WO2015076567A1 - Film stratifié en plastique - Google Patents

Film stratifié en plastique Download PDF

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Publication number
WO2015076567A1
WO2015076567A1 PCT/KR2014/011145 KR2014011145W WO2015076567A1 WO 2015076567 A1 WO2015076567 A1 WO 2015076567A1 KR 2014011145 W KR2014011145 W KR 2014011145W WO 2015076567 A1 WO2015076567 A1 WO 2015076567A1
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WO
WIPO (PCT)
Prior art keywords
plastic film
film laminate
coating layer
layer
plastic
Prior art date
Application number
PCT/KR2014/011145
Other languages
English (en)
Korean (ko)
Inventor
강준구
최항석
장영래
정혁
Original Assignee
주식회사 엘지화학
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
Priority claimed from KR1020140161177A external-priority patent/KR101686644B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US15/037,377 priority Critical patent/US10391748B2/en
Priority to CN201480063103.0A priority patent/CN105764688B/zh
Priority to EP14864129.3A priority patent/EP3040200B1/fr
Priority to JP2016531011A priority patent/JP6289637B2/ja
Publication of WO2015076567A1 publication Critical patent/WO2015076567A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/536—Hardness
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/584—Scratch resistance
    • 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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/22—Thermoplastic resins
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/08—Homopolymers or copolymers of acrylic acid esters

Definitions

  • the present invention relates to a plasma film laminate. More specifically, the present invention relates to a plastic film laminate exhibiting high hardness and excellent properties.
  • Plastic resin compositions are suitable for the trend toward a lighter mobile device because they are lightweight and less prone to breakage.
  • compositions have been proposed for coating a hard coat layer on a support substrate to achieve compositions having high hardness and wear resistance properties.
  • a method of increasing the thickness of the hard coating layer may be considered.
  • the surface hardness can be increased, but it is easy to apply practically because it becomes easy to cause cracks or peeling of the coating layer at the same time as wrinkles and curls increase due to the curing shrinkage of the hard coating layer.
  • Korean Unexamined Patent Publication No. 2010-0041992 is UV curable without the monomer
  • a coating composition using a binder resin containing a polyurethane acrylate oligomer is disclosed.
  • the hard coat composition disclosed above is not strong enough to replace the glass panel of the display with a pencil hardness.
  • the present invention provides a plastic film laminate having high hardness and excellent properties.
  • a first plastic film comprising at least one coating layer; And a second plastic film including at least one coating layer, wherein the first and second plastic films are bonded to each other by an adhesive layer.
  • plastic film laminate of the present invention exhibits high hardness, layer resistance, scratch resistance, and high transparency to replace glass in cover panels or device substrates of mobile communication terminals, touch panels of smartphones or tablet PCs, and various displays. It can be used for the purpose.
  • a first plastic film comprising at least one coating layer; And a second plastic film comprising at least one coating layer, wherein the first and second plastic films are bonded to each other by an adhesive layer.
  • each component when each component is referred to as being formed “on” or “on” of each component, it means that each component is directly formed on each component, or other components are each It can be formed between the layer, the object, the substrate additionally.
  • the present invention may be variously modified and may have various forms. It is intended to illustrate the specific embodiments of the bar and to be described in detail below. However, this is not intended to limit the present invention to a particular disclosed form, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.
  • the plastic film laminate of the present invention will be described in more detail.
  • the first plastic film comprising at least one coating layer; And a second plastic film including at least one coating layer, wherein the first and second plastic films are bonded to each other by an adhesive layer.
  • the first and second plastic films each independently include the same or different, the support substrate, and a coating layer formed on one or both sides of the support substrate, the coating layer is photocurable Cross-linked copolymers.
  • the first plastic film may include a coating layer on only one surface of the support substrate and the support substrate, or may include a coating layer on both surfaces of the support substrate.
  • the second plastic film may further include a coating layer on only one surface of the support substrate and the support substrate, or may include a coating layer on both surfaces of the support substrate.
  • the support substrate on which the coating layer is formed can be used without particular limitation as long as it is a transparent plastic resin substrate that is commonly used.
