WO2008059632A1 - Procédé de formation d'un film mince à couches multiples - Google Patents

Procédé de formation d'un film mince à couches multiples Download PDF

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Publication number
WO2008059632A1
WO2008059632A1 PCT/JP2007/062273 JP2007062273W WO2008059632A1 WO 2008059632 A1 WO2008059632 A1 WO 2008059632A1 JP 2007062273 W JP2007062273 W JP 2007062273W WO 2008059632 A1 WO2008059632 A1 WO 2008059632A1
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WO
WIPO (PCT)
Prior art keywords
thin film
phase separation
liquid
forming
substrate
Prior art date
Application number
PCT/JP2007/062273
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English (en)
Japanese (ja)
Inventor
Yasushi Ono
Takeshi Sinohara
Takashi Kawabe
Original Assignee
Eintesla, Inc.
Niigata University
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 Eintesla, Inc., Niigata University filed Critical Eintesla, Inc.
Publication of WO2008059632A1 publication Critical patent/WO2008059632A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment

Definitions

  • the present invention relates to a method for forming a multilayer thin film on a substrate in a single step.
  • the present invention particularly relates to a method for producing a conductive functional element composed of a multilayer thin film by an electrolytic polymerization method using a conductive polymer material as a conductive layer.
  • the processing method of forming a multilayer on a substrate in one step is a method of forming a multilayer on a substrate, and a single layer is formed on the substrate and then laminated on the layer in the next step.
  • a method of laminating by an LB (Langmuir 'Projet) film method but laminating by a plurality of steps is complicated.
  • LB Lithmuir 'Projet
  • Patent Document 1 discloses that a metal body serving as an anode is electrically connected to an electrolytic polymerization solution containing a polymerizable molecule while applying a voltage.
  • Patent Document 2 an electrolytic solution of an electropolymerizable organic substance and a non-conductive liquid that is soluble in the electrolytic solution are used.
  • Patent Document 3 discloses a continuous production method of a conductive polymer material in which a conductive polymer is continuously synthesized on both surfaces of a conductive sheet-like substrate by an electrolytic polymerization method.
  • Patent Document 4 discloses a method for producing a multilayer laminate by electrolytic polymerization.
  • Patent Document 1 a conductive polymer is obtained by pulling up a substrate which is an anode body by utilizing a polymerization reaction at a gas-liquid interface, so that it is difficult to obtain a uniform thin film and a highly oriented thin film. is there.
  • the next step is required to obtain a laminate.
  • a highly oriented polymerized film is formed by electrolytic polymerization from an electrolytic solution at a liquid interface, and this is wound up. Therefore, a polymerized film cannot be directly formed on a substrate. Although it is a continuous manufacturing method, the next step is required to obtain a laminate.
  • Patent Document 3 a multi-layer stack cannot be obtained.
  • Patent Document 4 lamination is performed in a separate process.
  • Patent Document 1 JP 2000-353641 A
  • Patent Document 2 JP-A-6-136101
  • Patent Document 3 JP-A-3-174435
  • Patent Document 4 JP-A-5-209043
  • the present invention is to solve the problems of the prior art, and an object of the present invention is to form a polymer film having a uniform thin film and excellent strength and stability on a substrate surface in a simple and large area. It is possible to simultaneously and reliably form a multilayer thin film simultaneously. Means for solving the problem
  • a method for simultaneously forming a plurality of thin films according to the present invention on a substrate as a multilayer thin film includes: (1) any one of water, an organic solvent, an ionic liquid, or a mixed solvent of at least two of them. (2) The electrolytic solution containing an electropolymerizable monomer and a supporting electrolyte in the above (1), (3) the solution in which the substance forming the film is dissolved and / or dispersed in the above (1), (4) the above (1) to (1) Select (3) a dispersion in which fine particles or powder are dispersed, (5) select at least two groups that are not mixed with each other from the layer in which the fine particles or powder are dispersed on the liquid surface, and at least one of them Contains liquid Then, arrange them sequentially above the lowest phase to form a phase-separated liquid phase, and bring the counter electrode into contact with them.
  • electropolymerization is performed by applying a voltage between the electrode and the metal counter electrode while pulling up the conductive base material that will be the electrode immersed in the lowest phase in advance from the bottom layer at a slow and constant speed.
  • This is a method of simultaneously forming two or more laminated films on at least one surface of the substrate.
  • the top phase does not necessarily require electrolytic polymerization. That is, first, an electrolyte thin film that forms a polymer film in the electrolyte is formed, and then a voltage is applied between the electrode and the counter electrode while the electrolyte thin film is moved while being oriented on the substrate surface.
