JPWO2018030351A1 - Imprint material - Google Patents

Abstract

To provide a novel imprint material. An imprint material comprising the following components (A), (B) and (C): (A): a compound represented by the following formula (1) (wherein, two R's each independently represent a hydrogen atom or a methyl group) (B): having 6 to 10 carbon atoms Alicyclic structure selected from the group consisting of linear alkylene group and / or cyclopentane structure, cyclohexane structure, norbornane structure, isobornyl structure and adamantane structure, and compound (C) having at least one polymerizable group: photopolymerization initiation No selection agent [Selection chart]

Description

The present invention relates to an imprinting material (imprinting film forming composition) and a film produced from the material and to which a pattern is transferred. More specifically, the present invention relates to a film made of the material, having high transparency even in a thick film state, and to which a pattern having a high refractive index and a high Abbe number has been transferred. As used herein, "thick film" refers to a film having a thickness of 0.01 mm to 1.5 mm.

In 1995, butterfly professors of the present Princeton University proposed a new technology called nanoimprint lithography (Patent Document 1). In nanoimprint lithography, a mold having an arbitrary pattern is brought into contact with a substrate on which a resin film is formed, the resin film is pressurized, and heat or light is used as an external stimulus to cure the target resin film. This nanoimprint lithography has an advantage that nanoscale processing can be performed easily and inexpensively as compared with photolithography and the like in the conventional semiconductor device manufacture.
Therefore, since nanoimprint lithography is a technology expected to be applied to the manufacture of semiconductor devices, opto devices, displays, storage media, biochips, etc. instead of optical lithography technology, it is for photo nanoimprint lithography used for nanoimprint lithography Various reports have been made on curable compositions (Patent Document 2, Patent Document 3).

Further, in the photo nanoimprint lithography, a roll-to-roll method has been proposed as a method of mass-producing a film to which a pattern has been transferred with high efficiency. The roll-to-roll method conventionally proposed in optical nanoimprint lithography uses a flexible film as a substrate, and a pattern as a material used in nanoimprint lithography (hereinafter abbreviated as "imprint material" in the present specification). The mainstream is a method of using a non-solvent type material to which no solvent is added so that the dimension does not easily change.

U.S. Pat. No. 5,772,905 JP 2008-105414 A JP, 2008-202022, A

As described above, a solventless type material is used for the conventionally proposed imprinting material, but after photoimprinting with a thick film, it has high transparency in the visible light region and high refractive index Moreover, no specific study or report has been made on materials having a high Abbe number.

The present invention has been made based on the above circumstances, and the problem to be solved is that after photoimprinting in thick film, it has high transparency in the visible light region, high refractive index and high Abbe. It is an object to provide an imprint material having a number.

MEANS TO SOLVE THE PROBLEM As a result of conducting earnest examination, as a result of the present inventors, in order to solve said subject, the compound which has a 1,3-dioxane ring and has a polymeric group at both ends, a C6-C10 linear chain A material having at least one compound having an alicyclic group selected from the group consisting of an alkylene group and / or a cyclopentane structure, a cyclohexane structure, a norbornane structure, an isobornyl structure and an adamantane structure and a polymerizable group, and a material containing a photopolymerization initiator The following findings were obtained by using as an imprint material, and the present invention was made. That is, the imprint material of the present invention has high transparency in the visible light region and high refractive index and high Abbe number after photoimprinting with a thick film.

（式中、２つのＲはそれぞれ独立に水素原子又はメチル基を表す。）
（Ｂ）：炭素原子数が６乃至１０の直鎖アルキレン基及び／又はシクロペンタン構造、シクロヘキサン構造、ノルボルナン構造、イソボルニル構造及びアダマンタン構造からなる群から選択される脂環構造、並びに重合性基を少なくとも１つ有する化合物
（Ｃ）：光重合開始剤
第２観点として、前記重合性基がアクリロイルオキシ基、メタアクリロイルオキシ基、ビニル基又はアリル基である、第１観点に記載のインプリント材料。
第３観点として、前記重合性基の数が１つ又は２つである、第１観点又は第２観点に記載のインプリント材料。
第４観点として、（Ａ）成分と（Ｂ）成分の総質量１００質量％に対し、該（Ａ）成分の割合が１０質量％乃至９０質量％である、第１観点乃至第３観点のいずれか一に記載のインプリント材料。
第５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４観点のいずれか一に記載のインプリント材料。
第６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５観点のいずれか一に記載のインプリント材料。
第７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６観点のいずれか一に記載のインプリント材料。
第８観点として、（Ｇ）成分として溶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材料。
第９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材料を用いて作製された、パターンが転写された膜。
第１０観点として、前記パターンがレンズ形状である、第９観点に記載のパターンが転写された膜。
第１１観点として、前記パターンが転写された膜がカメラモジュール用レンズである、第９観点又は第１０観点に記載のパターンが転写された膜。
第１２観点として、前記パターンが転写された膜の最大膜厚が１．５ｍｍである、第９観点乃至第１１観点のいずれか一に記載のパターンが転写された膜。
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材料を、接し合う基材とモールドとの間の空間、又は分割可能なモールドの内部の空間に充填する工程、及び該空間に充填されたインプリント材料を露光して光硬化する工程を含むパターンが転写された膜の作製方法。
第１４観点として、前記光硬化する工程の後、得られた光硬化物を取り出して離型する工程、並びに、該光硬化物を、該離型する工程の前、中途又は後において加熱する工程を含む第１３観点に記載のパターンが転写された膜の作製方法。That is, as the first aspect of the present invention,
An imprint material containing the following components (A), (B) and (C):
(A): a compound represented by the following formula (1)

(Wherein, two R's each independently represent a hydrogen atom or a methyl group)
(B): a linear alkylene group having 6 to 10 carbon atoms and / or an alicyclic structure selected from the group consisting of a cyclopentane structure, a cyclohexane structure, a norbornane structure, an isobornyl structure and an adamantane structure, and a polymerizable group Compound (C) having at least one: Photopolymerization initiator The imprint material according to the first aspect, wherein as the second aspect, the polymerizable group is an acryloyloxy group, a methacryloyloxy group, a vinyl group or an allyl group.
As a third aspect, the imprint material according to the first aspect or the second aspect, wherein the number of the polymerizable groups is one or two.
According to a fourth aspect, in any of the first to third aspects, the ratio of the component (A) is 10% by mass to 90% by mass with respect to 100% by mass of the total mass of the components (A) and (B). Imprint material as described in 1).
As the fifth aspect, the imprint material according to any one of the first to fourth aspects, which further contains a compound having at least one thiol group as the component (D).
The imprint material as described in any one of the 1st viewpoint thru | or 5th viewpoint which further contains an antioxidant as (E) component as a 6th viewpoint.
As a seventh aspect, the imprint material according to any one of the first to sixth aspects, which further contains a surfactant as the component (F).
As an eighth aspect, the imprint material according to any one of the first aspect to the seventh aspect, which further contains a solvent as the component (G).
The film which the pattern was transcribe | transferred using the imprint material as described in any one of a 1st viewpoint thru | or a 8th viewpoint as a 9th viewpoint.
As a tenth aspect, a film to which the pattern according to the ninth aspect is transferred, wherein the pattern is a lens shape.
As an eleventh aspect, a film according to the ninth aspect or tenth aspect, wherein the film to which the pattern is transferred is a camera module lens.
According to a twelfth aspect, a film as defined in any one of the ninth to eleventh aspects, wherein the maximum film thickness of the film to which the pattern is transferred is 1.5 mm.
As a thirteenth aspect, a step of filling the imprint material according to any one of the first aspect to the eighth aspect in a space between a base to be in contact with the mold or a space inside a divisible mold, And a method of producing a film to which a pattern has been transferred, including the steps of exposing the photo-imprint material filled in the space and photocuring it.
As a fourteenth aspect, after the step of photocuring, the step of taking out and releasing the obtained photocured product, and the step of heating the photocured product before, halfway or after the step of demoulding. The manufacturing method of the film by which the pattern as described in a 13th viewpoint containing is transferred.

