-4,4-bis(tert-butyldioxy)valerate, cyclohexanone peroxide, 2,2 ',5,5'-Tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-Tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-Tetra(tert -Amylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-hexylperoxycarbonyl)benzophenone, 3,3'-bis(tert-butylperoxycarbonyl)-4,4'-dicarboxybenzophenone, Organic peroxides such as tert-butylperoxybenzoate and di-tert-butyldiperoxyisophthalate; such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone and 1,2-benzanthraquinone Quinones; benzoin methyl, benzoin ethyl ether, α-methylbenzoin, α-phenylbenzoin and other benzoin derivatives; 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenyl ketone, 2- Hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy- 1-[4-{4-(2-hydroxy-2-methylpropionyl)benzyl}-phenyl]-2-methylpropan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1-[4- (Methylthio)phenyl]-2-morpholinopropan-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)-butan-1-one; bis( Acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyl)-phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; 2-(O-benzoyloxime)-1-[4-( Oxime esters such as phenylthio)phenyl]-1,2-octanedione and 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone System compounds.

The photoradical polymerization initiator of the component (a2) is available as a commercial product, and specific examples thereof include IRGACURE (registered trademark) 651, 184, 500, 2959, 127, 754, 907, 369, 379, 379EG, 819, 819DW, 1800, 1870, 784, OXE01, OXE02, 250, 1173, MBF, 4265, TPO (above, BASF Japan Ltd.), KAYACURE (registered trademark) DETX, MBP, DMBI, EPA, OA (Nippon Kayaku Co., Ltd.), VICURE-10, 55 (above, STAUFFER Co.). Ltd.), ESACURE (registered trademark) KIP150, TZT, 1001, KTO46, KB1, KL200, KS300, EB3, triazine-PMS, triazine A, triazine B (above, manufactured by Nippon Sibel Hegner Co., Ltd.). ), Adeka optomer N-1717, N-1414 and N-1606 (manufactured by ADEKA Corporation). The component (a2) may be used alone, or two or more kinds may be mixed and used. The content ratio of the photo radical 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).

[Component (b1)]
The component (b1) is a compound having a radically polymerizable group at every end 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 as 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, 2,2,3,3,4,4,4-hepta Fluorobutyl (meth)acrylate, 1H,1H-pentadecafluoro-n-octyl (meth)acrylate, 1H,1H,2H,2H-tridecafluorooctyl acrylate, 1,6-bis((meth)acryloyloxy)- 2,2,3,3,4,4,5,5-octafluorohexane may be mentioned.

The above compounds are available as commercial products, and specific examples thereof include 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3- 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-hydroxypropyl meta 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, (above, Daikin Industries ( Ltd.), 2,2,3,3-tetrafluoropropyl acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,3,3,4,4,4-heptafluorobutylmethacrylate Acrylate, 1H,1H-pentadecafluoro-n-octyl acrylate, 1,6-bis(acryloyloxy)-2,2,3,3,4,4,5,5-octafluorohexane (above, Tokyo Chemical Industry Co., Ltd.), LINC-151EPA, LINC-152EPA, LINC-102A, LINC-2 A, LINC-5A, LINC-162A, LINC-3A (all manufactured by Kyoeisha Chemical Co., Ltd.), FLUOROLINK (registered trademark) MD500, same MD700, same MD40, same MD1700, FOMBLIN (registered trademark) MT70 (above, Solvay) And manufactured by Viscoat 13F (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

The component (b1) has urethane groups at all terminals of a linear or chain molecular chain containing the group represented by the formula (1) and the group represented by the formula (2a) or the formula (2b). It may be a polyfunctional (meth)acrylate compound having a polymerizable group containing a group represented by the formula (3), that is, a (meth)acryloyloxy group, through a bond. Here, the polyfunctional (meth)acrylate compound is a bifunctional or higher functional acrylate compound or methacrylate compound excluding the monofunctional (meth)acrylate compound. The urethane bond means a structure represented by —NH—C(═O)—O—. The polyfunctional (meth)acrylate compound has 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 molecular chain is not particularly limited as long as it is a molecular chain containing the group represented by the formula (1) and the group represented by the formula (2a) or the formula (2b). In the above-mentioned 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 number is not particularly limited. Further, in the above linear or chain molecular chain, the group represented by the formula (1) and the group represented by the formula (2a) or the formula (2b) may be bonded by a single bond (direct bond). Alternatively, they may be bonded via a structure (linking group) such as an alkylene group having 1 to 3 carbon atoms, a perfluoroalkylene group having 1 to 3 carbon atoms, or a combination thereof.

