WO2021070424A1 - 印刷層付フィルム積層体、該印刷層付フィルム積層体を含む光学積層体、およびこれらを用いた画像表示装置 - Google Patents

印刷層付フィルム積層体、該印刷層付フィルム積層体を含む光学積層体、およびこれらを用いた画像表示装置 Download PDF

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WO2021070424A1
WO2021070424A1 PCT/JP2020/024373 JP2020024373W WO2021070424A1 WO 2021070424 A1 WO2021070424 A1 WO 2021070424A1 JP 2020024373 W JP2020024373 W JP 2020024373W WO 2021070424 A1 WO2021070424 A1 WO 2021070424A1
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Prior art keywords
film
print layer
layer
laminate
film laminate
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PCT/JP2020/024373
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English (en)
French (fr)
Japanese (ja)
Inventor
岳仁 淵田
康隆 石原
Original Assignee
日東電工株式会社
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Priority to KR1020207032486A priority Critical patent/KR102441978B1/ko
Priority to CN202080003453.3A priority patent/CN112955321A/zh
Publication of WO2021070424A1 publication Critical patent/WO2021070424A1/ja

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    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/14—Printing or colouring
    • B32B38/145—Printing
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/027—Thermal properties
    • B32B7/028—Heat-shrinkability
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G09F9/301—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements flexible foldable or roll-able electronic displays, e.g. thin LCD, OLED
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/206—Organic displays, e.g. OLED

Definitions

  • the present invention relates to a film laminate with a print layer, an optical laminate including the film laminate with a print layer, and an image display device using these.
  • a decorative film (film with a printing layer) is used as a means of improving the design of various products.
  • the portion corresponding to the non-display area of the front plate typically, the peripheral portion.
  • Is provided with a colored layer, a design layer, a decorative layer, or the like for example, Patent Documents 1 and 2).
  • Patent Documents 1 and 2 for example, Patent Documents 1 and 2.
  • the present invention has been made to solve the above-mentioned conventional problems, and an object of the present invention is to provide a film laminate with a print layer having high pencil hardness and suppressed curl. is there.
  • the film laminate with a print layer of the present invention includes a base film, a hard coat layer formed on one surface of the base film, a print layer formed on the other side of the base film, and the like. It has a protective film that is peelably laminated on the surface of the hard coat layer. The larger of the heat shrinkage rate in the first direction and the heat shrinkage rate in the second direction orthogonal to the first direction of the protective film is 0.1% or less, and the printing layer is attached. The amount of warpage after the film laminate is placed in an environment of 70 ° C. for 60 minutes is 19 mm or less.
  • the substrate film comprises a polyimide resin.
  • the base film has a thickness of 40 ⁇ m to 100 ⁇ m.
  • the hard coat layer is a cured layer of active energy ray-curable (meth) acrylate. In one embodiment, the thickness of the hard coat layer is 3 ⁇ m to 20 ⁇ m.
  • the protective film comprises polyethylene terephthalate. In one embodiment, the protective film has a thickness of 30 ⁇ m to 140 ⁇ m.
  • the film laminate with a print layer is a window film of an image display device. According to another aspect of the present invention, an optical laminate is provided. This optical laminate has the above-mentioned film laminate with a print layer and an optical film arranged on the opposite side of the base film of the base film in the print layer-attached film laminate to the above-mentioned hard coat layer.
  • an image display device includes the above-mentioned film laminate with a print layer or the above-mentioned optical laminate.
  • the image display device is a bendable and / or foldable organic electroluminescence display device.
  • a protective film having a heat shrinkage rate of a predetermined value or less in a predetermined direction in a film laminate with a print layer by laminating a protective film having a heat shrinkage rate of a predetermined value or less in a predetermined direction in a film laminate with a print layer, a high pencil hardness and curl are suppressed. It is possible to realize a film laminate with a printed layer.
  • FIG. 1 is a schematic cross-sectional view of the film laminate with print layer according to one embodiment of the present invention.
  • the film laminate 100 with a print layer of the illustrated example includes a base film 10, a hard coat layer 20 formed on one surface of the base film 10, and a print layer formed on the other side of the base film 10. It has 30 and a protective film 40 laminated on the surface of the hard coat layer 20.
  • the protective film 40 includes a base film (resin film) and an adhesive layer. The protective film 40 is releasably laminated on the surface of the hard coat layer 20 via the pressure-sensitive adhesive layer.
  • a hue adjusting layer may be provided between the base film 10 and the printing layer 30.
  • another protective film (sometimes referred to as a process protective film, not shown) may be temporarily attached to the surfaces of the print layer 30 and the base film 10 so as to be peelable.
