[go: up one dir, main page]

WO2019039391A1 - Film polymère mince ainsi que procédé de fabrication de celui-ci, et stratifié sous forme de film - Google Patents

Film polymère mince ainsi que procédé de fabrication de celui-ci, et stratifié sous forme de film Download PDF

Info

Publication number
WO2019039391A1
WO2019039391A1 PCT/JP2018/030475 JP2018030475W WO2019039391A1 WO 2019039391 A1 WO2019039391 A1 WO 2019039391A1 JP 2018030475 W JP2018030475 W JP 2018030475W WO 2019039391 A1 WO2019039391 A1 WO 2019039391A1
Authority
WO
WIPO (PCT)
Prior art keywords
thin film
polymer thin
film
polymer
less
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/JP2018/030475
Other languages
English (en)
Japanese (ja)
Inventor
千春 平野
宮田　壮
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.)
Lintec Corp
Original Assignee
Lintec 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 Lintec Corp filed Critical Lintec Corp
Priority to KR1020207003357A priority Critical patent/KR102548027B1/ko
Priority to JP2019529666A priority patent/JP6586546B2/ja
Priority to CN201880052489.3A priority patent/CN111032751B/zh
Publication of WO2019039391A1 publication Critical patent/WO2019039391A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/12—Spreading-out the material on a substrate, e.g. on the surface of a liquid
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/14—Monomers containing five or more carbon atoms
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms

Definitions

  • the present invention relates to a polymer thin film, a film-like laminate, and a method for producing a polymer thin film.
  • Patent Document 1 describes an olefin-based resin sheet containing a polymethylpentene-based resin.
  • This olefin-based resin sheet is formed by forming a coated film using a liquid composition in which a polymethylpentene-based resin is dissolved in a solvent in which hydrocarbons and ethers are mixed in a specific ratio, and then dried. It can be manufactured.
  • the resin film When the thickness of the resin film is in the range of several tens to several hundreds of nm, due to electrostatic force and wettability, the resin film may be in close contact with the adherend without using an adhesive or the like. However, the olefin-based resin sheet described in Patent Document 1 could not be adhered to an adherend. In addition, although it is described in Patent Document 1 that the average thickness of the olefin-based resin sheet is preferably 0.2 ⁇ m or more and 10 ⁇ m or less, in the method for producing an olefin-based resin sheet described in Patent Document 1, the thickness of the film is could not be nanoscaled.
  • a polymer thin film characterized by having:
  • the methylpentene-based polymer (A) is a methylpentene-based copolymer.
  • the polymer thin film preferably contains 50% by mass or more of the methylpentene-based polymer (A).
  • the melting point of the methylpentene polymer (A) is preferably 130 ° C. or more and 199 ° C. or less.
  • the surface carbon concentration of the polymer thin film is preferably 95 atomic% or more.
  • a film-like laminate comprising a process film and the polymer thin film according to the above-mentioned one aspect of the invention formed on the process film.
  • the surface free energy of the process film is preferably 40 mJ / m 2 or less.
  • the arithmetic mean roughness of the surface of the step film is preferably 40 nm or less.
  • a method of producing a polymer thin film for producing a polymer thin film according to the above-mentioned one aspect of the present invention which comprises the above-mentioned methylpentene polymer (A) on a process film.
  • Manufacturing a polymer thin film comprising the steps of: applying a solution for forming a molecular thin film; and drying to form the polymer thin film; and peeling the polymer thin film from the step film.
  • a method is provided.
  • the surface free energy of the process film is preferably 40 mJ / m 2 or less.
  • the arithmetic mean roughness of the surface of the step film is preferably 40 nm or less.
  • a polymer thin film having high water repellency and a method for producing a polymer thin film can be provided, which can be adhered to an adherend without using an adhesive or the like.
  • Another object of the present invention is to provide a film-like laminate having the polymer thin film.
  • the polymer thin film 1 according to the present embodiment is a thin film having a self-supporting property, as shown in FIG.
  • self-supporting property refers to the property that the polymer thin film 1 can form a film alone when the polymer thin film 1 is not laminated on another support, and more specifically In fact, it means that the membrane strength is 5 mN / mm ⁇ or more.
  • the film strength is preferably 10 mN / 1 mm ⁇ or more, more preferably 15 mN / 1 mm ⁇ or more.
  • the film strength can be measured with a creep meter (for example, trade name “cree meter RE2-3305 CYAMADEN” manufactured by Yamaden Co., Ltd.). Specifically, it can be measured by the method described in the examples described later.
  • the thickness of the polymer thin film 1 is 10 nm or more and 1000 nm or less.
  • the thickness of the polymer thin film 1 is described in J.I. A. It can be measured by a spectral ellipsometer (product name "M-2000") manufactured by Woollam.
  • the thickness of the polymer thin film 1 is preferably 30 nm or more, more preferably 50 nm or more, still more preferably 100 nm or more, and particularly preferably 150 nm or more.
  • the thickness of the polymer thin film 1 is preferably 900 nm or less, more preferably 700 nm or less, still more preferably 550 nm or less, and particularly preferably 400 nm or less.
  • the surface carbon concentration of the polymer thin film 1 is preferably 95 atomic% or more, more preferably 97 atomic% or more, and still more preferably 99 atomic% or more from the viewpoint of water repellency.
  • the surface carbon concentration can be measured by X-ray photoelectron spectroscopy (XPS).
  • the polymer thin film 1 needs to contain a methylpentene-based polymer (A) containing a constitutional unit represented by the following general formula (1).
  • a polymer thin film having a self-supporting property and a high water repellency can be obtained at a desired thickness. I can not.
  • the content of the constituent unit represented by the following general formula (1) in the polymer thin film 1 is preferably 50 mol% or more, and more preferably 80 mol% or more.
  • the methylpentene polymer (A) may be a methylpentene homopolymer or a methylpentene copolymer.
  • the methylpentene polymer (A) is a structural unit other than the structural unit represented by the general formula (1), for example, an ⁇ -olefin having 3 to 20 carbon atoms excluding ethylene and 4-methyl-1-pentene May be included.
  • ⁇ -olefins having 3 to 20 carbon atoms examples include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 1-octene, 1 -Decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like.
  • the methylpentene polymer (A) may contain a structural unit having a reactive functional group.
  • a reactive functional group for example, at least one reactive functional group selected from the group consisting of a carboxy group, an acid anhydride structure, an epoxy group, a hydroxyl group, an amino group, an amido group, an imide group, and a nitrile group. Can be mentioned.
  • a methyl pentene type polymer (A) is a copolymer which has the reactive functional group crosslinkable by the aliphatic polyisocyanate compound mentioned later.
  • a reactive functional group crosslinkable by an aliphatic polyisocyanate compound a carboxy group, an acid anhydride structure, an epoxy group, a hydroxyl group, an amino group, an amide group, an imide group, a nitrile group, etc. are mentioned.
  • a carboxy group and an acid anhydride structure are preferable.
  • ком ⁇ онент having these reactive functional groups that is, as the ethylenically unsaturated bond-containing monomer, unsaturated carboxylic acid, derivatives of unsaturated carboxylic acid (acid anhydride, acid amide, acid imide, ester, acid halogen Compounds and metal salts, etc.), hydroxyl group-containing ethylenic unsaturated compounds, epoxy group-containing ethylenic unsaturated compounds, and styrenic monomers can be mentioned.
  • unsaturated carboxylic acids unsaturated carboxylic acids, derivatives of unsaturated carboxylic acids, hydroxyl group-containing ethylenic unsaturated compounds and epoxy group-containing ethylenic unsaturated compounds are preferable. These may be used singly or in combination of two or more.
