WO2019172136A1 - Film multicouche, et procédé de fabrication de celui-ci - Google Patents

Film multicouche, et procédé de fabrication de celui-ci Download PDF

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Publication number
WO2019172136A1
WO2019172136A1 PCT/JP2019/008180 JP2019008180W WO2019172136A1 WO 2019172136 A1 WO2019172136 A1 WO 2019172136A1 JP 2019008180 W JP2019008180 W JP 2019008180W WO 2019172136 A1 WO2019172136 A1 WO 2019172136A1
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WO
WIPO (PCT)
Prior art keywords
multilayer film
polyurethane
acid
acid structure
carbon nanotubes
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PCT/JP2019/008180
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English (en)
Japanese (ja)
Inventor
広和 高井
宏晃 周
Original Assignee
日本ゼオン株式会社
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Priority to JP2020504989A priority Critical patent/JPWO2019172136A1/ja
Publication of WO2019172136A1 publication Critical patent/WO2019172136A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives

Definitions

  • the present invention relates to a multilayer film and a method for producing the same.
  • optical films are used for various image display devices such as liquid crystal display devices, organic EL display devices, and plasma displays. Such an optical film is used by being bonded to any member having various other functions such as a polarizer, a hard coat layer, an antireflection layer, an antistatic layer, an antiglare layer, and an antifouling layer. Therefore, such an optical film is required to adhere well to these members.
  • Patent Document 1 proposes a multilayer film in which an easy-adhesion layer obtained by curing a predetermined composition on a base film is provided. And according to patent document 1, the multilayer film mentioned above can adhere
  • the above-described conventional multilayer film is required to increase conductivity in order to prevent dust and the like from adhering to the easy-adhesive film side and to ensure handling. That is, the conventional multilayer film has room for further improvement in terms of enhancing the conductivity while ensuring the transparency required for an optical film and the adhesion to a member to be bonded.
  • the present inventor has intensively studied for the purpose of solving the above problems. And when this inventor forms the easily bonding layer by hardening the polyurethane composition containing a predetermined component in preparation of the multilayer film provided with an easily bonding layer on a base film, the multilayer film obtained The present inventors have found that the transparency, adhesiveness, and conductivity can be improved in a well-balanced manner.
  • the multilayer film of this invention is equipped with a base film and the easily bonding layer provided on the said base film. It is a multilayer film, and the easy-adhesion layer comprises an acid structure-containing polyurethane, a crosslinking agent capable of crosslinking the acid structure-containing polyurethane, a non-volatile organic base, and single-walled carbon nanotubes in a proportion of 50% or more. It consists of the hardened
  • the tensile elastic modulus of the acid structure containing polyurethane is preferably 1000 N / mm 2 or more 5000N / mm 2 or less. If an easily adhesive layer is formed using an acid structure-containing polyurethane having a tensile elastic modulus within the above range, the adhesiveness of the multilayer film provided with the easily adhesive layer is further improved and the easily adhesive layer is prevented from being damaged. be able to.
  • the “tensile modulus” of the acid structure-containing polyurethane can be measured using the method described in the examples of the present specification.
  • the cross-linking agent includes an epoxy-based cross-linking agent. If an epoxy-based crosslinking agent is used as the crosslinking agent, the polyurethane composition containing the acid structure-containing polyurethane can be cured well, and the adhesiveness of the multilayer film can be further improved.
  • the polyurethane composition contains 0.1 to 5.0 parts by mass of the carbon nanotubes per 100 parts by mass of the acid structure-containing polyurethane. If the easy-adhesion layer is formed using a polyurethane composition containing carbon nanotubes in an amount within the above-described range, the transparency of the multilayer film can be further improved and the conductivity can be further improved.
  • the method for producing a multilayer film of the present invention includes water containing the acid structure-containing polyurethane, the nonvolatile organic base, and water. It is preferable to include a step of preparing the polyurethane composition by mixing a dispersion, an aqueous dispersion containing the carbon nanotubes, a dispersant, and water, and the crosslinking agent. If an easy-adhesion layer is formed using the polyurethane composition prepared through the above-described steps, the aggregation of the carbon nanotubes is suppressed, and the transparency and conductivity of the multilayer film including the easy-adhesion layer are further improved. Can do.
  • the dispersant contains an anionic surfactant. If an anionic surfactant is used as the dispersant, the aggregation of the carbon nanotubes can be further suppressed, and the transparency and conductivity of the multilayer film including the easy-adhesion layer can be further improved.
  • the present invention it is possible to provide a multilayer film having excellent transparency and adhesiveness, and excellent conductivity, and a method for producing the multilayer film.
  • the multilayer film of this invention is not specifically limited, It can be used as optical films, such as a protective film, retardation film, and an optical compensation film. Moreover, the multilayer film of this invention can be manufactured using the manufacturing method of the multilayer film of this invention. And the multilayer film of this invention can be bonded to arbitrary members, for example, and can be used for various uses as a laminated body.
  • the multilayer film of this invention is equipped with a base film and the easily bonding layer provided in the one surface or both surfaces of the base film.
  • an easily bonding layer is normally provided directly on the surface of a base film, without passing through another layer (namely, an easily bonding layer is normally provided adjacent to a base film).
  • the film of this invention may be provided with layers (other layers) other than a base film and an easily bonding layer.
  • the easy-adhesion layer of the multilayer film of the present invention contains an acid structure-containing polyurethane, a crosslinking agent capable of crosslinking the acid structure-containing polyurethane, a non-volatile organic base, and single-walled carbon nanotubes in a proportion of 50% or more.
  • the multilayer film of the present invention forms an easy-adhesion layer by curing the polyurethane composition containing the above-described predetermined components, it has excellent transparency and adhesiveness, and also has excellent conductivity. .
  • the film (resin film) which consists of resin can be used.
  • resin which comprises a base film contains a polymer component, and can contain components (arbitrary components) other than a polymer component arbitrarily.