  • the larger of the heat shrinkage rate in the first direction and the heat shrinkage rate in the second direction orthogonal to the first direction of the protective film 40 is 0.1% or less, preferably 0.08. % Or less, more preferably 0.06% or less, still more preferably 0.05% or less.
  • the lower limit of the heat shrinkage rate can be, for example, 0.01%. When the heat shrinkage rate is within such a range, curling of the film laminate with a print layer can be remarkably suppressed.
  • the first direction is typically the transport direction of the protective film.
  • the transport direction in roll-to-roll (long film). Is typically the first direction. Therefore, in the film laminate with a print layer that is finally cut into a rectangle, for example, the first direction may be the long side direction or the short side direction. Specifically, when the laminate of the long base film / hard coat layer / protective film is cut into a rectangle so that the long direction is the long side direction, the first direction is the long side direction. It becomes.
  • the print layer is typically formed after cutting.
  • the heat shrinkage rate in the transport direction is larger than the heat shrinkage rate in the direction orthogonal to the transport direction (width direction).
  • the amount of warpage of the film laminate with a print layer after being placed in an environment of 70 ° C. for 60 minutes is 19 mm or less, preferably 15 mm or less, more preferably 10 mm or less, and further preferably 7 mm or less. ..
  • the lower limit of the amount of warpage can be, for example, 2 mm.
  • the amount of warpage (curl) can be made very small in the film laminate with a print layer. As a result, the film laminate with the print layer can be reliably and satisfactorily laminated on the optical film or the image display cell.
  • the visible side surface (substantially the surface of the hard coat layer) of the film laminate with the printing layer has a pencil hardness of preferably 2H or more, more preferably 3H or more, still more preferably 4H or more.
  • the film laminate with a print layer can function well as a window film.
  • Pencil hardness can be measured according to JIS K 5400-5-4.
  • the visible surface has scratch resistance that does not cause scratches even if it is rubbed back and forth preferably 300 times, more preferably 500 times, and even more preferably 1000 times under a load of 1000 g.
  • the scratch resistance can be evaluated in the state of scratches when steel wool # 0000 is used and the surface is reciprocated a predetermined number of times under a predetermined load (for example, 500 g / cm 2 , 1000 g / cm 2).
  • the film laminate with a printing layer has a radius of curvature of 3 mm or less (for example, 3 mm, 2 mm, 1 mm) and has flexibility that allows it to bend preferably 50,000 times, more preferably 100,000 times, and even more preferably 200,000 times. Since the film laminate with a print layer has such flexibility, it is possible to realize an image display device that is bendable or foldable when the film laminate with a print layer is applied to an image display device. The flexibility test is performed by bending with the hard coat layer inside.
  • a film laminate with a print layer is cut out into a strip of 100 mm ⁇ 20 mm and used as a measurement sample, and the test machine (“CL09-typeD01-FMC90” manufactured by Yuasa System Co., Ltd.) is used. Set the measurement sample so that the hard coat layer side is inside the bend, and perform under the following conditions.
  • the evaluation of the flexibility can be judged by visually observing the state of peeling at the bent portion of the sample after the test.
  • Environmental conditions 25 ° C, 55% RH Test speed: 60 rpm
  • the light transmittance of the film laminate with a print layer is preferably 85% or more, more preferably 87% or more, and further preferably 90% or more.
  • the haze of the film laminate with a print layer is preferably 1.5% or less, more preferably 1.2% or less, and further preferably 1.0% or less.
  • the film laminate with a print layer can be suitably used as, for example, a window film of an image display device, a front plate of a car navigation system, and a dust cover of a head-up display system.
  • the base film 10 can be made of any suitable material.
  • the constituent materials include polyethylene terephthalate resin, polyethylene naphthalate resin, acetate resin, polyether sulfone resin, polycarbonate resin, polyamide resin, polyimide resin, polyamideimide resin, and polyolefin resin.
  • examples thereof include (meth) acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, polyarylate resins, polyphenylene sulfide resins and the like. These resins may be used alone or in combination of two or more.
  • it is a polyamide-based resin, a polyimide-based resin, a polyamide-imide-based resin, a polyethylene naphthalate-based resin, or a polycarbonate-based resin. This is because it has excellent durability and mechanical strength. More preferably, it is a polyimide resin.
  • the base film may contain fine particles blended in the above constituent materials. More specifically, the base film may be a so-called nanocomposite film in which nanometer-order fine particles are dispersed in the matrix of the constituent materials. With such a configuration, very good hardness and scratch resistance can be imparted.
  • the average particle size of the fine particles is, for example, about 1 nm to 100 nm.
  • the fine particles are typically composed of inorganic oxides.
