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WO2018030351A1 - Matériau d'empreinte - Google Patents

Matériau d'empreinte Download PDF

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Publication number
WO2018030351A1
WO2018030351A1 PCT/JP2017/028619 JP2017028619W WO2018030351A1 WO 2018030351 A1 WO2018030351 A1 WO 2018030351A1 JP 2017028619 W JP2017028619 W JP 2017028619W WO 2018030351 A1 WO2018030351 A1 WO 2018030351A1
Authority
WO
WIPO (PCT)
Prior art keywords
component
imprint material
dog
phr
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2017/028619
Other languages
English (en)
Japanese (ja)
Inventor
淳平 小林
ダニエルアントニオ 櫻葉汀
偉大 長澤
圭介 首藤
加藤　拓
正睦 鈴木
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nissan Chemical Corp
Original Assignee
Nissan Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nissan Chemical Corp filed Critical Nissan Chemical Corp
Priority to JP2018533460A priority Critical patent/JP6802532B2/ja
Priority to SG11201901065TA priority patent/SG11201901065TA/en
Priority to KR1020197001499A priority patent/KR102401727B1/ko
Priority to CN201780048171.3A priority patent/CN109563194B/zh
Publication of WO2018030351A1 publication Critical patent/WO2018030351A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/303—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one or more carboxylic moieties in the chain
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F9/00—Registration or positioning of originals, masks, frames, photographic sheets or textured or patterned surfaces, e.g. automatically
    • G03F9/70—Registration or positioning of originals, masks, frames, photographic sheets or textured or patterned surfaces, e.g. automatically for microlithography
    • G03F9/7003—Alignment type or strategy, e.g. leveling, global alignment
    • G03F9/7042—Alignment for lithographic apparatus using patterning methods other than those involving the exposure to radiation, e.g. by stamping or imprinting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate

Definitions

  • the present invention relates to an imprint material (film-forming composition for imprint) and a film produced from the material and having a pattern transferred thereto. More specifically, the present invention relates to a film that is made of the material and has a pattern with a high refractive index and a high Abbe number, which retains high transparency even in a thick film state.
  • thick film represents a film having a thickness of 0.01 mm to 1.5 mm.
  • Nanoimprint lithography is a method in which 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 pattern.
  • This nanoimprint lithography has an advantage that nanoscale processing can be performed easily and inexpensively as compared with optical lithography or the like in conventional semiconductor device manufacturing. Therefore, nanoimprint lithography is a technology that is expected to be applied to the manufacture of semiconductor devices, opto-devices, displays, storage media, biochips, etc., instead of optical lithography technology.
  • Various reports have been made on curable compositions (Patent Documents 2 and 3).
  • a roll-to-roll method has been proposed as a method for mass-producing a film having a pattern transferred thereon with high efficiency.
  • the roll-to-roll method proposed in optical nanoimprint lithography uses a flexible film as a base material and a pattern as a material used in nanoimprint lithography (hereinafter abbreviated as “imprint material” in this specification).
  • imprint material used in nanoimprint lithography
  • the mainstream method is to use a solvent-free type material that does not add a solvent so that the dimensions are difficult to change.
  • solvent-free type materials are used for the conventionally proposed imprint materials, but after light imprinting with a thick film, it has high transparency in the visible light region and has a high refractive index. In addition, no specific study or report has been made on materials having a high Abbe number.
  • the present invention has been made on the basis of the above circumstances, and the problem to be solved is to have high transparency in the visible light region, high refractive index and high Abbe after light imprinting with a thick film.
  • the object is to provide an imprint material having a number.
  • the present inventors have found that a compound having a 1,3-dioxane ring and having a polymerizable group at both ends, a straight chain having 6 to 10 carbon atoms.
  • a material containing an alkylene group and / or a cyclopentane structure, a cyclohexane structure, a norbornane structure, an isobornyl structure, an alicyclic structure selected from the group consisting of an adamantane structure, a compound having at least one polymerizable group, and a photopolymerization initiator By using as an imprint material, the following knowledge was obtained and the present invention was completed. That is, the imprint material of the present invention has high transparency in the visible light region, high refractive index, and high Abbe number after light imprinting with a thick film.
  • An imprint material containing the following component (A), component (B) and component (C).
  • A Compound represented by the following formula (1) (In the formula, two Rs 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.
  • the imprint material according to the first aspect in which the polymerizable group is an acryloyloxy group, a methacryloyloxy group, a vinyl group, or an allyl group.
  • the imprint material according to the first aspect or the second aspect wherein the number of the polymerizable groups is one or two.
  • the ratio of the component (A) is 10% by mass to 90% by mass with respect to the total mass of 100% by mass of the component (A) and the component (B). The imprint material as described in one.
  • the imprint material according to any one of the first to fourth aspects further containing a compound having at least one thiol group as the component (D).
  • the imprint material according to any one of the first to seventh aspects which further contains a solvent as the component (G).
  • a film to which the pattern according to the ninth aspect is transferred wherein the pattern has a lens shape.
  • a film to which the pattern according to the ninth aspect or the tenth aspect is transferred wherein the film to which the pattern is transferred is a lens for a camera module.
  • a film to which the pattern according to any one of the ninth aspect to the eleventh aspect is transferred, wherein the maximum film thickness of the film to which the pattern is transferred is 1.5 mm.
  • a fourteenth aspect after the step of photocuring, a step of taking out and releasing the obtained photocured product, and a step of heating the photocured product before, during or after the step of releasing A method for producing a film to which the pattern according to the thirteenth aspect is transferred.
  • the imprint material of the present invention includes a compound represented by the 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.
  • the cured film produced from the imprint material has a high transparency in the visible light region even if it is a thick film by containing an alicyclic structure selected from the group consisting of and a compound having at least one polymerizable group. And a high refractive index and a high Abbe number.
  • the imprint material of the present invention can be photocured and does not peel off at a part of the pattern when peeled from the mold, a film in which a desired pattern is accurately formed can be obtained. Therefore, it is possible to form a good optical imprint pattern.
  • the imprint material of this invention can be formed into a film on arbitrary base materials,
  • membrane has high transparency in visible region, even if it is thick film, has a high refractive index and a high Abbe number.