  • the support substrate may include, for example, polyester such as polyethylene terephthalate (PET), polyethylene such as ethylene vinyl acetate (EVA) polyethylene), cyclic olefin polymers (COPs), cyclic olefin copolymers (COCs), polyacrylates (polyacrylates, PACs), polycarbonates (PCs), polyethylene PE), polymethylmethacrylate (PMMA), polyetheretherketon (PEEK), polyethylenenaphthalate (PEN),
  • the film may include a polyetherimide (PEI), a polyimide (PI), a triacetylcellulose (TAC), a methyl methacrylate (MMA), a fluorine resin, or the like.
  • the support substrate may be a single layer or a multilayer structure including two or more substrates made of the same or different materials as necessary, but is not particularly limited.
  • the supporting substrate is a multi-layered structure of polyethylene terephthalate (PET), the structure of two or more layers formed by co-extrusion of polymethyl methacrylate (PMMA) / polycarbonate (PC)
  • PET polyethylene terephthalate
  • PMMA polymethyl methacrylate
  • PC polycarbonate
  • the support substrate may be a substrate including a copolymer of polymethyl methacrylate (PMMA) and polycarbonate (PC).
  • PMMA polymethyl methacrylate
  • PC polycarbonate
  • the thickness of the support substrate is not particularly limited, but a support substrate having a thickness of about 30 to about 1,200, or about 50 to about 800 may be used.
  • the first and second plastic films of the present invention each independently include the same or different coating layers formed on one or both sides of the support substrate.
  • the coating layer includes a photocurable crosslinked copolymer
  • the photocurable crosslinked copolymer is a 3 to 6 functional acrylate monomer, 1 to 2 functional acrylate monomer, 1 to 6-functional acrylate monomer ⁇ ,.
  • the optical path there is a chemical conversion elastomer at least one of i binder is selected from the group consisting of may be each cross-linked polymerization.
  • Each coating layer formed on one or both surfaces of the first and second plastic films may independently include the same or different photocurable crosslinked copolymers.
  • the photocurable crosslinked copolymer may be a crosslinked copolymer of 1 to 6 functional acrylate monomers and a photocurable elastomer, or a crosslinked copolymer of 3 to 6 functional acrylate monomers and a photocurable elastomer. It may be coalescing.
  • the acrylate-based is not only an acrylate but also a methacrylate, or a substituent is introduced into the acrylate or methacrylate. All derivatives.
  • the photocurable elastomer means a polymer material that exhibits elasticity and includes a functional group capable of crosslinking polymerization by ultraviolet irradiation.
  • the photocurable elastomer is ASTM
  • It may have an elongation of at least about 15%, for example about 15 to about 200%, or about 20 to about 200%, or about 20 to about 150%, as measured by D638.
  • a photocurable elastomer having a range of the above range it is possible to form a coating layer that satisfies both high hardness and high impact resistance.
  • the photocurable crosslinked copolymer is a crosslinked polymerization of the photocurable elastomeric polymer and 1 to 6 functional acrylate monomers, it provides high hardness and flexibility to the coating layer including the same, and in particular, damages caused by external impact It can prevent and ensure excellent layer resistance.
  • the photocurable elastomer may be a polymer or oligomer having a weight average molecular weight in the range of about 1,000 to about 600,000 g / mol, or about 10,000 to about 600,000 g / mol.
  • the photocurable elastomer may be, for example, at least one member selected from the group consisting of polycaprolactone, urethane acrylate polymer, and polyrotaxane.
  • polycaprolactone is formed by ring-opening polymerization of caprolactone and has excellent physical properties such as flexibility, impact resistance, and durability.
  • the urethane acrylate polymer has excellent elasticity and durability, including urethane bonds.
  • the polyrotaxane refers to a compound in which a dumbbell shaped molecule and a cyclic compound are structurally fitted.
  • the dumbbell shaped molecule includes a constant linear molecule and a blocking group disposed at both ends of the linear molecule, the linear molecule penetrates the interior of the cyclic compound, and the cyclic compound can move along the linear molecule. And the departure is prevented by the blocker.
  • the cyclic compound may be used without any limitation as long as it has a size enough to penetrate or surround the linear molecule, and may be a hydroxyl group, an amino group, a carboxyl group, a thiol group or an aldehyde group that may react with other polymers or compounds. It may also contain a functional group. Specific examples of such cyclic compounds include ⁇ -cy-cyclodextrin, ⁇ -cyclodextrin, ⁇ -cyclodextrin, or a combination thereof.