  • examples of unsaturated carboxylic acids and derivatives thereof include unsaturated carboxylic acids and anhydrides thereof ((meth) acrylic acid, ⁇ -ethyl acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, Citraconic acid, crotonic acid, isocrotonic acid, endo-bicyclo [2.2.1] hept-2,3-dicarboxylic acid (nadic acid), nadic anhydride, and methyl-endos-bicyclo [2.2.1] hept -5-ene-2,3-dicarboxylic acid (methyl nadic acid) etc., unsaturated carboxylic acid ester (methyl methacrylate etc.), unsaturated carboxylic acid halide, unsaturated carboxylic acid amide, unsaturated carboxylic acid imide etc.
  • unsaturated carboxylic acids and anhydrides thereof ((meth) acrylic acid, ⁇ -ethyl acrylic acid
  • unsaturated carboxylic acids and derivatives thereof include malonyl chloride, maleimide, maleic anhydride, citraconic anhydride, nadic anhydride, acrylic acid, nadic acid, maleic acid, monomethyl maleate, dimethyl maleate, and methacrylic acid. Methyl and the like are preferable, and acrylic acid, maleic acid, nadic acid, maleic anhydride, nadic anhydride and methyl methacrylate are more preferable. These may be used singly or in combination of two or more.
  • hydroxyl-containing ethylenically unsaturated compound for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy-butyl (meth) acrylate , 3-hydroxy-butyl (meth) acrylate, 4-hydroxy-butyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono ( Meta) acrylate, pentaerythritol mono (meth) acrylate, trimethylol propane (meth) acrylate, tetramethylol ethane mono (meth) acrylate, butanediol mono (meth) acrylate, polyethylene glycol -Ol (meth) acrylate, 2- (6-hydroxyhexanoyloxy) eth
  • hydroxyl group-containing ethylenic unsaturated compound 10-undecen-1-ol, 1-octene-3-ol, 2-methanol norbornene, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) ) Acrylate, hydroxystyrene, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N-methylol acrylamide, 2- (meth) acryloyloxyethyl acid phosphate, glycerin monoallyl ether, allyl alcohol, aryloxyethanol, 2-butene-1,4- Diols and glycerin monoalcohols are preferable, and 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are more preferable.
  • the hydroxyl group-containing ethylenic unsaturated compound may be used alone or in combination of two or more.
  • epoxy group-containing ethylenically unsaturated compound examples include glycidyl acrylate, glycidyl methacrylate, mono- or diglycidyl ester of itaconic acid, mono- or di- or triglycidyl ester of butene tricarboxylic acid, mono- or diglycidyl tetraconic acid Ester, mono- or diglycidyl ester of endo-cis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (nadic acid), endo-cis-bicyclo [2.2.1] hept Mono- or diglycidyl ester of 5-ene-2,3-dimethyl-2,3-dicarboxylic acid (methyl nadic acid), mono- or diglycidyl ester of allyl succinic acid, glycidyl ester of p-styrenecarboxylic acid, allyl glycid
  • epoxy group-containing ethylenically unsaturated compound glycidyl acrylate and glycidyl methacrylate are preferable.
  • the epoxy group-containing ethylenically unsaturated compounds may be used alone or in combination of two or more.
  • ethylenically unsaturated bond-containing monomers more preferred are unsaturated carboxylic acids or derivatives thereof, even more preferred are unsaturated carboxylic acid anhydrides, and particularly preferred is maleic anhydride.
  • the ratio of the structural unit having a reactive functional group crosslinkable by the aliphatic polyisocyanate compound may be a value within the range of 0.1 mass% to 10 mass% with respect to 100 mass% of all the structural units. preferable.
  • the proportion of such constituent units is 0.1% by mass or more, the crosslink density does not become excessively low.
  • the proportion of such structural units is 10% by mass or less, the crosslink density does not become excessively high.
  • the proportion of constituent units having a reactive functional group crosslinkable with an aliphatic polyisocyanate compound is in the range of 0.3% by mass to 7% by mass with respect to 100% by mass of all constituent units.
  • the structural unit other than the structural unit having a reactive functional group crosslinkable by an aliphatic polyisocyanate compound may contain an ⁇ -olefin having 3 to 20 carbon atoms.
  • the melting point of the methylpentene polymer (A) is preferably 130 ° C. or more and 199 ° C. or less.
  • the melting point of the methylpentene polymer (A) is 130 ° C. or higher, it can be prevented that the polymer thin film is softened in the heating step.
  • the melting point of the methylpentene polymer (A) is 199 ° C. or less, the coating properties of the solution for forming a polymer thin film can be improved.
  • the methylpentene-based polymer (A), which is the main component of the polymer thin film, is a component of the solution for forming a polymer thin film, and thus can be dissolved in a solvent.
  • the polymer thin film 1 may contain an olefin-based polymer (B) other than the methylpentene-based polymer (A) (hereinafter, sometimes referred to as “non-MP olefin-based polymer (B)”).
  • non-MP olefin-based polymer (B) the content of the methylpentene polymer (A) is preferably 50% by mass or more based on the total amount of the polymer, from the viewpoint of self-supporting property and water repellency. It is more preferable that it is 70 mass% or more, and it is further more preferable that it is 90 mass% or more.
  • the non-MP olefin-based polymer (B) may be linear or have a side chain.
  • the non-MP olefin-based polymer (B) may have a functional group as long as it does not contain methylpentene, and the type of functional group and the substitution density are optional.
  • the functional group possessed by the non-MP olefin-based polymer (B) may be a functional group having low reactivity such as an alkyl group, or may be a functional group having high reactivity such as a carboxylic acid group.
  • the non-MP olefin-based polymer (B) is an olefin-based polymer containing an olefin as at least one monomer, and is an olefin-based polymer that does not have a methylpentene-based compound as a monomer. Therefore, the non-methylpentene polymer (B) is not particularly limited as long as it does not contain methylpentene in the polymer, and may be either an aromatic cyclic polyolefin or an acyclic polyolefin.
  • the aromatic cyclic polyolefin includes polyolefins having an olefin having a cyclic structure of an aromatic ring as at least one of monomers.
  • the non-MP olefin polymer (B) may be a homopolymer or a copolymer.
  • the polymer thin film 1 can be adhered to an adherend without using an adhesive or the like.
  • the adherend is not particularly limited.
  • stainless steel, polyethylene, polypropylene, polycarbonate, glass, PTFE (polytetrafluoroethylene), PVDF (polyvinylidene fluoride), a semiconductor circuit board, and the like can be mentioned.
  • PTFE polytetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • a semiconductor circuit board and the like.