  • the film to which the pattern formed after imprinting is transferred is used to manufacture optical members that require high transparency, high refractive index, and high Abbe number, such as solid-state imaging devices, camera module lenses, and sensor lenses. It can be used suitably.
  • examples of the lens include 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 (antireflection structure) on a curved surface.
  • the shape of the curved surface of the lens in the concave lens, the convex lens, the aspherical lens, the spherical lens, the Fresnel lens, the linear Fresnel lens, and the lens having a fine uneven shape (antireflection structure) on the curved surface is referred to as a lens shape. .
  • the imprint material of this invention can control a cure rate, dynamic viscosity, and a film thickness by changing the kind and content rate of the compound of the said (B) component. Therefore, the imprint material of the present invention can be designed suitably for the type of device to be manufactured, the type of exposure process and the type of baking process, and the process margin can be expanded. it can.
  • the compound of component (A) is a compound represented by the following formula (1). (In the formula, two Rs 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 compound represented by the above formula (1) can be obtained as a commercial product, and specific examples thereof include NK ester A-DOG (manufactured by Shin-Nakamura Chemical Co., Ltd.).
  • the compound of the said (A) component can be used individually by 1 type or in combination of 2 or more types.
  • 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 of 100% by mass of the component (A) and the component (B) described later. Is more preferable, and 40 mass% or more and 60 mass% or less are more preferable. If the proportion of the component (A) is less than 10% by mass or exceeds 90% by mass, the transparency of the film obtained by heating after photoimprinting may be lowered.
  • the component (B) compound is a straight chain 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 sex group.
  • the straight-chain alkylene group having 6 to 10 carbon atoms means (—CH 2 CH 2 CH 2 CH 2 CH 2 —), (—CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 —).
  • the alicyclic structure represents a cyclic and non-aromatic hydrocarbon.
  • the polymerizable group include an acryloyloxy group, a methacryloyloxy group, a vinyl group, and an allyl group.
  • the acryloyloxy group may be expressed as an acryloxy group
  • the methacryloyloxy group may be expressed as a methacryloxy group.
  • the compound of the component (B) may or may not have a group and structure other than the linear alkylene group having 6 to 10 carbon atoms, the alicyclic structure and the polymerizable group. It preferably has no group or structure other than the linear alkylene group, the alicyclic structure and the polymerizable group.
  • Specific examples of compounds having at least one straight chain alkylene group having 6 to 10 carbon atoms and a polymerizable group among the compounds of component (B) include n-hexyl (meth) acrylate and n- Ptyl (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 Examples include diol di (meth) acrylate.
  • 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.
  • a compound having at least one linear alkylene group having 6 to 10 carbon atoms and a polymerizable group can be obtained as a commercial product.
  • Specific examples thereof include Acrylic. acid n-hexylester, Methacrylic acid-n-hexyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.), n-Heptylacrylate, n-Heptylylmethacrylate, n-Octylylacrylate, n-Octylylate, n-Octylylate.
  • NK Esters A-HD-N, HD-N, A-NOD-N, NOD-N, A-DOD, DOD-N (Shin Nakamura Chemical Co., Ltd.), NOAA, Biscote ( (Registered trademark) # 230, # 260 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and FANCLIL (registered trademark) FA-129AS (above, manufactured by Hitachi Chemical Co., Ltd.).
  • compounds having at least one 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 are commercially available products. Specific examples include cyclopentyl acrylate, cyclopentyl methacrylate (above, manufactured by ABCR GmbH & Co. KG), cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate.
  • a linear alkylene group having 6 to 10 carbon atoms, and 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
  • the compound having at least one polymerizable group may be any compound having a linear alkylene group having 6 to 10 carbon atoms, the alicyclic structure, and a polymerizable group in one compound.
  • a linear alkylene group having 6 to 10 carbon atoms, and 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 compound having at least one polymerizable group can be obtained as a commercial product, and specific examples thereof include UM-90 (1/3) DA (manufactured by Ube Industries, Ltd.).
  • the photopolymerization initiator as the component (C) is not particularly limited as long as it has absorption in the light source used during photocuring.
  • the photopolymerization initiator as the component (C) is not particularly limited as long as it has absorption in the light source used during photocuring.
  • tert-butylperoxy-iso-butyrate 2,5-dimethyl-2,5-bis (benzoyldioxy) hexane
  • the photopolymerization initiator can be obtained as a commercial product. Specific examples thereof include IRGACURE (registered trademark) 651, 184, 500, 2959, 127, 754, 907, 369, 379, 379EG, 819, 819DW, 1800, 1870, 784, OXE01, OXE02, 250, 1173, MBF, 4265, TPO (above, manufactured by BASF Japan Ltd.) , KAYACURE (registered trademark) DETX, MBP, DMBI, EPA, OA (manufactured by Nippon Kayaku Co., Ltd.), VISURE-10, 55 (manufactured by STAUFFER Co.
  • IRGACURE registered trademark
  • 184 500, 2959, 127, 754, 907, 369, 379, 379EG, 819, 819DW, 1800, 1870, 784, OXE01, OXE02, 250, 1173, MBF, 4265, TPO (above, manufactured by BA
  • 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 component (A) and the component (B). More preferably 0.1 phr to 8 phr. This is because when the content ratio of the component (C) is less than 0.01 phr, sufficient curability cannot be obtained and patterning characteristics are deteriorated.
  • “phr” represents the mass of the photopolymerization initiator that is, for example, the component (C) with respect to 100 g of the total mass of the components (A) and (B).
  • [(D) component] Specific examples of the compound having at least one thiol group as 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-mercaptopropionate), trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tet Kiss (3-mercaptopropionate), pentaerythritol tetrakis (3-mercapto
  • the compound having at least one thiol group can be obtained as a commercial product.
  • Specific examples thereof include Thiocalcol (registered trademark) 20 (manufactured by Kao Corporation), Karenz MT (registered trademark) PE1, BD1, NR1, TPMB, TEMB (manufactured by Showa Denko KK) can be mentioned.