  • a substrate coated with a highly oriented polymer thin film is obtained by electrolytic oxidation or electrolytic reduction.
  • the substrate is pulled up at a slow speed and at a constant speed through the electrolyte-separated electrolyte thin phase formed on the thin film, so that the highly-oriented conductive material is at least in one direction of the substrate.
  • This is a method of simultaneously forming a multilayer thin film containing at least one polymer film.
  • a conductive base material is immersed in the lowermost phase, and (1) any one of water, an organic solvent, an ionic liquid, or the like is formed on this interface.
  • Electrolyte containing an electropolymerizable monomer and a supporting electrolyte in (1) above (3) Solution in which the substance forming the membrane is dissolved / dispersed in (1) above (4) At least two or more phase-separated liquid phases selected from a dispersion in which fine particles or powder are dispersed in the above (1) to (3), and (5) a layer in which the fine particles or powder are dispersed on the liquid surface
  • At least one of the phases contains an electrolyte solution, and the substrate is pulled up from the lowest phase of the phase separation solution while the substrate is placed between the counter electrode for electrolysis installed in the phase separation solution and the substrate.
  • Electropolymerization is performed by applying a voltage to the substrate, and it is composed of a plurality of thin and uniform layers on at least one surface
  • FIG. 1 shows a method for batch-forming a conductive multilayer thin film in Example 1 of the present invention.
  • a conventional method for producing a multilayer thin film including an electropolymerized film is to form a high molecular film on the surface of the substrate by electrolytic polymerization, and to form another type of thin film on the polymer film on the substrate after the electropolymerization.
  • the main method is a two-step process
  • the multilayer thin film formation method according to the present invention is a method in which the phase separation liquid force consisting of a plurality of phases is raised. Electropolymerization proceeds in the phase separation liquid to form a polymer membrane, and when passing through the phase separation liquid disposed further above, a thin film of the phase separation liquid is formed on the previous polymer membrane.
  • a multilayer thin film can be obtained continuously in a single process.
  • the method for forming a continuous multilayer thin film of the present invention is shown in a stepwise manner: (A) A thin layer of a liquid containing at least two or more electrolyte solutions or thin film forming materials that are not separated from each other. (B) A metal counter electrode is brought into contact with the electrolytic solution phase, and a conductive base material that serves as an electrode is previously immersed in the incompatible liquid phase. deep. (C) Electropolymerization is carried out by applying a voltage between the electrode and the metal counter electrode while pulling up the base material at a high speed and at a constant speed in a liquid phase force that is not compatible with the electrolyte phase. (D) The thin film is multilayered sequentially through the liquid phase arranged above. (E) Thus, at least a multilayer film including at least one conductive polymer thin film oriented in the same direction on the entire surface of the substrate is obtained. Form in size and shape.
  • the liquid phase (X) containing the electrolyte solution or thin film forming material which is a liquid phase separation liquid not mixed with each other is made into a thin layer.
  • the liquid phase (Y) which is poorly compatible with the liquid phase (X) and capable of forming a uniform thin layer, is used as the lower phase, and the liquid phase (X) is disposed on the surface of the liquid phase (Y). Most preferred to let you.
  • the compatibility of the two liquids is such that the liquid phase of the liquid containing the electrolytic solution or thin film forming material spreads on the surface of the liquid phase of the lower layer to easily form a thin film.
  • a surfactant or the like may be dissolved within a range.
  • a surfactant or the like may be added to the electrolytic solution so that the electrolytic solution phase easily forms a thin film on the lower layer surface. In any case, these additives should not appear to inhibit the orientation of the polymer formed by electropolymerization.
  • the liquid specific gravity is smaller than that of the liquid phase forming the lower layer. If a thin layer is held on the surface of the substrate during the process of moving together with the substrate, the specific gravity is not necessarily limited, but the specific gravity of the liquid phase that forms the upper phase is not necessary to form a stable thin layer. Is preferably smaller than the liquid specific gravity of the lower phase.