  • adherends water repellency can be easily given to arbitrary adherends.
  • examples of the adherend other than the above include humans, animals, clothes, hats, shoes, and decorations.
  • the polymer thin film 1 is preferable because it is very thin, so the site of application is inconspicuous and lightweight.
  • the polymer thin film 1 since the polymer thin film 1 has high water repellency, it is also resistant to sweat or rain. Therefore, the polymer thin film 1 can be particularly suitably used as a
  • the method for producing a polymer thin film according to the present embodiment is a method for producing a polymer thin film for producing the polymer thin film 1. And the manufacturing method of the polymer thin film which concerns on this embodiment apply
  • FIG. 2 is a schematic cross-sectional view showing a step film 2 used in the method for producing a polymer thin film according to the present embodiment.
  • the process film 2 has a first surface 2A and a second surface 2B.
  • the methylpentene polymer (A) is contained on the first surface 2A of the first surface 2A and the second surface 2B of the step film 2 as shown in FIG.
  • a solution for forming a polymer thin film is applied and dried to form a polymer thin film 1 to obtain a film-like laminate 100 as shown in FIG.
  • the process film and the solution for forming a polymer thin film used in the polymer thin film forming process will be described.
  • the process film 2 is not particularly limited.
  • the process film 2 preferably includes the release substrate 21 and the release agent layer 22 formed on at least one surface of the release substrate 21.
  • the surface of the release agent layer 22 corresponds to the first surface 2A
  • the surface of the release substrate 21 opposite to the surface on which the release agent layer 22 is formed corresponds to the second surface 2B.
  • the release substrate 21 include a paper substrate, a laminated paper obtained by laminating a thermoplastic resin such as polyethylene on the paper substrate, and a plastic film.
  • Paper substrates include glassine paper, wood free paper, coated paper, and cast coated paper.
  • Plastic films include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyolefin films such as polypropylene and polyethylene. These may be used singly or in combination of two or more.
  • the release agent layer 22 may be formed by applying a release agent.
  • the release agent include olefin resins, rubber elastomers (for example, butadiene resins, isoprene resins, etc.), long chain alkyl resins, alkyd resins, fluorine resins, and silicone resins.
  • the release agent any one selected from the group consisting of an olefin resin, a rubber elastomer (for example, a butadiene resin, an isoprene resin, etc.), a long chain alkyl resin, an alkyd resin, and a fluorine resin It is preferable that it is a release agent. These may be used singly or in combination of two or more.
  • the release agent layer may further contain an antistatic agent or may not contain an antistatic agent.
  • the surface free energy and the arithmetic mean roughness of the first surface 2A be adjusted by the release agent layer 22.
  • the first surface free energy of the surface 2A of the casting film 2 is preferably 40 mJ / m 2 or less, more preferably 20 mJ / m 2 or more 40 mJ / m 2 or less. If the surface free energy is 20 mJ / m 2 or more, the solution for forming a polymer thin film can be favorably coated on the process film 2, and if the surface free energy is 40 mJ / m 2 or less, the process film 2 is high. The molecular thin film 1 can be easily peeled off, and the productivity can be improved.
  • the surface free energy can be determined by Kitazaki-Hata theory based on the measured contact angles (measurement temperature: 25 ° C.) of various droplets.
  • the arithmetic mean roughness (Ra) of the surface of the first surface 2A of the process film 2 is preferably 40 nm or less, more preferably 0.1 nm to 30 nm, and still more preferably 0.5 nm to 25 nm Is particularly preferred. If the arithmetic mean roughness of the surface is within the above range, the unevenness formed on the polymer thin film 1 can be sufficiently suppressed, and the film strength of the polymer thin film 1 can be improved. Arithmetic mean roughness can be measured, for example, using a light interference microscope NT1100 manufactured by Veeco instruments.
  • the thickness of the process film 2 is not particularly limited.
  • the thickness of the process film 2 is usually 20 ⁇ m or more and 200 ⁇ m or less, and preferably 25 ⁇ m or more and 150 ⁇ m or less.
  • the thickness of the release agent layer 22 is not particularly limited.
  • the thickness of the release agent layer 22 is preferably 0.01 ⁇ m or more and 2.0 ⁇ m or less. More preferably, it is 03 ⁇ m or more and 1.0 ⁇ m or less.
  • the thickness of the plastic film is preferably 3 ⁇ m or more and 50 ⁇ m or less, more preferably 5 ⁇ m or more and 90 ⁇ m or less, and particularly preferably 10 ⁇ m or more and 40 ⁇ m or less .
  • the material for forming a polymer thin film as a solute in the solution for forming a polymer thin film is the methylpentene-based polymer (A) of the above-mentioned polymer thin film.
  • the methylpentene-based polymer (A) of the above-mentioned polymer thin film is the methylpentene-based polymer (A) of the above-mentioned polymer thin film.
  • the methylpentene-based polymer (A) and the non-MP olefin-based polymer (B) are omitted because they have already been described.
  • the type of the solvent in the solution for forming a polymer thin film is not particularly limited as long as it can dissolve or uniformly disperse the material for forming a polymer thin film, and evaporates by heating.
  • the solvent ethanol, propanol, isopropyl alcohol, acetone, toluene, cyclohexanone, ethyl acetate, butyl acetate, tetrahydrofuran, methyl ethyl ketone, dichloromethane, chloroform and the like are preferable. These may be used singly or in combination of two or more.
  • the boiling point of the solvent is preferably in the range of 30 ° C. to 160 ° C., and more preferably in the range of 35 ° C. to 120 ° C.
  • concentration of the material substance in the solution for polymer thin film formation into the value within the range of 0.1 mass% or more and 20 mass% or less. If the concentration of the material in the solution for forming a polymer thin film is 0.1% by mass or more, the problem that the required thickness may not be obtained and the problem that the viscosity of the solution is not optimum are suppressed it can. On the other hand, when the concentration of the material in the solution for forming a polymer thin film is 20% by mass or less, it is possible to suppress a problem that a uniform coating film may not be obtained.
  • the concentration of the material in the solution for forming a polymer thin film it is more preferable to set the concentration of the material in the solution for forming a polymer thin film to a value within the range of 0.3% by mass to 15% by mass, and 0.5% by mass to 10% by mass It is further preferable to set the value within the following range.