  • (D) component in the imprint material of this invention may be used individually by 1 type or in mixture of 2 or more types. Moreover, the content rate is 0.01 phr thru
  • antioxidants examples include phenolic antioxidants, phosphoric acid antioxidants, sulfide antioxidants, and the like, among which phenolic antioxidants are preferable.
  • phenolic antioxidants include IRGANOX (registered trademark) 245, 1010, 1035, 1076, 1135 [above, manufactured by BASF Japan Ltd.], Sumilizer (registered trademark) GA-80, GP, MDP-S, BBM-S, WX-R [above, manufactured by Sumitomo Chemical Co., Ltd.], ADK STAB (registered trademark) AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330 [above, manufactured by ADEKA Corporation].
  • (E) component in the imprint material of this invention may be used individually by 1 type or in mixture of 2 or more types.
  • the content ratio is, for example, 0.01 phr to 20 phr, more preferably 0.05 phr to 10 phr, based on the total mass of the component (A) and the component (B).
  • surfactant (F) component examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octyl.
  • Polyoxyethylene alkylaryl ethers such as phenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, Sorbitan fatty acid esters such as sorbitan trioleate and 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. Specific examples thereof include EFTOP (registered trademark) EF301, EF303, EF352 (above, manufactured by Mitsubishi Materials Electronic Chemical Co., Ltd.), MegaFuck (registered) Trademark) 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 (above, DIC) Co., Ltd.), FLORARD FC430, FC431 (above, manufactured by 3M Japan Co., Ltd.), Asahi Guard (registered trademark) AG710, Surflon (registered trademark) S-382, SC101, SC102, SC103, Fluorosurfactants such as SC104, SC105, SC106 (Asahi Glass Co., Ltd.); and organosilox
  • (F) component in the imprint material of this invention may be used individually by 1 type or in mixture of 2 or more types.
  • the content ratio is preferably 0.01 phr to 40 phr, more preferably 0.01 phr to 10 phr, based on the total mass of the component (A) and the component (B).
  • the imprint material of the present invention may contain a solvent as the component (G).
  • the solvent serves to adjust the viscosity of the component (A) and the component (B).
  • solvent examples include toluene, p-xylene, o-xylene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, Ethylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl Ether, dipropylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, diethylene glyco
  • the said solvent can be used individually by 1 type or in combination of 2 or more types.
  • all components of the imprint material of the present invention that is, components (G) are removed from components (A) to (F) described above and other components described later.
  • the solid content defined as is preferably 50% to 99% by weight, preferably 70% to 99% by weight.
  • a polymer compound As long as the imprint material of the present invention does not impair the effects of the present invention, a polymer compound, an epoxy compound, a photoacid generator, a photosensitizer, an ultraviolet absorber, a chain transfer agent, an adhesion assistant, and An additive selected from the group consisting of releasability improvers can be contained.
  • the polymer compound can be added to adjust the refractive index and the Abbe number without impairing the transparency, and the polymer compound preferably has a repeating structural unit represented by the following formula (2). .
  • the content is preferably 0.1% by mass or more and 90% by mass or less, more preferably 5% by mass or more and 70% by mass based on the total mass of the component (A), the component (B) and the polymer compound. It is below mass%.
  • R 1 represents a hydrogen atom or a methyl group
  • X represents an organic compound 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.
  • epoxy compound examples include Epolide (registered trademark) GT-401, PB3600, Celoxide (registered trademark) 2021P, 2000, 3000, EHPE3150, EHPE3150CE (manufactured by Daicel Corporation), EPICLON (registered trademark). 840, 840-S, N-660, N-673-80M (manufactured by DIC Corporation).
  • photoacid generator examples include IRGACURE (registered trademark) PAG103, PAG108, PAG121, PAG203, CGI725 (above, manufactured by BASF Japan Ltd.), WPAG-145, WPAG-170, WPAG-199, WPAG-281, WPAG-336, WPAG-367 (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 (manufactured by San Apro Co., Ltd.).
  • IRGACURE registered trademark
  • PAG103, PAG108, PAG121, PAG203, CGI725 above, manufactured by BASF Japan Ltd.
  • Examples of the photosensitizer include thioxanthene, thioxanthone, xanthene, ketone, thiopyrylium salt, base styryl, merocyanine, 3-substituted coumarin, 3,4-substituted coumarin, and cyanine. , Acridine, thiazine, phenothiazine, anthracene, coronene, benzanthracene, perylene, ketocoumarin, coumarin, and borate.
  • the photosensitizer is available as a commercial product.
  • UVS-581 examples thereof include Anthracure (registered trademark) UVS-581, UVS-1331 (above, manufactured by Kawasaki Kasei Kogyo Co., Ltd.), KAYACURE (registered). (Trademark) DETX-S (manufactured by Nippon Kayaku Co., Ltd.).
  • This photosensitizer can be used individually by 1 type or in combination of 2 or more types. The absorption wavelength in the UV region can be adjusted by using the photosensitizer.
  • Examples of the ultraviolet absorber include TINUVIN (registered trademark) PS, 99-2, 109, 328, 384-2, 400, 405, 460, 477, 479, 900, 928, 1130, 111FDL, 123, 144, 152, 292, 5100, 400-DW, 477-DW, 99-DW, 123-DW, 5050, 5060, 5151 (above, manufactured by BASF Japan Ltd.).
  • This ultraviolet absorber can be used individually by 1 type or in combination of 2 or more types. By using the ultraviolet absorber, the curing speed of the outermost surface of the film can be controlled during the photocuring of the imprint material of the present invention, and the releasability may be improved.
  • chain transfer agent examples include 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-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 (pyridin-2-yl) pyridyl disulfide, di (benzimidazole-2)
  • adhesion aid examples include 3-methacryloxypropyltrimethoxysilane and 3-acryloxypropyltrimethoxysilane.
  • the content of the adhesion aid is preferably 5 phr to 50 phr, more preferably 10 phr to 50 phr, based on the total mass of the component (A) and the component (B).
  • Examples of the mold release improver 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 (manufactured by Daikin Industries, Ltd.). It is done.
  • (D) component which is (A) component, (B) component, (C) component, and arbitrary components
  • (E) component, (F) component (G) component and other additives may be mixed if desired, and the imprint material may be in a uniform state.