  • linear molecule a compound having a straight chain form having a molecular weight of a predetermined or more may be used without great limitation, and a polyalkylene compound or a polylactone compound may be used.
  • a polyoxyalkylene compound containing a oxyalkylene repeating unit having 1 to 8 carbon atoms or a polylactone compound having a lactone repeating unit having 3 to 10 carbon atoms may be used.
  • the containment group can be appropriately adjusted according to the properties of the rotacein compound to be prepared, for example one selected from the group consisting of dinitrophenyl group, cyclotextrin group, adamantane group, trityl group, fluorescein group and pyrene group or Two or more kinds can be used.
  • the 1 to 6 functional acrylate monomers include, for example, hydroxyethyl acrylate ( ⁇ ), hydroxyethyl methacrylate ( ⁇ ), nucleic acid diol diacrylate (HDDA), tripropylene glycol diacrylate (TPGDA). ), Ethylene glycol diacrylate (EGDA), trimethyl to propane triacrylate ( ⁇ ), trimethyl to propane specific triacrylate ( ⁇ ), glycerin propoxylated triacrylate (GPTA), pentaerythritol tetra An acrylate (PETA) or a dipentaerythrium can be mentioned nucleated acrylate (DPHA).
  • the 1 to 6 functional acrylate monomers may be used alone or in combination with each other.
  • the content ratio thereof is Although not particularly limited, when the total weight of the photocurable crosslinked copolymer is 100 parts by weight, 20 to 80 parts by weight of the photocurable elastomer and 80 to 20 parts by weight of the 1 to 6 functional acrylate monomers Or, 20 to 60 parts by weight of the photocurable elastomer, 40 to 80 parts by weight of the 1 to 6 functional acrylate monomer may be a copolymer cross-linked.
  • the high elastic photocurable elastomer includes a photocurable crosslinked copolymer crosslinked with a high content, high impact resistance and good physical properties can be achieved.
  • the coating layer formed on one side or both sides of the support substrate are each 50 or more, for example about 50 to about 300 ⁇ m, or about 50 to about 200, or about 50 to about 150 j Or, from about 70 to about 150.
  • the photocurable crosslinked copolymer may be a crosslinked copolymer of 3 to 6 functional acrylate monomers.
  • the photocurable crosslinked copolymer may be a crosslinked copolymer of 3 to 6 functional acrylate monomers and 1 to 2 functional acrylate monomers.
  • the photocurable crosslinked copolymer may be a crosslinked copolymer of a 3 to 6 functional acrylate monomer and a photocurable elastomer.
  • the 3 to 6 functional acrylate monomers include trimethylolpropane triacrylate (TMPTA), trimethyl to propane specific triacrylate (TMPEOTA), glycerin propoxylated triacrylate (GPTA), and pentaerythritol tetra Acrylate (PETA) or dipentaerythrium can be mentioned nucleated acrylate (DPHA).
  • TMPTA trimethylolpropane triacrylate
  • TMPEOTA trimethyl to propane specific triacrylate
  • GPTA glycerin propoxylated triacrylate
  • PETA pentaerythritol tetra Acrylate
  • DPHA dipentaerythrium
  • the 3 to 6 functional acrylate monomers may be used alone or in combination with each other.
  • the coating layer may further include inorganic fine particles dispersed in the photocurable crosslinked copolymer.
  • the coating layer located at the outermost part contains inorganic fine particles in order to improve surface hardness.
  • the inorganic fine particles having a particle size of nanoscale Inorganic particulates such as nanoparticles having a particle diameter of about 100 nm or less, or about 10 to about 100 nm, or about 10 to about 50 nm, can be used.
  • the inorganic fine particles for example, silica fine particles, aluminum oxide particles, titanium oxide particles, or zinc oxide particles may be used.
  • the hardness of the coating layer can be further improved.
  • the coating layer comprises inorganic fine particles
  • the coating layer may further include additives commonly used in the technical field of the present invention, such as surfactants, anti-yellowing agents, leveling agents, antifouling agents.
  • additives commonly used in the technical field of the present invention such as surfactants, anti-yellowing agents, leveling agents, antifouling agents.