  • electropolymerizable monomer contained in the electrolytic solution phase acrylonitrile, methacrylic acid ester, styrene, butadiene, methylenemalonic acid ester, a -cyanoacrylic acid ester, nitroethylene and beylene carbonate or the like are used in electrolytic reduction.
  • electrooxidation aline, diphenolamine, pyrene, azulene, N-butylcarbazole, benzene, biphenyl, pyrrole, furan, indole, phenol, phthalocyanine and thiophene or their derivatives are generally used. It is done.
  • An organic compound having conductivity after electrolytic polymerization may be used by adding a dopant even if it has no conductivity.
  • the conductive polymer film produced by electropolymerization does not interfere with the conductivity, other polymerizable monomers may be used in combination.
  • the supporting electrolyte is a substance that can be ionized and is, for example, a general formula MX, R NX,
  • alkali metal ion alkaline earth metal ion, quaternary ammonium ion, transition metal ion, pyridinium ion, imidazolium ion, quaternary phosphonium ion, etc.
  • X A— (A is halogen), N (CF SO) —, BF—, PF—, CF SO—, CF CO—, NO—,
  • a supporting electrolyte that dissolves well in a solvent, dissociates into a cation and an anion, imparts ionic conductivity, and is stable in a wide potential range that is difficult to undergo oxidation and reduction is desirable.
  • the ionic liquid when an ionic liquid or a solvent containing an ionic liquid is used, the ionic liquid also serves as a supporting electrolyte, so the above supporting electrolyte need not be added.
  • Organic high molecules with a carbon skeleton include natural polymers (biopolymers) based proteins, nucleic acids, lipids, polysaccharides (cellulose, starch, etc.), natural rubber and synthetic polymer based synthetic resins (plastics). And synthetic salts (such as nylon, vinylon, polyester, and polyethylene terephthalate), synthetic rubber, and the like.
  • natural polymers biopolymers
  • nucleic acids lipids
  • polysaccharides cellulose, starch, etc.
  • polysaccharides cellulose, starch, etc.
  • synthetic salts such as nylon, vinylon, polyester, and polyethylene terephthalate
  • synthetic rubber such as nylon, vinylon, polyester, and polyethylene terephthalate
  • polymerizable monomers such as acrylic monomers and styrene monomers, oligomers, UV curable resins, photoresists and the like that form a polymer film by post-treatment are used.
  • polymer materials such as acrylic resin.
  • the fine particles or powders are not particularly limited, but as organic materials, polystyrene, phthalocyanine, organic magnetic particles, organic phosphor particles, etc., and inorganic materials such as alumina, titanium oxide, etc. Etc. are preferred.
  • the solvent used in the present invention is water, an organic solvent, an ionic liquid, or a mixed solvent of at least two of them.
  • Organic solvents include toluene, benzene, acetonitrile, hexane, jetyl ether, tetrahydrofuran, ethyl acetate, methanol, ethanol, etc. with high specific gravity-trobenzene, dichloroethane, chloroform, propylene carbonate, etc.
  • alkanes such as perfluoroalkanes that are immiscible with water and organic solvents, water-insoluble ethers such as perfluorocycloethers, and chlorine-based compounds such as trichloroethylene, tetrataroethylene, methylene chloride, and carbon tetrachloride Solvent compatibility with upper and lower layers
  • a single or mixed solvent can be used as the phase separation liquid.
  • a supporting electrolyte may be added to another solvent to impart conductivity, and an electrolytic solution phase capable of electrolytic polymerization may be obtained.
  • the substrate used in the present invention is not particularly limited as long as it is a material that can serve as an electrode to which a voltage is applied during electrolytic polymerization. Usually, it is selected from metals such as gold, platinum, copper, thallium, aluminum, tungsten and niobium and / or oxides thereof, base materials coated with these metals and metal oxides, and conductive organic substances.
  • the shape of the substrate to be used is not particularly limited, and a hard cam shape, rod shape or sheet shape can be used. Long objects that run continuously can also be used.
  • the electrolyte phase formed on the surface of the aqueous or non-aqueous liquid phase in which the conductive base material is immersed is kept in close contact with the base material surface serving as an electrode while the base material moves.
  • film formation can be performed by moving the substrate upward from the liquid phase of the immersion bath.
  • a voltage is applied between the electrode and the counter electrode to perform electropolymerization to obtain a highly oriented polymer thin film. It forms.
  • Fig. 1 is a representative batch type simultaneous forming method of the conductive multilayer thin film of the present invention
  • Fig. 2 is a diagram of the drum type laminated thin film of the present invention.
  • 1 shows electrolyte B
  • 2 is electrolyte A
  • 3 is tetrasalt carbon
  • 4 is the glass substrate (ITO)
  • 5 is the counter electrode
  • 6 Is a power source
  • 7 8 and 9 are incompatible phase separation liquids
  • 10 is a base material
  • 11 is a drum
  • 12 is a power source.
  • Electrolyte B was obtained by uniformly dissolving lmol / L.
  • Electrolyte solution A layer Z electrolyte solution B phase separation liquid having a layer force was also prepared.