  • the polymer component contained in the resin constituting the base film is not particularly limited, while sufficiently ensuring excellent transparency of the multilayer film including the base film, low hygroscopicity, dimensional stability, From the viewpoint of enhancing lightness, alicyclic structure-containing polymers and acrylic polymers are preferred, and alicyclic structure-containing polymers are more preferred.
  • a polymer component may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.
  • the alicyclic structure-containing polymer is a polymer containing a repeating unit having an alicyclic structure.
  • the alicyclic structure-containing polymer any of a polymer having an alicyclic structure in the main chain and a polymer having an alicyclic structure in the side chain can be used. From the viewpoint of exhibiting excellent mechanical strength and heat resistance in the multilayer film provided, a polymer having an alicyclic structure in the main chain is preferable.
  • an alicyclic structure containing polymer may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.
  • alicyclic structure examples include a saturated alicyclic hydrocarbon (cycloalkane) structure and an unsaturated alicyclic hydrocarbon (cycloalkene, cycloalkyne) structure.
  • cycloalkane saturated alicyclic hydrocarbon
  • cycloalkene unsaturated alicyclic hydrocarbon
  • cycloalkyne unsaturated alicyclic hydrocarbon
  • a cycloalkane structure and a cycloalkene structure are preferable, and a cycloalkane structure is more preferable.
  • the number of carbon atoms constituting the alicyclic structure is preferably 4 or more, more preferably 5 or more, and preferably 30 or less per alicyclic structure. Preferably, it is 20 or less, and more preferably 15 or less. If the number of carbon atoms constituting the alicyclic structure is within the above-described range, the mechanical strength and heat resistance of the multilayer film including the base film are exhibited while ensuring the moldability of the base film. be able to.
  • the ratio of the repeating unit which has an alicyclic structure in an alicyclic structure containing polymer shall be more than 50 mass% by making all the repeating units which comprise an alicyclic structure containing polymer into 100 mass%. It is preferably 55% by mass or more, more preferably 70% by mass or more, particularly preferably 90% by mass or more, and 100% by mass or less. If the ratio of the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer exceeds 50% by mass, the heat resistance can be improved while improving the transparency of the multilayer film including the base film. it can.
  • Specific examples of polymers containing alicyclic structures include a norbornene polymer, a monocyclic olefin polymer, a cyclic conjugated diene polymer, and a vinyl alicyclic hydrocarbon polymer.
  • a norbornene-based polymer is preferable from the viewpoint of exhibiting excellent transparency in the multilayer film including the base film while ensuring the moldability of the base film.
  • Examples of the norbornene-based polymer include a ring-opening polymer of a monomer having a norbornene structure, a ring-opening copolymer of a monomer having a norbornene structure and an arbitrary monomer, or a hydride thereof; An addition polymer of a monomer having a norbornene structure, an addition copolymer of a monomer having a norbornene structure and an arbitrary monomer, or a hydride thereof.
  • Examples of the monomer having a norbornene structure include bicyclo [2.2.1] hept-2-ene (common name: norbornene), tricyclo [4.3.0.1 2,5 ] deca-3,7. -Diene (common name: dicyclopentadiene), 7,8-benzotricyclo [4.3.0.1 2,5 ] dec-3-ene (common name: methanotetrahydrofluorene), tetracyclo [4.4. 0.1 2,5 . 1 7,10 ] dodec-3-ene (common name: tetracyclododecene) and derivatives of these compounds (for example, those having a substituent in the ring).
  • an alkyl group, an alkylene group, and a polar group can be mentioned, for example.
  • the polar group include heteroatoms and groups containing heteroatoms.
  • the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, and a halogen atom.
  • Any monomer that can be ring-opened or added copolymerized with the above-described monomer having a norbornene structure is not particularly limited, and for example, those listed in International Publication No. 2015/098750 may be used. it can.
  • a polymer having a norbornene structure can be prepared by subjecting a monomer composition containing at least the above-described monomer having a norbornene structure to ring-opening polymerization or addition polymerization, and optionally performing hydrogenation. .
  • the acrylic polymer is a polymer including at least one of a repeating unit derived from (meth) acrylic acid and a repeating unit derived from a (meth) acrylic acid derivative.
  • the acrylic polymer may optionally contain repeating units derived from monomers (other monomers) other than (meth) acrylic acid and (meth) acrylic acid derivatives.
  • (meth) acryl means acryl and / or methacryl.
  • (Meth) acrylic acid and (meth) acrylic acid derivatives examples include acrylic acid and methacrylic acid.
  • examples of the (meth) acrylic acid derivative include (meth) acrylic acid esters.
  • (meth) acrylic acid ester includes monofunctional (meth) acrylic acid ester and polyfunctional (meth) acrylic acid ester.
  • Monofunctional (meth) acrylic acid esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, sec-butyl acrylate, acrylic Acrylic acid esters such as t-butyl acid, n-hexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, n-dodecyl acrylate; methyl methacrylate, methacrylic acid Ethyl acetate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, n-hexyl me
  • Polyfunctional (meth) acrylic acid esters include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, glycerin dimethacrylate, 2-hydroxy-3-acryloxypropyl methacrylate, tetraethylenediethylene Acrylate, polyethylene glycol # 400 diacrylate, tricyclodecane dimethanol di (meth) acrylate, dipentaerythritol hexaacrylate, 1,6-hexanediol di (meth) acrylate, hydroxypivalic acid neopentyl glycol diacrylate, 1,9 -Nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythrito Tritriacrylate, pentaerythritol tetraacrylate, trimethylolpropane tri (meth)
  • ⁇ Other monomers Other monomers are not particularly limited, and any monomer copolymerizable with (meth) acrylic acid and (meth) acrylic acid derivatives can be used.
  • alkenyl aromatic monomers, conjugated diene monomers, non-conjugated diene monomers, vinyl cyanide monomers described in JP-A-2015-024511 Mention may be made of ⁇ , ⁇ -ethylenically unsaturated carboxylic acid amide monomers, carboxylic acid unsaturated alcohol esters and olefin monomers. These may be used alone or in combination of two or more at any ratio.