  • the viscosity (measurement temperature: 25 degreeC) of the solution for polymer thin film formation into the value within the range of 1 mPa * s or more and 500 mPa * s or less. If the viscosity of the solution for forming a polymer thin film is 1 mPa ⁇ s or more, it is possible to suppress the problem that repelling of the coating film occurs. On the other hand, when the viscosity of the solution for forming a polymer thin film is 500 mPa ⁇ s or less, it is possible to suppress the problem that a uniform coating film can not be obtained.
  • the viscosity (measurement temperature: 25 ° C.) of the solution for forming a polymer thin film it is more preferable to set the viscosity (measurement temperature: 25 ° C.) of the solution for forming a polymer thin film to a value within the range of 2 mPa ⁇ s to 400 mPa ⁇ s, and preferably 3 mPa ⁇ s to 300 mPa ⁇ s. It is further preferable to set the value within the range of The viscosity of the solution for forming a polymer thin film is measured in accordance with JIS K 7117-1 4.1 (Brookfield type rotational viscometer).
  • the drying conditions for forming the polymer thin film 1 on the coated layer of the solution for forming a polymer thin film formed on the step film 2 are not particularly limited.
  • the drying of the coating layer is preferably performed at a temperature of 40 ° C. to 120 ° C. and a drying time of 6 seconds to 300 seconds. If the drying temperature is 40 ° C. or more, it is possible to suppress the problem that the drying takes time or the drying becomes insufficient. On the other hand, if the drying temperature is 120 ° C. or less, it is possible to suppress a defect that wrinkles or curls occur. In addition, if the drying time is 6 seconds or more, it is possible to prevent the problem of insufficient drying.
  • the drying conditions for forming the coating layer of the polymer thin film forming solution as the polymer thin film 1 are the temperature conditions of 50 ° C. or more and 110 ° C. or less, and the drying time of 12 seconds or more and 180 seconds or less. It is more preferable that the temperature condition be 60 ° C. or more and 100 ° C. or less and the drying time be 18 seconds or more and 120 seconds or less.
  • the roll-to-roll method can form the polymer thin film 1 having a predetermined thickness more efficiently, so that the film-like laminate 100 can be mass-produced more efficiently. It is for.
  • a bar coater, a gravure coater, or a die coater is preferable, and a reverse gravure coater or a slot die coater is particularly preferable. The reason is that, with these coating devices, the polymer thin film 1 having a predetermined thickness can be formed more efficiently.
  • the polymer thin film 1 of nanometer order thickness can be formed with uniform thickness without generating wrinkles on the surface.
  • the bar coater, the reverse gravure coater and the slot die coater are simple in their structure and excellent in economics.
  • the peeling step the polymer thin film 1 in the film-like laminate 100 as shown in FIG. 3 is peeled from the process film 2 to obtain the polymer thin film 1 having a self-supporting property.
  • the peeling force of the step film 2 from the polymer thin film 1 in the peeling step is preferably 5 mN / 20 mm or more and 100 mN / 20 mm or less, more preferably 10 mN / 20 mm or more and 70 mN / 20 mm or less, and 15 mN / It is particularly preferable that the diameter is 20 mm or more and 50 mN / 20 mm or less.
  • the peeling force is 5 mN / 20 mm or more, it is possible to suppress the problem that the process film and the polymer thin film are easily peeled off in the polymer thin film forming step.
  • the above peeling force is 100 mN / 20 mm or less, in the peeling step, it becomes difficult to peel the step film from the polymer thin film, and it is possible to suppress the problem that the polymer thin film is broken.
  • the above peeling force can be adjusted, for example, by changing the type of the release agent used for the process film 2.
  • the film-like laminate 100 includes a polymer thin film 1 and a process film 2 as shown in FIG.
  • the film-like laminate 100 is obtained by applying the solution for forming a polymer thin film on a process film 2 and drying the applied layer to form a polymer thin film 1. That is, the film-like laminate 100 is obtained by the polymer thin film forming step in the method of manufacturing a polymer thin film according to the above-described embodiment.
  • the polymer thin film 1 having a thickness of 10 nm or more and 1000 nm or less and having a self-supporting property can be efficiently produced, including the methylpentene-based polymer (A) represented by the general formula (1).
  • A methylpentene-based polymer represented by the general formula (1).
  • the present embodiment is not limited to the above-described embodiment, but includes modifications, improvements, and the like as long as the object of the present embodiment can be achieved.
  • the process film 2 provided with the peeling base material 21 and the release agent layer 22 was used, it is not limited to this.
  • a single layer film consisting only of the release substrate 21 is a process film 2 It may be used as
  • Test Example 1 Selection of Process Film (1) Production of Process Film
  • the process film of Test Example 1 has a release substrate and a release agent layer provided on the release substrate.
  • a coating solution having a concentration of 2% by mass was prepared.
  • the obtained coating solution is coated on a 38 ⁇ m thick polyethylene terephthalate (PET) film ("Diafoil T100" manufactured by Mitsubishi Chemical Corporation) using a Meyer bar, and heated at 140 ° C for 60 seconds. It dried and the process film which formed the release agent layer of average thickness 0.1 micrometer was obtained.
  • PET polyethylene terephthalate
  • Measurement / Evaluation (1) Measurement of Surface Free Energy of Process Film
  • the surface free energy (mJ / m 2 ) on the surface (contact surface with the polymer thin film) to which the solution for forming a polymer thin film in the process film is applied is various liquids.
  • the contact angle of the drop (measurement temperature: 25 ° C.) was measured, and based on that value, it was determined by Kitazaki-Hata theory. That is, using diiodomethane as “dispersion component”, 1-bromonaphthalene as “dipolar component”, and distilled water as “hydrogen bond component” as droplets, DM-70 manufactured by Kyowa Interface Science Co., Ltd. is used.
  • Test Example 2 a film-like laminate and a polymer are prepared in the same manner as in Test Example 1 except that a polyethylene terephthalate film ("Diafoil T100" manufactured by Mitsubishi Chemical Corporation, 38 ⁇ m thick) is used as the process film. Thin films were produced and evaluated. The obtained results are shown in Table 1. The surface free energy and the arithmetic mean roughness on the surface of the process film used in Test Example 2 are shown in Table 1.