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

From the viewpoint of enhancing the mold releasability of the mold, the groups represented by the formula (1) include -(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 formula (1), -(OCF ₂ )- and -(OCF ₂ CF ₂ )- are molar ratio [-(OCF ₂ )-]: [-(OCF ₂ CF ₂ ). It is preferable that the group is contained in a ratio of −]=2:1 to 1:2, and it is more preferable that the group is contained in a ratio of about 1:1. These bonds may be block bonds or random bonds. The repeating number 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) is 1,000 to 5,000, preferably 1,500 to 3,000. is there.

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

The group represented by the formula (2a) is, for example, a poly(oxyethylene) group. The repeating number 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 in the range of 7 to 12. The range is.

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

The polymerizable group containing a (meth)acryloyloxy group is not limited to having one (meth)acryloyloxy group, and may have two or more. Examples of the polymerizable group containing a (meth)acryloyloxy group include structures (terminal groups) represented by the following formulas [X1] to [X5], and acryloyloxy groups in these structures (terminal groups). And 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, the following structural formula (A- Preferred examples are the compound represented by 1), the compound represented by (A-2) and the compound represented by (A-3), and the compound in which the acryloyloxy group in these compounds is substituted with a methacryloyloxy group. Can be mentioned as. In the structural formulas below, two X's or four X's each represent one of the structures (terminal groups) represented by the above formulas [X1] to [X5], and PFPE is poly(oxyperfluoro). Alkylene) group, q ₁ and q ₂ each independently represent the number of oxyethylene groups, for example, an integer of 2 to 15, preferably an integer of 2 to 12, or an integer of 5 to 12, 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. The structure (terminal group) represented by the above formulas [X3] to [X5] is preferable, which has two or more groups.

The component (b1) may be used alone or in combination of two or more. The component (b1) is preferably 0.1% by mass based on 100% by mass of the total amount of the component (b1) and the components (b2), (b3) described below and other additives which are optional components. It is desirable to use it in an amount of 10 to 10% by mass, more preferably 0.5 to 8% by mass.

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

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

The composition for forming the layer B of the replica mold for imprinting of the present invention is, in addition to the component (b1), a group represented by the formula (1) and the formula (2a) or the formula (2b). Having a polymerizable group containing a (meth)acryloyloxy group through a urethane bond only at a part of the terminal of a linear or chain molecular chain containing a group represented by A compound having a hydroxy group at the other end of its molecular chain (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 not having the above-mentioned polymerizable group may be contained. The composition for forming the B layer may be referred to as a release agent.

[Component (b2)]
The photoradical polymerization initiator of the component (b2) is not particularly limited as long as it has absorption in the light source used during photocuring of the composition for forming the layer B of the replica mold for imprint of the present invention. Not a thing. Examples of the component (b2) include the same radical photopolymerization initiator as the component (a2). The component (b2) may be used alone or in combination of two or more. The content ratio of the photo radical polymerization initiator of the component (b2) is 0.05% by mass to 15% by mass based on 100% by mass of the component (b1).

[Component (b3)]
The solvent which is 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, 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-decafluoro-3-methoxy-4-(tri Fluoromethyl)-pentane, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, 1,1,1,2,3,4,4,5,5,5-deca Fluoropentane, pentafluorononane, hexafluorobenzene, heptadecafluoro-n-octyl bromide, 1,1,1,3,3,3-hexafluoro-2-methoxypropane, octadecafluorooctane, octafluorocyclopentene, per Fluorotributylamine, perfluorodecalin, perfluorohexane, perfluoromethylcyclohexane, perfluoroheptane, octafluorotoluene, perfluorotripentylamine, perfluorotriethylamine, perfluoro(1,3-dimethylcyclohexane), perfluoroisohexane Is mentioned.