  • an acrylic polymer preparation method The preparation method of an acrylic polymer is not specifically limited, A well-known method can be used.
  • an acrylic polymer containing a repeating unit derived from a polyfunctional (meth) acrylic acid ester is obtained by using a known photopolymerization initiator for a monomer composition containing a polyfunctional (meth) acrylic acid ester. It can be prepared by addition polymerization.
  • components that the resin constituting the base film can optionally include in addition to the polymer components described above include, for example, colorants, plasticizers, fluorescent brighteners, dispersants, heat stabilizers, light stabilizers, and UV absorbers. And additives such as agents, antistatic agents, antioxidants, lubricants and surfactants. These components may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios. In addition, it is preferable that components other than the polymer component mentioned above contained in resin which comprises a base film are 0 mass% or more and 20 mass% or less, and it is more preferable that they are 0 mass% or more and 10 mass% or less. preferable.
  • the base film may be a single-layer film composed of only one layer, or may be a multilayer film composed of two or more layers. Moreover, when a base film has a multilayer structure, resin used for formation of each layer may be the same and may differ.
  • the total light transmittance of the base film is preferably 85% or more, more preferably 90% or more, and 95% or more from the viewpoint of exhibiting good transparency in the multilayer film. More preferably it is.
  • the haze of the base film is preferably 0.3% or less, and more preferably 0.2% or less, from the viewpoint of allowing the multilayer film to exhibit good transparency.
  • the “total light transmittance” and “haze” of the base film are measured in the same manner as the “total light transmittance” and “haze” of the multilayer film described in the examples of this specification. can do.
  • the thickness of the base film is preferably 5 ⁇ m or more, more preferably 20 ⁇ m or more, preferably 500 ⁇ m or less, and more preferably 300 ⁇ m or less.
  • the easy adhesion layer is a layer made of a cured product of a predetermined polyurethane composition.
  • the polyurethane composition comprises at least an acid structure-containing polyurethane, a crosslinking agent capable of crosslinking the acid structure-containing polyurethane, a non-volatile organic base, and a carbon nanotube containing a single-walled carbon nanotube at a ratio of 50% or more.
  • the polyurethane composition may contain a solvent such as water.
  • the polyurethane composition may contain components (other components) other than the acid structure-containing polyurethane, the crosslinking agent, the organic base, the carbon nanotube, and the solvent.
  • the acid structure-containing polyurethane is a polymer having a urethane bond (—NHCOO—) in the main chain and an acid structure in the main chain and / or side chain.
  • examples of the acid structure contained in the acid structure-containing polyurethane include acidic groups such as a hydroxyl group (—OH), a carboxyl group (—COOH), and a sulfonic acid group (—SO 3 H). Groups are preferred.
  • the acid structure-containing polyurethane may have one acid structure or two or more acid structures in any ratio.
  • the polyurethane having an acid structure described above is a polyurethane composition containing water as a solvent, even if the amount of the surfactant capable of assisting the dispersion of the acid structure-containing polyurethane is small (or the polyurethane composition contains a surfactant). Even if it is not included, it can be dispersed in the form of particles in the composition. As described above, the fact that the acid structure-containing polyurethane particles can be dispersed and stabilized in water without a surfactant is referred to as “self-emulsifying type”.
  • the polyurethane containing the acid structure described above it is expected to improve the water resistance of the multilayer film provided with the easy-adhesion layer, and the amount of the surfactant can be reduced.
  • the transparency can be further improved while further improving the adhesiveness of the resulting multilayer film.
  • Examples of the polyol that can be used for preparing the polyester polyol include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4- Butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexane glycol, 2,5-hexanediol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, tricyclode Examples include candimethanol, 1,4-cyclohexanedimethanol, 2,2-dimethylpropanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octamethylenediol, glycerin, and trimethylolpropane. It is. These may be used alone or in combination of two or more at any ratio.
  • polyester polyol examples include a condensate of ethylene glycol and adipic acid, a condensate of 1,4-butanediol and adipine, a condensate of 1,6-hexanediol and adipic acid, 1,6 -Condensates of hexanediol, propylene glycol and adipic acid.
  • the polyester polyol also includes a polylactone diol obtained by ring-opening polymerization of a lactone using a glycol as an initiator.
  • Polyether polyols include alkylene oxide adducts of polyols described above as “polyols that can be used to prepare polyester polyols”; ring-opening copolymers of alkylene oxides and cyclic ethers (such as tetrahydrofuran); polyethylene glycol, polypropylene glycol, ethylene Glycol-propylene glycol copolymer, 1,4-butanediol copolymer; glycols such as glycol, polytetramethylene glycol, polyhexamethylene glycol, polyoctamethylene glycol; and the like.
  • Specific examples of the polyether polyol include poly (oxypropylene ether) polyol, poly (oxyethylene-propylene ether) polyol, and the like.
  • the aliphatic polyisocyanate compound is preferably an aliphatic diisocyanate having 1 to 12 carbon atoms, such as hexamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, and hexane diisocyanate (HDI).
  • the alicyclic polyisocyanate compound is preferably an alicyclic diisocyanate having 4 to 18 carbon atoms, such as 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (HMDI). Is mentioned.
  • the aromatic polyisocyanate include tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate, and xylylene diisocyanate.
  • the acid value of the acid structure-containing polyurethane is preferably 20 mgKOH / g or more, more preferably 25 mgKOH / g or more, preferably 250 mgKOH / g or less, and 150 mgKOH / g or less. More preferred.
  • the acid value of the acid structure-containing polyurethane is 20 mgKOH / g or more, the dispersibility of the acid structure-containing polyurethane in water can be sufficiently ensured.
  • the acid value of the acid structure-containing polyurethane is 250 mgKOH / g or less, the water resistance of the multilayer film including the easy-adhesion layer can be improved.