  • the order of mixing the components (A) to (G) and other additives as desired is not particularly limited as long as a uniform imprint material can be obtained.
  • the component (A) and the component (B) are mixed at a predetermined ratio, and the component (C), and optionally the component (D), the component (E),
  • the method of mixing (F) component and (G) component suitably and making it a uniform imprint material is also mentioned. Furthermore, in an appropriate stage of this preparation method, there may be mentioned a method in which other additives are further added and mixed as necessary.
  • the imprint material of the present invention can be coated on a substrate and photocured to obtain a desired film.
  • a coating method a known or well-known method such as a spin coating method, a dip method, a flow coating method, an ink jet method, a spray method, a bar coating method, a gravure coating method, a slit coating method, a roll coating method, a transfer printing method, Examples thereof include brush coating, blade coating, and air knife coating.
  • a base material for applying the imprint material of the present invention for example, glass on which silicon, indium tin oxide (ITO) is formed (ITO substrate), glass on which silicon nitride (SiN) is formed (SiN substrate), glass formed with indium zinc oxide (IZO), polyethylene terephthalate (PET), triacetyl cellulose (TAC), acrylic, plastic, glass, quartz, ceramics, etc. it can.
  • ITO substrate glass on which silicon, indium tin oxide (ITO) is formed
  • SiN substrate glass on which silicon nitride (SiN substrate)
  • IZO indium zinc oxide
  • PET polyethylene terephthalate
  • TAC triacetyl cellulose
  • flexible flexible substrates such as triacetyl cellulose, polyethylene terephthalate, polymethyl methacrylate, cycloolefin (co) polymer, polyvinyl alcohol, polycarbonate, polystyrene, polyimide, polyamide, polyolefin, polypropylene, polyethylene, polyethylene naphthalate. It is also possible to use a substrate made of phthalate, polyethersulfone, and a copolymer obtained by combining these polymers.
  • the light source for photocuring the imprint material of the present invention is not particularly limited.
  • 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, an F 2 excimer laser, an electron Line (EB), extreme ultraviolet (EUV), ultraviolet LED (UV-LED) can be mentioned.
  • the wavelength generally, a 436 nm G line, a 405 nm H line, a 365 nm I line, or a GHI mixed line can be used.
  • 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.
  • the baking equipment is not particularly limited, and can be fired in an appropriate atmosphere, that is, in an inert gas such as air or nitrogen, or in a vacuum using, for example, a hot plate, an oven, or a furnace. If it is.
  • the firing temperature is not particularly limited for the purpose of evaporating the solvent, but can be performed at 40 ° C. to 200 ° C., for example.
  • a film to which a pattern is transferred, which is produced using the imprint material of the present invention has a high transparency in the visible light region even with a thick film of 1 mm, for example, and exhibits a higher refractive index and Abbe number. It can be suitably used as an optical article such as a module lens or a resin mold for imprinting.
  • the optical imprinting apparatus is not particularly limited as long as a target pattern can be obtained.
  • ST50 manufactured by Toshiba Machine Co., Ltd.
  • Sindre registered trademark
  • NM-0801HB manufactured by Meisho Kiko Co., Ltd.
  • a method can be used in which the substrate and the mold are pressure-bonded to the roller, and the cured product is released from the mold after photocuring.
  • examples of the mold material used for the optical imprint used in the present invention include quartz, silicon, nickel, alumina, carbonylsilane, and glassy carbon.
  • the target pattern it is particularly limited.
  • the mold may be subjected to a mold release treatment for forming a thin film of a fluorine compound or the like on the surface thereof in order to improve the mold release property.
  • examples of the mold release agent used for the mold release treatment include OPTOOL (registered trademark) HD and DSX manufactured by Daikin Industries, Ltd., but are not particularly limited as long as the target pattern can be obtained.
  • the pattern size of the optical imprint in the present invention is not particularly limited.
  • a good pattern can be obtained in any order of nanometer order, micrometer order, or millimeter order.
  • the weight average molecular weights of the polymers shown in Synthesis Examples 1 and 2 described later are measurement results by gel permeation chromatography (hereinafter abbreviated as “GPC” in this specification).
  • GPC gel permeation chromatography
  • a GPC system manufactured by Shimadzu Corporation was used.
  • the configuration and measurement conditions of the GPC system are as follows.
  • GPC system configuration System controller: CBM-20A, column oven: CTO-20, autosampler: SIL-10AF, detector: SPD-20A and RID-10A, exhaust unit: DGU-20A3
  • G2 obtained corresponds to a polymer compound among the above-mentioned other additives, and its weight average molecular weight measured by GPC was 11322.
  • Example 1 1 g of NK ester A-DOG (hereinafter abbreviated as “A-DOG” in this specification) (manufactured by Shin-Nakamura Chemical Co., Ltd.) and 9 g of UM-90 (1/3) DA (manufactured by Ube Industries, Ltd.) And 0.2 g (A-DOG, UM-90 (1) in this specification) of IRGACURE (registered trademark) 184 (manufactured by BASF Japan Ltd.) (hereinafter abbreviated as “IRGACURE 184”). / 3) 2 phr) of the total mass of DA was added to prepare an imprint material PNI-a1.
  • A-DOG NK ester A-DOG
  • Example 2 2 g of A-DOG and 8 g of UM-90 (1/3) DA were mixed, and the mixture was mixed with 0.2 g of IRGACURE 184 (2 phr based on the total mass of A-DOG and UM-90 (1/3) DA). In addition, an imprint material PNI-a2 was prepared.
  • Example 3 3 g of A-DOG and 7 g of UM-90 (1/3) DA were mixed, and 0.2 gram of IRGACURE 184 was added to the mixture (2 phr with respect to the total mass of A-DOG, UM-90 (1/3) DA). In addition, an imprint material PNI-a3 was prepared.
  • Example 4 4 g of A-DOG and 6 g of UM-90 (1/3) DA were mixed, and the mixture was mixed with 2 g of IRGACURE 184 (0.2 phr based on the total mass of A-DOG, UM-90 (1/3) DA). In addition, an imprint material PNI-a4 was prepared.
