JP6997417B2 - Replica mold material for imprint - Google Patents

Description

The present invention relates to a replica mold material for imprinting and a replica mold having a pattern made from the material. More specifically, the replica mold material has a small shrinkage rate at the time of curing (hereinafter, abbreviated as "curing shrinkage rate" in the present specification), and even a thick film maintains high transparency in the ultraviolet region. Further, it relates to a replica mold having a pattern, which has a high Young's modulus. As used herein, the term "thick film" refers to a film having a thickness of 0.01 mm or more and a maximum thickness of 2.0 mm.

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

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

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

However, the commonly used replica mold material has a low transmittance of UV light used in the manufacturing process of a resin lens, particularly a wavelength of 365 nm, and a high curing shrinkage rate at the time of curing the replica mold material. Therefore, there are problems such as poor curing of the resin lens material, a long photocuring process, and low reproducibility of the pattern shape of the master mold. In addition, the replica mold has a high Young's modulus in order to reduce the mold release force from the master mold when manufacturing the replica mold and the mold release force when molding the resin lens material using the manufactured replica mold. You will need it.

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

As described above, there is still no replica mold material that can be used for producing a replica mold for molding a lens for a camera module, exhibits a low curing shrinkage rate at the time of curing, and has a high transparency and a high Young's modulus of the cured product. Its development was desired. The present invention has been made in view of such circumstances, and exhibits a low curing shrinkage rate at the time of curing, the cured product has high transparency and Young's modulus, and a replica mold for wafer level molding is produced. It is an object of the present invention to provide a replica mold material suitable for this purpose, and a replica mold having a pattern made from the replica mold material.

As a result of diligent studies to solve the above problems, the present inventors have found that a compound having an alkylene oxide-modified hydrogenated bisphenol A skeleton and having polymerizable groups at both ends is contained in one molecule (meth). ) By using a compound having 2 to 4 acryloyloxy groups and a material containing a photopolymerization initiator as a replica mold material, the following findings were obtained, and the present invention was made. That is, the imprint replica mold material of the present invention has high transparency in the ultraviolet region after optical imprinting with a thick film, and has a low curing shrinkage rate and a high Young's modulus.

（式中、Ｒ^１及びＲ^２はそれぞれ独立に水素原子又はメチル基を表し、Ｒ^３及びＲ^４はそれぞれ独立に炭素原子数１乃至４のアルキレン基を表し、Ｒ^５及びＲ^６はそれぞれ独立に水素原子又はメチル基を表し、ｒ^１及びｒ^２はそれぞれ独立に１乃至５の整数を表す。）
（Ｂ）：下記式（２）で表される基を一分子中に２つ乃至４つ有する化合物（但し、前記式（１）で表されるジ（メタ）アクリレート化合物を除く。）

（式中、Ｘは単結合又は炭素原子数１乃至４のアルキレン基を表し、Ｒ^７は水素原子又はメチル基を表す。）
（Ｃ）：前記（Ａ）成分と前記（Ｂ）成分との合計１００質量％に対し、０．０１質量％乃至１質量％の光重合開始剤
第２観点として、
前記（Ａ）成分と前記（Ｂ）成分との合計１００質量％に対し、該（Ａ）成分を３０質量％乃至９０質量％含む、第１観点に記載のインプリント用レプリカモールド材料。
第３観点として、
前記（Ｂ）成分が下記式（３）で表される化合物と下記式（４）で表される化合物との混合体である、第１観点又は第２観点に記載のインプリント用レプリカモールド材料。

（式中、Ｒ^７は前記式（２）における定義と同義である。）
第４観点として、
前記（Ｂ）成分がエーテル結合を少なくとも１つ含む又はエーテル結合を含まない脂環構造を一分子中に１つ有し、かつ前記式（２）で表される基を一分子中に２つ有する化合物である、第１観点又は第２観点に記載のインプリント用レプリカモールド材料。
第５観点として、
前記（Ｂ）成分が下記式（５）で表される化合物である、第１観点、第２観点又は第４観点に記載のインプリント用レプリカモールド材料。

（式中、２つのＲ^７は前記式（２）における定義と同義である。）
第６観点として、
（Ｄ）成分としてチオール基を少なくとも１つ有する化合物をさらに含有する第１観点乃至第５観点のいずれか一に記載のインプリント用レプリカモールド材料。
第７観点として、
（Ｅ）成分として酸化防止剤をさらに含有する第１観点乃至第６観点のいずれか一に記載のインプリント用レプリカモールド材料。
第８観点として、
（Ｆ）成分として界面活性剤をさらに含有する第１観点乃至第７観点のいずれか一に記載のインプリント用レプリカモールド材料。
第９観点として、
第１観点至第８観点のいずれか一に記載のインプリント用レプリカモールド材料から作製された、パターンを有するインプリント用レプリカモールド。
第１０観点として、
前記パターンがレンズ形状の反転パターンである、第９観点に記載のインプリント用レプリカモールド。
第１１観点として、
前記インプリント用レプリカモールドの最大厚さが２．０ｍｍである、第９観点又は第１０観点に記載のインプリント用レプリカモールド。
第１２観点として、
第１観点乃至第８観点のいずれか一に記載のインプリント用レプリカモールド材料をマスターモールド上に塗布する工程、
前記レプリカモールド材料を介して前記マスターモールドを基材と圧着する工程、
前記マスターモールドを前記基材に圧着させたまま該基材を通して前記レプリカモールド材料を露光し、該レプリカモールド材料を光硬化する工程、及び
前記光硬化する工程の後、前記基材上に得られた光硬化物を前記マスターモールドから離型する工程、を含むインプリント用レプリカモールドの作製方法。
第１３観点として、
第１観点乃至第８観点のいずれか一に記載のインプリント用レプリカモールド材料を基材上に塗布する工程、
前記レプリカモールド材料を介して前記基材をマスターモールドと圧着する工程、
前記マスターモールドを前記基材に圧着させたまま該基材を通して前記レプリカモールド材料を露光し、該レプリカモールド材料を光硬化する工程、及び
前記光硬化する工程の後、前記基材上に得られた光硬化物を前記マスターモールドから離型する工程、を含むインプリント用レプリカモールドの作製方法に関する。That is, the present invention, as a first aspect,
A replica mold material for imprint containing the following components (A), (B) and (C).
(A): Di (meth) acrylate compound represented by the following formula (1)

(In the formula, R ¹ and R ² independently represent a hydrogen atom or a methyl group, R ³ and R ⁴ independently represent an alkylene group having 1 to 4 carbon atoms, and R ⁵ and R ⁶ are independent, respectively. Represents a hydrogen atom or a methyl group, and r ¹ and r ² each independently represent an integer of 1 to 5).
(B): A compound having 2 to 4 groups represented by the following formula (2) in one molecule (excluding the di (meth) acrylate compound represented by the formula (1)).

(In the formula, X represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R ⁷ represents a hydrogen atom or a methyl group.)
(C): As a second aspect of the photopolymerization initiator, 0.01% by mass to 1% by mass with respect to 100% by mass of the total of the component (A) and the component (B).
The replica mold material for imprint according to the first aspect, which contains 30% by mass to 90% by mass of the component (A) with respect to a total of 100% by mass of the component (A) and the component (B).
As a third point of view
The replica mold material for imprint according to the first aspect or the second aspect, wherein the component (B) is a mixture of a compound represented by the following formula (3) and a compound represented by the following formula (4). ..