  • the content can be variously adjusted within a range that does not lower the physical properties of the plastic film of the present invention, it is not particularly limited, for example, about 0.1 to about 10 weight by weight based on 100 parts by weight of the photocurable crosslinked copolymer It can be included as a wealth.
  • the coating layer may include a surfactant as an additive
  • the surfactant may be a 1 to 2 functional fluorine-based acrylate, fluorine-based surfactant or silicone-based surfactant.
  • the surfactant may be included in the form of being dispersed or crosslinked in the crosslinked copolymer.
  • the additive may include a yellowing inhibitor, and the yellowing inhibitor may include a benzophenone compound or a benzotriazole compound.
  • the coating layer may be formed by applying the above-described binder, a photoinitiator, and optionally a coating composition including an organic solvent, inorganic fine particles, and additives on a supporting substrate and then photocuring the same.
  • photoinitiator examples include 1-hydroxycyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone and 2-hydroxy-1- [4- (2-hydroxy Phenyl] -2-methyl-1-propane, Methylbenzoylformate, ⁇ , ⁇ -dimethoxy- ⁇ -phenylacetophenone, 2-benzoyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2 ⁇ methyl-l- [4- (methylthio) phenyl] -2- (4-morpholinyl) -l-propanone diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide, or bis ( 2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like, but is not limited thereto.
  • Irgacure 184 Commercially available products include Irgacure 184, Irgacure 500, Irgacure 651, Irgacure 369, Irgacure 907, Darocur 1 173, Darocur MBF, Irgacure 819, Darocur TPO, Irgacure 907, and Esacure KIP 100F.
  • These photoinitiators can be used individually or in mixture of 2 or more types different from each other.
  • organic solvent examples include methane, an alcoholic solvent such as ethanol, isopropyl alcohol and butane, an alkoxy alcohol solvent such as 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propane, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl propyl ketone, cyclo hex rice fields based, solvent, propylene glycol monopropyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol Ether solvents such as monobutyl ether, diethylene glycol monomethyl ether, diethyl glycol monoethyl ether, diethyl glycol monopropyl ether, diethyl glycol monobutyl ether, diethylene glycol-2-ethyl nucleosil ether, benzene, Aromatic solvents, such as l,
  • the organic solvent may include a weight ratio of the solid content: the organic solvent to about 70:30 to about 99: 1 based on a solid content including a binder, a photoinitiator, and other additives.
  • a high viscosity composition may be obtained, thereby enabling thick coating to form a coating layer having a high thickness, for example, 50 ⁇ or more.
  • the first and second plastic films described above are laminated in a form bonded to each other by an adhesive layer.
  • the thickness of the adhesive layer may be about 1 to about 200, or about 1 to 100 ⁇ , or about 5 to 50 / .
  • the storage modulus of the adhesive layer (Storage modulus, G ') is measured by dynamic viscoelasticity according to the conventional measurement method.
  • the storage modulus at room temperature (25 ° C.) after curing is about 40 to about 700 kPa, preferably about 40 to about 500 kPa, more preferably about 40 to about 200 kPa. It features. If the storage elastic modulus of the adhesive layer is less than 40 kPa, bubbles are more likely to occur in the adhesive layer, and if it exceeds 700 kPa, the interfacial adhesion of the first and second plastic films may be deteriorated due to the too hard property. , Layer resistance, and flexibility may be lowered.
  • the adhesive layer may be formed by photocuring and / or thermosetting an adhesive layer composition including a photocurable acrylate polymer, an oligomer, a monomer, or a mixture thereof as an acrylate monomer component.
  • acrylate-type monomer component it is (meth) acrylate, the alkyl (meth) acrylate which has a C1-C14 linear or branched alkyl group, for example, methyl (meth) acrylate, ethyl (meth) ) Acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, butyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, nuclear chamber (meth Acrylate, 2-ethylnuclear (meth) acrylate, ethylbutyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) Examples include, but are not limited to, ligomers or
  • the acrylate monomer may have a weight average molecular weight of 1 million to 5 million g / mol, preferably 1 million to 4 million g / ii) l, more preferably 1.5 million to 3 million g / m.
  • the adhesive layer composition is a thermosetting composition
  • it may further include a curing agent capable of crosslinking the acrylate monomer component.