The solvent which is the component (b3) is available as a commercial product, and specific examples thereof include Novec (registered trademark) 7000, 7100, 7200, and 7300 (above, manufactured by 3M Japan Co., Ltd.). , ASAHIKLIN (registered trademark) AE-3000, AE-3100E (above, manufactured by AGC Corporation), Vertrel (registered trademark) XF, XF-UP, XE-XP, X-E10, X- P10, X-D, X-GY, MCA, SDG, SMT, SFR, DC, Cinera, Supraion, Psion (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 layer A of the replica mold for imprints 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 contain a surfactant, a chain transfer agent, and a photosensitizer, if necessary, as long as the effects of the present invention are not impaired. Sensitizers may be included.

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

Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, and other polyoxyethylene alkyl ethers, polyoxyethylene octylphenyl ether, polyoxyethylene. Polyoxyethylene alkylaryl ethers such as ethylene nonylphenyl ether, polyoxyethylene/polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan Sorbitan fatty acid esters such as tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc. Examples include nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters. The above-mentioned surfactant is available as a commercial product, and specific examples thereof include Ftop (registered trademark) EF301, EF303, EF352 (above, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megafac ( (Registered trademark) F-171, F-173, F-477, F-486, F-554, F-556, R-08, R-30, R-30N, R- 40, same R-40-LM, same RS-56, same RS-75, same RS-72-K, same RS-76-E, same RS-76-NS, same RS-78, same RS-90 ( As above, DIC Corporation's product, Florade FC430, the same FC431 (above, 3M Japan's product), Asahi Guard (registered trademark) AG710, Surflon (registered trademark) S-382, the same SC101, the same SC102, the same SC103. , SC104, SC105, SC106 (above, manufactured by AGC Co., Ltd.) and the like; and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-302, BYK-307, BYK. -322, BYK-323, BYK-330, BYK-333, BYK-370, BYK-375, BYK-378, BYK-UV 3500, BYK-UV 3570 (above, manufactured by BYK Japan KK) .. The above surfactants 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 surfactant, the content ratio thereof is 0.01 mass with respect to 100 mass% of the component (a1). % To 10% by mass is preferable.

Examples of the chain transfer agent include thiol compounds such as methyl mercaptoacetate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, 3-methoxybutyl 3-mercaptopropionate, and n-mercaptopropionate. Octyl, stearyl 3-mercaptopropionate, 1,4-bis(3-mercaptopropionyloxy)butane, 1,4-bis(3-mercaptobutyryloxy)butane, trimethylolethane tris(3-mercaptopropionate) , Trimethylolethane tris(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptopropionate), Pentaerythritol tetrakis(3-mercaptobutyrate), dipentaerythritol hexakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptobutyrate), tetraethylene glycol bis(3-mercaptopropionate) , Tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, tris[2-(3-mercaptobutyryloxy)ethyl]isocyanurate, 1,3,5-tris(3-mercaptobutyryloxyethyl) Mercaptocarboxylic acid esters such as -1,3,5-triazine-2,4,6-(1H,3H,5H)-trione; ethanethiol, 2-methylpropane-2-thiol, 1-dodecanethiol, 2 ,3,3,4,5,5-hexamethylhexane-2-thiol (tert-dodecanethiol), ethane-1,2-dithiol, propane-1,3-dithiol, benzylthiol and other alkylthiols; benzene Aromatic thiols such as thiol, 3-methylbenzenethiol, 4-methylbenzenethiol, naphthalene-2-thiol, pyridine-2-thiol, benzimidazol-2-thiol, benzothiazole-2-thiol; 2-mercaptoethanol , 4-mercapto-1-butanol and other mercapto alcohols; 3-(trimethoxysilyl)propane-1-thiol, 3-(triethoxysilyl)propane-1-thiol and other silane-containing thiols; bis(2- Mercaptoethyl) ether, and as a disulfide compound, Didisulfide, dipropyl disulfide, diisopropyl disulfide, dibutyl disulfide, di-tert-butyl disulfide, dipentyl disulfide, diisopentyl disulfide, dihexyl disulfide, dicyclohexyl disulfide, didecyl disulfide, bis(2,3,3,4,4,4) Alkyl disulfides such as 5-hexamethylhexan-2-yl)disulfide (di-tert-dodecyldisulfide), bis(2,2-diethoxyethyl)disulfide, bis(2-hydroxyethyl)disulfide and dibenzyldisulfide; Aromatic disulfides such as diphenyl disulfide, di-p-tolyl disulfide, di(pyridin-2-yl)pyridyl disulfide, di(benzimidazol-2-yl)disulfide, di(benzothiazol-2-yl)disulfide; tetra Examples include thiuram disulfides such as methyl thiuram disulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, and bis(pentamethylene) thiuram disulfide; α-methylstyrene dimer. This chain transfer agent can be used alone or in combination of two or more. 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 with respect to 100 mass% of the component (a1). % To 20% by mass is preferable.