  • the surface of the fine particles is modified with a predetermined functional group.
  • Examples of the inorganic oxides constituting the fine particles include zirconium oxide, ittoria-added zirconium oxide, lead zirconate, strontium titanate, tin titanate, tin oxide, bismuth oxide, niobium oxide, tantalum oxide, potassium tantalate, and tungsten oxide. , Cerium oxide, lanthanum oxide, gallium oxide and the like, silica, alumina, titanium oxide, zirconium oxide, barium titanate and the like.
  • the thickness of the base film is preferably 40 ⁇ m to 100 ⁇ m, more preferably 50 ⁇ m to 80 ⁇ m. With such a thickness, the balance between thinning, handleability, and mechanical strength is excellent.
  • the pencil hardness of the base film is preferably B or higher, more preferably F or higher, and even more preferably H or higher.
  • the hard coat layer 20 is typically a hardened layer of an active energy ray-curable (meth) acrylate.
  • the active energy ray-curable (meth) acrylate include an ultraviolet curable (meth) acrylate and an electron beam-curable (meth) acrylate.
  • a UV curable (meth) acrylate is preferred. This is because the hard coat layer can be efficiently formed by a simple processing operation.
  • the UV curable (meth) acrylate contains UV curable monomers, oligomers, polymers and the like.
  • the UV curable (meth) acrylate contains a monomer component and an oligomer component having preferably 2 or more, more preferably 3 to 6 UV polymerization functional groups.
  • the ultraviolet curable (meth) acrylate contains a photopolymerization initiator.
  • the curing method may be a radical polymerization method or a cationic polymerization method.
  • an organic-inorganic hybrid material in which silica particles, a polysilsesquioxane compound, or the like is mixed with (meth) acrylate may be used.
  • a constituent material and a method for forming the hard coat layer are described in, for example, Japanese Patent Application Laid-Open No. 2011-237789. The description of this publication is incorporated herein by reference.
  • (meth) acrylate means acrylate and / or methacrylate.
  • the hard coat layer may be formed by blending a slide ring material with an ultraviolet curable (meth) acrylate. Good flexibility can be imparted by blending the slide ring material.
  • Polyrotaxane is a typical example of the slide ring material. Polyrotaxane typically has a structure in which a cyclodextrin (CD) cyclic molecule slides on a linear polyethylene glycol (PEG) main chain. Both ends of the PEG backbone are modified with adamantaneamine to prevent shedding of the CD cyclic molecule. In polyrotaxane, preferably, the CD cyclic molecule is chemically modified to impart an active energy ray-polymerizable group.
  • a radically polymerizable monomer having a radically polymerizable group is preferably used as the ultraviolet curable (meth) acrylate.
  • the radically polymerizable group include a (meth) acryloyl group and a (meth) acryloyloxy group. This is because it has excellent compatibility with polyrotaxane and various material selections are possible.
  • polyrotaxane substantially a polymerizable group of a CD cyclic molecule
  • the hard coat layer may be formed by blending nanofibers and / or nanocrystals with ultraviolet curable (meth) acrylate.
  • Typical examples of nanofibers include cellulose nanofibers, chitin nanofibers, and chitosan nanofibers. By blending these, a hard coat layer having excellent flexibility, pencil hardness, scratch resistance, and abrasion resistance can be obtained while maintaining excellent transparency.
  • the nanofibers and / or nanocrystals (the total when used in combination) can be blended in a proportion of 0.1% to 40% by weight, preferably 0.1% by weight, based on the entire hard coat layer.
  • Nanofibers have an average fiber diameter of, for example, 1 nm to 100 nm, and an average fiber length of, for example, 10 nm to 1000 nm.
  • the hard coat layer containing nanofibers is described in, for example, Japanese Patent Application Laid-Open No. 2012-131201 and Japanese Patent Application Laid-Open No. 2012-171171. The description of this publication is incorporated herein by reference.
  • the thickness of the hard coat layer is preferably 3 ⁇ m to 20 ⁇ m, more preferably 3 ⁇ m to 15 ⁇ m. When the thickness is in such a range, curling can be satisfactorily suppressed, and both excellent surface hardness and flexibility and / or foldability can be achieved at the same time.
  • a print layer is a colored layer that is colored by printing depending on the application and the desired design. Examples of the color of the print layer include black, brown, white, dark blue, red, gold, and silver.
  • the printing layer may be a design layer having a predetermined design, or may be a solid colored layer.
  • the printing layer is preferably a solid colored layer, and more preferably a black colored layer.
  • wiring, terminals, a backlight, and other parts can be concealed in a non-display area. That is, the print layer can function as a concealment layer.
  • the print layer can be formed in any suitable pattern depending on the purpose. In one embodiment, the print layer may be formed in a position corresponding to the bezel.