  • Example 5 5 g of A-DOG and 5 g of UM-90 (1/3) DA were mixed, and 2 phr of IRGACURE 184 was added to the mixture with a total mass of 0.2 g of IRGACURE 184 (A-DOG, UM-90 (1/3) DA). In addition, an imprint material PNI-a5 was prepared.
  • Example 6 6 g of A-DOG and 4 g of UM-90 (1/3) DA were mixed, and 2 phr of IRGACURE 184 was added to the mixture with respect to the total mass of IRGACURE 184 (A-DOG, UM-90 (1/3) DA). In addition, an imprint material PNI-a6 was prepared.
  • Example 7 7 g of A-DOG and 3 g of UM-90 (1/3) DA were mixed, and the mixture was mixed with 2 g of IRGACURE 184 (0.2 phr based on the total mass of A-DOG, UM-90 (1/3) DA). In addition, an imprint material PNI-a7 was prepared.
  • Example 8 8 g of A-DOG and 2 g of UM-90 (1/3) DA were mixed, and 0.2 gram of IRGACURE 184 was added to the mixture (2 phr with respect to the total mass of A-DOG, UM-90 (1/3) DA). In addition, an imprint material PNI-a8 was prepared.
  • Example 9 9 g of A-DOG and 1 g of UM-90 (1/3) DA were mixed, and 0.2 gram of IRGACURE 184 was added to the mixture (2 phr with respect to the total mass of A-DOG, UM-90 (1/3) DA). In addition, an imprint material PNI-a9 was prepared.
  • Example 10 1 g of A-DOG and 9 g of UM-90 (1/3) DA were mixed, and 0.2 gram of IRGACURE 184 was added to the mixture (2 phr with respect to the total mass of A-DOG, UM-90 (1/3) DA). ), Thiocalcol (registered trademark) 20 (manufactured by Kao Corporation) (hereinafter abbreviated as “thiocalcol 20” in this specification) 0.05 g (A-DOG, UM-90 (1/3) DA (0.5 phr with respect to mass) was added to prepare (imprint material PNI-a10).
  • Thiocalcol 20 registered trademark
  • Example 11 2 g of A-DOG and 8 g of UM-90 (1/3) DA were mixed, and the mixture was mixed with 0.2 g of IRGACURE 184 (2 phr based on the total mass of A-DOG and UM-90 (1/3) DA). ), 0.05 g of thiocalcol 20 (0.5 phr with respect to the total mass of A-DOG, UM-90 (1/3) DA) was added to prepare imprint material PNI-a11.
  • Example 12 3 g of A-DOG and 7 g of UM-90 (1/3) DA were mixed, and 0.2 gram of IRGACURE 184 was added to the mixture (2 phr with respect to the total mass of A-DOG, UM-90 (1/3) DA). ), 0.05 g of thiocalcol 20 (0.5 phr with respect to the total mass of A-DOG, UM-90 (1/3) DA) was added to prepare imprint material PNI-a12.
  • Example 13 4 g of A-DOG and 6 g of UM-90 (1/3) DA were mixed, and the mixture was mixed with 2 g of IRGACURE 184 (0.2 phr based on the total mass of A-DOG, UM-90 (1/3) DA). ), 0.05 g of thiocalcol 20 (0.5 phr with respect to the total mass of A-DOG, UM-90 (1/3) DA) was added to prepare imprint material PNI-a13.
  • Example 14 5 g of A-DOG and 5 g of UM-90 (1/3) DA were mixed, and 2 phr of IRGACURE 184 was added to the mixture with a total mass of 0.2 g of IRGACURE 184 (A-DOG, UM-90 (1/3) DA). ), 0.05 g of thiocalcol 20 (0.5 phr with respect to the total mass of A-DOG, UM-90 (1/3) DA) was added to prepare imprint material PNI-a14.
  • Example 15 5 g of A-DOG and 5 g of UM-90 (1/3) DA were mixed, and 2 phr of IRGACURE 184 was added to the mixture with a total mass of 0.2 g of IRGACURE 184 (A-DOG, UM-90 (1/3) DA).
  • IRGACURE 184 A-DOG, UM-90 (1/3) DA.
  • Karenz MT (registered trademark) PE1 manufactured by Showa Denko KK) (hereinafter abbreviated as “Karens MT PE1” in this specification)
  • the imprint material PNI-a15 was prepared by adding 0.5 phr) to the total mass of DA.
  • Example 16 6 g of A-DOG and 4 g of UM-90 (1/3) DA were mixed, and 2 phr of IRGACURE 184 was added to the mixture with respect to the total mass of IRGACURE 184 (A-DOG, UM-90 (1/3) DA). ), 0.05 g of thiocalcol 20 (0.5 phr with respect to the total mass of A-DOG, UM-90 (1/3) DA) was added to prepare imprint material PNI-a16.
  • Example 17 7 g of A-DOG and 3 g of UM-90 (1/3) DA were mixed, and the mixture was mixed with 2 g of IRGACURE 184 (0.2 phr based on the total mass of A-DOG, UM-90 (1/3) DA). ), 0.05 g of thiocalcol 20 (0.5 phr with respect to the total mass of A-DOG, UM-90 (1/3) DA) was added to prepare imprint material PNI-a17.
  • Example 18 8 g of A-DOG and 2 g of UM-90 (1/3) DA were mixed, and 0.2 gram of IRGACURE 184 was added to the mixture (2 phr with respect to the total mass of A-DOG, UM-90 (1/3) DA). ), 0.05 g of thiocalcol 20 (0.5 phr with respect to the total mass of A-DOG, UM-90 (1/3) DA) was added to prepare imprint material PNI-a18.
  • Example 19 9 g of A-DOG and 1 g of UM-90 (1/3) DA were mixed, and 0.2 gram of IRGACURE 184 was added to the mixture (2 phr with respect to the total mass of A-DOG, UM-90 (1/3) DA). ), 0.05 g of thiocalcol 20 (0.5 phr with respect to the total mass of A-DOG, UM-90 (1/3) DA) was added to prepare imprint material PNI-a19.