  • Test Example 3 In Test Example 3, a film-like laminate and a polymer thin film were produced and evaluated in the same manner as in Test Example 1 except that “SP-PET 381031” manufactured by Lintec Corporation was used as the process film. The obtained results are shown in Table 1. Further, the surface free energy on the surface of the release agent layer of the step film used in Test Example 3 and the arithmetic mean roughness are shown in Table 1.
  • Test Example 4 a film-like laminate and a polymer thin film were produced and evaluated in the same manner as in Test Example 1 except that “SP-PET38T100X” manufactured by Lintec Corporation was used as a process film. The obtained results are shown in Table 1. Further, the surface free energy on the surface of the release agent layer of the step film used in Test Example 4 and the arithmetic mean roughness are shown in Table 1.
  • Example 1 Method for Producing Polymer Thin Film (1) Production of Process Film The process film of Example 1 has a release substrate and a release agent layer provided on the release substrate. Dilute 100 parts by weight of a mixture of silicone-modified alkyd resin and amino resin (Shin-Etsu Chemical Co., Ltd .: trade name "KS-882") and 1 part by weight of p-toluenesulfonic acid (hardening agent) with toluene, and solidify it. A coating solution having a concentration of 2% by mass was prepared.
  • KS-882 silicone-modified alkyd resin and amino resin
  • p-toluenesulfonic acid hardening agent
  • the obtained coating solution is coated on a 38 ⁇ m thick polyethylene terephthalate (PET) film ("Diafoil T100" manufactured by Mitsubishi Resins Co., Ltd.) with a Meyer bar, and dried by heating at 140 ° C for 60 seconds.
  • PET polyethylene terephthalate
  • the process film which formed the release agent layer of average thickness 0.1 micrometer was obtained.
  • peeling Force of Polymer Thin Film The peeling force at the time of peeling the polymer thin film from the process film in the obtained film-like laminate was measured. That is, after bonding an adhesive tape (No. 31B, manufactured by Nitto Denko Corporation) to a polymer thin film in a film-like laminate, the polymer thin film in a state where the adhesive tape is bonded is 180 ° from the process film The peeling force (mN / 20 mm) at the time of peeling was measured. The obtained results are shown in Table 2. (2) Surface Carbon Concentration of Polymer Thin Film In order to obtain the surface carbon concentration of the polymer thin film, XPS measurement of the surface of the polymer thin film was performed.
  • PHI Quantera SXM manufactured by ULVAC-PHI, Inc.
  • the measurement was carried out at a photoelectron extraction angle of 45 ° using monochromatized Al ⁇ K ⁇ as the X-ray source, and the elemental concentration (unit: atomic%) of carbon present on the surface was calculated.
  • the obtained results are shown in Table 2.
  • (3) Sticking Property of Polymer Thin Film a double-sided tape was stuck to the square end of a support base (“Crisper 75K2323” manufactured by Toyobo Co., Ltd.) to prepare a support having a double-sided tape-sticked part. Next, the double-sided tape sticking part of this support was stuck on the polymer thin film of the film-like laminate.
  • the support and the polymer thin film were peeled off from the process film to transfer the polymer thin film to the surface of the support.
  • the double-sided tape sticking part was cut off from the support body to which the polymer thin film transferred, and the laminated body of a polymer thin film and a support base material was produced.
  • This laminate was placed on the adherend so that the polymer thin film side was in contact with the following adherend, and the polymer thin film and the adherend were pressed together by moving the 2 kg roller twice from the support base . The stickability at that time was evaluated.
  • PP Polypropylene board ("PP-N-BN” manufactured by Hitachi Chemical Co., Ltd., size 2 mm x 70 mm x 150 mm)
  • Glass float plate glass ("float plate glass R3202 thread surface processing” manufactured by Asahi Glass Co., Ltd., size 2 mm x 70 mm x 150 mm)
  • a contact angle meter (DM-701, manufactured by Kyowa Interface Science Co., Ltd.) was used. The contact angle to water was measured (23 ° C., 50% RH). The obtained results are shown in Table 2.
  • the film strength was measured with a creep meter (trade name “cree meter RE2-3305 CYAMADEN” manufactured by Yamaden Co., Ltd.). Specifically, the polymer thin film surface of the film-like laminate, which was allowed to stand for 24 hours in an environment of temperature 23 ° C. and humidity 50% RH, was attached to a jig with a hole of 1 cm in diameter, and the process film was peeled off . A cylindrical plunger with a diameter of 1 mm ⁇ was advanced to a location corresponding to the center of the hole of the polymer thin film jig. The penetration speed of the plunger was 0.5 mm / sec.
  • the maximum stress (unit: mN / 1 mm ⁇ ) was measured when the plunger was advanced to a depth of 5 mm in the depth direction of the hole. The measurement was performed 10 times, and the average value was taken as the film strength of the polymer thin film. The obtained results are shown in Table 2.
  • Examples 2 to 4 A film-like laminate and a polymer thin film were produced and evaluated in the same manner as in Example 1 except that the melting point of the PMP resin and the thickness of the polymer thin film were changed as shown in Table 2. The obtained results are shown in Table 2. Further, the melting point of the PMP resin used in Examples 2 to 4 and the viscosity of the solution for forming a polymer thin film are shown in Table 2.
  • Comparative Examples 1 and 2 A film-like laminate and a polymer thin film were produced and evaluated in the same manner as in Example 1 except that the melting point of the PMP resin and the thickness of the polymer thin film were changed as shown in Table 2. The obtained results are shown in Table 2. Further, the melting point of the PMP resin and the viscosity of the solution for forming a polymer thin film used in Comparative Examples 1 and 2 are shown in Table 2. In Comparative Example 1, the polymer could not be dissolved to a desired concentration, and it was not possible to produce a film-like laminate and a polymer thin film in the same manner as in Example 1.
  • the polymer thin film (Examples 1 to 4) containing methylpentene polymer (A) and having a thickness of 10 nm or more and 1000 nm or less has good adhesion and a contact angle of water. It was confirmed that the sliding angle of water was small. From this, it was confirmed that the polymer thin films obtained in Examples 1 to 4 can be adhered to an adherend without using an adhesive or the like and have high water repellency. Also, it was confirmed that the polymer thin films obtained in Examples 1 to 4 have high film strength and have self-supporting properties.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