(In the formula, R ⁷ has the same meaning as the definition in the above formula (2).)
As a fourth point of view
The component (B) has one alicyclic structure containing at least one ether bond or no ether bond in one molecule, and two groups represented by the formula (2) are contained in one molecule. The replica mold material for imprint according to the first aspect or the second aspect, which is a compound having.
As a fifth point of view
The replica mold material for imprint according to the first aspect, the second aspect or the fourth aspect, wherein the component (B) is a compound represented by the following formula (5).

(In the equation, the two R ^7s are synonymous with the definition in the equation (2).)
As a sixth point of view
(D) The replica mold material for imprint according to any one of the first aspect to the fifth aspect, further containing a compound having at least one thiol group as a component.
As a seventh point of view
(E) The replica mold material for imprint according to any one of the first aspect to the sixth aspect, further containing an antioxidant as a component.
As the eighth viewpoint
(F) The replica mold material for imprint according to any one of the first aspect to the seventh aspect, further containing a surfactant as a component.
As a ninth point of view
A replica mold for imprint having a pattern, which is produced from the replica mold material for imprint according to any one of the first aspect to the eighth aspect.
As a tenth point of view
The replica mold for imprint according to the ninth aspect, wherein the pattern is an inverted pattern of a lens shape.
As the eleventh viewpoint
The replica mold for imprint according to the ninth aspect or the tenth aspect, wherein the maximum thickness of the replica mold for imprint is 2.0 mm.
As a twelfth point of view
The step of applying the replica mold material for imprint according to any one of the first aspect to the eighth aspect on the master mold.
A step of crimping the master mold to a base material via the replica mold material,
Obtained on the substrate after a step of exposing the replica mold material through the substrate while the master mold is pressure-bonded to the substrate and photocuring the replica mold material, and a step of photocuring the material. A method for producing a replica mold for imprint, which comprises a step of removing the photo-cured product from the master mold.
As the thirteenth viewpoint
The step of applying the replica mold material for imprint according to any one of the first aspect to the eighth aspect on the substrate.
A step of crimping the base material to the master mold via the replica mold material,
Obtained on the substrate after a step of exposing the replica mold material through the substrate while the master mold is pressure-bonded to the substrate and photocuring the replica mold material, and a step of photocuring the material. The present invention relates to a method for producing a replica mold for imprint, which comprises a step of removing the photo-cured product from the master mold.

The replica mold material for imprint of the present invention contains a di (meth) acrylate compound represented by the above formula (1) and a compound having two to four (meth) acryloyloxy groups in one molecule. Thereby, the replica mold having a pattern made from the replica mold material has high transparency in the ultraviolet region even with a thick film and has a high Young's modulus.

Further, the replica mold material for imprint of the present invention can be photocured, and a part of the pattern does not peel off when peeled from the master mold. Since the replica mold material has a low curing shrinkage rate at the time of photocuring, a replica mold in which a desired pattern is accurately formed can be obtained. Therefore, good pattern formation is possible by performing optical imprinting using this replica mold.

Further, the replica mold material for imprint of the present invention can be formed on an arbitrary substrate, and the film formed on the substrate has high transparency in the ultraviolet region even if it is a thick film. Has a high Young's modulus. Therefore, the replica mold produced from the replica mold material for imprint of the present invention can be suitably used for manufacturing optical members such as solid-state image sensors and sensor lenses, which require shape accuracy.

Further, in the replica mold material for imprint of the present invention, the curing rate, the dynamic viscosity, and the film thickness can be controlled by changing the type and content ratio of the compound of the component (B). Therefore, the replica mold material for imprint of the present invention can be designed according to the type of device to be manufactured and the type of exposure process and baking process, and the process margin can be expanded. It can be suitably used.

（式中、Ｒ^１及びＲ^２はそれぞれ独立に水素原子又はメチル基を表し、Ｒ^３及びＲ^４はそれぞれ独立に炭素原子数１乃至４のアルキレン基を表し、Ｒ^５及びＲ^６はそれぞれ独立に水素原子又はメチル基を表し、ｒ^１及びｒ^２はそれぞれ独立に１乃至５の整数を表す。）[(A) component]
The compound of the component (A) is a di (meth) acrylate compound represented by the following formula (1).

(In the formula, R ¹ and R ² independently represent a hydrogen atom or a methyl group, R ³ and R ⁴ independently represent an alkylene group having 1 to 4 carbon atoms, and R ⁵ and R ⁶ are independent, respectively. Represents a hydrogen atom or a methyl group, and r ¹ and r ² each independently represent an integer of 1 to 5).

Examples of the di (meth) acrylate compound represented by the above formula (1) include ethoxy-modified hydrogenated bisphenol A diacrylate, ethoxy-modified hydrogenated bisphenol A dimethacrylate, propoxy-modified hydrogenated bisphenol A diacrylate, and propoxy-modified water. Additive 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 Examples thereof include diacrylate and ethoxy-modified hydrogenated bisphenol F dimethacrylate.

The di (meth) acrylate compound represented by the above formula (1) is available as a commercially available product, and specific examples thereof include New Frontier (registered trademark) HBPE-4 and HBPEM-10 (above, No. 1). (Manufactured by Kogyo Seiyaku Co., Ltd.).

The di (meth) acrylate compound of the component (A) can be used alone or in combination of two or more.

The content ratio of the component (A) in the replica mold material for imprint of the present invention is 30% by mass or more and 90% by mass or less based on the total mass of 100% by mass of the component (A) and the component (B) described later. It is preferably 30% by mass or more and 75% by mass or less. If the content ratio of the component (A) is less than 30% by mass, a low curing shrinkage rate cannot be obtained when the replica mold material for imprint is cured, and the content ratio of the component (A) is 90% by mass. If it exceeds, the cured product obtained from the replica mold material cannot obtain a high Young's modulus.

[(B) component]
The compound of the component (B) is a compound having two to four groups represented by the following formula (2) in one molecule (however, the di (meth) acrylate compound represented by the above formula (1) is excluded. ).

Examples of the compound of the component (B) include neopentyl glycol di (meth) acrylate, ethanediol di (meth) acrylate, 2-hydroxypropanediol di (meth) acrylate, and 1,4-butanediol di (meth). Acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, glycerin di (meth) acrylate, 3-methyl-1 , 5-Pentanediol di (meth) acrylate, hydroxypivalate neopentyl glycol acrylic acid adduct, 2-hydroxy-3-acryloyloxypropyl methacrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate , Polypropylene glycol di (meth) acrylate, 2-methacryloyloxyethyl acid phosphate, polymethylene glycol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, dioxane glycol diacrylate, 1,3-diacryloyl Oxyadamantan, pentaerythritol tri (meth) acrylate, trimethylol propanetri (meth) acrylate, glycerin tri (meth) acrylate, ethoxylated trimethylol propanetri (meth) acrylate, propoxylated trimethylol propanetri (meth) acrylate, ethoxy Glycerintri (meth) acrylate, Tri (meth) ethoxylated isocyanuric acid tri (meth) acrylate, ε-caprolactone-modified tris- (2- (meth) acryloxyethyl) isocyanurate, tris (meth) acryloyloxyethyl phosphate, dimethylolpropane Examples thereof include tetraacrylate, pentaerythritol tetraacrylate, and ethoxylated pentaerythritol tetraacrylate.