  • the curing agent may be used commonly used in the field of adhesive layer production, for example, may be used at least one selected from epoxy-based and isocyanate-based.
  • the curing agent is based on 100 parts by weight of the acrylate monomer component. 0.01 parts by weight to 10 parts by weight may be included, but the ratio may be changed according to the desired elastic modulus and tackiness.
  • the adhesive layer composition is a photocurable composition
  • it may further include a photoinitiator.
  • the adhesive composition may further include additives such as 3 ⁇ 4 other curable resins, monomers, UV stabilizers, or antioxidants as necessary.
  • the adhesive layer may refer to any filling having adhesiveness while satisfying the above conditions regardless of its name or form, such as a freestanding layer, a film, a film, or a cured resin layer of a coating composition.
  • the total thickness of the plastic film laminate of the present invention in which the above-mentioned first and second plastic films are laminated by an adhesive layer is about 0.3 to about 1.5 mm, or about 0.5 to about 1.5 mm, or about 0.7 to about 1.0 mm. Can be.
  • the plastic film laminate of the present invention may be a laminate in which five or more layers or substrates distinguished from each other are laminated.
  • the plastic film laminate of the present invention may have a structure of a coating layer-a supporting substrate-an adhesive layer-a supporting substrate-a coating layer, or a coating layer-a supporting substrate-a coating substrate-an adhesive layer-a structure of a supporting substrate-a coating layer, or a coating layer-a supporting substrate- The structure of the adhesive layer-coating layer-supporting substrate-coating layer or the structure of the coating layer-supporting substrate-coating layer-adhesive layer-coating layer-supporting substrate-coating layer.
  • the components constituting the coating layer are independent of each other, each may be the same or different.
  • the plastic film stacker of the present invention is another plastic resin film, adhesive film, release film, conductive film, conductive layer on at least one plastic film of the first or second plastic film
  • the coating layer, the cured resin layer, a non-conductive film, a metal mesh layer or a layer such as a patterned metal layer may further include one or more.
  • the layer, film, film or the like may be in any form of a single layer, a double layer or a laminate.
  • the layer, film, or film may be laminated on the coating layer by a method such as laminating a freestanding film using an adhesive or an adhesive film, or by coating, vapor deposition, sputtering, or the like. It is not limited to this.
  • the plasma (plasma) treatment on the surface of the plastic film in contact Corona discharge treatment or surface treatment with a basic solution such as sodium or potassium hydroxide may be performed.
  • the first and second plastic films may be prepared by coating and photocuring the coating composition on one or both surfaces of the support substrate, respectively.
  • the coating layer may be formed by a conventional method used in the art.
  • a coating composition comprising the aforementioned components is applied to one side of the support substrate.
  • the method of applying the coating composition is not particularly limited as long as it can be used in the technical field to which the present technology belongs, for example, bar coating method, knife coating method, coating method, blade coating method, die coating method, micro A gravure coating method, a comma coating method, a slot die coating method, a lip coating method, or a solution casting method may be used.
  • the coating composition is formed by irradiating the coated composition with ultraviolet light to photocuring the same.
  • the irradiation amount of ultraviolet light may be, for example, about 20 to about 600 mJ / cm 2 or about 50 to about 500 mJ / cm 2 .
  • the light source for ultraviolet irradiation is not particularly limited as long as it can be used in the art to which the present technology belongs, and for example, a high pressure mercury lamp, a metal halide lamp, a black light fluorescent lamp, or the like can be used. Irradiation for about 30 seconds to about 15 minutes, or about 1 minute to about 10 minutes with the above irradiation amount may be performed to photocuring.
  • the thickness of the coating layer may be about 50 to about 300 urn, or about 50 to about 200! M, or about 50 to about 150 urn, or about 70 to about 150 after fully cured.
  • the thickness of the coating layer may exhibit high hardness without problems of curl or cracks.
  • the coating composition is applied to the other side of the support substrate, that is, the back side.
  • the coating layer is formed by irradiating the coated composition with ultraviolet light to photocuring the same.
  • curing of the previously applied coating composition by performing ultraviolet irradiation on the opposite side of the coating composition The ' curl ' which can be caused by shrinkage can be offset in the opposite direction to obtain a flat plastic film. Therefore, no additional planarization process is necessary.