Le film polymère mince de l'invention est caractéristique en ce qu'il contient un polymère à base de méthylpenthène (A) comprenant une unité structurale représentée par la formule générale (1), son épaisseur est supérieure ou égale à 10nm et inférieure ou égale à 1000nm, et présente des caractéristiques autoportantes.
PCT/JP2018/030475 2017-08-23 2018-08-17 Film polymère mince ainsi que procédé de fabrication de celui-ci, et stratifié sous forme de film Ceased WO2019039391A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020207003357A KR102548027B1 (ko) 2017-08-23 2018-08-17 고분자 박막, 필름상 적층체, 및, 고분자 박막의 제조 방법
JP2019529666A JP6586546B2 (ja) 2017-08-23 2018-08-17 高分子薄膜、フィルム状積層体、および、高分子薄膜の製造方法
CN201880052489.3A CN111032751B (zh) 2017-08-23 2018-08-17 高分子薄膜、膜状层叠体、及高分子薄膜的制造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017160643 2017-08-23
JP2017-160643 2017-08-23

Publications (1)

Publication Number Publication Date
WO2019039391A1 true WO2019039391A1 (fr) 2019-02-28

Family

ID=65438689

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/030475 Ceased WO2019039391A1 (fr) 2017-08-23 2018-08-17 Film polymère mince ainsi que procédé de fabrication de celui-ci, et stratifié sous forme de film

Country Status (5)

