WO2022097872A1 - Film de libération et son procédé de préparation - Google Patents

Film de libération et son procédé de préparation Download PDF

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Publication number
WO2022097872A1
WO2022097872A1 PCT/KR2021/008193 KR2021008193W WO2022097872A1 WO 2022097872 A1 WO2022097872 A1 WO 2022097872A1 KR 2021008193 W KR2021008193 W KR 2021008193W WO 2022097872 A1 WO2022097872 A1 WO 2022097872A1
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Prior art keywords
release film
inorganic particles
organic
formula
substituted
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PCT/KR2021/008193
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English (en)
Korean (ko)
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김태근
우혜미
권진우
이지훈
김현철
최영경
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도레이첨단소재 주식회사
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Priority to CN202180002509.8A priority Critical patent/CN114729145B/zh
Publication of WO2022097872A1 publication Critical patent/WO2022097872A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C08K5/5445—Silicon-containing compounds containing nitrogen containing at least one Si-N bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition

Definitions

  • It relates to a release film and a method for manufacturing the same.
  • One aspect is to provide a release film excellent in light peelability, residual adhesion, and coating appearance.
  • the substrate and the release layer are sequentially positioned
  • the release layer includes organic and inorganic particles,
  • a moiety including a fluorine-containing silane compound is introduced on the surface,
  • M F may be the content of element F (atomic %)
  • M Si may be the content of element Si (atomic %).
  • the fluorinated silane compound moiety may include a fluorinated silane compound represented by the following Chemical Formula 1:
  • R a , R b may be a substituted or unsubstituted C1-C20 alkoxy group
  • * may be a binding site with the surface of the organic/inorganic particle.
  • R d may be a hydrogen atom or a substituted or unsubstituted C1-C20 alkyl group
  • R e , R g may be a substituted or unsubstituted C1-C20 alkoxy group
  • R f may be a C4-C20 alkyl group substituted with fluorine
  • n 1 may be an integer from 1 to 10;
  • * may be a binding site with a Si atom.
  • the weight ratio of the organic-inorganic particles to the fluorinated silane compound may be 1:1 to 20:1.
  • a peak in a wavelength range of 1064 to 1066 cm -1 in the IR spectrum may be shifted to the right compared to organic/inorganic particles that do not include a fluorinated silane compound moiety on their surface.
  • the fluorinated polysiloxane may include an organo polysiloxane represented by the following Chemical Formula 3:
  • R 1 may be a substituted or unsubstituted C1-C10 monovalent hydrocarbon group, or a substituted or unsubstituted C2-C10 alkenyl group;
  • R 2 may be a substituted or unsubstituted C1-C10 monovalent hydrocarbon group, a substituted or unsubstituted C2-C10 alkenyl group, or hydrogen;
  • R 3 may be a fluorinated alkyl group represented by Formula 4, a fluorine-containing ether group represented by Formula 5, or a combination thereof;
  • n may be an integer from 1 to 8
  • m may be an integer from 1 to 5;
  • A may be an oxygen atom or a single bond
  • x, y, z may each be an integer of 1 or more;
  • Preparing the above-mentioned release film by forming a release layer by coating and drying a composition for forming a release layer comprising a polymer or copolymer including a fluorinated polysiloxane, and organic/inorganic particles on at least one surface of the substrate; including; do,
  • the weight ratio of the inorganic particles to the fluorinated silane compound is 4:1 to 20:1, a method for producing a release film is provided.
  • the weight ratio of the inorganic particles to the fluorinated silane compound may be 1:1 to 20:1.
  • the surface energy of the release layer is 24 dyne/cm or less
  • the release layer includes organic-inorganic particles
  • the organic-inorganic particles include a moiety including a fluorinated silane compound. Introduced to the surface, the organic-inorganic particles may satisfy the content ratio (M F /M Si ) range of the F/Si element represented by Equation 1 above.
  • the release film may provide a release film excellent in light peelability, residual adhesion rate, and coating appearance.
  • FIG. 1 is a schematic cross-sectional view of a release film according to an embodiment.
  • Example 2 is an inorganic silica particle as a starting material of the release film prepared in Example 1, an inorganic silica particle having aminosilane introduced thereinto as an intermediate reactant, and an aminosilane and a fluorinated silane compound on the surface as a final product. This is the IR spectrum result of silica inorganic particles.
  • ⁇ -based resin means " ⁇ resin”, “ ⁇ polymer”, “ ⁇ copolymer”, or/and “ ⁇ resin, polymer, Or a derivative of a copolymer” is a broad concept including all.
  • polymer or copolymer crosslinked with these resins means “polymer or copolymer crosslinked with the above-mentioned resins”.
  • aminosilane-based co-reactant is a broad concept including both “aminosilane co-reactant” and “co-reactant including aminosilane”.
  • a substrate and a release layer are sequentially positioned, the surface energy of the release layer is 24 dyne/cm or less, the release layer includes organic/inorganic particles, and the organic/inorganic particles are fluorine-containing A moiety including a silane compound may be introduced to the surface thereof, and the organic/inorganic particles may satisfy the F/Si element content ratio (M F /M Si ) range represented by the following formula 1:
  • a known substrate film or sheet may be used as a substrate for a release film.
  • a polyester-based resin film may be used as the substrate.
  • a known base film commonly used in the field of release film may be used.
  • the polyester-based base film may be a polyester-based base film disclosed in Korean Patent Registration No. 10-1268584, Korean Patent Application Laid-Open No. 2012-45213, and 2012-99546.
  • the polyester-based base film is described without limitation, but it should be understood as including the technical features of the known polyester-based base film. .
  • the polyester-based resin forming the base film may be polyester obtained by polycondensation of aromatic dicarboxylic acid and aliphatic glycol, and aromatic dicarboxylic acids include isophthalic acid, phthalic acid, terephthalic acid, and 2,6-naphthalenedica.
  • aromatic dicarboxylic acids include isophthalic acid, phthalic acid, terephthalic acid, and 2,6-naphthalenedica.
  • Leric acid, adipic acid, sebacic acid, oxycarboxylic acid (eg, ⁇ -oxybenzoic acid or 4-hydroxybenzoic acid) can be used, and the aliphatic glycol is ethylene glycol, diethylene glycol, propylene glycol, butanediol. , 1,4-cyclohexanedimethanol, neopentyl glycol, etc.
  • These polyester-based resins may use two or more of a dicarboxylic acid component and a glycol component in combination, and a
  • polyester-based base film a uniaxial or biaxially oriented film having high transparency and excellent productivity and processability may be used.
  • polyester-based base film polyethylene terephthalate (PET) or polyethylene-2,6-naphthalene dicarboxylate (PEN) may be used.
  • the hardness, specific gravity and color of the particles are not limited, but two or more types may be used in parallel as needed, and the average particle diameter of the particles used may be 0.1 to 5 ⁇ m, for example, 0.1 to 2 ⁇ m that can be used At this time, if the average particle diameter of the particles is less than 0.1 ⁇ m, aggregation between particles may occur, resulting in poor dispersion. can occur.
  • the content of the particles may be 0.01 to 5 wt%, for example, 0.01 to 3 wt%, based on the total weight of the polyester-based base film. If the content of the particles is less than 0.01% by weight, the sliding properties of the polyester film may deteriorate and the running characteristics between the rolls may deteriorate, and if the content of the particles exceeds 5% by weight, the surface smoothness of the film may deteriorate.
  • the thickness of the polyester-based base film is not limited, but may be 30 to 125 ⁇ m.
  • the release layer includes organic-inorganic particles, and a moiety including a fluorinated silane compound is introduced into the organic-inorganic particles on the surface, and the organic-inorganic particles are F/Si elements represented by Formula 1 below.
  • the content ratio (M F /M Si ) may satisfy the range:
  • M F may be the content of element F (atomic %)
  • M Si may be the content of element Si (atomic %).
  • the fluorinated silane compound moiety may include a fluorinated silane compound represented by the following Chemical Formula 1:
  • R a , R b may be a substituted or unsubstituted C1-C20 alkoxy group
  • R c may be represented by the following formula (2),
  • * may be a binding site with the surface of the organic/inorganic particle.
  • R d may be a hydrogen atom or a substituted or unsubstituted C1-C20 alkyl group
  • R e , R g may be a substituted or unsubstituted C1-C20 alkoxy group
  • * may be a binding site with a Si atom.
  • a peak in a wavelength range of 1064 to 1066 cm -1 in the IR spectrum may be shifted to the right compared to organic/inorganic particles that do not include a fluorinated silane compound moiety on their surface.
  • the fluorinated polysiloxane may include an organo polysiloxane represented by the following Chemical Formula 3:
  • * may be a binding site with a neighboring atom
  • R′ 1 may be a substituted or unsubstituted C1-C10 monovalent hydrocarbon group, or a substituted or unsubstituted C2-C10 alkenyl group;
  • R′ 2 may be a fluorine-containing ether group represented by Formula 7;
  • n' may be an integer from 1 to 8
  • m' may be an integer from 3 to 17;
  • the release layer may further include at least one of hydrogen polysiloxane and an acid catalyst.
  • the acid catalyst may use one or more metals or amphoteric elements selected from Group 4 to Group 14 elements, for example, one or more selected from Rh, Pt, Sn, Ti, Pd, Ir, W, and Co.
  • the acid catalyst may include a platinum chelate catalyst.
  • FIG. 1 is a schematic cross-sectional view of a release film 100 according to an embodiment.
  • a release film 120 has a structure in which a substrate 100 and a release layer 110 are sequentially positioned.
  • a method of manufacturing a release film comprises the steps of preparing a substrate; preparing organic/inorganic particles by adding and stirring inorganic particles, a fluorinated silane compound, and an aminosilane-based co-reactant, followed by heating; And preparing the above-described release film by forming a release layer by coating and drying a composition for forming a release layer comprising a polymer or copolymer including a fluorinated polysiloxane, and organic/inorganic particles on at least one surface of the substrate; Including, the weight ratio of the inorganic particles to the fluorinated silane compound may be 4:1 to 20:1.