The compound of the component (B) is available as a commercially available product, and specific examples thereof include A-200, A-400, A-600, A-1000, 1G, 2G, 3G, 4G, and 9G. 14G, 23G, APG-100, APG-200, APG-400, APG-700, 3PG, 9PG, 701A, 701, A-HD-N, HD-N, A-NOD-N, NOD-N, A- DOD, DOD-N, A-DCP, DCP, A-DOG, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, TMPT, A-TMPT-3EO, A- GLY-3E, A-GLY-9E, A-GLY-20E, A-9300, A-9300-1CL, A-9300-3CL, A-9300-6CL, AD-TMP, A-TMMT, ATM-4E, ATM-35E (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Light Ester (registered trademark) P-2M, EG, 2EG, 3EG, 4EG, 9EG, 14EG, 1.4BG, 1.4BG NP, 1.6HX, 1.9ND, 1.10DC, G-101P, PTMGA-250, NP-A, MPD-A, 1.6HX-A, 1.9ND-A , DCP-A, HPP-A, G-201P, TMP-A, TMP-3EO-A, TMP-6EO-3A, PE-3A, PE-4A (above, Kyoeisha Chemical Co., Ltd. (Manufactured by Co., Ltd.), Diapurest (registered trademark) ADDA (above, manufactured by Mitsubishi Gas Chemicals Co., Ltd.), Viscort (registered trademark) # 195, # 230, # 260, # 310, # 335, same. # 295, # 300, # 400, # 360, # 3PA, # 3PMA (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), KAYARAD (registered trademark) NPGDA, PEG400DA, FM-400, R-604, R-684, GPO-303, TMPTA, THE-330, TPA-330, PET-30, T-1420 (T), RP-1040 (above, Japanese localization) (Made by Yakuhin Co., Ltd.).

The compound of the above component (B) can be used alone or in combination of two or more.

[(C) component]
The photopolymerization initiator as the component (C) is not particularly limited as long as it absorbs light from the light source used during photocuring of the replica mold material for imprinting of the present invention. For example, tert-butylperoxy-iso-butyrate, 2,5-dimethyl-2,5-bis (benzoyldioxy) hexane, 1,4-bis [α- (tert-butyldioxy) -iso-propoxy] benzene, di. -Tert-Butyl peroxide, 2,5-dimethyl-2,5-bis (tert-butyldioxy) hexene hydroperoxide, α- (iso-propylphenyl) -iso-propyl hydroperoxide, tert-butyl hydroperoxide, 1,1 -Bis (tert-butyldioxy) -3,3,5-trimethylcyclohexane, butyl-4,4-bis (tert-butyldioxy) peroxide, cyclohexanone peroxide, 2,2', 5,5'-tetra (tert-butylperoxy) Carbonyl) benzophenone, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (tert-amylperoxycarbonyl) benzophenone, 3,3', 4 , 4'-tetra (tert-hexylperoxycarbonyl) benzophenone, 3,3'-bis (tert-butylperoxycarbonyl) -4,4'-dicarboxybenzophenone, tert-butylperoxybenzoate, di-tert-butyldiperoxy Organic peroxides such as isophthalates; quinones such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone; benzoinmethyl, benzoinethyl ether, α-methyl Benzoin derivatives such as benzoin and α-phenylbenzoin; 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl- Propane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1- [4- {4- ( 2-Hydroxy-2-methyl-propionyl) benzyl} -phenyl] -2-methyl-propane-1-one, phenylglycylic acid methyl ester, 2-methyl-1- [4- (methylthio) phenyl] -2 -Morholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-dimethi Alkylphenone compounds such as luamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1-one; bis (2,4,6-trimethylbenzoyl)- Acylphosphine oxide compounds such as phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octane Examples thereof include oxime ester compounds such as dione, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] etanone.

The photopolymerization initiator is available as a commercially available product, and specific examples thereof include IRGACURE (registered trademark) 651, 184, 500, 2959, 127, 754, 907, 369, and so on. 379, 379EG, 819, 819DW, 1800, 1870, 784, OXE01, OXE02, 250, 1173, MBF, 4265, TPO (above, BASF Japan Co., Ltd.) ), KAYACURE (registered trademark) DETX, MBP, DMBI, EPA, OA (above, manufactured by Nippon Kayaku Co., Ltd.), VICURE-10, 55 (above, manufactured by STAUFFER Co. LTD), ESACURE ( Registered Trademarks) KIP150, TZT, 1001, KTO46, KB1, KL200, KS300, EB3, Triazine-PMS, Triazine A, Triazine B (all manufactured by Japan Sibel Hegner Co., Ltd.), ADEKA PTOMER N -1717, N-1414, N-1606 (all manufactured by ADEKA CORPORATION) can be mentioned.

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

The content ratio of the component (C) in the replica mold material for imprint of the present invention is, for example, 0.01% by mass to 1% by mass with respect to the total mass of the components (A) and (B) of 100% by mass. Yes, preferably 0.01% by mass to 0.5% by mass, and more preferably 0.05% by mass to 0.5% by mass. When the content ratio of the component (C) is less than 0.01% by mass, the replica mold material for imprint does not have sufficient curability, and therefore the patterning characteristics deteriorate, and the component (C) is contained. This is because if the proportion is more than 1% by mass, the cured product obtained from the replica mold material cannot have sufficient transparency in the ultraviolet region.

[(D) component]
Examples of the compound having at least one thiol group as a component (D) include methyl mercaptoacetate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, 3-methoxybutyl 3-mercaptopropionate, and 3 -N-octyl mercaptopropionate, stearyl 3-mercaptopropionate, 1,4-bis (3-mercaptopropionyloxy) butane, 1,4-bis (3-mercaptobutyryloxy) butane, trimethylol ethanetris (3) -Mercaptpropionate), Trimethylol ethanetris (3-mercaptobutyrate), Trimethylol propanetris (3-mercaptopropionate), Trimethylol propanetris (3-mercaptobutyrate), Pentaerythritol tetrakis (3- Mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakiss (3-mercaptopropionate), dipentaerythritol hexakiss (3-mercaptobutyrate), tris [2- (3) -Mercaptocarboxylic acid esters such as mercaptopropionyloxy) ethyl] isocyanurate, tris [2- (3-mercaptobutyryloxy) ethyl] isocyanurate; ethanethiol, 2-methylpropane-2-thiol, 1-dodecanethiol , 2,3,3,4,5-hexamethylhexane-2-thiol (tert-dodecanethiol), ethane-1,2-dithiol, propane-1,3-dithiol, benzylthiol and other alkylthiols Aromatic thiols such as benzenethiol, 3-methylbenzenethiol, 4-methylbenzenethiol, naphthalene-2-thiol, pyridine-2-thiol, benzoimidazole-2-thiol, benzothiazole-2-thiol; 2- Mercapto alcohols such as mercaptoethanol and 4-mercapto-1-butanol; silane-containing thiols such as 3- (trimethoxysilyl) propan-1-thiol and 3- (triethoxysilyl) propan-1-thiol can be mentioned. ..

The compound having at least one thiol group can be obtained as a commercially available product, and specific examples thereof include Thiocalcol (registered trademark) 20 (manufactured by Kao Corporation), Karenz MT (registered trademark) PE1, and BD1. , NR1, TPMB, TEMB (all manufactured by Showa Denko KK).

The component (D) in the replica mold material for imprinting of the present invention may be used alone or in combination of two or more. The content ratio thereof is, for example, 0.01% by mass to 30% by mass, more preferably 0.05% by mass to 20% by mass, based on 100% by mass of the total mass of the components (A) and (B). It is mass%.

[(E) component]
Examples of the antioxidant as the component (E) include a phenol-based antioxidant, a phosphoric acid-based antioxidant, and a sulfide-based antioxidant.