  • the “acid value” of the acid structure-containing polyurethane can be measured according to JIS K 0070: 1992.
  • the acid structure-containing polyurethane is neutralized by a nonvolatile organic base described later in the polyurethane composition. That is, the polyurethane composition preferably includes an acid structure-containing polyurethane neutralized with a nonvolatile organic base. If the acid structure of the acid structure-containing polyurethane is neutralized with an organic base, the adhesiveness of the multilayer film can be further improved. In addition, even after the multilayer film is exposed to a high temperature, the transparency can be sufficiently exhibited.
  • the acid structure-containing polyurethane can be present in any state in the polyurethane composition.
  • the acid structure-containing polyurethane may be dispersed in the form of particles in a solvent, or may be dissolved in the solvent. And are preferably dispersed in the form of particles.
  • the average particle diameter of the acid structure-containing polyurethane particles is 0.01 ⁇ m or more and 0.000 or more from the viewpoint of further improving the transparency of the multilayer film provided with the easy adhesion layer. It is preferable that it is 4 micrometers or less.
  • the “average particle size” the particle size distribution is measured by a laser diffraction method, and the particle size at which the cumulative volume calculated from the small diameter side in the measured particle size distribution is 50% is adopted.
  • the crosslinking agent a compound having two or more functional groups capable of forming a bond by reacting with a reactive group of the acid structure-containing polyurethane can be used.
  • a crosslinking agent it is preferable to use the compound which has two or more functional groups in 1 molecule which can react with the carboxyl group which the acid structure containing polyurethane has, or its anhydride group, and can form a bond.
  • the “functional group capable of reacting with the carboxyl group of the acid structure-containing polyurethane or its anhydride group to form a bond” include an epoxy group, a carbodiimide group, an oxazoline group, and an isocyanate group.
  • the crosslinking agent may have only 1 type of these functional groups, and may have 2 or more types.
  • an epoxy group is preferable from the viewpoint of further improving the adhesiveness of the multilayer film including the easy adhesion layer.
  • epoxy-based crosslinking agent carbodiimide-based crosslinking agent, oxazoline-based crosslinking agent, and isocyanate-based crosslinking agent
  • epoxy compound epoxy compound
  • oxazoline compound oxazoline compound
  • isocyanate compounds an epoxy-type crosslinking agent is preferable from a viewpoint of further improving the adhesiveness of the multilayer film provided with an easily bonding layer.
  • polyols used for the preparation of the epoxy-based crosslinking agent include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexane glycol, neo
  • examples include pentyl glycol, glycerin (glycerol), polyglycerin (polyglycerol), trimethylolpropane, pentaerythritol, and sorbitol. These may be used alone or in combination of two or more at any ratio.
  • dicarboxylic acid used for preparing the epoxy-based crosslinking agent examples include phthalic acid, terephthalic acid, oxalic acid, and adipic acid. These may be used alone or in combination of two or more at any ratio.
  • phthalic acid usually, 2 moles of epichlorohydrin are reacted with 1 mole of polyols.
  • dicarboxylic acid and epichlorohydrin usually, 2 mol of epichlorohydrin is reacted with 1 mol of dicarboxylic acid.
  • epoxy-based crosslinking agent examples include ethylene glycol diglycidyl ether, glycerol polyglycidyl ether, 1,4-bis (2 ′, 3′-epoxypropyloxy) butane, 1,3,5-tri Glycidyl isocyanurate, 1,3-diglycidyl-5- ( ⁇ -acetoxy- ⁇ -oxypropyl) isosinurate, sorbitol polyglycidyl ethers, polyglycerol polyglycidyl ethers, pentaerythritol polyglycidyl ethers, diglycerol polyglycidyl ether 1,3,5-triglycidyl (2-hydroxyethyl) isocyanurate, glycerol polyglycerol ethers and trimethylolpropane polyglycidyl ethers.
  • the polyurethane composition preferably contains 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 7 parts by mass or more, per 100 parts by mass of the acid structure-containing polyurethane. It is particularly preferred to contain at least part by mass, more preferably at most 200 parts by mass, more preferably at most 100 parts by mass, even more preferably at most 60 parts by mass, particularly preferably at most 30 parts by mass. If the blending amount of the cross-linking agent in the polyurethane composition is within the above-mentioned range, the cross-linking reaction proceeds well, and the adhesiveness of the multilayer film having the easy-adhesion layer is further improved and the mechanical strength is improved. Can do.
  • the non-volatile organic base is an organic base that does not evaporate under the conditions of 1 atm and 100 ° C. as described above.
  • the nonvolatile organic base can be said to be an organic base having a melting point of less than 100 ° C. but a boiling point of 100 ° C. or higher, or an organic base having a melting point of 100 ° C. or higher. If a non-volatile organic base is not used, for example, if an organic base having a boiling point of less than 100 ° C. is used, the adhesive layer of the multilayer film including the easy-adhesion layer cannot be sufficiently improved.
  • the melting point of the organic base is, for example, preferably 110 ° C.
  • the melting point of the organic base is not particularly limited, but is usually 250 ° C. or lower.
  • the boiling point of the organic base is, for example, preferably 120 ° C. or higher, and more preferably 150 ° C. or higher.
  • the upper limit of the boiling point of an organic base is not specifically limited, Usually, it is 300 degrees C or less.
  • non-volatile organic bases for example, 2-amino-2-methyl-1-propanol (AMP), triethanolamine, triisopropanolamine (TIPA), monoethanolamine, diethanolamine, tri [(2- Hydroxy) -1-propyl] amine, 2-amino-2-methyl-1,3-propanediol (AMPD), 2-amino-2-hydroxymethyl-1,3-propane potassium hydroxide, zinc ammonium complex, copper Ammonium complex, silver ammonium complex, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) - ⁇ -amino Propyltrimethyldimethoxysilane, N-phenyl- ⁇ -amino Propyl
  • non-volatile amine compounds such as adipic acid dihydrazide are preferable from the viewpoint of further improving the adhesive layer of the multilayer film having an easy-adhesion layer.