Examples of the photosensitizer include thioxanthene type, thioxanthone type, xanthene type, ketone type, thiopyrylium salt type, base styryl type, merocyanine type, 3-substituted coumarin type, 3,4-substituted coumarin type, cyanine type , Acridine-based, thiazine-based, phenothiazine-based, anthracene-based, coronene-based, benzanthracene-based, perylene-based, ketocoumarin-based, coumarin-based, and borate-based. The photosensitizer is commercially available, and specific examples thereof include Anthracure (registered trademark) UVS-581, UVS-1331 (all manufactured by Kawasaki Kasei Kogyo Co., Ltd.), and KAYACURE (trade name). Registered trademark) DETX-S (manufactured by Nippon Kayaku Co., Ltd.). This photosensitizer can be used alone or in combination of two or more. The absorption wavelength in the UV region can be adjusted by using the above-mentioned photosensitizer. When the composition for forming the A layer and the composition for forming the B layer contain the photosensitizer, the content ratio is 100 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 imprint 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 as necessary may be mixed so that the composition is in a uniform state. .. In the case of the composition for forming the B layer, for example, the component (b1), the component (b2), the component (b3) and, if necessary, other additives are mixed to obtain a uniform composition. It should be. The order of mixing the respective components of the composition for forming the A layer and the composition for forming the B layer is not particularly limited as long as a uniform composition can be obtained, and is not particularly limited.

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

The layer A of the replica mold for imprint of the present invention is obtained by applying a composition containing the above-mentioned components (a1) and (a2) onto a base material or a master mold, and bonding the base material and the master mold together. Then, the desired structure can be obtained by photo-curing and releasing. The method of applying the composition containing the component (a1) and the component (a2) is a known or well-known method, for example, a potting method, a spin coating method, a dipping method, a flow coating method, an inkjet method, a spray method, a bar coating method. Method, gravure coating method, slit coating method, roll coating method, transfer printing method, brush coating, blade coating method, and air knife coating method.

Examples of the base material on which the layer A of the imprint replica mold of the present invention is formed include silicon, glass (ITO substrate) on which indium tin oxide (ITO) is formed, and silicon nitride (SiN). Film-formed glass (SiN substrate), indium zinc oxide (IZO) film-formed glass, polyethylene terephthalate (PET), triacetyl cellulose (TAC), acrylic, plastic, glass, quartz, ceramics, etc. Can be mentioned. Further, a flexible base material having flexibility, for example, 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 base material composed of naphthalate, polyether sulfone, and a copolymer obtained by combining these polymers.

The light source to be photo-cured to form the A layer of the replica mold for imprint of the present invention is not particularly limited, but examples thereof include a high pressure mercury lamp, a low pressure mercury lamp, an electrodeless lamp, a metal halide lamp, a KrF excimer laser, and an ArF. Examples include excimer laser, F ₂ excimer laser, electron beam (EB), extreme ultraviolet (EUV), and ultraviolet LED (UV-LED). As the wavelength of the light source, generally, 436 nm G line, 405 nm H line, 365 nm I line, or 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, at least one of the coating film before light irradiation and the photocured product obtained after light irradiation is used for the purpose of evaporating the solvent. A baking step may be added. The equipment used in the baking step is not particularly limited, and for example, baking is performed using a hot plate, an oven, a furnace in a suitable atmosphere, that is, in the atmosphere, an inert gas such as nitrogen, or a vacuum. Anything can be used. The baking temperature is not particularly limited as long as it can achieve the purpose of evaporating the solvent, but for example, it can be performed at 40°C to 200°C.