  • the release film prepared by the method for manufacturing a release film according to an embodiment can provide a release film excellent in light peelability, residual adhesion, and coating appearance.
  • the solvent used in the composition for forming the release layer may be used without limitation as long as it can be applied on the substrate by dispersing the solid content of the composition for forming the release layer. If the total solids content of the composition for forming the release layer is less than 0.5% by weight, a uniform release layer is not formed and problems such as not being properly peeled between the silicone-based adhesive layer and the release film may occur, and 10% by weight If it exceeds, the viscosity of the composition for forming the release layer may be high, and thus leveling unevenness may occur, and thus the thickness uniformity of the release layer may be deteriorated.
  • Examples of the solvent used in the composition for forming the release layer include aromatic hydrocarbon-based solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, isooctane, decane, cyclohexane, methyl cyclohexane and isoparaffin; Hydrocarbon solvents, such as industrial gasoline (rubber gasoline etc.), petroleum benzene, and solvent naphtha; Acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, methyl isobutyl ketone, diisobutyl ketone, acetonyl acetone, cyclohexanone, etc.
  • aromatic hydrocarbon-based solvents such as toluene and xylene
  • aliphatic hydrocarbon solvents such as hexane, h
  • ester solvents such as ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, and isobutyl acetate
  • ether solvents such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, 1,2-dimethoxyethane, and 1,4-dioxane
  • solvents having ester and ether moieties such as 2-methoxyethyl acetate, 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, and 2-butoxyethyl acetate
  • siloxane solvents such as hexamethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, decanemethylcyclopentasiloxane, tris(trimethylsiloxy)methylsilane, and tetra
  • an offline coating method available in the art such as bar coating, gravure coating, and die coating, may be used.
  • the energy source for curing the composition for forming the release layer is not particularly limited, but heat treatment, ultraviolet irradiation, or electron beam irradiation may be used, and these may be used alone or in combination, but heat treatment alone or combination treatment of heat and ultraviolet light may be used.
  • the weight ratio of the inorganic particles to the fluorinated silane compound may be 1:1 to 20:1. If the weight ratio of the inorganic particles to the fluorine-containing silane compound is within the above range, the peeling force may be further lowered to implement better light peelability.
  • substitution is derived by exchanging one or more hydrogens with another atom or functional group in an unsubstituted mother group.
  • a functional group when a functional group is considered to be “substituted,” it means that the functional group is an alkyl group having 1 to 40 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, an alkynyl group having 2 to 40 carbon atoms, or a cyclo group having 3 to 40 carbon atoms. It means substituted with one or more substituents selected from an alkyl group, a cycloalkenyl group having 3 to 40 carbon atoms, and an aryl group having 7 to 40 carbon atoms.
  • a functional group is described as being “optionally substituted”, it is meant that the functional group may be substituted with the aforementioned substituents.
  • the C1-C10 monovalent hydrocarbon group includes, for example, a linear alkyl group such as a methyl group, an ethyl group, a hexyl group, an octyl group, and a decyl group; branched alkyl groups such as isopropyl group, tert-butyl group, neopentyl group and hexyl group; Cyclic alkyl groups, such as a cyclopentyl group and a cyclohexyl group, Aryl groups, such as a vinyl group, a henyl group, and a tolyl group, Aralkyl groups, such as a benzyl group and a phenethyl group; means etc. Among them, it may be an alkyl group in consideration of the ease of procurement of raw materials, and may be a methyl group or an ethyl group in consideration of the usefulness of the product.
  • the C2-C10 alkenyl group refers to a branched or unbranched hydrocarbon having at least one carbon-carbon double bond.
  • alkenyl groups include vinyl, allyl, butenyl, isopropenyl, or isobutenyl.
  • inorganic silica particles manufactured by ABC Nanotech, SILNOS 160
  • Triethoxy-1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane manufactured by TCI
  • aminosilane (KBP-90, manufactured by ShinEtsu, KBP-90) as a co-reactant was slowly added in an amount of 1/4 based on the weight of inorganic silica particles, and then reacted for 24 hours to obtain a reactant. Then, organic-inorganic particles were prepared by removing the solvent from the reactant through a filter.
  • inorganic silica particles manufactured by ABC Nanotech, SILNOS 160
  • triethoxy-1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane Triethoxy-1H, 1H, 2H
  • Organic-inorganic particles were prepared in the same manner as in Preparation Example 1, except that 2H-tridecafluoro-n-octylsilane (manufactured by TCI) was added in a weight ratio of 20:1.
  • Silica inorganic particles (manufactured by ABC Nanotech, E540+) were prepared.
  • a 38 ⁇ m thick polyester film (Toray Advanced Materials, XD500P) was prepared.