The antioxidant component (E) is available as a commercial product, and specific examples thereof include IRGANOX (registered trademark) 245, 1010, 1035, 1076, and 1135 [above, BASF Japan Ltd.]. ), Smilizer (registered trademark) GA-80, GP, MDP-S, BBM-S, WX-R [above, manufactured by Sumitomo Chemical Co., Ltd.], ADEKA STAB (registered trademark) AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO-330, PEP-36, PEP-8, PEP-10, 2112, 2112RG, 1178, 1500, C, 135A, 3010, TPP, AO-412S, AO-503, (all manufactured by ADEKA CORPORATION). Be done.

The component (E) in the replica mold material for imprinting of the present invention may be used alone or in combination of two or more. The content ratio is, for example, 0.01% by mass to 20% by mass, more preferably 0.05% by mass or more, based on the total mass of the components (A) and (B) of 100% by mass. It is 10% by mass.

[(F) component]
Examples of the surfactant as the component (F) include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, and polyoxyethylene octyl. Polyoxyethylene alkylaryl ethers such as phenyl ethers and polyoxyethylene nonylphenyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurates, sorbitan monopalmitates, sorbitan monostearates, sorbitan monooleates, Solbitan fatty acid esters such as sorbitan trioleate and sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan. Examples thereof include nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as tristearate.

The above-mentioned surfactant is available as a commercially available product, and specific examples thereof include Ftop (registered trademark) EF301, EF303, EF352 (all manufactured by Mitsubishi Materials Electronics Co., Ltd.), Megafuck (above, manufactured by Mitsubishi Materials Electronics Co., Ltd.). Registered Trademarks) F-171, F-173, F-477, F-486, F-554, F-556, R-08, R-30, R-30N, R- 40, R-40-LM, RS-56, RS-75, RS-72-K, RS-76-E, RS-76-NS, RS-78, RS-90 ( DIC Co., Ltd., Florard FC430, FC431 (3M Japan Co., Ltd.), Asahi Guard (registered trademark) AG710, Surfron (registered trademark) S-382, SC101, SC102, SC103 , SC104, SC105, SC106 (all manufactured by Asahi Glass Co., Ltd.); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), BYK-302, BYK-307, BYK. -322, BYK-323, BYK-330, BYK-333, BYK-370, BYK-375, BYK-378, BYK-UV3500, BYK-UV3570 (all manufactured by Big Chemie Japan Co., Ltd.) can be mentioned. ..

The surfactant in the replica mold material for imprinting of the present invention may be used alone or in combination of two or more. The content ratio is preferably 0.01% by mass to 40% by mass, more preferably 0.01% by mass, based on the total mass of the components (A) and (B) of 100% by mass. To 10% by mass.

[Other additives]
The replica mold material for imprint of the present invention is, if necessary, a compound having one (meth) acryloyloxy group in one molecule, an epoxy compound, a photoacid generator, as long as the effect of the present invention is not impaired. It can contain a photosensitizer, an ultraviolet absorber, a chain transfer agent, an adhesion aid, a releasability improver and a solvent.

The compound having one (meth) acryloyloxy group in one molecule can be added to adjust the viscosity without impairing the transparency, the shrinkage shrinkage rate and the young rate, for example, methyl (meth). ) Acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, Normal octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl ( Meta) acrylate, 2-methoxyethyl (meth) acrylate, ethylcarbitol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (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, 1- Examples thereof include adamantyl (meth) acrylate, γ-butyrolactone (meth) acrylate, and dicyclopentanyl (meth) acrylate. Among these, a compound having an alicyclic structure is preferable in that the curing shrinkage rate and the transparency in the ultraviolet region are not impaired.

Compounds having one (meth) acryloyloxy group in the above molecule are available as commercial products, and specific examples thereof include HEA, HPA, 4-HBA, AIB, TBA, NOAA, IOAA, and INAA. LA, STA, ISTA, IBXA, 2-MTA, Vismar # 155, Biscort # 160, Viscort # 192, Viscort # 150, Viscort # 190, Viscort # MTG, Bismer MPE400A, Bismer MPE550A, MEDOL-10, CHDOL-10, OXE-10, OXE-30, 1-ADA, 1-ADMA, GBLA, GBLMA (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), Funkrill (registered trademark) FA-513AS, FA-513M (above, Hitachi) (Made by Kasei Co., Ltd.).

Examples of the epoxy compound include Epolide (registered trademark) GT-401, PB3600, Celoxide (registered trademark) 2021P, 2000, 3000, EHPE3150, EHPE3150CE (all manufactured by Daicel Co., Ltd.), and EPICLON (registered). Trademarks) 840, 840-S, N-660, N-673-80M (all manufactured by DIC Co., Ltd.) can be mentioned.

Examples of the photoacid generator include IRGACURE (registered trademark) PAG103, PAG108, PAG121, PAG203, CGI725 (all manufactured by BASF Japan Ltd.), WPAG-145, WPAG-170, and WPAG-199. , WPAG-281, WPAG-336, WPAG-376 (all manufactured by Wako Pure Chemical Industries, Ltd.), TFE-triazine, TME-triazine, MP-triazine, dimethoxytriazine, TS-91, TS-01 (Co., Ltd.) ) Sanwa Chemical Industries, Ltd.), CPI-100P, CPI-101A, CPI-200K, CPI-110P, CPI-210S, CPI-110B ((all manufactured by Sun Appro Co., Ltd.)).

Examples of the photosensitizer include thioxanthene-based, thioxanthone-based, xanthene-based, ketone-based, thiopyrilium salt-based, basestyryl-based, merocyanine-based, 3-substituted coumarin-based, 3,4-substituted coumarin-based, and cyanine-based. , Acridine, thiazine, phenothiazine, anthracene, coronen, benzanthracene, perylene, ketocoumarin, coumarin, borate. The above photosensitizer is available as a commercially available product, and specific examples thereof include Antracure (registered trademark) UVS-581, UVS-1331 (all manufactured by Kawasaki Kasei Chemicals Co., Ltd.), and KAYACURE (! A registered trademark) DETX-S (manufactured by Nippon Kayaku Co., Ltd.) can be mentioned. This photosensitizer can be used alone or in combination of two or more. By using the photosensitizer, the absorption wavelength in the UV region can also be adjusted.

Examples of the ultraviolet absorber include TINUVIN (registered trademark) PS, 99-2, 109, 328, 384-2, 400, 405, 460, 477, 479, 900, and so on. 928, 1130, 111FDL, 123, 144, 152, 292, 5100, 400-DW, 477-DW, 99-DW, 123-DW, 5050, 5060, The same 5151 (above, manufactured by BASF Japan Ltd.) can be mentioned. This ultraviolet absorber can be used alone or in combination of two or more. By using the ultraviolet absorber, the curing rate of the outermost surface of the film can be controlled during photocuring of the replica mold material for imprint of the present invention, and the mold can be removed from the master mold when producing the replica mold. In some cases, it is possible to improve the property and the releasability from the replica mold when molding the material for a resin lens by using the manufactured replica mold.

Examples of the chain transfer agent include diethyl disulfide, dipropyl disulfide, diisopropyl disulfide, dibutyl disulfide, di-tert-butyl disulfide, dipentyl disulfide, diisopentyl disulfide, dihexyl disulfide, dicyclohexyl disulfide, didecyl disulfide, and bis (2). , 3,3,4,4,5-hexamethylhexane-2-yl) disulfide (di-tert-dodecyl disulfide), bis (2,2-diethoxyethyl) disulfide, bis (2-hydroxyethyl) disulfide, Alkyl disulfides such as dibenzyl disulfide; diphenyl disulfide, di-p-tolyl disulfide, di (pyridine-2-yl) pyridyl disulfide, di (benzoimidazole-2-yl) disulfide, di (benzothiazole-2-yl) Aromatic disulfides such as disulfides; thiuram disulfides such as tetramethylthiuram disulfides, tetraethylthium disulfides, tetrabutylthium disulfides, bis (pentamethylene) thiuram disulfides; α-methylstyrene dimers. This chain transfer agent can be used alone or in combination of two or more.