The apparatus for performing the optical imprint is not particularly limited as long as the target pattern is obtained, but examples thereof include ST50 manufactured by Toshiba Machine Co., Ltd., Sindre (registered trademark) 60 manufactured by Obducat, and NM manufactured by Meisho Kiko Co., Ltd. A method in which a base material and a master mold are pressure-bonded with a commercially available device such as −0801HB and the cured product is released from the master mold after photocuring can be used.

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

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

The layer B of the imprint replica mold of the present invention has a desired coating formed by applying a composition containing the component (b1), the component (b2) and the component (b3) onto the layer A and photocuring the composition. Obtainable. The method of applying the composition containing the component (b1), the component (b2) and the component (b3) is a known or well-known method, for example, a potting method, a spin coating method, a dipping method, a flow coating method, an inkjet method, The spray method, the bar coating method, the gravure coating method, the slit coating method, the roll coating method, the transfer printing method, the brush coating, the blade coating method, and the air knife coating method can be mentioned.

The light source to be photo-cured 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, ArF. Examples include excimer laser, F ₂ excimer laser, electron beam (EB), extreme ultraviolet (EUV), and ultraviolet LED (UV-LED). As the wavelength of the light source, generally, 436 nm G line, 405 nm H line, 365 nm I line, or 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 replica mold for imprint 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 step is not particularly limited, and for example, using a hot plate, an oven, or a furnace, in a suitable atmosphere, that is, in the atmosphere, an inert gas such as nitrogen, or in a vacuum. Anything that can be baked may be used. The baking temperature in the baking step may be, for example, 40° C. to 200° C. at which the solvent can be evaporated.

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 in the order of nanometer, micrometer, or millimeter.

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 equipment and conditions used for the analysis of the physical properties of the compound obtained in the following synthesis example are as follows.

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

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

<Synthesis example 1>
178.84 g of PGMEA was put into a 2 L four-necked flask, and the mixture was stirred under a nitrogen atmosphere at an internal temperature of 80°C. Here, 120 g of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), isobornyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 249.66 g, AIBN (manufactured by Kanto Chemical Co., Ltd.) 5.904 g, and PGMEA 697. A solution obtained by mixing 48 g was added dropwise over 2 hours, and after the addition, reaction was performed for 17 hours. 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 reduced pressure of 133.3 Pa to obtain 330.4 g of 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>
An eggplant flask was charged with 10.5 g (5 mmol) of PFPE1, 2.39 g (10.0 mmol) of BEI, 0.129 g of DBTDL and 12.9 g of MEK. The mixture in the eggplant flask was stirred with a stirrer chip at room temperature (about 23° C.) for 24 hours to obtain a reaction product. To this reaction product, 30.37 g of PGMEA was added, and MEK was distilled off by an evaporator to obtain a PGMEA solution containing SM1 as the component (b1) 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>
An eggplant flask was charged with 10.5 g (5 mmol) of PFPE1, 2.39 g (10.0 mmol) of BEI, 0.0644 g of DOTDD and 12.9 g of PGMEA. The mixture in the eggplant flask was stirred at room temperature (about 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 the component (b1) at a solid content of 20% by mass. The weight average molecular weight Mw of the obtained SM2 measured by GPC in terms of polystyrene was 3,410, and the dispersity: Mw (weight average molecular weight)/Mn (number average molecular weight) was 1.1.

<Synthesis example 4>
An eggplant flask was charged with 11.45 g (5 mmol) of PFPE2, 4.79 g (20.0 mmol) of BEI, 0.162 g of DOTDD and 16.24 g of MEK. The mixture in the eggplant flask was stirred under a nitrogen atmosphere with a stirrer chip at room temperature (about 23° C.) for 72 hours to obtain a reaction product. 64.96 g of PGMEA was added to this reaction product, and MEK was distilled off by an evaporator to obtain a PGMEA solution containing SM3 as the component (b1) at a solid content of 20% by mass. The weight average molecular weight Mw of the obtained SM3 measured by GPC in terms of polystyrene was 2,750, and the dispersity: Mw (weight average molecular weight)/Mn (number average molecular weight) was 1.1.