  • the plastic film laminate of the present invention can be produced by bonding the first and second plastic films obtained by the above method by lamination or the like by the above-described adhesive layer.
  • plastic film to be used as a cover of a mobile communication terminal or a tablet PC it is important to improve the hardness of the plastic film to a level capable of replacing glass.
  • the plastic film laminate according to the present invention is formed to a high thickness so that the overall thickness is 03 mm or more, there is little curl or cracks, and a plastic film having high transparency and layer resistance can be obtained.
  • the multi-layer coating layer is laminated structure, while exhibiting high transparency and high hardness, the plurality of coating layers can effectively absorb or offset the layer gap from the outside to achieve high layer resistance.
  • the plastic film laminate of the present invention may have excellent hardness and layer resistance to replace glass.
  • cracks may not occur when 22 g of iron balls are freely dropped 10 times at a height of 60 cm.
  • the plastic film locust of the present invention the pencil hardness at 1 kg load may be 7H or more, or 8H or more, or 9H or more.
  • plastic film laminate of the present invention after mounting the steel wool (0000) wool steel (0000) in the friction tester may occur less than two scratches when reciprocating 400 times with a load of 500g.
  • the plastic film laminate of the present invention may have a light transmittance of about 90.0% or more, or about 91.0% or more, and a haze of about 1.5% or less, or about 1.0% or less, or about 0.8% or less.
  • the plastic film laminate of the present invention the initial color b value (CIE 1976 L * a * b * B *) by the color space may be 1.5 or less.
  • the difference between the initial color b value and the color b value after 72 hours or more exposure to the UV lamp in the UVB wavelength region may be less than or equal to 5, or less than 0.4.
  • the plastic film laminate of the present invention when exposed at a temperature of 50 ° C or more and 80% or more at least 70 hours, when placed in a plane, the distance of each corner or one side of the plastic film laminate spaced apart from the plane May have a maximum of about 1.0 mm or less, or about 0.6 mm or less, or about 0.3 mm or less. More specifically, each of the edges or one side of the plastic film laminate spaced apart from the plane when placed in the plane after exposure to 70 to 100 hours at a silver of 50 to 90 ° C and humidity of 80 to 90% The maximum value may be about 1.0 mm or less, or about 0.6 mm or less, or about 0.3 mm or less.
  • the plastic film laminate of the present invention exhibits high hardness, layer resistance, scratch resistance, high transparency, durability, light resistance, high transmittance, and the like, and thus may be usefully used in various fields.
  • the plastic film laminate of the present invention can be utilized in various fields.
  • it can be used for a touch panel of a mobile communication terminal, a smartphone or a tablet PC, and a cover substrate or an element substrate of various displays.
  • the weight average molecular weight of the obtained polyrotasein was 600,000 g / mol, and elongation measured by ASTM D638 was 20%.
  • An adhesive layer composition was prepared by mixing dipentaerythr with 30 parts by weight of nucleated acrylate (DPHA), 1.5 parts by weight of a photoinitiator (trade name: Irgacure 184), and 1 part by weight of coronate L, which is an isocyanate curing agent.
  • DPHA nucleated acrylate
  • Irgacure 184 photoinitiator
  • TMPTA trimethylolpropane triacrylate
  • polyrotasein of Preparation Example 1 6 g
  • photoinitiator trade name: Darocur TPO
  • 0.1 g of banjotriazole-based yellowing inhibitor trade name: Tinuvin 400
  • fluorine-based interface 0.05 g of the active agent (trade name: FC4430) and 1 g of methyl ethyl ketone were mixed to prepare a first coating composition.
  • the Crab 1 coating composition was applied on a 15 cm x 20 cm, 188 thick PET support substrate. Next, photocuring was performed by irradiating ultraviolet rays with a wavelength of 280-350 nm using a black light fluorescent lamp to form a coating layer having a thickness of 100 ⁇ on one side. 1 plastic film was prepared.
  • Silica ⁇ dipentaerythroxy nucleoacrylate (DPHA) complex 9 g (3.6 g silica, DPHA 5.4 g), polyrotase of Preparation Example 1 1 g of phosphorus, 0.2 g of photoinitiator (trade name: Darocur TPO), 0.1 g of benzotriazole-based yellowing inhibitor (trade name: Tinuvin 400), 0.05 g of fluorine-based surfactant (trade name: FC4430), and 1 g of methyl ethyl ketone were mixed.