Examples of the adhesion aid include 3-methacryloxypropyltrimethoxysilane and 3-acryloxypropyltrimethoxysilane. By using the adhesion aid, the adhesion to the substrate is improved. The content of the adhesion auxiliary agent is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 50% by mass, based on the total mass of the components (A) and (B) of 100% by mass. %.

Examples of the releasability improving agent include fluorine-containing compounds. Examples of the fluorine-containing compound include R-5410, R-1420, M-5410, M-1420, E-5444, E-7432, A-1430, and A-1630 (all manufactured by Daikin Industries, Ltd.). Can be mentioned.

Examples of the solvent include toluene, p-xylene, o-xylene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monoisopropyl ether. , Ethylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene Glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol, 1-octanol, ethylene glycol, hexylene glycol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, propylene glycol, Benzyl alcohol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, γ-butyrolactone, acetone, methyl ethyl ketone, methyl isopropyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone, cyclohexanone, 2-Heptanone, ethyl acetate, isopropyl acetate, n-propyl acetate, isobutyl acetate, n-butyl acetate, ethyl lactate, ethyl pyruvate, methanol, ethanol, isopropanol, tert-butanol, allyl alcohol, n-propanol, 2-methyl -2-butanol, isobutanol, n-butanol, 2-methyl-1-butanol, 1-pentanol, 2-methyl-1-pentanol, 2-ethylhexanol, trimethylene glycol, 1-methoxy-2-butanol , Isopropyl ether, 1,4-dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethylsulfoxide, N-cyclohexyl -2-Pyrrolidine can be mentioned. The solvent is not particularly limited as long as it can adjust the viscosities of the components (A) and (B).

The above solvent can be used alone or in combination of two or more. When a solvent is used, it is defined as all the components of the replica mold material for imprinting of the present invention, that is, all the components including the above-mentioned components (A) to (F) and other additives, excluding the solvent. The solid content is 50% by mass to 99% by mass, preferably 70% by mass to 99% by mass.

[Preparation of replica mold material for imprint]
The method for preparing the replica mold material for imprint of the present invention is not particularly limited, but the component (A), the component (B), the component (C), and optionally the component (D), the component (E), (F). It is sufficient that the components and other additives are mixed so that the replica molding material for imprinting is in a uniform state. Further, the order in which the components (A) to (C) and, if desired, the components (D) to (F) and other additives are mixed is no problem as long as a uniform replica mold material for imprinting can be obtained. , Not particularly limited. As a method for preparing the replica mold material, for example, the component (A) and the component (B) are mixed in a predetermined ratio, and the component (C) and, if desired, the component (D), the component (E) and the component (E) are further mixed. (F) There is also a method of appropriately mixing the components to obtain a uniform replica mold material for imprinting. Further, at an appropriate stage of this preparation method, a method of further adding and mixing other additives as necessary can be mentioned.

[Replica mold with optical imprint and pattern]
The replica mold material for imprint of the present invention is applied on a base material or a master mold, the base material and the master mold are bonded and photo-cured, and the obtained photo-cured product is released from the master mold. By doing so, a desired replica mold for imprint can be obtained. The coating method includes known or well-known methods such as potting method, spin coating method, dip method, flow coating method, inkjet method, spray method, bar coating method, gravure coating method, slit coating method, roll coating method, and transfer. Examples include a printing method, a brush coating method, a blade coating method, and an air knife coating method.

The replica mold obtained from the replica mold material for imprinting of the present invention can improve the transparency in the ultraviolet region by heating after mold release from the master mold. Examples of the heating method include the use of a hot plate, an oven, or the like.

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

The light source for photocuring the replica mold material 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, an ArF excimer laser, and an F2 excimer. Examples include lasers, electron beams (EB), extreme ultraviolet rays (EUV), and ultraviolet LEDs (UV-LEDs). Further, as the wavelength, generally, a G line of 436 nm, an H line of 405 nm, an I line of 365 nm, or a GHI mixed line can be used. The exposure amount is preferably 30 mJ / cm ² to 10000 mJ / cm ² , and more preferably 100 mJ / cm ² to 8000 mJ / cm ² .

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

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

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

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 nanometer order, the micrometer order, and the millimeter order, for example.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

[Preparation of replica mold material for imprint]
<Example 1>
New Frontier (registered trademark) HBPE-4 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) (hereinafter abbreviated as "HBPE-4" in the present specification) 3 g, KAYARAD (registered trademark) PET-30 (Nippon Kayaku) (Manufactured by Co., Ltd.) (hereinafter, abbreviated as “PET-30” in the present specification) and IRGACURE (registered trademark) 184 (manufactured by BASF Japan Co., Ltd.) (hereinafter, “IRGACURE184” in the present specification). (Abbreviated as) was added in an amount of 0.01 g (0.1% by mass based on 100% by mass of the total mass of HBPE-4 and PET-30) to prepare a replica mold material RM-a1 for imprinting. The replica mold material for imprint of this embodiment contains (A) component, (B) component and (C) component.

<Example 2>
Add 5 g of HBPE-4, 5 g of PET-30, and 0.01 g of IRGACURE184 (0.1% by mass with respect to 100% by mass of the total mass of HBPE-4 and PET-30), and the replica mold material RM for imprinting. -A2 was prepared. The replica mold material for imprint of this embodiment contains (A) component, (B) component and (C) component.

<Example 3>
Add 7 g of HBPE-4, 3 g of PET-30, and 0.01 g of IRGACURE184 (0.1% by mass with respect to 100% by mass of the total mass of HBPE-4 and PET-30), and the replica mold material RM for imprinting. -A3 was prepared. The replica mold material for imprint of this embodiment contains (A) component, (B) component and (C) component.

<Example 4>
7 g of HBPE-4, 2.5 g of PET-30, 0.5 g of 1-ADMA (manufactured by Osaka Organic Chemical Industry Co., Ltd.), and 0.01 g of IRGACURE 184 (total mass of HBPE-4 and PET-30 100). 0.1% by mass with respect to% by mass) was added to prepare a replica mold material RM-a4 for imprinting. The replica mold material for imprint of this embodiment contains (A) component, (B) component and (C) component.

<Example 5>
3 g of HBPE-4, 7 g of NK ester A-DOG (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) (hereinafter abbreviated as "A-DOG"), and 0.01 g of IRGACURE 184 (HBPE- 4 and 0.1% by mass with respect to 100% by mass of the total mass of A-DOG) were added to prepare a replica mold material RM-a5 for imprinting. The replica mold material for imprint of this embodiment contains (A) component, (B) component and (C) component.

<Example 6>
Add 5 g of HBPE-4, 5 g of A-DOG, and 0.01 g of IRGACURE184 (0.1% by mass with respect to 100% by mass of the total mass of HBPE-4 and A-DOG), and the replica mold material RM for imprinting. -A6 was prepared. The replica mold material for imprint of this embodiment contains (A) component, (B) component and (C) component.