  • Example 20 5 g of A-DOG and 5 g of UM-90 (1/3) DA were mixed, and 2 phr of IRGACURE 184 was added to the mixture with a total mass of 0.2 g of IRGACURE 184 (A-DOG, UM-90 (1/3) DA). ), 0.05 g of thiocalcol 20 (0.5 phr with respect to the total mass of A-DOG, UM-90 (1/3) DA), and Adekastab (registered trademark) AO-60 (manufactured by ADEKA Corporation) in an amount of 0.0. 01 g (A-DOG, 0.1 phr with respect to the total mass of UM-90 (1/3) DA) was added to prepare an imprint material PNI-a20.
  • Adekastab registered trademark
  • Example 21 5 g of A-DOG and 5 g of UM-90 (1/3) DA were mixed, and 2 phr of IRGACURE 184 was added to the mixture with a total mass of 0.2 g of IRGACURE 184 (A-DOG, UM-90 (1/3) DA). ), 0.05 g of thiocalcol 20 (0.5 phr with respect to the total mass of A-DOG, UM-90 (1/3) DA), and Adekastab (registered trademark) AO-80 (manufactured by ADEKA Corporation) in an amount of 0.0 g. 01 g (A-DOG, 0.1 phr with respect to the total mass of UM-90 (1/3) DA) was added to prepare an imprint material PNI-a21.
  • Adekastab registered trademark
  • Example 22 5 g of A-DOG and 5 g of UM-90 (1/3) DA were mixed, and 2 phr of IRGACURE 184 was added to the mixture with a total mass of 0.2 g of IRGACURE 184 (A-DOG, UM-90 (1/3) DA). ), 0.05 g of thiocalcol 20 (0.5 phr with respect to the total mass of A-DOG, UM-90 (1/3) DA), 0.01 g of BYK-UV 3570 (manufactured by Big Chemie Japan Co., Ltd.) Imprint material PNI-a22 was prepared by adding 0.1 phr) to the total mass of A-DOG and UM-90 (1/3) DA.
  • Example 23 5 g of A-DOG and 5 g of UM-90 (1/3) DA were mixed, and 2 phr of IRGACURE 184 was added to the mixture with a total mass of 0.2 g of IRGACURE 184 (A-DOG, UM-90 (1/3) DA). ), 0.05 g of thiocalcol 20 (0.5 phr with respect to the total mass of A-DOG, UM-90 (1/3) DA) and 1.139 g of PGMEA were added to prepare imprint material PNI-a23.
  • A-DCP NK ester A-DCP
  • Example 25 5 g of A-DOG and 5 g of ADMA were mixed, and 0.2 g of IRGACURE 184 (2 phr with respect to the total mass of ADMA) and 0.05 g of thiocalcol 20 (total of A-DOG and ADMA) were added to the mixture.
  • the imprint material PNI-a25 was prepared by adding 0.5 phr) to the mass.
  • Example 26 5 g of A-DOG and 5 g of IBXA (manufactured by Osaka Organic Chemical Industry Co., Ltd.) are mixed, 0.2 g of IRGACURE 184 is added to the mixture (2 phr with respect to the total mass of A-DOG and IBXA), and thiocalcol 20 is 0.00.
  • Imprint material PNI-a26 was prepared by adding 05 g (A-DOG, 0.5 phr based on the total mass of IBXA).
  • Example 27 5 g of A-DOG and 5 g of New Frontier (registered trademark) HBPE-4 (Daiichi Kogyo Seiyaku Co., Ltd.) (hereinafter abbreviated as “HBPE-4”) are mixed, and IRGACURE is added to the mixture.
  • HBPE-4 New Frontier (registered trademark) HBPE-4 (Daiichi Kogyo Seiyaku Co., Ltd.)
  • IRGACURE is added to the mixture.
  • Add 0.2 g of 184 (2 phr to the total mass of A-DOG and HBPE-4) and 0.05 g of thiocalcol 20 (0.5 phr to the total mass of A-DOG and HBPE-4) and imprint Material PNI-a27 was prepared.
  • Example 28 5 g of A-DOG and 5 g of Viscote # 230 (manufactured by Osaka Organic Chemical Co., Ltd.) (hereinafter abbreviated as “V # 230”) are mixed, and 0.2 g of IRGACURE 184 is added to the mixture ( A-DOG, 2 phr with respect to the total mass of V # 230) and 0.05 g of thiocalcol 20 (0.5 phr with respect to the total mass of A-DOG, V # 230) were added to prepare imprint material PNI-a28. did.
  • Example 29 5 g of A-DOG and 5 g of Biscote # 260 (produced by Osaka Organic Chemical Co., Ltd.) (hereinafter abbreviated as “V # 260”) are mixed, and 0.2 g of IRGACURE 184 is added to the mixture ( A-DOG, 2 phr with respect to the total mass of V # 260) and 0.05 g of thiocalcol 20 (0.5 phr with respect to the total mass of A-DOG, V # 260) were added 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) 2 phr with respect to the total mass of DA), 0.05 g of thiocalcol 20 (0.5 phr with respect to the total mass of A-DOG, ADMA, UM-90 (1/3) DA), and imprint material PNI-a30 was prepared.
  • Example 31 5 g of A-DOG, 2.5 g of ADMA, and 2.5 g of HBPE-4 are mixed, and 0.2 g of IRGACURE 184 is added to the mixture (2 phr based on the total mass of A-DOG, ADMA, and HBPE-4). Then, 0.05 g of thiocalcol 20 (0.5 phr based on the total mass of A-DOG, ADMA, and HBPE-4) was added to prepare an imprint material PNI-a31.
  • 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, and 0.2 g of IRGACURE 184 was added to the mixture (based on the total mass of A-DOG, ADMA, and G1). 2 phr) and 0.05 g of thiocalcol 20 (0.5 phr based on the total mass of A-DOG, ADMA, and G1) were added to prepare an imprint material PNI-a32.
  • 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, and 0.2 g of IRGACURE 184 was added to the mixture (based on the total mass of A-DOG, ADMA, and G2). 2 phr) and 0.05 g of thiocalcol 20 (0.5 phr based on the total mass of A-DOG, ADMA, and G2) were added to prepare an imprint material PNI-a33.