The imprint material of the present invention comprises a compound represented by the above formula (1), a linear alkylene group having 6 to 10 carbon atoms and / or a cyclopentane structure, a cyclohexane structure, a norbornane structure, an isobornyl structure and an adamantane structure By containing an alicyclic structure selected from the group consisting of: and a compound having at least one polymerizable group, a cured film produced from the imprint material has high transparency in the visible light region even if it is a thick film. And have a high refractive index and a high Abbe number.

Moreover, since the imprint material of the present invention can be photocured and peeling does not occur in part of the pattern at the time of peeling from the mold, a film on which a desired pattern is accurately formed can be obtained. Therefore, it is possible to form a good light imprint pattern.

In addition, the imprint material of the present invention can be deposited on any base material, and the film has high transparency in the visible light region even if it is a thick film, and has a high refractive index and a high Abbe number. For this reason, the film to which the pattern formed after imprinting is transferred is for producing an optical member such as a solid imaging device, a lens for a camera module, a lens for a sensor, etc. where high transparency, high refractive index and high Abbe number are required. It can be used suitably. Here, as the lens, for example, a concave lens, a convex lens, an aspheric lens, a spherical lens, a Fresnel lens, a linear Fresnel lens, and a lens having a fine uneven shape (reflection preventing structure) on a curved surface can be mentioned. In the present specification, the shape of the curved surface of the lens in the above concave lens, convex lens, aspheric lens, spherical lens, Fresnel lens, linear Fresnel lens, and lens having a fine concavo-convex shape (reflection preventing structure) on the curved surface is called lens shape. .

Furthermore, in the imprint material of the present invention, the curing speed, the dynamic viscosity, and the film thickness can be controlled by changing the type and the content ratio of the compound of the component (B). Therefore, since the imprint material of the present invention can design materials corresponding to the type of device to be manufactured and the types of exposure process and baking process, and can expand the process margin, it should be suitably used for manufacturing an optical member it can.

（式中、２つのＲはそれぞれ独立に水素原子又はメチル基を表す。）[(A) component]
The compound of component (A) is a compound represented by the following formula (1).

(Wherein, two R's each independently represent a hydrogen atom or a methyl group)

Specific examples of the compound represented by the formula (1) include dioxane glycol diacrylate and dioxane glycol dimethacrylate.

The compounds represented by the above formula (1) are commercially available, and specific examples thereof include NK ester A-DOG (manufactured by Shin-Nakamura Chemical Co., Ltd.).

The compounds of the component (A) can be used singly or in combination of two or more.

The content ratio of the component (A) in the imprint material of the present invention is 10% by mass or more and 90% by mass or less based on the total mass 100% by mass of the component (A) and the component (B) described later. Is more preferably 40% by mass to 60% by mass. If the proportion of the component (A) is less than 10% by mass, or more than 90% by mass, the transparency of the film obtained by heating may decrease after photoimprinting.

[(B) component]
The compound of component (B) is a linear alkylene group having 6 to 10 carbon atoms and / or an alicyclic structure selected from the group consisting of a cyclopentane structure, a cyclohexane structure, a norbornane structure, an isobornyl structure and an adamantane structure, and polymerization It refers to a compound having at least one sexual group. Examples of the linear alkylene group having 6 to 10 carbon atoms include (—CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —) and (—CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ — ), (-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ), (-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ) or (-CH ₂ ) _{CH 2 CH 2 CH 2 CH 2} CH 2 CH 2 CH 2 CH 2 CH 2 -) represents a. The alicyclic structure represents a cyclic and non-aromatic hydrocarbon. Examples of the polymerizable group include acryloyloxy group, methacryloyloxy group, vinyl group and allyl group. Here, the acryloyloxy group may be expressed as an acryloxy group, and the methacryloyloxy group may be expressed as a methacryloxy group. The compound of the component (B) may or may not have a group and a structure other than the linear alkylene group having 6 to 10 carbon atoms, the alicyclic structure, and the polymerizable group, It is preferable that it does not have groups and structures other than the said linear alkylene group, the said alicyclic structure, and the said polymeric group.

As specific examples of the compound having a linear alkylene group having 6 to 10 carbon atoms and at least one polymerizable group among the compounds of the component (B), n-hexyl (meth) acrylate, n- to Butyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9 nonanediol di (meth) acrylate, 1,10-decane Diol di (meth) acrylate is mentioned. In addition, in this specification, a (meth) acrylate compound means both an acrylate compound and a methacrylate compound, for example, (meth) acrylic acid means both acrylic acid and methacrylic acid.

Among the compounds of the above component (B), compounds having a linear alkylene group having 6 to 10 carbon atoms and at least one polymerizable group are commercially available products, and specific examples thereof include Acrylic acid n-hexyl ester, methhacrylic acid n-hexyl ester (above, manufactured by Tokyo Chemical Industry Co., Ltd.), n-heptyl acrylate, n-heptyl methacrylate, n-octyl acrylate, n-octyl methacrylate, n-nonacrylate, n- Nonyl methacrylate, n-Decyl acrylate, n-Decyl methacrylate (above, made by ABCR GmbH & Co. KG), NK Esthetic A-HD-N, HD-N, A-NOD-N, NOD-N, A-DOD, DOD-N (above, Shin-Nakamura Chemical Co., Ltd. made), NOAA, Viscote (registered trademark) And # 260 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and Funkril (registered trademark) FA-129AS (manufactured by Hitachi Chemical Co., Ltd.).

Among the compounds of the component (B), specific examples of the compound having at least one alicyclic structure and at least one polymerizable group selected from the group consisting of cyclopentane structure, cyclohexane structure, norbornane structure, isobornyl structure and adamantane structure , Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexane spiro-2- (1,3-dioxolan-4-yl) methyl acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 1- Acryloyl 3-hydroxyadamantane, 3-hydroxy-1-methacryloyloxyadamantane, 2-methacryloyloxy-2-methyladamantane, 1,3-diacryloyloxyadamantane, 2-ethyl-2-methaquat Yl oxy adamantane, 2-isopropyl-2-meth acryloyloxyadamantane include 3,4-epoxycyclohexylmethyl (meth) acrylate.

Among the compounds of the component (B), compounds having at least one alicyclic structure selected from the group consisting of cyclopentane structure, cyclohexane structure, norbornane structure, isobornyl structure and adamantane structure and at least one polymerizable group are commercially available products. It is available, and specific examples thereof include cyclopentyl acrylate, cyclopentyl methacrylate (above, manufactured by ABCR GmbH & Co. KG), cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate. Acrylate, 1-acryloyloxy-3-hydroxyadamantane, 3-hydroxy-1-methacryloyloxyadamantane, 2-methacryloyloxy-2-methyladamantane, 2-ethyl-2-methacryloyloxy Adamantane, 2-isopropyl-2-methacryloyloxyadamantane (above, made by Tokyo Chemical Industry Co., Ltd.), IBXA, Biscoat # 155, CHDOL-10, 1-ADA, 1-ADMA (above, Osaka Organic Chemical Industry Co., Ltd. made by ), Light ester CH, the same IB-X, light acrylate (registered trademark) IB-XA (above, Kyoeisha Chemical Co., Ltd.), the diamond (registered trademark) HADM, HADA, DHADM, ADPM, ADDA (above, Mitsubishi Gas Chemical Co., Ltd., New Frontier (registered trademark) HBPE-4 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and Cyclomer (registered trademark) M100 (all manufactured by Daicel Co., Ltd.).