  • the coating composition was prepared.
  • the second coating composition was applied on another PET support substrate 15 cm ⁇ 20 cm, thickness 188 ⁇ .
  • photocuring was performed by irradiating ultraviolet rays with a wavelength of 280-350 nm using a black light fluorescent lamp to prepare a second plastic film having a coating layer having a thickness of 100 mm 3 on one side.
  • TMPTA trimethyl propane triacrylate
  • urethane acrylate polymer trade name: UA200PA, Shinnakamura Chemical, weight average molecular weight 2,600 g / mol, elongation at 170% by ASTM D638
  • photoinitiator trade name: Darocur TPO
  • benzotriazole yellowing inhibitor trade name: Tinuvin 400
  • FC4430 fluorine-based surfactant
  • silica-dipentaeryri (DPHA) composites (3.6 g of silica, 5.4 g of silica) dispersed in about 40% by weight of nano silica having a particle diameter of 20-30 nm, urethane acrylate polymer (UA200PA) 1 g, 0.2 g of photoinitiator (trade name: Darocur TPO), 0.1 g of benzotriazole-based yellowing inhibitor (trade name: Tinuvin 400), 0.05 g of fluorine-based surfactant (trade name: FC4430), and 1 g of methyl ethyl ketone were mixed.
  • the first coating composition was applied on a PET support substrate of 15 cm ⁇ 20 cm, thickness 188.
  • photocuring was carried out by irradiating ultraviolet rays with a wavelength of 280-350 nm using a blow light fluorescent lamp to form a first coating layer having a thickness of 100 Hz.
  • a second coating composition was applied to the back side of the support substrate.
  • photocuring was performed by irradiating ultraviolet rays with a wavelength of 280-350 nm using a black light fluorescent lamp. It was carried out to form a crab 2 coating layer having a thickness of 100 to prepare a plastic film having a first and a second coating layer on each side.
  • TMPTA trimethylolpropane triacrylate
  • urethane acrylate polymer trade name: UA340P, Shinnakamura Chemical, weight average molecular weight 13,000 g / mol, elongation 150% according to ASTM D638
  • photoinitiator brand name: Darocur TPO
  • benzotriazole yellowing inhibitor trade name: Timivin 400
  • fluorine-based surfactant trade name: FC4430
  • the particle diameter is 20-30nm nano silica is about 40 wt 0/0 dispersed silica-hex the dipentaerythritol EPO Li acrylate (DPHA) complex 9 g (silica 3.6 g, DPHA 5.4 g), urethane acrylate-based polymer (UA340P ) 1 g, photoinitiator (trade name: Darocur TPO) 0.2 g, benzotriazole yellowing inhibitor (trade name: Timivin 400) 0.1 g, fluorine-based surfactant (trade name: FC4430) 0.05 g, 1 g methyl ethyl ketone
  • the coating composition was prepared.
  • the first coating composition was applied on a PET support substrate 15 cm ⁇ 20 cm, thickness 188 / m.
  • ultraviolet rays having a wavelength of 280-350 nm were irradiated with a black light fluorescent lamp to perform photocuring to form a first coating layer having a thickness of 100.
  • a second coating composition was applied to the back side of the support substrate.
  • photocuring was performed by irradiating ultraviolet rays with a wavelength of 280-350 nm using a black light fluorescent lamp to form a second coating layer having a thickness of 100 to prepare a plastic film having first and second coating layers formed on both surfaces, respectively. .
  • the first and second coating layer formed plastic A film was prepared.
  • the adhesive layer composition of Preparation Example 3 was applied between two plastic films to have a thickness of 50, and laminated, and then prepared into a plastic film laminate by thermal curing at a temperature of 60 ° C. Comparative Example 2
  • Adhesive Layer (Manufacturing Example 2) -PET Substrate-Second
  • Example 2 First Coating Layer—PET Substrate—Secondary 69 kPa 826
  • Coating layer-window layer (production example 3)-1st
  • the storage modulus (G ′) of the adhesive layer was measured using a dynamic viscoelasticity measuring instrument (ARES-RDA, TA instruments Inc.). The measurement conditions were measured at room temperature (25 ° C), a frequency of 1 rad / s, using a plate of 8mm stainless steel disk type, the thickness of the adhesive layer was 1mm.