<Synthesis example 5>
An eggplant flask was charged with 11.45 g (5 mmol) of PFPE2, 4.79 g (20.0 mmol) of BEI, 0.162 g of DOTDD and 16.24 g of PGMEA. The mixture in the eggplant flask was stirred under a nitrogen atmosphere with a stirrer chip at room temperature (about 23° C.) for 72 hours to obtain a reaction product. To this reaction product, 48.72 g of PGMEA was added to obtain a PGMEA solution containing SM4 as the 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 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 this specification) 7 g, KAYARAD (registered trademark) PET-30 (Nippon Kayaku) 3 g of IRGACURE (registered trademark) 184 (manufactured by BASF Japan Ltd.) (hereinafter referred to as “IRGACURE 184”). 0.01 g (0.1% by mass relative to the total mass of HBPE-4 and PET-30) was added to prepare Composition A1.

<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, and the composition A3 was added. 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 relative to the total mass of HBPE-4 and MI55) were added, and the composition A4 was added. 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 Co., Ltd.), and 0.01 g of IRGACURE 184 (HBPE -4, 0.1% by mass relative to the total mass of A-DOG) was added to prepare a composition A5.

<Preparation Example 6>
7 g of PET-30, 1.5 g of NK Ester A-200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), 1.5 g of A-DOG, and 0.01 g of IRGACURE 184 (PET-30, A-200, 0.1% by mass based on the total mass of A-DOG) was added to prepare a composition A6.

<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 Co., Ltd.), and 0.01 g of IRGACURE 184 (HBPE -4, 0.1% by mass relative to the total mass of A-DCP) was added to prepare a 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 and 1-ADMA), Composition A8 was prepared.

<Preparation Example 9>
5 g of A-DCP, 1-ADMA (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and 0.5 g of IRGACURE 184 (A-DCP, 5% by mass relative to the total mass of 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 LINC-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 (stock) Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide) (hereinafter, abbreviated as “IRGACURE 819” in the present specification), and PGMEA (8.44 g) are mixed to form a composition. The product (release agent) B1 was prepared.

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

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

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

<Preparation Example 14>
A 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 a 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) A composition (release agent) B6 was prepared by mixing 0.0060 g of propionyl)benzyl}-phenyl]-2-methylpropan-1-one) and 7.67 g of PGMEA as the component (C).

<Preparation Example 16>
1.00 g of the 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, referred to as "DETX- S)) and 4.80 g of PGMEA were mixed to prepare a composition (release agent) B7.

<Preparation Example 17>
A 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>
A 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. ..

[Preparation of replica mold for imprint]
<Example 1>
The composition A1 obtained in Preparation Example 1 was release-treated in advance with NOVEC (registered trademark) 1720 (manufactured by 3M Japan Co., Ltd.) (hereinafter, abbreviated as “NOVEC 1720” in this specification). Nanoimprinting device NM-0801HB (manufactured by Meisho Kiko Co., Ltd.) by potting on a mold (15 concave lenses of 2 mm diameter × 300 μm depth arranged in 3 rows × 5 rows) and covering it with a quartz glass substrate. ) Was used for optical imprint. The optical imprint is always 23° C., a) pressurizing to 500 N for 10 seconds, b) exposing to 5000 mJ/cm ² using a high-pressure mercury lamp, c) depressurizing for 10 seconds, and d) nickel. The mold and the quartz glass substrate were separated and released from the mold, 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 subjected to adhesion treatment by heating on a hot plate at 150° C. for 5 minutes. The composition (release agent) B1 obtained in Preparation Example 10 was formed on the obtained layer A by a spin coater, and baked at 80° C. for 5 minutes using a hot plate. Then, under a nitrogen atmosphere, a batch type UV irradiation device (high pressure mercury lamp 2 kW x 1 lamp) (manufactured by Eye Graphics Co., Ltd.) was used to pass an i-line transmission filter, and UV exposure was performed at 40 mW/cm ² for 125 seconds. A layer B was formed on the layer A to prepare an imprint replica mold RM-1.