  • the polyurethane composition preferably contains 0.5 parts by mass or more of a nonvolatile organic base per 100 parts by mass of the acid structure-containing polyurethane, more preferably 1 part by mass or more, and 2 parts by mass or more. Is more preferable, preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less. If the blending amount of the non-volatile organic base in the polyurethane composition is 0.5 parts by mass or more per 100 parts by mass of the acid structure-containing polyurethane, the adhesiveness of the multilayer film including the easy adhesion layer can be further improved. If it is 30 parts by mass or less, color loss of the polarizer can be prevented when the multilayer film is adhered to a polyvinyl alcohol polarizer.
  • a carbon nanotube is a component which can contribute to the electroconductivity improvement of the multilayer film mainly provided with an easily bonding layer.
  • the carbon nanotube includes a single-walled carbon nanotube and a multi-walled carbon nanotube.
  • the carbon nanotubes contained in the polyurethane composition are required to contain single-walled carbon nanotubes in a proportion of 50% to 100%, and contain single-walled carbon nanotubes in a proportion of 70% or more.
  • the single-walled carbon nanotubes are contained in a proportion of 80% or more, more preferably the single-walled carbon nanotubes are contained in a proportion of 85% or more, and the single-walled carbon nanotubes are contained in a proportion of 90% or more. It is particularly preferable to contain When carbon nanotubes having a ratio of single-walled carbon nanotubes of less than 50% are used, not only the conductivity of the multilayer film having an easy-adhesion layer cannot be ensured, but also the transparency is lowered.
  • the “specific surface area” refers to the nitrogen adsorption specific surface area measured using the BET method.
  • the carbon nanotube preferably has a ratio of diameter distribution (3 ⁇ ) to average diameter (Av) (3 ⁇ / Av) of more than 0.20, more preferably 0.30 or more, and 0.40 or more. Is more preferably 0.50 or more, and preferably less than 0.60.
  • the average diameter (Av) of the carbon nanotubes is preferably 0.5 nm or more, more preferably 1 nm or more, from the viewpoint of further improving the conductivity of the multilayer film including the easy adhesion layer, and 15 nm.
  • diameter distribution (3 ⁇ ) refers to a value obtained by multiplying the sample standard deviation ( ⁇ ) of the diameter of the carbon nanotube by 3.
  • average diameter of carbon nanotube (Av)”, “sample standard deviation of carbon nanotube diameter ( ⁇ )”, and “average length of carbon nanotube” are respectively observed with a transmission electron microscope. Below, the diameter (outer diameter) and length of 100 randomly selected carbon nanotubes can be measured and determined.
  • the average diameter (Av) and standard deviation ( ⁇ ) of the carbon nanotubes may be adjusted by changing the manufacturing method and manufacturing conditions of the carbon nanotubes, or a plurality of carbon nanotubes obtained by different manufacturing methods are combined. You may adjust by.
  • the G / D ratio of the carbon nanotube used in the present invention that is, the ratio of the G band peak intensity to the D band peak intensity in the Raman spectrum is preferably 10 or less, and preferably 4 or less.
  • the G / D ratio is 10 or less, there are many structural defects of carbon nanotubes and the number of bending points increases, so that the dispersed particle size can be reduced by loosening the bundle structure of carbon nanotubes, and the amount of defects due to coarse particles (repelling) Unevenness) can be reduced.
  • the G / D ratio is an index generally used for evaluating the quality of CNT.
  • the G band is a vibration mode derived from a hexagonal lattice structure of graphite, which is a cylindrical surface of CNT
  • the D band is a vibration mode derived from an amorphous part.
  • the lower limit of the G / D ratio is not particularly limited, but is preferably 1.0 or more. If G / D ratio is 1.0 or more, the electroconductivity of a multilayer film provided with an easily bonding layer can fully be ensured.
  • the carbon nanotubes having the above-described properties can be obtained, for example, by supplying a raw material compound and a carrier gas onto a substrate having a catalyst layer for producing carbon nanotubes on the surface, and by chemical vapor deposition (CVD).
  • CVD chemical vapor deposition
  • a method of dramatically improving the catalytic activity of the catalyst layer by making a small amount of oxidizing agent (catalyst activating substance) present in the system (super growth method; International Publication No. 2006/011655) No.) can be used.
  • the carbon nanotube obtained by the super growth method may be referred to as “SGCNT”.
  • the polyurethane composition preferably contains 0.1 parts by mass or more, more preferably 0.4 parts by mass or more, and 0.8 parts by mass or more per 100 parts by mass of the acid structure-containing polyurethane. More preferably, it is more preferably 1.1 parts by mass or more, particularly preferably 1.2 parts by mass or more, more preferably 5.0 parts by mass or less, and more preferably 3.4 parts by mass or less. Preferably, 3.0 parts by mass or less is particularly preferable.
  • the compounding amount of the carbon nanotubes in the polyurethane composition is 0.1 parts by mass or more per 100 parts by mass of the acid structure-containing polyurethane, the conductivity of the multilayer film including the easy adhesion layer can be further improved. If it is 0.0 mass part or less, the transparency of a multilayer film provided with an easily bonding layer can be improved further.
  • solvent Although it does not specifically limit as a solvent which a polyurethane composition can contain, Water and a water-soluble solvent can be mentioned preferably.
  • the water-soluble solvent include methanol, ethanol, isopropyl alcohol, acetone, tetrahydrofuran, N-methylpyrrolidone, dimethyl sulfoxide, ethylene glycol monomethyl ether, and ethylene glycol monobutyl ether.
  • water is preferably used as the solvent.
  • a solvent may be used individually by 1 type and may be used combining 2 or more types by arbitrary ratios.
  • the amount of the solvent contained in the polyurethane composition can be appropriately adjusted so that, for example, the viscosity of the polyurethane composition is in a range suitable for coating.