Among the compounds of the component (B), an alicyclic structure selected from the group consisting of a linear alkylene group having 6 to 10 carbon atoms, a cyclopentane structure, a cyclohexane structure, a norbornane structure, an isobornyl structure and an adamantane structure, and The compound having at least one polymerizable group may be a compound having a linear alkylene group having 6 to 10 carbon atoms, the alicyclic structure, and the polymerizable group in one compound.

Among the compounds of the component (B), an alicyclic structure selected from the group consisting of a linear alkylene group having 6 to 10 carbon atoms, a cyclopentane structure, a cyclohexane structure, a norbornane structure, an isobornyl structure and an adamantane structure, and Compounds having at least one polymerizable group are commercially available, and specific examples thereof include UM-90 (1/3) DA (manufactured by Ube Industries, Ltd.).

[(C) ingredient]
The photopolymerization initiator which is the component (C) is not particularly limited as long as the light source used for light curing has absorption. For example, tert-butylperoxy-iso-butylate, 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) valerate, cyclohexanone peroxide, 2,2 ', 5,5'-tetra (tert-butylperoxy) Carbonyl) benzopheno 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (tert-amylperoxycarbonyl) benzophenone, 3,3 ', 4,4' -Tetra (tert-hexylperoxy carbonyl) benzophenone, 3,3'-bis (tert- butyl peroxy carbonyl) -4,4'- dicarboxy benzophenone, tert- butyl peroxy benzoate, di-tert- butyl diperoxy isophthalate etc Organic peroxides of 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone, quinones such as 1,2-benzanthraquinone; benzoin methyl, benzoin ethyl ether, α-methylbenzoin, α -Phenyl be Benzoin derivatives such as zoin; 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one , 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- [4- {4- (2-hydroxy-2) -Methyl-propionyl) benzyl} -phenyl] -2-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 -One, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-dimethylamino-2- ( Alkylphenone compounds such as 4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one; bis (2,4,6-trimethylbenzoyl) -phenyl phosphine oxide, 2 Acyl phosphine oxide compounds such as 4, 4, 6-trimethylbenzoyl-diphenyl-phosphine oxide; 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione; Examples include oxime ester compounds such as O-acetyl oxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone.

The photopolymerization initiator is available as a commercial product, and specific examples thereof include IRGACURE (registered trademark) 651, 184, 500, 2959, 127, 754, 907, 369, 379, 379 EG, 819, 819 DW, 1800, 1870, 784, OXE01, OXE 02, 250, 1173, MBF, 4265, TPO (above, BASF Japan Ltd.) , KAYACURE (registered trademark) DETX, MBP, DMBI, EPA, OA (above, Nippon Kayaku Co., Ltd. made), VICURE-10, 55 (above, made by STAUFFER Co. LTD), ESACURE (registered trademark) ) KIP150, TZT, 1001, KTO 46, KB1, KL200, KS300 The EB3, triazine -PMS, triazine A, triazine B (or, Nippon Siber Hegner KK), Adekaoptomer N-1717, the N-1414, the N-1606 (manufactured by KK ADEKA) and the like.

The said photoinitiator can be used individually by 1 type or in combination of 2 or more types.

The content ratio of the component (C) in the imprint material of the present invention is, for example, 0.01 phr to 30 phr, preferably 0.05 phr to 20 phr, based on the total mass of the components (A) and (B). And more preferably 0.1 phr to 8 phr. If the content ratio of the component (C) is less than 0.01 phr, sufficient curability can not be obtained, and deterioration of patterning characteristics occurs. In the present specification, "phr" represents the mass of the photopolymerization initiator which is, for example, the component (C) relative to 100 g in total mass of the components (A) and (B).

[(D) component]
Specific examples of the compound having at least one thiol group which is the component (D) include methyl mercaptoacetate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, 3-methoxybutyl 3-mercaptopropionate, N-octyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, 1,4-bis (3-mercaptopropionyloxy) butane, 1,4-bis (3-mercaptobutyryloxy) butane, trimethylolethane tris 3-Mercapto propionate), trimethylol ethane tris (3-mercapto butyrate), trimethylol propane tris (3-mercapto propionate), trimethylol propane tris (3- mercapto butyrate), pentaerythritol teto Kiss (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptobutyrate), tris [ 2- (3-Mercaptopropionyloxy) ethyl] isocyanurate, tetraethylene glycol bis (3-mercaptopropionate), tris [2- (3-mercaptobutyryloxy) ethyl] isocyanurate, 1,3,5- Mercaptocarboxylic acid esters such as tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione; ethanethiol, 2-methylpropane 2-thiol, n-dodecanethiol, Alkylthiols such as 3,3,3,4,4,5-hexamethylhexane-2-thiol (tert-dodecanethiol), ethane-1,2-dithiol, propane-1,3-dithiol, benzylthiol; benzene Aromatic thiols such as thiol, 3-methylbenzenethiol, 4-methylbenzenethiol, naphthalene-2-thiol, pyridine-2-thiol, benzimidazole-2-thiol, benzothiazole-2-thiol; 2-mercaptoethanol Mercapto alcohols such as 4-mercapto-1-butanol; silane-containing thiols such as 3- (trimethoxysilyl) propane-1-thiol, 3- (triethoxysilyl) propane-1-thiol; bis (2- Mercaptoethyl) ether is mentioned.

The compounds having at least one thiol group are commercially available, and specific examples thereof include Thiocarcol (registered trademark) 20 (manufactured by Kao Corporation), Karenz MT (registered trademark) PE1, BD1 and the like. The same NR 1, TPMB, TEMB (manufactured by Showa Denko KK) can be mentioned.

The component (D) in the imprint material of the present invention may be used alone or in combination of two or more. In addition, the content thereof is, for example, 0.01 phr to 30 phr, more preferably 0.05 phr to 20 phr, based on the total mass of the components (A) and (B).

[(E) ingredient]
Examples of the antioxidant which is the component (E) include phenol-based antioxidants, phosphoric acid-based antioxidants, sulfide-based antioxidants and the like, among which phenolic antioxidants are preferable. As a phenolic antioxidant, For example, IRGANOX (registered trademark) 245, 1010, 1035, 1076, 1135 [above, BASF Japan Ltd. make], Sumilyzer (registered trademark) GA-80, the same GP, Same MDP-S, same BBM-S, same WX-R [above, Sumitomo Chemical Co., Ltd. product], Adekastab (registered trademark) AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330 [above, made by ADEKA, Inc.] are mentioned.

The component (E) in the imprint material of the present invention may be used alone or in combination of two or more. Also, the content ratio thereof is, for example, 0.01 phr to 20 phr, more preferably 0.05 phr to 10 phr, based on the total mass of the above-mentioned (A) component and (B) component.

[(F) component]
As the surfactant which is the component (F), for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, etc., polyoxyethylene octyl Polyoxyethylene alkyl aryl ethers such as phenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, Sorbitan fatty acid esters such as sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polio Shi sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan tristearate and the like.