<Example 7>
Add 7 g of HBPE-4, 3 g of A-DOG, and 0.01 g of IRGACURE184 (0.1% by mass with respect to 100% by mass of the total mass of HBPE-4 and A-DOG), and the replica mold material RM for imprinting. -A7 was prepared. The replica mold material for imprint of this embodiment contains (A) component, (B) component and (C) component.

<Example 8>
7 g of HBPE-4, 3 g of NK ester A-TMPT (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) (hereinafter, abbreviated as "A-TMPT" in the present specification), and 0.01 g of IRGACURE 184 (HBPE-). 4 and 0.1% by mass based on 100% by mass of the total mass of A-TMPT) were added to prepare a replica mold material RM-a8 for imprinting. The replica mold material for imprint of this embodiment contains (A) component, (B) component and (C) component.

<Example 9>
7 g of HBPE-4, 3 g of NK ester A-DCP (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and 0.01 g of IRGACURE184 (0.1 with respect to 100% by mass of the total mass of HBPE-4 and A-DCP). In addition, RM-a9, a replica mold material for imprinting, was prepared. The replica mold material for imprint of this embodiment contains (A) component, (B) component and (C) component.

<Example 10>
5 g of HBPE-4, 5 g of PET-30, 0.01 g of IRGACURE184 (0.1% by mass with respect to 100% by mass of the total mass of HBPE-4 and PET-30), and 0.05 g of thiocalcole 20 (HBPE). -4 and 0.5% by mass with respect to 100% by mass of the total mass of PET-30) were added to prepare a replica mold material RM-a10 for imprinting. The replica mold material for imprint of this embodiment contains (A) component, (B) component, (C) component and (D) component.

<Example 11>
7 g of HBPE-4, 3 g of PET-30, 0.01 g of IRGACURE184 (0.1% by mass with respect to 100% by mass of the total mass of HBPE-4 and PET-30), and 0.05 g of thiocalcole 20 (HBPE). -4 and 0.5% by mass with respect to 100% by mass of the total mass of PET-30) were added to prepare a replica mold material RM-a11 for imprinting. The replica mold material for imprint of this embodiment contains (A) component, (B) component, (C) component and (D) component.

<Example 12>
5 g of HBPE-4, 5 g of A-DOG, 0.01 g of IRGACURE184 (0.1% by mass with respect to 100% by mass of the total mass of HBPE-4 and A-DOG), and 0.05 g of thiocalcole 20 (HBPE). -4 and 0.5% by mass with respect to 100% by mass of the total mass of A-DOG) were added to prepare a replica mold material RM-a12 for imprinting. The replica mold material for imprint of this embodiment contains (A) component, (B) component, (C) component and (D) component.

<Example 13>
7 g of HBPE-4, 3 g of A-DOG, 0.01 g of IRGACURE184 (0.1% by mass with respect to 100% by mass of the total mass of HBPE-4 and A-DOG), and 0.05 g of thiocalcole 20 (HBPE). -4 and 0.5% by mass with respect to 100% by mass of the total mass of A-DOG) were added to prepare a replica mold material RM-a13 for imprinting. The replica mold material for imprint of this embodiment contains (A) component, (B) component, (C) component and (D) component.

<Example 14>
5 g of HBPE-4, 5 g of PET-30, 0.01 g of IRGACURE184 (0.1% by mass with respect to 100% by mass of the total mass of HBPE-4 and PET-30), and Karenz MT (registered trademark) PE1 (registered trademark). Showa Denko KK) (hereinafter abbreviated as "PE1" in the present specification) is added in an amount of 0.05 g (0.5% by mass with respect to 100% by mass of the total mass of HBPE-4 and PET-30). , RM-a14, a replica mold material for imprint, was prepared. The replica mold material for imprint of this embodiment contains (A) component, (B) component, (C) component and (D) component.

<Example 15>
7 g of HBPE-4, 3 g of PET-30, 0.01 g of IRGACURE184 (0.1% by mass with respect to 100% by mass of the total mass of HBPE-4 and PET-30), and 0.05 g of PE1 (HBPE-). 4 and 0.5% by mass with respect to 100% by mass of the total mass of PET-30) were added to prepare a replica mold material RM-a15 for imprinting. The replica mold material for imprint of this embodiment contains (A) component, (B) component, (C) component and (D) component.

<Example 16>
5 g of HBPE-4, 5 g of A-DOG, 0.01 g of IRGACURE184 (0.1% by mass with respect to 100% by mass of the total mass of HBPE-4 and A-DOG), and 0.05 g of PE1 (HBPE- 4 and 0.5% by mass based on 100% by mass of the total mass of A-DOG) were added to prepare a replica mold material RM-a16 for imprinting. The replica mold material for imprint of this embodiment contains (A) component, (B) component, (C) component and (D) component.

<Example 17>
7 g of HBPE-4, 3 g of A-DOG, 0.01 g of IRGACURE184 (0.1% by mass with respect to 100% by mass of the total mass of HBPE-4 and A-DOG), and 0.05 g of PE1 (HBPE- 4 and 0.5% by mass based on 100% by mass of the total mass of A-DOG) were added to prepare a replica mold material RM-a17 for imprinting. The replica mold material for imprint of this embodiment contains (A) component, (B) component, (C) component and (D) component.

<Example 18>
5 g of HBPE-4, 5 g of PET-30, 0.01 g of IRGACURE184 (0.1% by mass with respect to 100% by mass of the total mass of HBPE-4 and PET-30), and IRGANOX® 1010 (BASF). Japan Co., Ltd.) (hereinafter, abbreviated as "IRGANOX1010" in the present specification) is added in an amount of 0.01 g (0.1% by mass with respect to 100% by mass of the total mass of HBPE-4 and PET-30). A replica mold material RM-a18 for imprint was prepared. The replica mold material for imprint of this embodiment contains (A) component, (B) component, (C) component and (E) component.

<Example 19>
7 g of HBPE-4, 3 g of PET-30, 0.01 g of IRGACURE184 (0.1% by mass with respect to 100% by mass of the total mass of HBPE-4 and PET-30), and 0.01 g of IRGANOX1010 (HBPE- 4 and 0.1% by mass with respect to 100% by mass of the total mass of PET-30) were added to prepare a replica mold material RM-a19 for imprinting. The replica mold material for imprint of this embodiment contains (A) component, (B) component, (C) component and (E) component.

<Example 20>
5 g of HBPE-4, 5 g of A-DOG, 0.01 g of IRGACURE184 (0.1% by mass with respect to 100% by mass of the total mass of HBPE-4 and A-DOG), and 0.01 g of IRGANOX1010 (HBPE- 4 and 0.1% by mass based on 100% by mass of the total mass of A-DOG) were added to prepare a replica mold material RM-a20 for imprinting. The replica mold material for imprint of this embodiment contains (A) component, (B) component, (C) component and (E) component.

<Example 21>
7 g of HBPE-4, 3 g of A-DOG, 0.01 g of IRGACURE184 (0.1% by mass with respect to 100% by mass of the total mass of HBPE-4 and A-DOG), and 0.01 g of IRGANOX1010 (HBPE- 4 and 0.1% by mass based on 100% by mass of the total mass of A-DOG) were added to prepare a replica mold material RM-a21 for imprinting. The replica mold material for imprint of this embodiment contains (A) component, (B) component, (C) component and (E) component.

<Example 22>
7 g of HBPE-4, 3 g of PET-30, 0.01 g of IRGACURE184 (0.1% by mass with respect to 100% by mass of the total mass of HBPE-4 and PET-30), and BYK-UV3570 (Big Chemie Japan (Big Chemie Japan) RM-a22 for imprint was prepared by adding 0.01 g (0.1% by mass with respect to 100% by mass of the total mass of HBPE-4 and PET-30) (manufactured by Co., Ltd.). The replica mold material for imprint of this embodiment contains (A) component, (B) component, (C) component and (F) component.