  • the solid content concentration of the polyurethane composition is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more, and 15% by mass or less. It is preferable that it is 10 mass% or less. If the solid content concentration of the polyurethane composition is within the above-described range, the handleability and applicability of the polyurethane composition can be ensured.
  • the dispersant contained in the polyurethane composition is used, for example, when preparing a dispersion of carbon nanotubes prior to the preparation of the polyurethane composition. Specifically, “a method for producing a multilayer film” And surfactants and polysaccharides which will be described later.
  • the above-mentioned polyurethane composition can be cured by, for example, the method described in “Method for producing multilayer film” of the present invention described later to obtain an easy adhesion layer.
  • the easy-adhesion layer which is a cured product of the polyurethane composition, contains components derived from the components contained in the polyurethane composition.
  • the easy-adhesion layer includes at least an acid structure-containing polyurethane crosslinked with a crosslinking agent, a nonvolatile organic base, and a single-walled carbon nanotube containing 50% or more of single-walled carbon nanotubes. Including.
  • the thickness of the easy-adhesion layer (when the multilayer film has easy-adhesion layers on both sides), the thickness of each easy-adhesion layer is preferably 0.005 ⁇ m or more, and 0.01 ⁇ m or more. Is more preferably 0.03 ⁇ m or more, preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less. If the thickness of an easily bonding layer is in the range mentioned above, the curvature of a multilayer film provided with an easily bonding layer can be suppressed, fully contacting an easily bonding layer to a base film.
  • Examples of the layer that the multilayer film of the present invention can include in addition to the base film and the easy-adhesion layer described above include an antireflection layer, a hard coat layer, an antistatic layer, an antiglare layer, an antifouling layer, and a separator film. It is done.
  • the multilayer film of the present invention usually has these other layers on the surface opposite to the surface on which the easy adhesion layer is provided.
  • the multilayer film provided with an easily bonding layer can be manufactured with the manufacturing method of this invention which hardens the polyurethane composition mentioned above.
  • the method for producing a multilayer film of the present invention includes a step of supplying the above-described polyurethane composition onto the above-described base film (supplying step), and the polyurethane composition supplied onto the base film. A step of curing (hardening step).
  • the multilayer film of this invention is 50% or more of the water dispersion (aqueous dispersion of acid structure containing polyurethane) containing an acid structure containing polyurethane, a non-volatile organic base, and water before a supply process.
  • Polyurethane composition by mixing an aqueous dispersion (carbon nanotube aqueous dispersion) containing carbon nanotubes containing a single-walled carbon nanotube, a dispersant, and water with a crosslinking agent capable of crosslinking an acid structure-containing polyurethane. It is preferable that the process (composition preparation process) of adjusting a thing is included. Moreover, the manufacturing method of the multilayer film of this invention may contain processes (other processes) other than the composition preparation process mentioned above, a supply process, and a hardening process.
  • the polyurethane composition supplied onto the base film in the supplying step is preferably prepared by separately preparing an aqueous dispersion of acid structure-containing polyurethane and an aqueous dispersion of carbon nanotubes, and combining them.
  • a polyurethane composition aggregation of a carbon nanotube can be suppressed and the transparency of a multilayer film provided with an easily bonding layer can be improved further.
  • a network-like conductive path is satisfactorily formed in the easy-adhesion layer, and the conductivity can be further increased.
  • the acid structure-containing polyurethane aqueous dispersion and the carbon nanotube aqueous dispersion can both be prepared by known methods.
  • the aqueous dispersion of carbon nanotubes preferably contains 10 parts by mass or more, more preferably 100 parts by mass or more, preferably 1500 parts by mass or less, preferably 1000 parts by mass, per 100 parts by mass of carbon nanotubes. More preferably, it is more preferably 500 parts by mass or less, still more preferably 300 parts by mass or less.
  • the blending amount of the dispersant in the aqueous dispersion is 10 parts by mass or more per 100 parts by mass of the carbon nanotubes, the transparency and conductivity of the multilayer film provided with the easy adhesion layer by sufficiently suppressing the aggregation of the carbon nanotubes. If it is 1500 mass parts or less, the electroconductivity of a multilayer film can fully be ensured.
  • the method for supplying the polyurethane composition onto the base film is not particularly limited, but it is preferable to use a coating method.
  • Specific coating methods include, for example, a wire bar coating method, a dip method, a spray method, a spin coating method, a roll coating method, a gravure coating method, an air knife coating method, a curtain coating method, a slide coating method, and an extrusion coating method. Etc.
  • the method for curing the polyurethane composition on the base film is not particularly limited.
  • the polyurethane composition contains a solvent
  • heating conditions are not specifically limited, For example, heating temperature can be 70 degreeC or more and 90 degrees C or less, and heating time can be 1 minute or more and 30 minutes or less.
  • the manufacturing method of the multilayer film of this invention may also include the process of giving a hydrophilization surface treatment to the surface of the easily bonding layer obtained through the hardening process mentioned above.
  • a hydrophilization surface treatment By performing the hydrophilic surface treatment, it is possible to sufficiently improve the adhesiveness of the multilayer film including the easy adhesion layer.
  • the hydrophilized surface treatment include corona discharge treatment, plasma treatment, saponification treatment, and ultraviolet irradiation treatment described in International Publication No. 2015/098750.
  • the manufacturing method of the multilayer film of this invention may also include the process of providing the other layer mentioned above in the surface on the opposite side to the surface provided with the easily bonding layer of a base film.
  • the multilayer film of the present invention described above can be used as a laminate comprising a multilayer film and another member bonded to another member.
  • the case where the multilayer film of the present invention is bonded to a polarizer and used as a polarizing plate is described below as an example.
  • Polarizer It does not specifically limit as a polarizer, A well-known polarizer can be used.
  • a polarizer containing polyvinyl alcohol is preferable.