The surfactant is available as a commercial product, and specific examples thereof include F-Top (registered trademark) EF 301, EF 303, EF 352 (above, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megafuck (registered trademark) Trademarks F-171, F-173, F-477, F-486, F-556, 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 (above, DIC) Florard FC430, FC 431 (above, 3M Japan KK), Asahi Guard (registered trademark) AG 710, Surflon (registered trademark) S-382, SC 101, SC 102, SC 103, Fluorinated surfactants such as SC104, SC105, SC106 (all manufactured by Asahi Glass Co., Ltd.); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-302, BYK-307, BYK-322, BYK -323, BYK-330, BYK-333, BYK-370, BYK-375, BYK-378, BYK-UV 3500, BYK-UV 3570 (above, manufactured by Big Chemie Japan Co., Ltd.).

The component (F) in the imprint material of the present invention may be used alone or in combination of two or more. Also, the content ratio thereof is preferably 0.01 phr to 40 phr, more preferably 0.01 phr to 10 phr, based on the total mass of the above-mentioned (A) component and (B) component.

[(G) component]
The imprint material of the present invention may contain a solvent as the component (G). The solvent plays the role of adjusting the viscosity of the components (A) and (B).

As the solvent, for example, toluene, p-xylene, o-xylene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, Ethylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether 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, acetic acid -Propyl, isobutyl acetate, n-butyl acetate, ethyl lactate, ethyl pyruvate, methanol, ethanol, isopropanol, tert-butanol, allyl alcohol, n-propanol, 2-methyl-2-butanol, isobutanol, n-butanol, 2-Methyl-1-butanol, 1-pentanol, 2-methyl-1-pentanol, 2-ethylhexanol, trimethylene glycol, 1-methoxy-2-butanol, isopropyl ether, 1,4-dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, N-cyclohexyl-2-pyrrolidine, and the like (A) Adjust the viscosity of component and component (B) It is not particularly limited as long as it can be carried out.

The said solvent can be used individually by 1 type or in combination of 2 or more types. When a solvent is used, the solvent of the component (G) is removed from all components of the imprint material of the present invention, that is, all components including the components (A) to (F) described above and other additives described later. The solids content defined as is preferably from 50% by weight to 99% by weight, preferably from 70% by weight to 99% by weight.

[Other additives]
The imprint material of the present invention may, if necessary, be a polymer compound, an epoxy compound, a photoacid generator, a photosensitizer, a UV absorber, a chain transfer agent, an adhesion aid, and the like as long as the effects of the present invention are not impaired An additive selected from the group consisting of releasability improvers can be included.

（式中、Ｒ₁は水素原子又はメチル基を表し、Ｘはシクロペンタン構造、シクロヘキサン構造、ノルボルナン構造、イソボルニル構造、アダマンタン構造及びトリシクロデカン構造からなる群から選択される脂環構造を有する有機基を表す。）The above-mentioned polymer compound can be added to adjust the refractive index and the Abbe number without impairing the transparency, and it is preferable that the polymer compound has a repeating structural unit represented by the following formula (2) . The content ratio is preferably 0.1% by mass to 90% by mass, and more preferably 5% by mass to 70% by mass, based on the total mass of the component (A), the component (B) and the polymer compound. It is less than mass%.

(Wherein, R ₁ represents a hydrogen atom or a methyl group, and X represents an organic group having an alicyclic structure selected from the group consisting of a cyclopentane structure, a cyclohexane structure, a norbornane structure, an isobornyl structure, an adamantane structure and a tricyclodecane structure Represents a group)

Examples of the epoxy compound include EPIDEALD (registered trademark) GT-401 and PB3600, Celoxide (registered trademark) 2021 P, 2000 and 3000, EHPE 3150, and EHPE 3150 CE (all manufactured by Daicel Corporation), EPICLON (registered trademark) 840, 840-S, N-660, N-673-80M (all manufactured by DIC Corporation).

Examples of the photoacid generator include IRGACURE (registered trademark) PAG 103, PAG 108, PAG 121, PAG 203, and CGI 725 (above, manufactured by BASF Japan Ltd.), WPAG-145, WPAG-170, WPAG-199, WPAG-281, WPAG-336, WPAG-367 (all, manufactured by Wako Pure Chemical Industries, Ltd.), TFE triazine, TME-triazine, MP-triazine, dimethoxytriazine, TS-91, TS-01 (Sanwa Chemical Co., Ltd.) CPI-100P, CPI-101A, CPI-200K, CPI-110P, 210S, CPI-110P, CPI-110B (all manufactured by San-Apro Co., Ltd.).

As the photosensitizer, for example, 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 And acridine type, thiazine type, phenothiazine type, anthracene type, coronene type, benzanthracene type, perylene type, ketocoumarin type, coumarin type and borate type. The photosensitizer is available as a commercial product, and specific examples thereof include Anthracure (registered trademark) UVS-581, UVS-1331 (above, manufactured by Kawasaki Kasei Kogyo Co., Ltd.), and KAYACURE (registered trademark). Trademarks DETX-S (made by Nippon Kayaku Co., Ltd.) is mentioned. These photosensitizers can be used alone or in combination of two or more. The absorption wavelength in the UV region can also be adjusted by using the photosensitizer.

Examples of the UV absorber include TINUVIN (registered trademark) PS, 99-2, 109, 328, 384-2, 400, 405, 460, 477, 479, 900, and the like. 928, 1130, 111 FDL, 123, 144, 152, 292, 5100, 400-DW, 477-DW, 99-DW, 123-DW, 5050, 5060, 5151 (all manufactured by BASF Japan Ltd.). These ultraviolet absorbers can be used alone or in combination of two or more. By using the said ultraviolet absorber, the curing speed of the outermost surface of a film | membrane can be controlled at the time of photocuring of the imprint material of this invention, and releasability may be able to be improved.

As the above-mentioned chain transfer agent, for example, diethyl disulfide, dipropyl disulfide, diisopropyl disulfide, dibutyl disulfide, di-tert-butyl disulfide, dipentyl disulfide, diisopentyl disulfide, dihexyl disulfide, dicyclohexyl disulfide, didecyl disulfide, bis (2 , 3,3,4,4,5-hexamethylhexan-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 (pyridin-2-yl) pyridyl disulfide, di (benzimidazole-2 Aromatic disulfides such as diyl chloride, di (benzothiazol-2-yl) disulfide; tetramethyl thiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, thiuram disulfides such as bis (pentamethylene) thiuram disulfide; α- Methyl styrene dimer is mentioned. These chain transfer agents can be used singly or in combination of two or more.

As said adhesion | attachment adjuvant, 3-methacryloxypropyl trimethoxysilane and 3-acryloxy propyl trimethoxysilane are mentioned, for example. The adhesion to the substrate is improved by using the adhesion aiding agent. The content of the adhesion adjuvant is preferably 5 phr to 50 phr, more preferably 10 phr to 50 phr, based on the total mass of the components (A) and (B).

Examples of the releasability improver include fluorine-containing compounds. As a fluorine-containing compound, R-5410, R-1420, M-5410, M-1420, E-5444, E-7432, A-1430, A-1630 (above, Daikin Industries, Ltd. make) are mentioned, for example. Be

[Preparation of imprint material]
Although the preparation method of the imprint material of this invention is not specifically limited, (A) component, (B) component, (C) component, and (D) component which is an optional component, (E) component, (F) component The component (G) and, if desired, other additives may be mixed so that the imprint material is in a uniform state. Further, the order of mixing the components (A) to (G) and optionally other additives is not particularly limited as long as a uniform imprint material can be obtained. As a method of preparing the imprint material, for example, the component (A) and the component (B) are mixed at a predetermined ratio, and the component (C) and optionally the component (D) and the component (E) are further added thereto. There is also a method of appropriately mixing the (F) component and the (G) component to obtain a uniform imprint material. In addition, other additives may be further added and mixed, as necessary, at appropriate stages of the preparation method.