<Example 23>
7 g of HBPE-4, 3 g of PET-30, 0.01 g of IRGACURE184 (0.1% by mass with respect to 100% by mass of the total mass of HBPE-4 and PET-30), and 0.1 g of BYK-UV3570 (0.1% by mass). 1% by mass with respect to 100% by mass of the total mass of HBPE-4 and PET-30) was added to prepare a replica mold material RM-a23 for imprinting. The replica mold material for imprint of this embodiment contains (A) component, (B) component, (C) component and (F) component.

<Example 24>
7 g of HBPE-4, 3 g of PET-30, 0.01 g of IRGACURE184 (0.1% by mass with respect to 100% by mass of the total mass of HBPE-4 and PET-30), and 0.5 g of BYK-UV3570 ( 5% by mass with respect to 100% by mass of the total mass of HBPE-4 and PET-30) was added to prepare a replica mold material RM-a24 for imprinting. The replica mold material for imprint of this embodiment contains (A) component, (B) component, (C) component and (F) component.

<Example 25>
7 g of HBPE-4, 3 g of PET-30, 0.01 g of IRGACURE184 (0.1% by mass with respect to 100% by mass of the total mass of HBPE-4 and PET-30), and 1 g of BYK-UV3570 (HBPE-). 4 and 10% by mass with respect to 100% by mass of the total mass of PET-30) were added to prepare a replica mold material RM-a24 for imprinting. The replica mold material for imprint of this embodiment contains (A) component, (B) component, (C) component and (F) component.

<Example 26>
7 g of HBPE-4, 3 g of PET-30, 0.01 g of IRGACURE184 (0.1% by mass with respect to 100% by mass of the total mass of HBPE-4 and PET-30), and 2 g of BYK-UV3570 (HBPE-). 4 and 20% by mass with respect to 100% by mass of the total mass of PET-30) were added to prepare a replica mold material RM-a26 for imprinting. The replica mold material for imprint of this embodiment contains (A) component, (B) component, (C) component and (F) component.

<Comparative Example 1>
10 g of HBPE-4 and 0.01 g of IRGACURE 184 were added to prepare a replica mold material RM-b1 for imprinting. The replica mold material for imprint of this comparative example contains the component (A) and the component (C), but does not contain the component (B).

<Comparative Example 2>
10 g of PET-30 and 0.01 g of IRGACURE 184 were added to prepare a replica mold material RM-b2 for imprinting. The replica mold material for imprint of this comparative example contains the component (B) and the component (C), but does not contain the component (A).

<Comparative Example 3>
10 g of A-TMPT and 0.01 g of IRGACURE 184 were added to prepare a replica mold material RM-b3 for imprinting. The replica mold material for imprint of this comparative example contains the component (B) and the component (C), but does not contain the component (A).

<Comparative Example 4>
10 g of NK ester APG-700 and 0.01 g of IRGACURE 184 were added to prepare a replica mold material RM-b5 for imprinting. The replica mold material for imprint of this comparative example contains the component (B) and the component (C), but does not contain the component (A).

<Comparative Example 5>
5 g of Viscoat # 230, 5 g of PET-30, and 0.01 g of IRGACURE 184 were added to prepare a replica mold material RM-b6 for imprinting. Since the biscoat # 230 used in this comparative example does not correspond to the component (A), the replica mold material for imprint in this comparative example contains the component (B) and the component (C) but does not contain the component (A). ..

<Comparative Example 6>
5 g of Viscoat # 230, 5 g of A-DOG, and 0.01 g of IRGACURE 184 were added to prepare a replica mold material RM-b7 for imprinting. Since the biscoat # 230 used in the comparative example does not correspond to the component (A), the replica mold material for imprint of the comparative example contains the component (B) and the component (C) but does not contain the component (A).

<Comparative Example 7>
7 g of HBPE-4, 3 g of PET-30, and 0.2 g of IRGACURE184 (2% by mass based on the total mass of HBPE-4 and PET-30) were added to prepare a replica mold material RM-b8 for imprinting. .. In the replica mold material for imprint of this comparative example, the content ratio of the component (C) is the upper limit of 0.01% by mass to 1% by mass with respect to the total mass of 100% by mass of the component (A) and the component (B). The value is exceeded.

<Comparative Example 8>
Add 7 g of HBPE-4, 3 g of PET-30, and 0.0005 g of IRGACURE184 (0.005% by mass with respect to the total mass of HBPE-4 and PET-30), and add the replica mold material RM-b9 for imprinting. Prepared. In the replica mold material for imprint of this comparative example, the content ratio of the component (C) is the lower limit of 0.01% by mass to 1% by mass with respect to the total mass of 100% by mass of the component (A) and the component (B). Less than the value.

[Making replica mold for imprint]
Each imprint replica mold material obtained in Examples 1 to 26 and Comparative Examples 1 to 8 is previously subjected to NOVEC (registered trademark) 1720 (manufactured by 3M Japan Ltd.) (hereinafter, in the present specification). It is potted into a nickel mold (15 pieces of 2 mm diameter x 300 μm deep concave lens molds arranged in 3 rows x 5 rows) that has been demolded using "NOVEC1720"), and quartz glass is placed on it. The substrate was covered, and optical imprinting was performed using a nanoimprinting apparatus NM-0801HB (manufactured by Meisho Kiko Co., Ltd.). Optical imprint is always performed under the condition of 23 ° C., a) pressurizing to 500 N over 10 seconds, b) exposing to 5000 mJ / cm ² using a high-pressure mercury lamp, c) depressurizing over 10 seconds, d) nickel. A convex lens pattern was obtained on the quartz glass substrate by separating the mold and the quartz glass substrate and releasing the mold. The convex lens pattern obtained on the quartz glass substrate was heated on a hot plate at 150 ° C. for 5 minutes to obtain a replica mold for imprinting. The quartz glass substrate used was spin-coated with KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) in advance and heated on a hot plate at 150 ° C. for 5 minutes to perform adhesion treatment. With respect to the obtained replica mold for imprint, the presence or absence of peeling / cracking of the convex lens pattern was observed using an industrial microscope ECLIPSE L150 (manufactured by Nikon Corporation). The results are shown in Tables 1 and 2.

[Replica mold release process]
Of the replica molds obtained by the above method, NOVEC1720 is spin-coated on the surface of the convex lens pattern of the replica mold in which no peeling or cracking of the convex lens pattern is observed, and the replica mold is heated on a hot plate at 100 ° C. for 10 minutes. As a result, the surface of the replica mold was mold-released.

[Preparation of imprint material]
5 g of A-DOG and 5 g of UM-90 (1/3) DA (manufactured by Ube Industries, Ltd.) were mixed, and 0.2 g of IRGACURE184 was added to the mixture to prepare an imprint material.

[Making a concave lens pattern using a replica mold]
The prepared imprint material is potted on a quartz glass substrate subjected to the above-mentioned adhesion treatment, and the above-mentioned mold release-treated replica mold is placed on the potting, and a nanoimprint apparatus NM-0801HB (manufactured by Meisho Kiko Co., Ltd.) is installed. Optical imprint was performed using. Optical imprint is always performed at 23 ° C. for a) pressurization to 500 N over 10 seconds, b) exposure to 5000 mJ / cm ² using a high-pressure mercury lamp, c) decompression over 10 seconds, d) replica. The mold and the quartz glass substrate were separated and released in a sequence, and a concave lens pattern was obtained on the quartz glass substrate. Using an industrial microscope ECLIPSE L150 (manufactured by Nikon Corporation), the presence or absence of peeling / cracking of the obtained concave lens pattern was observed. The results are shown in Tables 1 and 2.