Country Link
JP (1) JP6586546B2 (fr)
KR (1) KR102548027B1 (fr)
CN (1) CN111032751B (fr)
TW (1) TW201920391A (fr)
WO (1) WO2019039391A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116887984A (zh) * 2021-03-02 2023-10-13 三井化学株式会社 多层膜、容器、细胞培养用包装和多层膜的制造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5692925A (en) * 1979-12-27 1981-07-28 Teijin Ltd Preparation of ultrathin film
JP2006131723A (ja) * 2004-11-04 2006-05-25 Daicel Chem Ind Ltd メチルペンテン系樹脂を含有する液状組成物
WO2015045414A1 (fr) * 2013-09-30 2015-04-02 三井化学株式会社 Film pelliculaire, pellicule l'utilisant, plaque originale d'exposition et dispositif d'exposition, et procédé de fabrication de dispositif à semi-conducteurs
JP2016135567A (ja) * 2015-01-23 2016-07-28 王子ホールディングス株式会社 剥離性フィルム
JP2017132251A (ja) * 2016-01-21 2017-08-03 王子ホールディングス株式会社 剥離性フィルム

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5728473B2 (ja) * 2009-06-19 2015-06-03 東レバッテリーセパレータフィルム株式会社 多層微多孔フィルム
KR101916687B1 (ko) * 2010-08-12 2018-11-08 도레이 배터리 세퍼레이터 필름 주식회사 미다공막, 이러한 막의 제조 방법, 및 이러한 막의 사용 방법
WO2017125810A1 (fr) * 2016-01-21 2017-07-27 王子ホールディングス株式会社 Film anti-adhésif
JP6647890B2 (ja) * 2016-02-02 2020-02-14 リンテック株式会社 シート状積層体およびシート状積層体の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5692925A (en) * 1979-12-27 1981-07-28 Teijin Ltd Preparation of ultrathin film
JP2006131723A (ja) * 2004-11-04 2006-05-25 Daicel Chem Ind Ltd メチルペンテン系樹脂を含有する液状組成物
WO2015045414A1 (fr) * 2013-09-30 2015-04-02 三井化学株式会社 Film pelliculaire, pellicule l'utilisant, plaque originale d'exposition et dispositif d'exposition, et procédé de fabrication de dispositif à semi-conducteurs
JP2016135567A (ja) * 2015-01-23 2016-07-28 王子ホールディングス株式会社 剥離性フィルム
JP2017132251A (ja) * 2016-01-21 2017-08-03 王子ホールディングス株式会社 剥離性フィルム

Also Published As

Publication number Publication date
CN111032751B (zh) 2022-10-28
TW201920391A (zh) 2019-06-01
KR102548027B1 (ko) 2023-06-26
KR20200043982A (ko) 2020-04-28
JP6586546B2 (ja) 2019-10-02
JPWO2019039391A1 (ja) 2019-11-07
CN111032751A (zh) 2020-04-17

Similar Documents

Publication Publication Date Title
TWI693268B (zh) 半導體晶圓表面保護膜以及半導體裝置的製造方法
TWI693153B (zh) 陶瓷生片製造製程用剝離薄膜
TW201137020A (en) Curable composition, dicing-die bonding tape, connecting structure and method for producing semiconductor tape with cohesive/adhesive layer
TWI770057B (zh) 黏著劑組合物、密封片及密封體
WO2018047919A1 (fr) Composition d'adhésif, feuille de scellement, et corps de scellement
TW200914573A (en) Dicing/die bonding tape and method for manufacturing semiconductor chip
TWI841705B (zh) 黏著薄片及半導體裝置之製造方法
TW201542743A (zh) 感溫性黏著劑
TW201708477A (zh) 樹脂膜形成用薄片、及樹脂膜形成用複合薄片
TWI633014B (zh) 脫模膜及其製造方法
JP6586546B2 (ja) 高分子薄膜、フィルム状積層体、および、高分子薄膜の製造方法
TW201233754A (en) Radiation-curable adhesive composition and adhesive sheet
WO2019039392A1 (fr) Film polymère mince ainsi que procédé de fabrication de celui-ci, et stratifié sous forme de film
WO2016111286A1 (fr) Article décoratif et stratifié pour décoration
JP2004190011A (ja) 離型剤、粘着性積層体および粘着性積層テープ
JP7248572B2 (ja) 接着剤組成物、接着シート、及び封止体
TW201224100A (en) Adhesive composition and adhesive film
JP6013398B2 (ja) 樹脂フィルム、積層体及びその製造方法並びに燃料電池の製造方法
TW201807147A (zh) 感溫性黏著劑
TWI621515B (zh) 脫模膜及其製造方法
JP2012212816A (ja) ダイシング・ダイボンディングテープ及びその製造方法並びに半導体チップの製造方法
TW202239907A (zh) 黏著片材
JP2014201636A (ja) 耐熱性粘着フィルム
JP2014192228A (ja) ダイシング・ダイボンディングフィルムの製造方法
TW200815563A (en) Dicing/die-bonding tape and method for manufacturing semiconductor chip

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18847952

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019529666

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18847952

Country of ref document: EP

Kind code of ref document: A1