  • the top layer (second coating layer) of each film laminate was reciprocated three times at a load of 1.0 kg according to the measurement standard JIS K5400, and then the hardness without grooves was confirmed.
  • Each plastic film laminate is wound around a 3 cm diameter cylindrical mantel with the first coating layer on the outside of the film laminate, and it is determined whether or not cracks have occurred. Evaluated as.
  • the surface state of the film was visually observed to observe whether there were any grooves such as bubble generation, foreign matter, cracks, and adhesion state.
  • the physical property measurement results are shown in Table 2 below.
  • the plastic film laminates of Examples 1 to 3 of the present invention exhibited good properties in all of their physical properties.
  • Comparative Example 1 in which the storage elastic modulus of the adhesive layer was low, bubbles were generated in the adhesive layer, and in Comparative Example 2 in which the storage elastic modulus was too high, the adhesive force was reduced, so that the first and second plastic films were not properly bonded, and thus the impact resistance and curling were not achieved. Properties and the like appeared poor.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un film en plastique et, plus particulièrement, un film en plastique présentant une résistance aux chocs et d'excellentes caractéristiques. Selon l'invention, un film en plastique est produit, qui présente des caractéristiques élevées de dureté, de résistance aux chocs, de résistance aux rayures et de transparence, ainsi qu'une excellente aptitude au traitement.
PCT/KR2014/011145 2013-11-19 2014-11-19 Film stratifié en plastique WO2015076567A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US15/037,377 US10391748B2 (en) 2013-11-19 2014-11-19 Plastic film laminate
CN201480063103.0A CN105764688B (zh) 2013-11-19 2014-11-19 塑料薄膜层压制件
EP14864129.3A EP3040200B1 (fr) 2013-11-19 2014-11-19 Film stratifié en plastique
JP2016531011A JP6289637B2 (ja) 2013-11-19 2014-11-19 プラスチックフィルム積層体

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20130140664 2013-11-19
KR10-2013-0140664 2013-11-19
KR10-2014-0161177 2014-11-18
KR1020140161177A KR101686644B1 (ko) 2013-11-19 2014-11-18 플라스틱 필름 적층체

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Cited By (5)

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US20170028677A1 (en) * 2015-07-31 2017-02-02 Samsung Sdi Co., Ltd. Window film and flexible display including the same
CN107123370A (zh) * 2016-02-25 2017-09-01 三星Sdi株式会社 柔性显示装置
US10476037B2 (en) 2016-04-22 2019-11-12 Samsung Sdi Co., Ltd. Flexible display apparatus
US11041057B2 (en) 2016-12-13 2021-06-22 Samsung Sdi Co., Ltd. Window film, manufacturing method thereof, and display device including same
EP3418782B1 (fr) * 2016-12-26 2023-05-03 LG Chem, Ltd. Film de protection de polariseur, plaque de polarisation le comprenant, appareil d'affichage à cristaux liquides comprenant une plaque de polarisation, et composition de revêtement pour film de protection de polariseur

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170028677A1 (en) * 2015-07-31 2017-02-02 Samsung Sdi Co., Ltd. Window film and flexible display including the same
US10696016B2 (en) * 2015-07-31 2020-06-30 Samsung Sdi Co., Ltd. Window film and flexible display including the same
CN107123370A (zh) * 2016-02-25 2017-09-01 三星Sdi株式会社 柔性显示装置
CN107123370B (zh) * 2016-02-25 2019-10-18 三星Sdi株式会社 柔性显示装置
US10603876B2 (en) 2016-02-25 2020-03-31 Samsung Sdi Co., Ltd. Flexible display apparatus
US10476037B2 (en) 2016-04-22 2019-11-12 Samsung Sdi Co., Ltd. Flexible display apparatus
US11041057B2 (en) 2016-12-13 2021-06-22 Samsung Sdi Co., Ltd. Window film, manufacturing method thereof, and display device including same
EP3418782B1 (fr) * 2016-12-26 2023-05-03 LG Chem, Ltd. Film de protection de polariseur, plaque de polarisation le comprenant, appareil d'affichage à cristaux liquides comprenant une plaque de polarisation, et composition de revêtement pour film de protection de polariseur

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