[Preparation of cured film and evaluation of optical characteristics]
The replica mold materials for imprints obtained in Examples 1 to 26 and Comparative Examples 1 to 8 were surface-treated with NOVEC 1720 together with a 0.5 mm thick silicone rubber spacer on two glass substrates. I sandwiched it. The sandwiched replica mold material for imprint was exposed to UV at 40 mW / cm ² for 125 seconds using a batch type UV irradiation device (high pressure mercury lamp 2 kW × 1 lamp) (manufactured by Eye Graphics Co., Ltd.). After peeling the obtained cured product from the glass substrate, it was heated on a hot plate at 150 ° C. for 5 minutes to prepare a cured film having a thickness of 0.5 mm. The transmittance of the obtained cured film at a wavelength of 365 nm was measured using a spectrophotometer UV2600 (manufactured by Shimadzu Corporation) with the reference in air. The results are shown in Tables 3 and 4.

[Measurement of Young's modulus of cured film]
The above-mentioned cured film having a thickness of 0.5 mm was cut into strips of 5 mm × 60 mm. Both ends 15 mm of the strip-shaped cured film are fixed to a jig, and a tensile test is performed using an Autograph AGX-500NX (manufactured by Shimadzu Corporation) at a test speed of 5 mm / min, and the displacement is 0.5% to 1%. Young's modulus in. The results are shown in Tables 3 and 4.

[Measurement of curing shrinkage rate]
The dry automatic density of each imprint replica mold material (both liquid) obtained in Examples 1 to 26 and Comparative Examples 1 to 8 and the above-mentioned cured film obtained from the replica mold material. The density was measured using a total Accupic 1330-01 (manufactured by Shimadzu Corporation). Then, the curing shrinkage rate was calculated from the following formula.
Curing shrinkage rate = ((film density after curing-density of replica mold material before curing) / film density after curing) x 100%
The obtained results are shown in Tables 3 and 4.

From the results shown in Table 1, no cracking or peeling was observed in the convex lens pattern of the replica mold produced from the replica mold materials for imprint prepared in Examples 1 to 26. In addition, no cracking or peeling was observed in the concave lens pattern produced by optical imprinting using the obtained replica mold. On the other hand, from the results shown in Table 2, at least one of cracking and peeling was observed in the replica mold prepared from the replica mold materials for imprint prepared in Comparative Example 2, Comparative Example 4 and Comparative Example 8. Then, peeling was observed in each of the concave lens patterns prepared by optical imprint using the replica molds prepared from the replica mold materials for imprint prepared in Comparative Example 3 and Comparative Example 7.

From the results shown in Table 3, all of the cured films prepared from the replica mold materials for imprint prepared in Examples 1 to 26 have a transmittance of 80% at a wavelength of 365 nm in a thick film of 0.5 mm. As mentioned above, high transparency in the ultraviolet region was confirmed. Further, the cured films prepared from the replica mold materials for imprint prepared in Examples 1 to 26 all show a high Young's modulus of 1.0 GPa or more, and the cured shrinkage rate is 8.5%. It showed the following low value. On the other hand, from the results shown in Table 4, the cured film prepared from the replica mold material for imprint prepared in Comparative Examples 1 to 8 has a transmittance of less than 80% at a wavelength of 365 nm or a Young's modulus. The result was that it was less than 1.0 GPa or the curing shrinkage rate was more than 8.5%.

From the above results, the replica mold material for imprint of the present invention has a low curing shrinkage rate at the time of photocuring, and the molded product produced from the replica mold material has high transparency in the ultraviolet region and a high Young's modulus. It will have at the same time.

Claims (15)

A replica mold material for imprint containing the following components (A), (B) and (C).
(A): Di (meth) acrylate compound represented by the following formula (1)

(In the formula, R ¹ and R ² independently represent a hydrogen atom or a methyl group, R ³ and R ⁴ independently represent an alkylene group having 1 to 4 carbon atoms, and R ⁵ and R ⁶ are independent, respectively. Represents a hydrogen atom or a methyl group, and r ¹ and r ² each independently represent an integer of 1 to 5.) (B): A compound represented by the following formula (3) and a compound represented by the following formula (4). Mixture with compound

(In the formula, R ⁷ represents a hydrogen atom or a methyl group.)
(C): 0.01% by mass to 1% by mass of the photopolymerization initiator with respect to 100% by mass of the total of the component (A) and the component (B). The replica mold material for imprint according to claim 1, wherein the component (A) is contained in an amount of 30% by mass to 90% by mass with respect to a total of 100% by mass of the component (A) and the component (B). (D) The replica mold material for imprint according to claim 1 or 2, further comprising a compound having at least one thiol group as a component. (E) The replica mold material for imprint according to any one of claims 1 to 3, further containing an antioxidant as a component. (F) The replica mold material for imprint according to any one of claims 1 to 4, further containing a surfactant as a component. A replica mold material for imprint containing the following components (A), (B) and (C).
(A): Di (meth) acrylate compound represented by the following formula (1)

(In the formula, R ¹ and R ² independently represent a hydrogen atom or a methyl group, R ³ and R ⁴ independently represent an alkylene group having 1 to 4 carbon atoms, and R ⁵ and R ⁶ are independent, respectively . Represents a hydrogen atom or a methyl group, and r ¹ and r ² each independently represent an integer of 1 to 5.) (B): A compound represented by the following formula (5).

(In the formula, the two R ^7s represent a hydrogen atom or a methyl group .)
(C): 0.01% by mass to 1% by mass of the photopolymerization initiator with respect to 100% by mass of the total of the component (A) and the component (B). The replica mold material for imprint according to claim 6, wherein the component (A) is contained in an amount of 30% by mass to 90% by mass with respect to a total of 100% by mass of the component (A) and the component (B). (D) The replica mold material for imprint according to claim 6 or 7 , further comprising a compound having at least one thiol group as a component. (E) The replica mold material for imprint according to any one of claims 6 to 8 , further comprising an antioxidant as a component. (F) The replica mold material for imprint according to any one of claims 6 to 9 , further containing a surfactant as a component. An imprint replica mold having a pattern, made from the imprint replica mold material according to any one of claims 1 to 10 . The replica mold for imprint according to claim 11 , wherein the pattern is an inverted pattern of a lens shape. The replica mold for imprint according to claim 11 or 12 , wherein the maximum thickness of the replica mold for imprint is 2.0 mm. The step of applying the replica mold material for imprint according to any one of claims 1 to 10 onto the master mold.
A step of crimping the master mold to a base material via the replica mold material,
Obtained on the substrate after a step of exposing the replica mold material through the substrate while the master mold is pressure-bonded to the substrate and photocuring the replica mold material, and a step of photocuring the material. A method for producing a replica mold for imprint, which comprises a step of removing the photo-cured product from the master mold. The step of applying the replica mold material for imprint according to any one of claims 1 to 10 onto a substrate.
A step of crimping the base material to the master mold via the replica mold material,
Obtained on the substrate after a step of exposing the replica mold material through the substrate while the master mold is pressure-bonded to the substrate and photocuring the replica mold material, and a step of photocuring the material. A method for producing a replica mold for imprint, which comprises a step of removing the photo-cured product from the master mold.