<Example 2>
Replica mold for imprinting was performed 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 was performed 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 was carried out 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 made.

<Example 5>
Replica mold for imprinting was performed 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 was carried out 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 made.

<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 obtained as 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 obtained as 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 obtained as 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 obtained as 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 obtained as 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 obtained as 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 obtained as 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>
A 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. NOVEC 1720 was spin-coated on the obtained layer A and heated on a hot plate at 150° C. for 5 minutes to prepare an imprint replica mold RM-19.

<Comparative example 2>
A 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 imprint.

<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. An imprint replica mold RM-21 was produced in the same manner as in Example 1 except that the release agent was changed to B2.

[Preparation of imprint material]
5 g of NK ester A-DOG (manufactured by Shin-Nakamura Chemical Co., Ltd.) and 5 g of a radical-polymerizable group-containing polycarbonate ETERNACOLL (registered trademark) UM-90 (1/3) DA (manufactured by Ube Industries, Ltd.) were mixed. Then, 0.2 g of IRGACURE 184 was added to the mixture to prepare an imprint material.

[Fabrication of concave lens pattern using replica mold for imprint]
The prepared imprint material was potted onto a quartz glass substrate that had been subjected to a contact treatment by the method described in Example 1, and the imprint obtained in each of Examples 1 to 16 and Comparative Examples 1 to 3 was formed thereon. A replica mold for printing was covered, and optical imprint was performed using a nanoimprint apparatus NM-0801HB (manufactured by Meisho Kiko Co., Ltd.). The optical imprint is always 23° C. under conditions of a) pressurizing to 500 N for 10 seconds, b) exposing to 5000 mJ/cm ² using a high pressure mercury lamp, c) depressurizing for 10 seconds, and d) replica. The mold and the quartz glass substrate were separated and released in a sequence to obtain a concave lens pattern on the quartz glass substrate. Using an industrial microscope ECLIPSE L150 (manufactured by Nikon Corporation), the presence or absence of peeling or cracking of the obtained concave lens pattern was observed. The results are shown in Tables 1 and 2.

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

[Measurement of the number of times imprinting can be repeated]
Using each of the imprint replica molds obtained in Examples 1 to 16 and Comparative Examples 1 to 3, the same optical imprint as described above was repeated up to 10 times and 2 mm diameter×300 μm. The number of optical imprints was measured until the concave lens-shaped pattern of depth was not formed. The obtained results are shown in Tables 1 and 2.

From the results shown in Tables 1 and 2, neither cracking nor peeling was observed in the concave lens patterns produced using the imprint replica molds produced in Examples 1 to 16. The imprint replica molds produced in Examples 1 to 16 were all capable of repeating imprinting eight times or more. Further, the imprint replica molds produced in Examples 1 to 16 all had a transmittance at 365 nm of 80% or more, and high transparency in the ultraviolet region was confirmed. On the other hand, peeling was observed in the concave lens patterns produced using the imprint replica molds produced in Comparative Examples 2 and 3. The imprint replica molds produced in Comparative Example 1 and Comparative Example 2 were capable of repeating imprint once or 0 times. Further, the replica mold for imprint produced in Comparative Example 3 had a transmittance of less than 80% at a wavelength of 365 nm.

From the above results, the imprint replica mold of the present invention has high transparency in the ultraviolet region, and repeated imprints are possible. Further, the pattern produced by using the replica mold for imprint has no cracking or peeling.