  • a platinum counter electrode is provided in the phase separation liquid.
  • a glass electrode (ITO) which has been previously immersed in the bottom layer of tetrachloride carbon, is used as the working electrode, and a voltage of 3 V is applied between the counter electrode and the working electrode.
  • Nanodip coater manufactured by SDI Co., Ltd., MD-0407-S1
  • a multilayer thin film was formed at the same time.
  • Carbon tetrachloride is the bottom layer, and the electrolyte solution A is placed on it, and UV curable resin (Jujo Chemical, 4100GA) is placed on the electrolyte solution A layer.
  • Carbon layer Z electrolyte A layer A phase separation liquid composed of a ZUV curable resin layer was prepared. The phase separation liquid was provided with a platinum counter electrode.
  • a glass electrode which is a base material previously immersed in the lowest layer of tetrasalt carbon, is used as the working electrode, while applying a voltage of 8V between the counter electrode and the working electrode, It was pulled up at lmm / sec using a micro dip coater (manufactured by SDI, MD-0408-S2).
  • a UV lamp (Funakoshi Co., Ltd., UVGL-15) was used for irradiation for an irradiation distance of 10 cm to 20 seconds, and a multilayer thin film composed of a polyarin layer and a UV curable resin layer on the working electrode ( A glass electrode substrate and an electropolymerized film (ZUV cured film) were simultaneously formed.
  • Carbon tetrachloride is the lowest layer, and the electrolyte A is placed on the bottom.
  • Alumina powder was dispersed on the layer, and a phase separation liquid having a tetrasalt / carbon layer Z electrolyte A layer Z powder layer force was prepared.
  • the phase separation liquid is provided with a platinum counter electrode, and the bottom electrode is a base electrode such as a tetrasalt-carbon carbon substrate (ITO) as the working electrode, and a voltage of 3 V is applied between the counter electrode and the working electrode.
  • Fine constant speed pulling device Pulled up by micro dip coater manufactured by SDI, MD-0408-S2 at 0.1 mm / sec.
  • Multi-layer thin film composed of poly-phosphorus layer and alumina layer on working electrode were formed simultaneously.
  • Ethyl acetate was used as the solvent, and 1-butyl-3-methylimidazole hexafluorophosphate 0.1 mol / L and thiophene 0.1 mol / L were uniformly dissolved as the supporting electrolyte and the electropolymerizable monomer, respectively. Electrolyte C was obtained.
  • suspension A ′ A dispersion in which 1% of polystyrene particles (Mortex, Inc., fluorescent particle G830, particle size 830 mm) was dispersed in electrolyte solution A was prepared, and it was designated as suspension A ′.
  • a platinum counter electrode is provided in the phase separation liquid, while a glass electrode (ITO), which is a base material previously immersed in the lowermost tetrachloride carbon, is used as the working electrode, and a voltage of 3 V is applied between the counter electrode and the working electrode.
  • ITO glass electrode
  • a nano-dip coater MD-0407-S1 manufactured by SDI Co., Ltd.
  • a multilayer thin film composed of a layer made of a carrier and a polythiophene layer was simultaneously formed.
  • Resist solution manufactured by Printec Co., Ltd., MT-UV-6602 (negative type)
  • composition acrylic resin 15 to 25%, acrylic monomer 5 to 15%, photopolymerization initiator 1 to 5%, methylethyl Ketone 4 5% or less and propylene glycol monomethyl ether acetate 20-25%)
  • Add 5g of titanium oxide particles Fluji Titanium Co., Ltd., TA-100, particle size 300nm
  • Carbon tetrachloride is the lowest layer, and the above electrolyte A is placed gently on it, and the suspension D is placed gently on the electrolyte A layer.
  • a phase separation liquid consisting of a ZD layer was prepared.
  • a platinum counter electrode is provided, and a glass electrode (ITO), which is a base material such as a lowermost tetrasalt-carbon carbon, is used as a working electrode, and a voltage of 10 V is applied between the counter electrode and the working electrode.
  • ITO glass electrode
  • a micro dip coater manufactured by SDI Co., Ltd., MD-0408-S2
  • a layer that also has a poly-linker on the working electrode, titanium oxide, and a photoresist was formed simultaneously.
  • the suspension A 'above is gently placed on it, and alumina powder is dispersed on the suspension A', and the tetrasalt carbon layer ZA 'layer Z A phase separation liquid consisting of a powder layer was prepared.
  • a platinum counter electrode is provided in the phase separation liquid, and the glass electrode (ITO), which is the base material, is used as the base electrode from the lowermost tetrasaltary carbon, while a voltage of 5 V is applied between the counter electrode and the working electrode,
  • ITO glass electrode
  • a nano dip coater MD-0407-S1 manufactured by SDI Co., Ltd.
  • a layer of polystyrene particles and poly-linker on the working electrode and alumina A multilayer thin film composed of layers (base ZPS particles + electrolytic polymerization film Z powder film) was formed simultaneously.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Laminated Bodies (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