  • a polarizer containing polyvinyl alcohol may be produced, for example, by adsorbing iodine or a dichroic dye to a polyvinyl alcohol film and then uniaxially stretching in a boric acid bath. It may be produced by adsorbing and stretching a chromatic dye and further modifying a part of the polyvinyl alcohol unit in the molecular chain into a polyvinylene unit.
  • polarizer for example, a polarizer having a function of separating polarized light into reflected light and transmitted light, such as a grid polarizer, a multilayer polarizer, and a cholesteric liquid crystal polarizer, may be used.
  • the polarization degree of the polarizer is preferably 98% or more, more preferably 99% or more.
  • the thickness of the polarizer is preferably 5 ⁇ m or more and 80 ⁇ m or less.
  • the multilayer film may be adhered to the polarizer through only the easy adhesion layer, but may be adhered to the polarizer through the easy adhesion layer and the adhesive layer.
  • the easily bonding layer of a multilayer film functions as a foundation
  • the adhesive for forming the adhesive layer is not particularly limited, and for example, a known adhesive described in International Publication No. 2015/098750 can be used.
  • the thickness of the adhesive layer is preferably 0.05 ⁇ m or more, preferably 0.1 ⁇ m or more, preferably 5 ⁇ m or less, and more preferably 1 ⁇ m or less.
  • ⁇ Tensile modulus> The aqueous dispersion of acid structure-containing polyurethane was poured into a glass container and allowed to stand at room temperature for 24 hours. The aqueous dispersion after standing for 24 hours was dried at 50 ° C. for 3 hours and 120 ° C. for 20 minutes to obtain a polyurethane sheet having a thickness of 100 ⁇ m. The obtained polyurethane sheet was punched into a dumbbell shape in accordance with JIS K7162 to obtain a test piece.
  • the test piece was subjected to a tensile test at a tensile speed of 5 mm / min using a tensile tester (“Tensile Tester 5564” manufactured by Instron Japan), and the tensile elastic modulus was measured from the slope of the obtained SS curve.
  • a tensile tester (“Tensile Tester 5564” manufactured by Instron Japan)
  • the tensile elastic modulus was measured from the slope of the obtained SS curve.
  • ⁇ Transparency> Using a “turbidimeter NDH-300A” manufactured by Nippon Denshoku Industries Co., Ltd., the total light transmittance and haze of the multilayer film were measured according to JIS K7361-1: 1997 and JIS K7136: 2000. It shows that a multilayer film is excellent in transparency, so that the value of total light transmittance is large and the value of haze is small.
  • ⁇ Conductivity> Using a high resistance resistivity meter (product name “HIRESTA (registered trademark) -UX MCP-HT800” manufactured by Mitsubishi Chemical Analytech Co., Ltd.), the surface resistance ( ⁇ ) at any three locations on the easy adhesion layer side of the multilayer film / ⁇ ) was measured, and the average value of these was taken as the surface resistance of the multilayer film. It shows that a multilayer film is excellent in electroconductivity, so that the value of surface resistance is small.
  • HIRESTA registered trademark
  • UX MCP-HT800 manufactured by Mitsubishi Chemical Analytech Co., Ltd.
  • the surface of the polarizing plate opposite to the easy-adhesion layer of the multilayer film and the glass substrate were bonded together via an adhesive sheet (“LUCIACS CS9621T” manufactured by Nitto Denko Corporation) to prepare a sample.
  • the obtained sample was allowed to stand for 200 hours in a constant temperature and humidity chamber at 60 ° C. and 90% RH.
  • the sample was taken out from the end and the surface of the sample taken out from the constant temperature and humidity chamber with a cutter.
  • the sample polarizing plate was pulled to attempt peeling.
  • peeling occurred between the multilayer film and the glass substrate the easy-adhesive layer and the adhesive had sufficient adhesive strength, and the adhesiveness was evaluated as “good”.
  • the adhesive strength of the easy-adhesive layer and the adhesive was insufficient, and the adhesiveness was evaluated as “bad”.
  • Carbon compound as raw material compound ethylene; feed rate 50 sccm Atmosphere (carrier gas): Helium, hydrogen mixed gas; supply rate 1000 sccm Catalyst activation material: amount of steam added; 300 ppm Catalyst layer: Iron thin film (thickness 1 nm)
  • Substrate Silicon wafer
  • the obtained SGCNT has a BET specific surface area of 1,050 m 2 / g and a G / D ratio of 3.0, and is characteristic of single-walled carbon nanotubes in measurement with a Raman spectrophotometer.
  • a spectrum of radial breathing mode (RBM) was observed in the low frequency region of ⁇ 300 cm ⁇ 1 .
  • Example 1 ⁇ Preparation of aqueous dispersion of acid structure-containing polyurethane>
  • an aqueous dispersion of acid structure-containing polyurethane an aqueous dispersion of polyether polyurethane (“Superflex (registered trademark) 870” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was prepared.
  • ⁇ Preparation of aqueous dispersion of carbon nanotube> To 90 mL of 1% sodium dodecyl sulfate aqueous solution, 90 mg of SGCNT of Production Example 2 was added and treated 20 times using a jet mill (“JN-20” manufactured by Joko Corporation) to obtain an aqueous dispersion containing 0.1% SGCNT. Obtained.
  • the resulting aqueous dispersion contained 1000 parts of sodium dodecyl sulfate per 100 parts of SGCNT.
  • ⁇ Preparation of polyurethane composition > 7.0 g of an aqueous dispersion of the acid structure-containing polyurethane described above, 0.04 g of adipic acid dihydrazide (melting point: 180 ° C.) as a nonvolatile organic base (2 parts of adipic acid dihydrazide per 100 parts of the acid structure-containing polyurethane), 0.3 g of glycerol polyglycidyl ether (“Denacol EX-313” manufactured by Nagase ChemteX Corporation) as an epoxy-based crosslinking agent (15 parts of glycerol polyglycidyl ether per 100 parts of acid structure-containing polyurethane) and water dispersion of the above-mentioned carbon nanotubes
  • a polyurethane composition was prepared by adding 34 g of liquid (1.7 parts of carbon nano
  • Example 1 Comparative Example 1 In the same manner as in Example 1, except that an aqueous dispersion of a polyurethane not containing an acid structure (“Superflex E-2000” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used in place of the aqueous dispersion of the acid structure-containing polyurethane. A polyurethane composition was prepared. However, when an aqueous dispersion of polyurethane and a dispersion of carbon nanotubes were mixed, precipitation occurred and could not be applied on the substrate film.