[Films to which light imprint and pattern are transferred]
The imprint material of the present invention can be applied on a substrate and light cured to obtain a desired film. The coating method may be a known or known method, such as spin coating, dipping, flow coating, inkjet, spraying, bar coating, gravure coating, slit coating, roll coating, transfer printing, Brush coating, blade coating, and air knife coating can be mentioned.

As a substrate for applying the imprint material of the present invention, for example, silicon, glass (ITO substrate) on which indium tin oxide (ITO) is formed, and glass on which silicon nitride (SiN) is formed. (SiN substrate), glass on which indium zinc oxide (IZO) is formed, polyethylene terephthalate (PET), triacetylcellulose (TAC), acrylic, plastic, glass, quartz, ceramics, etc. it can. Also, flexible flexible substrates 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 comprising phthalate, polyether sulfone, and a copolymer obtained by combining these polymers.

As the light source for photocuring imprinting material of the present invention is not particularly limited, for example, a high pressure mercury lamp, low pressure mercury lamp, electrodeless lamp, a metal halide lamp, KrF excimer laser, ArF excimer laser, F ₂ excimer laser, electron There may be mentioned ray (EB), extreme ultraviolet (EUV), ultraviolet LED (UV-LED). In addition, as the wavelength, 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 addition, when using the solvent which is the above-mentioned (G) component, you may add a baking process in order to evaporate a solvent with respect to at least one of the coating film before light irradiation, and the hardened | cured material after light irradiation. . The firing apparatus is not particularly limited, and can be fired, for example, in an appropriate atmosphere, that is, in the atmosphere, an inert gas such as nitrogen, or vacuum using a hot plate, an oven, or a furnace. If it is The calcination temperature is not particularly limited for the purpose of evaporating the solvent, but can be performed, for example, at 40 ° C. to 200 ° C.

A film to which a pattern has been transferred, which is produced using the imprint material of the present invention, has high transparency even in the visible light region even with a thick film of, for example, 1 mm, and further exhibits high refractive index and Abbe number. It can be suitably used as an optical article such as a lens for module or a resin mold for imprint.

The apparatus for performing light imprinting is not particularly limited as long as the target pattern can be obtained. For example, ST50 manufactured by Toshiba Machine Co., Ltd., Sindre (registered trademark) 60 manufactured by Obducat, NM-8001HB manufactured by Meisho Kiko Co., Ltd. In a commercially available apparatus, a method may be used in which the substrate and the mold are press-bonded with a roller, and after photocuring, the cured product is released from the mold.

Moreover, as a mold material used for optical imprint used by this invention, although quartz, silicon, nickel, an alumina, a carbonylsilane, and glassy carbon can be mentioned, for example, if the target pattern is obtained, it will be especially limited I will not. Further, the mold may be subjected to a release treatment for forming a thin film of a fluorine-based compound or the like on the surface thereof in order to enhance the release property. As a mold release agent used for mold release treatment, for example, Optool (registered trademark) HD and product DSX manufactured by Daikin Industries, Ltd. can be mentioned, but there is no particular limitation as long as a desired pattern can be obtained.

The pattern size of the optical imprint in the present invention is not particularly limited. For example, good patterns can be obtained on the order of nanometers, micrometers, or millimeters.

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited to these examples.

The weight average molecular weight of the polymer shown in Synthesis Example 1 and Synthesis Example 2 described later is a measurement result by gel permeation chromatography (hereinafter, abbreviated as "GPC" in the present specification). For the measurement, a GPC system manufactured by Shimadzu Corporation was used. The structure of the said GPC system and measurement conditions are as follows.
GPC system configuration system controller: CBM-20A, column oven: CTO-20, auto sampler: SIL-10AF, detector: SPD-20A and RID-10A, exhaust unit: DGU-20A3
GPC column: Shodex (registered trademark) KF-804L and KF-803L
Column temperature: 40 ° C
Solvent: tetrahydrofuran Flow rate: 1 mL / min Standard sample: 6 types of polystyrene of different weight average molecular weights (197000, 55100, 12800, 3950, 1260, 580)

Synthesis Example 1
9.18 g of tricyclo [5.2.1.0 ^2,6 ] decanedimethanol, 2.72 g of 2-hydroxyethyl acrylate, 0.013 g of 2,6-di-t-butyl-p-cresol, 0 dibutyltin dilaurate In a three-necked flask, .019 g and 37.4 g of ethyl acetate were placed and heated to 80.degree. Thereto, 13.00 g of isophorone diisocyanate was dropped over 3 hours and reacted at 80 ° C. for 12 hours. The reaction solution was cooled to room temperature and then poured into hexane, and the precipitated solid was collected and dried under the conditions of 40 ° C. and 1 mmHg, to obtain compound G1. The obtained G1 corresponds to the component (B), and the weight average molecular weight was 3610 as measured by GPC.

Synthesis Example 2
In a three-necked flask, 34.58 g of propylene glycol monomethyl ether acetate (hereinafter abbreviated as "PGMEA") was placed, heated to 90 ° C. after degassing and nitrogen substitution. Then 10.00 g of 1-ADMA (Osaka Organic Chemical Industry Co., Ltd.) (hereinafter referred to as "ADMA" for short in the present specification), 0.75 g of azobisisobutyronitronyl, and 48.41 g of PGMEA are uniformly phased. The dissolved solution was added dropwise over 3 hours and allowed to react at 90 ° C. for 24 hours. The reaction solution was cooled to room temperature and then poured into methanol, and the precipitated solid was collected and dried under vacuum at 80 ° C. to give compound G2. The obtained G2 corresponds to a polymer compound among the above-mentioned other additives, and when the weight average molecular weight was measured by GPC, it was 11322.

[Preparation of imprint material]
Example 1
NK ester A-DOG (hereinafter, abbreviated as "A-DOG" in the present specification) (made by Shin-Nakamura Chemical Co., Ltd.) 1 g and UM-90 (1/3) DA (made by Ube Industries, Ltd.) 9 g Are mixed, and 0.2 g (A-DOG, UM-90 (1) of IRGACURE (registered trademark) 184 (manufactured by BASF Japan Ltd.) (hereinafter abbreviated as "IRGACURE 184") is added to the mixture. 3) Add 2 phr) to the total mass of DA to prepare imprint material PNI-a1.

Example 2
2 g of A-DOG and 8 g of UM-90 (1/3) DA are mixed, 0.2 g of IRGACURE 184 is added to the mixture (2 phr based on the total mass of A-DOG, UM-90 (1/3) DA) ) In addition, imprint material PNI-a2 was prepared.

Example 3
3 g of A-DOG and 7 g of UM-90 (1/3) DA are mixed, 0.2 g of IRGACURE 184 is added to the mixture (2 phr based on the total mass of A-DOG, UM-90 (1/3) DA) In addition, imprint material PNI-a3 was prepared.

Example 4
4 g of A-DOG and 6 g of UM-90 (1/3) DA are mixed, 0.2 g of IRGACURE 184 is added to the mixture (2 phr based on the total mass of A-DOG, UM-90 (1/3) DA) ), And prepared imprinting material PNI-a4.

Example 5
5 g of A-DOG and 5 g of UM-90 (1/3) DA are mixed, 0.2 g of IRGACURE 184 is added to the mixture (2 phr based on the total mass of A-DOG, UM-90 (1/3) DA) ) In addition, imprint material PNI-a5 was prepared.

Example 6
6 g of A-DOG and 4 g of UM-90 (1/3) DA are mixed, 0.2 g of IRGACURE 184 is added to the mixture (2 phr based on the total mass of A-DOG, UM-90 (1/3) DA) In addition, imprint material PNI-a6 was prepared.