L'invention concerne la formation d'un film mince à couches multiples composé d'au moins deux films minces ou plus sur une surface de substrat en une étape, consistant à fournir des liquides de séparation de phases non miscibles les uns avec les autres, et, tout en remontant un substrat conducteur sélectionné parmi une substance organique conductrice, un métal, un oxyde métallique et une substance enduite de celui-ci depuis la phase la plus inférieure des liquides de séparation de phases, à appliquer une tension entre le substrat et les contre-électrodes électrolytiques disposées dans les liquides de séparation de phases pour ainsi réaliser une polymérisation électrolytique.
PCT/JP2007/062273 2006-11-15 2007-06-19 Procédé de formation d'un film mince à couches multiples WO2008059632A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006309636A JP2008120981A (ja) 2006-11-15 2006-11-15 多層薄膜の形成方法
JP2006-309636 2006-11-15

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WO2008059632A1 true WO2008059632A1 (fr) 2008-05-22

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019163482A (ja) * 2015-06-01 2019-09-26 シラス・インコーポレイテッド １，１−二置換アルケン化合物を有する組成物の電解開始重合

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102215191B1 (ko) * 2018-11-15 2021-02-16 단국대학교 산학협력단 전기 전도성이 향상된 분해성 나노멤브레인 및 이의 제조방법

Citations (5)

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JPS61243197A (ja) * 1985-04-19 1986-10-29 Hitachi Chem Co Ltd 導電性電解重合体と絶縁性プラスチツクからなる複合体の連続製造方法
JPH01234422A (ja) * 1988-03-12 1989-09-19 Mitsubishi Kasei Corp 高分子超薄膜
JPH02127472A (ja) * 1988-11-08 1990-05-16 Res Dev Corp Of Japan 超ミクロヘテロ層含有高分子構造体
JPH0649184A (ja) * 1992-03-10 1994-02-22 Sumitomo Chem Co Ltd 導電性樹脂複合体の製造方法
JP2006126474A (ja) * 2004-10-28 2006-05-18 Sony Corp 塗布型光学膜およびその作製方法、光学多層膜、反射型スクリーン、並びに浸漬塗布装置

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61243197A (ja) * 1985-04-19 1986-10-29 Hitachi Chem Co Ltd 導電性電解重合体と絶縁性プラスチツクからなる複合体の連続製造方法
JPH01234422A (ja) * 1988-03-12 1989-09-19 Mitsubishi Kasei Corp 高分子超薄膜
JPH02127472A (ja) * 1988-11-08 1990-05-16 Res Dev Corp Of Japan 超ミクロヘテロ層含有高分子構造体
JPH0649184A (ja) * 1992-03-10 1994-02-22 Sumitomo Chem Co Ltd 導電性樹脂複合体の製造方法
JP2006126474A (ja) * 2004-10-28 2006-05-18 Sony Corp 塗布型光学膜およびその作製方法、光学多層膜、反射型スクリーン、並びに浸漬塗布装置

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019163482A (ja) * 2015-06-01 2019-09-26 シラス・インコーポレイテッド １，１−二置換アルケン化合物を有する組成物の電解開始重合

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