  • Example 34 7 g of A-DOG and 3 g of HBPE-4 were mixed, and 0.01 g of IRGACURE 184 (0.1 phr with respect to the total mass of A-DOG and HBPE-4) was added to the mixture, and imprint material PNI-a34 was added. Prepared.
  • Example 35 6 g of A-DOG and 4 g of HBPE-4 were mixed, and 0.01 g of IRGACURE 184 (0.1 phr with respect to the total mass of A-DOG and HBPE-4) was added to the mixture, and imprint material PNI-a35 was added. Prepared.
  • Example 36 5 g of A-DOG and 5 g of HBPE-4 were mixed, and 0.01 g of IRGACURE 184 (0.1 phr with respect to the total mass of A-DOG and HBPE-4) was added to the mixture, and imprint material PNI-a36 was added. Prepared.
  • Example 37 4 g of A-DOG and 6 g of HBPE-4 were mixed, and 0.01 g of IRGACURE 184 (0.1 phr with respect to the total mass of A-DOG and HBPE-4) was added to the mixture, and imprint material PNI-a37 was added. Prepared.
  • Example 38 3 g of A-DOG and 7 g of HBPE-4 were mixed, and 0.01 g of IRGACURE 184 (0.1 phr with respect to the total mass of A-DOG and HBPE-4) was added to the mixture, and imprint material PNI-a38 was added. Prepared.
  • Example 39 5 g of A-DOG and 5 g of HBPE-4 were mixed, and 0.01 g of IRGACURE 184 (0.1 phr with respect to the total mass of A-DOG and HBPE-4) and 0.05 g of thiocalcol 20 (A -DOG, 0.5 phr) based on the total mass of HBPE-4), and imprint material PNI-a39 was prepared.
  • Example 40 5 g of A-DOG and 5 g of HBPE-4 were mixed, and 0.01 g of IRGACURE 184 (0.1 phr with respect to the total mass of A-DOG and HBPE-4) and 0.05 g of Karenz MT PE1 ( A-DOG, 0.5 phr with respect to the total mass of HBPE-4) was added to prepare an imprint material PNI-a40.
  • Example 41 5 g of A-DOG and 5 g of HBPE-4 were mixed, and 0.01 g of IRGACURE 184 (0.1 phr with respect to the total mass of A-DOG and HBPE-4) and Karenz MT (registered trademark) NR1 ( 0.05 g (0.5 phr based on the total mass of A-DOG and HBPE-4) was added to Showa Denko Co., Ltd. to prepare imprint material PNI-a41.
  • 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 mass of A-DOG).
  • the imprint material of this comparative example contains the component (A) and the component (C) but does not contain the component (B).
  • 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 with respect to the mass of UM-90 (1/3) DA).
  • the imprint material of this comparative example contains the component (B) and the component (C) but does not contain the component (A).
  • Imprint material PNI-b3 was prepared by adding 10 g of ADMA and 0.2 g of IRGACURE 184 (2 phr with respect to the mass of ADMA).
  • the imprint material of this comparative example contains the component (B) and the component (C) but does not contain the component (A).
  • Imprint material PNI-b4 was prepared by adding 10 g of V # 230 and 0.2 g of IRGACURE 184 (2 phr with respect to the mass of V # 230).
  • the imprint material of this comparative example contains the component (B) and the component (C) but does not contain the component (A).
  • the imprint material PNI-b6 was prepared by adding 2 phr) to the mass. Since NPGDA used in this comparative example does not correspond to the component (B), the imprint material of this comparative example includes the component (A), the component (C), and the component (D), but does not include the component (B). .
  • a silicon mold having a 20 ⁇ m line and space pattern (hereinafter referred to as L / S), Optool (registered trademark) DSX (manufactured by Daikin Industries, Ltd.), Novec (registered trademark) HFE-7100 (hydrofluoroether, 3M Japan Ltd.) (Hereinafter, referred to as “Novec HFE-7100” in this specification).
  • a high temperature and high humidity apparatus having a temperature of 90 ° C. and a humidity of 90 RH% is immersed in a solution diluted to 0.1% by mass. And then rinsed with Novec HFE-7100 and dried with air.
  • the molded object of diameter 40mm and thickness 1mm was produced by heating for 5 minutes with a 170 degreeC hotplate.
  • the transmittance at 410 nm of the produced molded body was measured using a spectrophotometer UV2600 (manufactured by Shimadzu Corporation) in a state where the reference was air.
  • the refractive index n D and Abbe number ⁇ D at a wavelength of 589.3 nm (D line) were measured using an automatic refractometer (multi-wavelength) Abbemat-WR / MW type (manufactured by Anton Paar). The obtained results are shown in Table 1, Table 2 and Table 3.
  • the molded bodies produced using the imprint materials prepared in Examples 1 to 23 and Examples 25 to 41 are all 1 mm. Even a thick film has a high transparency of 90% or more at 410 nm, a high refractive index of 1.49 or more at a wavelength of 589.3 nm (D-line), and a high Abbe number of 56 or more.
  • all of the molded articles produced using the imprint materials prepared in Comparative Examples 1 to 8 had a transmittance of less than 90% at 410 nm and low transparency.
  • Comparative Examples 2 to 8 had a refractive index lower than 1.49, or an Abbe number lower than 56, and did not show a high refractive index and a high Abbe number at the same time.
  • the molded object produced using the imprint material of this invention has high transparency in visible region, and has a high refractive index and a high Abbe number simultaneously.

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Abstract

Le problème décrit par la présente invention est de fournir un nouveau matériau d'empreinte. La solution selon l'invention consiste en un matériau d'empreinte contenant le composant (A), le composant (B) et le composant (C) suivants. (A) : composé représenté par la formule générale (1) (dans la formule, chacun des deux R représente indépendamment un atome d'hydrogène ou un groupe méthyle) ; (B) : composé comportant un groupe alkylène linéaire en C6 à C10 et/ou une structure alicyclique choisie dans le groupe constitué des structures de cyclopentane, des structures de cyclohexane, des structures de norbornane, des structures d'isobornyle et des structures d'adamantane, et comportant au moins un groupe polymérisable ; (C) : initiateur de photopolymérisation.