Example 7
7 g of A-DOG and 3 g of UM-90 (1/3) DA are mixed, 0.2 g of IRGACURE 184 is added to the mixture (2 phr based on the total mass of A-DOG, UM-90 (1/3) DA) In addition, imprint material PNI-a7 was prepared.

Example 8
8 g of A-DOG and 2 g of UM-90 (1/3) DA are mixed, 0.2 g of IRGACURE 184 is added to the mixture (2 phr based on the total mass of A-DOG, UM-90 (1/3) DA) In addition, imprint material PNI-a8 was prepared.

Example 9
9 g of A-DOG and 1 g of UM-90 (1/3) DA are mixed, 0.2 g of IRGACURE 184 is added to the mixture (2 phr based on the total mass of A-DOG, UM-90 (1/3) DA) ) In addition, imprint material PNI-a9 was prepared.

Example 10
1 g of A-DOG and 9 g of UM-90 (1/3) DA are mixed, 0.2 g of IRGACURE 184 is added to the mixture (2 phr based on the total mass of A-DOG, UM-90 (1/3) DA) And 0.05 g (A-DOG, UM-90 (1/3) DA) of Thio Carcol (registered trademark) 20 (manufactured by Kao Corporation) (hereinafter abbreviated as “Thio Carcol 20” in the present specification). 0.5 phr was added to the mass to prepare (imprint material PNI-a10).

Example 11
2 g of A-DOG and 8 g of UM-90 (1/3) DA are mixed, 0.2 g of IRGACURE 184 is added to the mixture (2 phr based on the total mass of A-DOG, UM-90 (1/3) DA) ), 0.05 g (A-DOG, 0.5 phr based on the total mass of UM-90 (1/3) DA) of thiocarcol 20 was added to prepare imprint material PNI-a11.

Example 12
3 g of A-DOG and 7 g of UM-90 (1/3) DA are mixed, 0.2 g of IRGACURE 184 is added to the mixture (2 phr based on the total mass of A-DOG, UM-90 (1/3) DA) ), 0.05 g (A-DOG, 0.5 phr based on the total mass of UM-90 (1/3) DA) of thiocarcol 20 was added to prepare imprint material PNI-a12.

Example 13
4 g of A-DOG and 6 g of UM-90 (1/3) DA are mixed, 0.2 g of IRGACURE 184 is added to the mixture (2 phr based on the total mass of A-DOG, UM-90 (1/3) DA) ), Thiocarcol 20 was added by 0.05 g (A-DOG, 0.5 phr based on the total mass of UM-90 (1/3) DA) to prepare an imprint material PNI-a13.

Example 14
5 g of A-DOG and 5 g of UM-90 (1/3) DA are mixed, 0.2 g of IRGACURE 184 is added to the mixture (2 phr based on the total mass of A-DOG, UM-90 (1/3) DA) ), Thiocarcol 20 was added by 0.05 g (A-DOG, 0.5 phr based on the total mass of UM-90 (1/3) DA) to prepare imprint material PNI-a14.

Example 15
5 g of A-DOG and 5 g of UM-90 (1/3) DA are mixed, 0.2 g of IRGACURE 184 is added to the mixture (2 phr based on the total mass of A-DOG, UM-90 (1/3) DA) 0.05 g (A-DOG, UM-90 (1/3)), Kalens MT (registered trademark) PE1 (manufactured by Showa Denko KK) (hereinafter abbreviated as "Kalens MT PE1" in the present specification). 0.5 phr) based on the total mass of DA was added to prepare imprint material PNI-a15.

Example 16
6 g of A-DOG and 4 g of UM-90 (1/3) DA are mixed, 0.2 g of IRGACURE 184 is added to the mixture (2 phr based on the total mass of A-DOG, UM-90 (1/3) DA) ), 0.05 g (A-DOG, 0.5 phr based on the total weight of UM-90 (1/3) DA) of thiocarcol 20 was added to prepare imprint material PNI-a16.

Example 17
7 g of A-DOG and 3 g of UM-90 (1/3) DA are mixed, 0.2 g of IRGACURE 184 is added to the mixture (2 phr based on the total mass of A-DOG, UM-90 (1/3) DA) ), Thiocarcol 20 was added by 0.05 g (A-DOG, 0.5 phr based on the total mass of UM-90 (1/3) DA) to prepare imprint material PNI-a17.

Example 18
8 g of A-DOG and 2 g of UM-90 (1/3) DA are mixed, 0.2 g of IRGACURE 184 is added to the mixture (2 phr based on the total mass of A-DOG, UM-90 (1/3) DA) ), 0.05 g (A-DOG, 0.5 phr with respect to the total mass of UM-90 (1/3) DA) of thiocarcol 20 was added to prepare imprint material PNI-a18.

Example 19
9 g of A-DOG and 1 g of UM-90 (1/3) DA are mixed, 0.2 g of IRGACURE 184 is added to the mixture (2 phr based on the total mass of A-DOG, UM-90 (1/3) DA) ), 0.05 g (A-DOG, 0.5 phr based on the total weight of UM-90 (1/3) DA) of thiocarcol 20 was added to prepare imprint material PNI-a19.

Example 20
5 g of A-DOG and 5 g of UM-90 (1/3) DA are mixed, 0.2 g of IRGACURE 184 is added to the mixture (2 phr based on the total mass of A-DOG, UM-90 (1/3) DA) And 0.05 g (A-DOG, 0.5 phr based on the total mass of UM-90 (1/3) DA), and Adekastab (registered trademark) AO-60 (manufactured by ADEKA Corporation) in an amount of 0. 01 g (A-DOG, 0.1 phr based on the total mass of UM-90 (1/3) DA) was added to prepare an imprint material PNI-a20.

Example 21
5 g of A-DOG and 5 g of UM-90 (1/3) DA are mixed, 0.2 g of IRGACURE 184 is added to the mixture (2 phr based on the total mass of A-DOG, UM-90 (1/3) DA) And 0.05 g (A-DOG, 0.5 phr based on the total mass of UM-90 (1/3) DA), and Adekastab (registered trademark) AO-80 (manufactured by ADEKA Corporation) in an amount of 0. 01 g (A-DOG, 0.1 phr based on the total mass of UM-90 (1/3) DA) was added to prepare imprint material PNI-a21.

Example 22
5 g of A-DOG and 5 g of UM-90 (1/3) DA are mixed, 0.2 g of IRGACURE 184 is added to the mixture (2 phr based on the total mass of A-DOG, UM-90 (1/3) DA) 0.05 g (A-DOG, 0.5 phr based on the total mass of UM-90 (1/3) DA), 0.01 g of BYK-UV 3570 (manufactured by BIC Chemie Japan Ltd.) A-DOG, 0.1 phr based on the total mass of UM-90 (1/3) DA was added to prepare imprint material PNI-a22.

Example 23
5 g of A-DOG and 5 g of UM-90 (1/3) DA are mixed, 0.2 g of IRGACURE 184 is added to the mixture (2 phr based on the total mass of A-DOG, UM-90 (1/3) DA) ), 0.05 g (A-DOG, 0.5 phr based on the total mass of UM-90 (1/3) DA) of thiocarcol 20, 1.139 g of PGMEA was added to prepare imprint material PNI-a23.

Reference Example 24
5 g of A-DOG and 5 g of NK ester A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.) (hereinafter abbreviated as “A-DCP” in the present specification) are mixed, and IRGACURE 184 is 0.1. 2 g (A-DOG, 2 phr based on the total mass of A-DCP), 0.05 g (0.5 phr based on the total mass of A-DOG, A-DCP) of thiocarcol 20, imprint material PNI-a24 Was prepared.