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Abstract

Est divulgué un film de libération et son procédé de préparation. Le film de libération a un substrat et un film de libération qui sont disposés de manière séquentielle, le film de libération ayant une énergie de surface de 24 dyne/cm ou moins et contenant des particules organiques et inorganiques. Les particules organiques et inorganiques ont une fraction introduite sur la surface de celles-ci, la fraction portant un composé de silane contenant du fluor, et peuvent satisfaire une plage d'un rapport de teneur (MF/MSi) en éléments F/Si, exprimé par la formule 1 ci-dessous : [Formule 1] 0,1 ≤ MF/MSi ≤ 1,0, dans laquelle MF est la teneur (% atomique) en élément F et MSi est la teneur (% atomique) en élément Si.
PCT/KR2021/008193 2020-11-06 2021-06-29 Film de libération et son procédé de préparation WO2022097872A1 (fr)

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CN202180002509.8A CN114729145B (zh) 2020-11-06 2021-06-29 一种离型膜和其制备方法

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KR1020200148144A KR102531723B1 (ko) 2020-11-06 2020-11-06 이형필름 및 이의 제조방법
KR10-2020-0148144 2020-11-06

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CN115536890A (zh) * 2022-11-04 2022-12-30 惠州市鑫亚凯立科技有限公司 一种具有立体微纳米结构的光学氟素离型膜及其制造方法

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KR102601242B1 (ko) 2022-12-27 2023-11-14 이에프티솔루션주식회사 기능성 나노 복합 이형필름

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