PCT/JP2017/028619 2016-08-10 2017-08-07 Matériau d'empreinte Ceased WO2018030351A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2018533460A JP6802532B2 (ja) 2016-08-10 2017-08-07 インプリント材料
SG11201901065TA SG11201901065TA (en) 2016-08-10 2017-08-07 Imprint material
KR1020197001499A KR102401727B1 (ko) 2016-08-10 2017-08-07 임프린트재료
CN201780048171.3A CN109563194B (zh) 2016-08-10 2017-08-07 压印材料

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018155013A1 (fr) * 2017-02-22 2018-08-30 日産化学工業株式会社 Composition photodurcissable pour impression
KR20230083284A (ko) 2020-10-08 2023-06-09 디아이씨 가부시끼가이샤 활성 에너지선 경화성 조성물, 경화물, 렌즈 및 카메라 모듈

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01121370A (ja) * 1987-11-05 1989-05-15 Nippon Kayaku Co Ltd 光ディスク用オーバーコート組成物
JP2003206318A (ja) * 2002-01-16 2003-07-22 Nippon Kayaku Co Ltd 重合性化合物、これを含有する樹脂組成物及びその硬化物
JP2003206323A (ja) * 2002-01-16 2003-07-22 Nippon Kayaku Co Ltd 光導波路用樹脂組成物及びその硬化物
JP2006343709A (ja) * 2004-10-07 2006-12-21 Jsr Corp 感放射線性樹脂組成物、マイクロレンズとその形成方法および液晶表示素子
JP2012130863A (ja) * 2010-12-22 2012-07-12 Kansai Paint Co Ltd 複層塗膜形成方法及び塗装物品
WO2015016360A1 (fr) * 2013-08-02 2015-02-05 日立化成株式会社 Composition de résine photosensible
JP2015189883A (ja) * 2014-03-28 2015-11-02 富士フイルム株式会社 感光性樹脂組成物、積層体、半導体デバイスの製造方法、半導体デバイス
JP2016035042A (ja) * 2014-07-31 2016-03-17 太陽インキ製造株式会社 硬化性樹脂組成物、ドライフィルム、硬化物およびプリント配線板

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5772905A (en) 1995-11-15 1998-06-30 Regents Of The University Of Minnesota Nanoimprint lithography
JP2008202022A (ja) 2007-01-23 2008-09-04 Fujifilm Corp 光ナノインプリントリソグラフィ用硬化性組成物およびそれを用いたパターン形成方法
KR20080105414A (ko) 2007-05-31 2008-12-04 (주)티에이치엔 절단/박피날
WO2009001629A1 (fr) * 2007-06-26 2008-12-31 Konica Minolta Opto, Inc. Film de revêtement dur transparent, et film anti-reflet, plaques de polarisation et écrans, fabriqués en utilisant ledit film
EP2436704A4 (fr) * 2009-05-29 2012-12-05 Nissan Chemical Ind Ltd Polymère fluoré fortement ramifié et composition de résine contenant celui-ci
WO2011132616A1 (fr) * 2010-04-19 2011-10-27 日産化学工業株式会社 Matériau d'empreinte à grande résistance à l'abrasion
KR101615795B1 (ko) * 2010-07-02 2016-04-26 가부시끼가이샤 도꾸야마 광경화성 임프린트용 조성물 및 상기 조성물을 이용한 패턴의 형성 방법
JP6061073B2 (ja) * 2012-09-27 2017-01-18 日産化学工業株式会社 インプリント材料
WO2014171302A1 (fr) * 2013-04-18 2014-10-23 日産化学工業株式会社 Matière d'impression
US9920227B2 (en) * 2014-01-29 2018-03-20 Hitachi Chemical Company, Ltd. Resin composition, method for manufacturing semiconductor device using resin composition, and solid-state imaging element
JP6477504B2 (ja) * 2014-01-29 2019-03-06 日立化成株式会社 接着剤組成物、接着剤組成物を用いた半導体装置の製造方法、及び固体撮像素子
TWI514073B (zh) * 2014-06-11 2015-12-21 Chi Mei Corp Photosensitive resin composition and its application
JP6704701B2 (ja) * 2014-12-15 2020-06-03 キヤノン株式会社 密着層形成組成物、密着層の製造方法、硬化物パターンの製造方法、光学部品の製造方法、回路基板の製造方法、インプリント用モールドの製造方法、およびデバイス部品

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01121370A (ja) * 1987-11-05 1989-05-15 Nippon Kayaku Co Ltd 光ディスク用オーバーコート組成物
JP2003206318A (ja) * 2002-01-16 2003-07-22 Nippon Kayaku Co Ltd 重合性化合物、これを含有する樹脂組成物及びその硬化物
JP2003206323A (ja) * 2002-01-16 2003-07-22 Nippon Kayaku Co Ltd 光導波路用樹脂組成物及びその硬化物
JP2006343709A (ja) * 2004-10-07 2006-12-21 Jsr Corp 感放射線性樹脂組成物、マイクロレンズとその形成方法および液晶表示素子
JP2012130863A (ja) * 2010-12-22 2012-07-12 Kansai Paint Co Ltd 複層塗膜形成方法及び塗装物品
WO2015016360A1 (fr) * 2013-08-02 2015-02-05 日立化成株式会社 Composition de résine photosensible
JP2015189883A (ja) * 2014-03-28 2015-11-02 富士フイルム株式会社 感光性樹脂組成物、積層体、半導体デバイスの製造方法、半導体デバイス
JP2016035042A (ja) * 2014-07-31 2016-03-17 太陽インキ製造株式会社 硬化性樹脂組成物、ドライフィルム、硬化物およびプリント配線板

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018155013A1 (fr) * 2017-02-22 2018-08-30 日産化学工業株式会社 Composition photodurcissable pour impression
KR20230083284A (ko) 2020-10-08 2023-06-09 디아이씨 가부시끼가이샤 활성 에너지선 경화성 조성물, 경화물, 렌즈 및 카메라 모듈

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SG11201901065TA (en) 2019-03-28
CN109563194A (zh) 2019-04-02
KR20190039082A (ko) 2019-04-10
JPWO2018030351A1 (ja) 2019-06-13
JP6802532B2 (ja) 2020-12-16

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