  • Superflex E-2000 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • Example 2 Comparative Example 2 except that 0.04 g of triethylamine (boiling point: 89 ° C.) (2 parts of triethylamine with respect to 100 parts of acid structure-containing polyurethane) was used instead of adipic acid dihydrazide in preparing the aqueous dispersion of acid structure-containing polyurethane.
  • an aqueous dispersion of acid structure-containing polyurethane, an aqueous dispersion of carbon nanotubes, a polyurethane composition, a multilayer film, and a polarizing plate were prepared and subjected to various evaluations. The results are shown in Table 1.
  • the ratio of nanotubes 0%, average diameter (Av): 9.3 nm, diameter distribution (3 ⁇ ): 2.6 nm, 3 ⁇ / Av: 0.28)
  • An aqueous dispersion of a structure-containing polyurethane, an aqueous dispersion of carbon nanotubes, a polyurethane composition, a multilayer film, and a polarizing plate were prepared and subjected to various evaluations.
  • the surface resistance (conductivity) could not be measured because it exceeded the measurement upper limit of the high resistivity meter.
  • the results other than the conductivity are shown in Table 1.
  • ADH refers to adipic acid dihydrazide
  • TAA indicates triethylamine
  • CNT indicates carbon nanotube
  • EX-313 indicates “Denacol EX-313” manufactured by Nagase ChemteX Corporation
  • alicyclic indicates an alicyclic structure-containing polymer.
  • a polyurethane composition comprising an acid structure-containing polyurethane, a crosslinking agent capable of crosslinking the acid structure-containing polyurethane, a non-volatile organic base, and a carbon nanotube in which the proportion of single-walled carbon nanotubes is 50% or more
  • a multilayer film excellent in transparency and conductivity can be obtained.
  • a polarizing plate using the multilayer film It turns out that a multilayer film and a polarizer can adhere
  • Comparative Example 1 using polyurethane that does not contain an acid structure, precipitation occurred as described above, and the polyurethane composition could not be applied on the base film. Furthermore, it turns out that it replaces with a non-volatile organic base and the multilayer film and polarizer cannot adhere
  • the present invention it is possible to provide a multilayer film having excellent transparency and adhesiveness, and excellent conductivity, and a method for producing the multilayer film.

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Abstract

L'invention a pour objet de fournir un film multicouche qui possède une excellente transparence ainsi que d'excellentes propriétés d'adhésion, et simultanément qui est doté d'une excellente conductivité. Le film multicouche de l'invention est équipé d'un film de substrat, et d'une couche facilement adhésive agencée sur ledit film de substrat. Ladite couche facilement adhésive est constituée d'un objet durci d'une composition de polyuréthane qui contient un polyuréthane comprenant une structure d'acide, un agent de réticulation destiné à réticuler ledit polyuréthane comprenant une structure d'acide, une base organique non volatile, et des nanotubes de carbone comprenant des nanotubes de carbone monoparoi selon une proportion de 50% ou plus.
PCT/JP2019/008180 2018-03-08 2019-03-01 Film multicouche, et procédé de fabrication de celui-ci WO2019172136A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2022163372A1 (fr) * 2021-01-26 2022-08-04 日本ゼオン株式会社 Nanotubes de carbone oxydés et leur méthode de production

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JP2009086138A (ja) * 2007-09-28 2009-04-23 Toray Ind Inc 光学用易接着フィルムおよび光学用積層フィルム
WO2015098750A1 (fr) * 2013-12-26 2015-07-02 日本ゼオン株式会社 Feuille multicouche et son procédé de fabrication
JP2015189607A (ja) * 2014-03-27 2015-11-02 日本ゼオン株式会社 カーボンナノチューブ分散液、及び導電性フィルム
WO2015182058A1 (fr) * 2014-05-30 2015-12-03 日本ゼオン株式会社 Procédé de production d'une dispersion de nanotubes de carbone et dispersion de nanotubes de carbone, procédé de production d'une composition pour matériau composite et procédé de production d'un matériau composite, et matériau composite et article moulé en matériau composite
JP2016084423A (ja) * 2014-10-27 2016-05-19 理想科学工業株式会社 活性エネルギー線硬化型帯電防止性組成物及びこれを含有する帯電防止用塗料

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Publication number Priority date Publication date Assignee Title
JP2009086138A (ja) * 2007-09-28 2009-04-23 Toray Ind Inc 光学用易接着フィルムおよび光学用積層フィルム
WO2015098750A1 (fr) * 2013-12-26 2015-07-02 日本ゼオン株式会社 Feuille multicouche et son procédé de fabrication
JP2015189607A (ja) * 2014-03-27 2015-11-02 日本ゼオン株式会社 カーボンナノチューブ分散液、及び導電性フィルム
WO2015182058A1 (fr) * 2014-05-30 2015-12-03 日本ゼオン株式会社 Procédé de production d'une dispersion de nanotubes de carbone et dispersion de nanotubes de carbone, procédé de production d'une composition pour matériau composite et procédé de production d'un matériau composite, et matériau composite et article moulé en matériau composite
JP2016084423A (ja) * 2014-10-27 2016-05-19 理想科学工業株式会社 活性エネルギー線硬化型帯電防止性組成物及びこれを含有する帯電防止用塗料

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022163372A1 (fr) * 2021-01-26 2022-08-04 日本ゼオン株式会社 Nanotubes de carbone oxydés et leur méthode de production

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