Example 25
Mix 5g A-DOG and 5g ADMA, add 0.2g IRGACURE 184 (2 phr to A-DOG, total mass of ADMA), 0.05g thiocarcol 20 (A-DOG, total ADMA) in the mixture 0.5 phr) based on mass was added to prepare imprint material PNI-a25.

Example 26
A mixture of 5 g of A-DOG and 5 g of IBXA (manufactured by Osaka Organic Chemical Industry Co., Ltd.), 0.2 g of IRGACURE 184 (A-DOG, 2 phr based on the total mass of IBXA), 0.2 g of thiocarcol 20, 05 g (A-DOG, 0.5 phr based on the total mass of IBXA) was added to prepare imprint material PNI-a26.

Example 27
5 g of A-DOG and 5 g of New Frontier® HBPE-4 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) (hereinafter abbreviated as “HBPE-4” in the present specification) are mixed, and IRGACURE is added to the mixture. 0.2g (A-DOG, 2 phr based on the total mass of HBPE-4), 0.05 g (0.5 phr based on the total mass of A-DOG, HBPE-4) of thiocarcol 20, and imprinted Material PNI-a27 was prepared.

Example 28
5 g of A-DOG and 5 g of Viscoat # 230 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) (hereinafter abbreviated as “V # 230” in this specification) are mixed, 0.2 g of IRGACURE 184 is added to the mixture, A-DOG, 2 phr to the total mass of V # 230, 0.05 g of thiocarcol 20 (A-DOG, 0.5 phr to the total mass of V # 230), to prepare imprint material PNI-a28 did.

Example 29
5 g of A-DOG and 5 g of Viscote # 260 (Osaka Organic Chemical Industry Co., Ltd.) (hereinafter referred to as “V # 260” in the present specification) are mixed, 0.2 g of IRGACURE 184 is added to the mixture, A-DOG, 2 phr to the total mass of V # 260, 0.05 g of thiocarcol 20 (A-DOG, 0.5 phr to the total mass of V # 260), to prepare imprint material PNI-a29 did.

Example 30
5 g of A-DOG, 2.5 g of ADMA, and 2.5 g of UM-90 (1/3) DA were mixed, and 0.2 g of IRGACURE 184 was added to the mixture (A-DOG, ADMA, UM-90 (1 / 3) Add 2 phr to the total mass of DA, 0.05 g of thiocarcol 20 (0.5 phr to the total mass of A-DOG, ADMA, UM-90 (1/3) DA), imprint material PNI-a30 was prepared.

Example 31
Mix 5 g A-DOG, 2.5 g ADMA, and 2.5 g HBPE-4 and add 0.2 g IRGACURE 184 to the mixture (2 phr based on the total weight of A-DOG, ADMA, HBPE-4) An imprint material PNI-a31 was prepared by adding 0.05 g (0.5 phr based on the total weight of A-DOG, ADMA, HBPE-4) of thiocarcol 20.

Example 32
5 g of A-DOG, 2.5 g of ADMA, and 2.5 g of G1 obtained in Synthesis Example 1 were mixed, 0.2 g of IRGACURE 184 was added to the mixture (based on the total mass of A-DOG, ADMA, G1) An imprint material PNI-a32 was prepared by adding 2 phr) and thiocarcol 20 at 0.05 g (A-DOG, ADMA, 0.5 phr based on the total weight of G1).

Example 33
5 g of A-DOG, 2.5 g of ADMA, and 2.5 g of G2 obtained in Synthesis Example 2 were mixed, 0.2 g of IRGACURE 184 was added to the mixture (relative to the total mass of A-DOG, ADMA, G2 An imprint material PNI-a33 was prepared by adding 2 phr) and thiocarcol 20 at 0.05 g (0.5 phr based on the total weight of A-DOG, ADMA, G2).

Example 34
7 g of A-DOG and 3 g of HBPE-4 are mixed, 0.01 g (A-DOG, 0.1 phr based on the total weight of HBPE-4) of IRGACURE 184 is added to the mixture, and the imprint material PNI-a34 is added. Prepared.

Example 35
6 g of A-DOG and 4 g of HBPE-4 are mixed, 0.01 g (A-DOG, 0.1 phr based on the total weight of HBPE-4) of IRGACURE 184 is added to the mixture, and the imprint material PNI-a35 is added. Prepared.

Example 36
5 g of A-DOG and 5 g of HBPE-4 are mixed, 0.01 g (A-DOG, 0.1 phr based on the total weight of HBPE-4) of IRGACURE 184 is added to the mixture, and the imprint material PNI-a36 is added. Prepared.

Example 37
4 g of A-DOG and 6 g of HBPE-4 are mixed, 0.01 g (A-DOG, 0.1 phr based on the total weight of HBPE-4) of IRGACURE 184 is added to the mixture, and the imprint material PNI-a37 is added. Prepared.

Example 38
3 g of A-DOG and 7 g of HBPE-4 are mixed, 0.01 g (A-DOG, 0.1 phr based on the total weight of HBPE-4) of IRGACURE 184 is added to the mixture, and the imprint material PNI-a38 is added. Prepared.

Example 39
A mixture of 5 g of A-DOG and 5 g of HBPE-4, 0.01 g (A-DOG, 0.1 phr based on the total mass of HBPE-4) of IRGACURE 184 and 0.05 g of thiocarcol 20 (A The imprint material PNI-a39 was prepared by adding-0.5 phr to the total mass of DOG and HBPE-4.

Example 40
A mixture of 5 g of A-DOG and 5 g of HBPE-4, 0.01 g (A-DOG, 0.1 phr based on the total mass of HBPE-4) of IRGACURE 184 and 0.05 g of Karenz MT PE1 in the mixture A-DOG, 0.5 phr based on the total mass of HBPE-4) was added to prepare imprint material PNI-a40.

Example 41
5 g of A-DOG mixed with 5 g of HBPE-4, 0.01 g (A-DOG, 0.1 phr based on the total weight of HBPE-4) of IRGACURE 184 is added to the mixture, Karenz MT (registered trademark) NR1 ( An imprint material PNI-a41 was prepared by adding 0.05 g (A-DOG, 0.5 phr based on the total mass of HBPE-4) of Showa Denko KK.

Comparative Example 1
Imprint material PNI-b1 was prepared by adding 10 g of A-DOG and 0.2 g of IRGACURE 184 (2 phr based on the weight of A-DOG). The imprint material of the present comparative example includes the (A) component and the (C) component but does not include the (B) component.

Comparative Example 2
An imprint material PNI-b2 was prepared by adding 10 g of UM-90 (1/3) DA and 0.2 g of IRGACURE 184 (2 phr based on the mass of UM-90 (1/3) DA). The imprint material of this comparative example includes the (B) component and the (C) component but does not include the (A) component.

Comparative Example 3
Imprint material PNI-b3 was prepared by adding 10 g of ADMA and 0.2 g of IRGACURE 184 (2 phr based on the weight of ADMA). The imprint material of this comparative example includes the (B) component and the (C) component but does not include the (A) component.

Comparative Example 4
Imprint material PNI-b4 was prepared by adding 10 g of V # 230 and 0.2 g of IRGACURE 184 (2 phr based on the weight of V # 230). The imprint material of this comparative example includes the (B) component and the (C) component but does not include the (A) component.