Claims (13)

1. A replica mold for imprinting, which comprises the following A layer and the following B layer adhered to the A layer.
   Layer A: Structure (a1) component comprising a cured product of a composition containing the following (a1) component and (a2) component: Compound (a2) component having at least one radically polymerizable group in one molecule: the above ( a1) 0.01 mass% to 0.3 mass% of photoradical polymerization initiator B layer relative to 100 mass% of the component: a film composed of a cured product of a composition containing the following (b1) component and (b2) component ( Component b1): a compound having a linear or chain molecular chain containing a fluorine atom and having radically polymerizable groups at all terminals of the molecular chain (b2) component: 100% by mass of the component (b1) To 0.05 mass% to 15 mass% of photoradical polymerization initiator
2. The compound of the component (b1) is a compound represented by the following formula (1) and all terminals of the linear or chain molecular chain containing a group represented by the following formula (2a) or formula (2b). The replica mold for imprint 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 carbon atom having 2 or 3 carbon atoms. Represents a hydrogen group, * represents a bond for bonding to the —O— group of the urethane bond, p and q represent the number of repeating groups of the formula (1) and the formula (2a), respectively. Represents a repeating number of a group represented by 2 and independently represents an integer of 2 or more, and R ³ represents a methyl group or a hydrogen atom.)
3. The imprint replica mold according to claim 2, wherein q, which represents the number of repetitions of the group represented by the formula (2a), is an integer of 5 to 12.
4. The replica mold for imprint according to claim 2 or 3, wherein the group represented by the formula (2a) is a poly(oxyethylene) group.
5. The imprinting 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.
6. The replica mold for imprint according to claim 1, wherein the compound of the component (b1) is a macromonomer or a polymer having a weight average molecular weight of 1,000 to 30,000.
7. The replica mold for imprints according to any one of claims 1 to 6, wherein the composition containing the component (b1) and the component (b2) further contains a photosensitizer.
8. The component (a1) contains at least two kinds of compounds, and at least one kind of the two kinds of compounds is a compound having at least two (meth)acryloyloxy groups in one molecule. The replica mold for imprint described in.
9. The replica mold for imprinting 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 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 are each independently Represents a hydrogen atom or a methyl group, and r ¹ and r ² each independently represent an integer of 1 to 5.)
10. The replica mold for imprint according to claim 1, wherein the A layer has a lens-shaped inverted pattern.
11. 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.
12. A step of applying a composition containing the following component (a1) and component (a2) onto a master mold,
    A step of pressure-bonding the master mold to a substrate through a composition containing the following component (a1) and component (a2),
    A step of exposing the composition containing the following component (a1) and component (a2) through the base material while keeping the master mold pressed against the base material, and photocuring the composition;
    After the photo-curing step, a step of releasing the cured product obtained on the base material from the master mold to form an A layer,
    A step of applying a composition containing the following components (b1) to (b3) on the layer A, and a composition containing the following components (b1) to (b3) are baked at 40° C. to 200° C., and then And a step of forming the B layer adhered to the A layer by exposure to light.
    Component (a1): Compound having at least one radical-polymerizable group in one molecule (a2) Component: 0.1% by mass to 1% by mass of photoradical polymerization initiator based on 100% by mass of the component (a1). Component (b1): a compound composed of a linear or chain molecular chain containing a fluorine atom and having a radical polymerizable group at all terminals of the molecular chain (b2) component: 100 mass of the component (b1) % To 0.05% by mass to 15% by mass of the radical photopolymerization initiator (b3) component: solvent
13. A step of applying a composition containing the following component (a1) and component (a2) onto a substrate,
    A step of pressure-bonding the base material to a master mold through a composition containing the following component (a1) and component (a2),
    A step of exposing the composition containing the following component (a1) and component (a2) through the base material while keeping the master mold pressed against the base material, and photocuring the composition;
    After the photo-curing step, a step of releasing the cured product obtained on the base material from the master mold to form an A layer,
    A step of applying a composition containing the following components (b1) to (b3) on the layer A, and a composition containing the following components (b1) to (b3) are baked at 40° C. to 200° C., and then And a step of forming the B layer adhered to the A layer by exposure to light.
    Component (a1): Compound having at least one radical-polymerizable group in one molecule (a2) Component: 0.1% by mass to 1% by mass of photoradical polymerization initiator based on 100% by mass of the component (a1). Component (b1): a compound composed of a linear or chain molecular chain containing a fluorine atom and having a radical polymerizable group at all terminals of the molecular chain (b2) component: 100 mass of the component (b1) % To 0.05% by mass to 15% by mass of the radical photopolymerization initiator (b3) component: solvent