Comparative Example 5
5 g of A-DOG and 5 g of KAYARAD (registered trademark) NPGDA (manufactured by Nippon Kayaku Co., Ltd.) (hereinafter abbreviated as “NPGDA” in the present specification) are mixed, and 0.2 g of IRGACURE 184 is added to the mixture. (2 phr based on the total mass of A-DOG and NPGDA) was added to prepare imprint material PNI-b5. Since NPGDA used in the present comparative example does not correspond to the component (B), the imprint material of the present comparative example contains the components (A) and (C) but does not contain the component (B).

Comparative Example 6
A mixture of 5 g of A-DOG and 5 g of NPGDA, 0.2 g of IRGACURE 184 (2 phr based on the total mass of A-DOG, NPGDA) and 0.05 g of thiocarcol 20 (total of A-DOG, NPGDA) 2 phr) was added to the mass to prepare imprint material PNI-b6. Since NPGDA used in this comparative example does not fall under component (B), the imprint material of this comparative example contains components (A), (C) and (D) but does not contain component (B) .

Comparative Example 7
5 g of A-DOG, and NK ester APG-400 (manufactured by Shin-Nakamura Chemical Co., Ltd.) Hereinafter, this specification is abbreviated as "APG-400". 5 g) and 0.2 g (A-DOG, 2 phr based on the total weight of APG-400) of IRGACURE 184 was added to the mixture to prepare imprint material PNI-b7. Since APG-400 used in this comparative example does not correspond to the component (B), the imprint material of this comparative example contains the components (A) and (C) but does not contain the component (B).

Comparative Example 8
5 g of A-DOG and 5 g of APG-400 are mixed, 0.2 g (A-DOG, 2 phr based on the total mass of APG-400) of IRGACURE 184 in the mixture, 0.05 g of thiocarcol 20 (A-DOG) , 2 phr) based on the total mass of APG-400, to prepare imprint material PNI-b8. Since the APG-400 used in this comparative example does not correspond to the component (B), the imprint material of this comparative example contains the components (A), (C) and (D), but the component (B) Not included.

[Mold release treatment]
Silicon mold having a line and space pattern (hereinafter, L / S) of 20 μm, Optool (registered trademark) DSX (manufactured by Daikin Industries, Ltd.), Novec (registered trademark) HFE-7100 (hydrofluoroether, 3M Japan stock) Immersed in a solution diluted to 0.1% by mass with a company (hereinafter referred to as "Novec HFE-7100" in this specification), and a high-temperature, high-humidity device with a temperature of 90 ° C and a humidity of 90RH% It was treated for 1 hour, rinsed with Novec HFE-7100, and dried with air.

[Light imprint]
The imprinting materials obtained in Examples 1 to 23, Examples 25 to 41, Reference 24, and Comparative Examples 1 to 8 are potted into a mold subjected to the above-described release treatment. Then, quartz glass was put thereon, and photoimprinting was performed using a nanoimprinting apparatus NM-0801HB (manufactured by Meisho Kikai Co., Ltd.).
Photoimprinting is always carried out at 23 ° C., a) Pressurized to 500 N for 10 seconds, b) Exposure of 6000 mJ / cm ² using a high-pressure mercury lamp, c) Depressurization for 10 seconds, d) Mold And release the substrate, and the resulting L / S pattern on quartz glass was heated on a hot plate at 170 ° C. for 5 minutes. And the presence or absence of peeling and a crack of L / S pattern was observed using industrial microscope ECLIPSE L150 (made by Nikon Corporation). The obtained results are shown in Tables 1 and 2.

[Preparation of cured product and evaluation of optical properties]
Each of the imprint materials obtained in Examples 1 to 23, Examples 25 to 41, Reference 24, and Comparative Examples 1 to 8 was combined with a 1 mm thick silicone rubber spacer to obtain Novec (registered It was sandwiched between two glass substrates surface-treated with a trademark 1720 (manufactured by 3M Japan Co., Ltd.). This sandwiching polymerizable composition was subjected to UV exposure at 20 mW / cm ² for 300 seconds using a batch-type UV irradiation apparatus (high-pressure mercury lamp 2 kW × 1 lamp) (manufactured by Eye Graphics Co., Ltd.). The obtained cured product was peeled off from the glass substrate, and then heated for 5 minutes on a hot plate at 170 ° C. to produce a molded product having a diameter of 40 mm and a thickness of 1 mm. The transmittance | permeability in 410 nm of the produced molded object was measured in the state which made the reference air, using spectrophotometer UV2600 (made by Shimadzu Corp.). The refractive index n _D at a wavelength of 589.3 nm (D line) and the Abbe number [nu _D, was measured using an automatic refractometer (Multi-Wavelength) Abbemat-WR / MW (manufactured Anton Paar). The obtained results are shown in Table 1, Table 2 and Table 3.

From the results shown in Table 1, Table 2 and Table 3, all the molded articles produced using the imprint material prepared in Examples 1 to 23 and Examples 25 to 41 have a diameter of 1 mm. Even in a thick film, high transparency with a transmittance of at least 90% at 410 nm is confirmed, and a refractive index at a wavelength of 589.3 nm (D line) has a high refractive index of 1.49 or more and a high Abbe number of 56 or more The result was to have On the other hand, in all the molded articles produced using the imprint materials prepared in Comparative Examples 1 to 8, the transmittance at 410 nm was less than 90%, and the transparency was low. Moreover, it was confirmed that all of Comparative Examples 2 to 8 have a refractive index lower than 1.49 or an Abbe number lower than 56, and do not simultaneously show a high refractive index and a high Abbe number. As mentioned above, the molded object produced using the imprint material of this invention has high transparency in visible region, and also has high refractive index and high Abbe number simultaneously.

Claims (14)

An imprint material containing the following components (A), (B) and (C):
(A): a compound represented by the following formula (1)

(Wherein, two R's each independently represent a hydrogen atom or a methyl group)
(B): a linear alkylene group having 6 to 10 carbon atoms and / or an alicyclic structure selected from the group consisting of a cyclopentane structure, a cyclohexane structure, a norbornane structure, an isobornyl structure and an adamantane structure, and a polymerizable group Compound (C) having at least one: Photopolymerization initiator The imprint material according to claim 1, wherein the polymerizable group is an acryloyloxy group, a methacryloyloxy group, a vinyl group or an allyl group. The imprint material according to claim 1, wherein the number of the polymerizable groups is one or two. The ratio of the said (A) component is 10 mass%-90 mass% with respect to 100 mass% of total mass of (A) component and (B) component as described in any one of Claim 1 thru | or 3 Imprint material. The imprint material according to any one of claims 1 to 4, further comprising a compound having at least one thiol group as the component (D). The imprint material according to any one of claims 1 to 5, further comprising an antioxidant as the component (E). The imprint material according to any one of claims 1 to 6, further comprising a surfactant as the component (F). The imprint material according to any one of claims 1 to 7, further comprising a solvent as the component (G). A film having a pattern transferred, which is produced using the imprint material according to any one of claims 1 to 8. The film according to claim 9, wherein the pattern is a lens shape. The film according to claim 9, wherein the film to which the pattern is transferred is a lens for a camera module. The film according to any one of claims 9 to 11, wherein the maximum film thickness of the film to which the pattern is transferred is 1.5 mm. A process for filling the space between the substrate and the mold in contact with each other, or the space inside the mold which can be divided, and the space for the imprint material according to any one of claims 1 to 8; A method for producing a film to which a pattern has been transferred, which comprises the steps of exposing and photocuring a filled imprint material. After the step of photocuring, the step of taking out and releasing the obtained photocured product, and the step of heating the photocured product before, halfway or after the step of releasing the mold, The manufacturing method of the film to which the pattern as described in was transferred.