  • the non-display area can be concealed without using a bezel, so that an image display device that does not use a bezel can be realized.
  • an image display device having an extremely excellent appearance with no step on the outermost surface.
  • the print layer can be formed by any suitable printing method using any suitable ink or paint.
  • Specific examples of the printing method include gravure printing, offset printing, silk screen printing, and transfer printing from a transfer sheet.
  • the ink or paint used typically includes a binder, a colorant, a solvent and any suitable additive that may be used as needed.
  • the binder include chlorinated polyolefins (for example, chlorinated polyethylene and chlorinated polypropylene), polyester resins, urethane resins, acrylic resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymers, and cellulose resins. ..
  • the binder resin may be used alone or in combination of two or more.
  • the binder resin is a thermosetting resin. Since the thermosetting resin can be used in a smaller amount than the photopolymerizable resin, the amount of the colorant used (colorant content in the colored layer) can be increased.
  • the binder resin is a (meth) acrylic resin, preferably a (meth) acrylic resin containing a polyfunctional monomer (eg, pentaerythritol tri (meth) acrylate) as a copolymerization component.
  • a polyfunctional monomer eg, pentaerythritol tri (meth) acrylate
  • a printed layer having an appropriate elastic modulus can be formed.
  • a step is also formed due to the thickness of the print layer, and the step can effectively function to prevent blocking.
  • any suitable colorant can be used depending on the purpose and the desired color.
  • colorants include inorganic pigments such as titanium white, zinc flower, carbon black, iron black, valve handle, chrome vermilion, ultramarine blue, cobalt blue, yellow lead, and titanium yellow; phthalocyanine blue, induslen blue, and iso.
  • Organic pigments or dyes such as indolinone yellow, benzidine yellow, quinacridone red, polyazo red, perylene red, aniline black; metal pigments composed of scaly foil pieces such as aluminum and brass; scales such as titanium dioxide coated mica and basic lead carbonate. Examples thereof include pearl luster pigments (pearl pigments) composed of shaped foil pieces.
  • a black colored layer carbon black, iron black, and aniline black are preferably used.
  • a colorant in combination. This is because it can absorb visible light over a wide range and evenly to form a non-colored (ie, black) colored layer.
  • azo compounds and / or quinone compounds can be used.
  • the colorant comprises carbon black as a main component and other colorants (eg, azo compounds and / or quinone compounds). According to such a configuration, it is possible to form a colored layer that is not colored and has excellent stability over time.
  • the colorant When forming a black colored layer, the colorant can be used in a ratio of preferably 50 parts by weight to 200 parts by weight with respect to 100 parts by weight of the binder resin.
  • the content ratio of carbon black in the colorant is preferably 80% to 100%.
  • the thickness of the print layer is preferably 3 ⁇ m to 15 ⁇ m. Further, the printed layer has a total light transmittance of preferably 0.01% or less, more preferably 0.008% or less at a thickness of 3 ⁇ m to 15 ⁇ m. When the total light transmittance is in such a range, the non-display area of the image display device can be well concealed without using the bezel.
  • the protective film 40 has a larger heat shrinkage rate in the first direction (typically, the transport direction) and the second direction (typically, the width direction).
  • the heat shrinkage rate (typically, the heat shrinkage rate in the transport direction) is 0.1% or less, preferably 0.08% or less, more preferably 0.06% or less, still more preferably. It is 0.05% or less.
  • Such properties regarding the coefficient of thermal shrinkage in the protective film can be realized by lowering the glass transition temperature or increasing the coefficient of linear expansion.
  • the protective film can be made of any suitable material that can achieve the heat shrinkage as described above.
  • the constituent materials include polyester resins such as polyethylene terephthalate, cycloolefin resins such as norbornene resins, polyamide resins, polycarbonate resins, and copolymer resins thereof.
  • a polyester resin is preferable, and polyethylene terephthalate is more preferable.
  • the thickness of the protective film is preferably 30 ⁇ m to 140 ⁇ m, preferably 35 ⁇ m to 135 ⁇ m. With such a thickness, curling of the film laminate with a print layer can be remarkably suppressed due to a synergistic effect with the above-mentioned characteristics related to the heat shrinkage rate.
  • the protective film includes the base film (resin film) and the pressure-sensitive adhesive layer, and the thickness of the protective film is the total thickness of the base film and the pressure-sensitive adhesive layer.
  • the elastic modulus of the protective film is preferably 2.2 kN / mm 2 to 4.8 kN / mm 2 .
  • the elastic modulus is measured according to JIS K 6781.
  • the tensile elongation of the protective film is preferably 90% to 170%.
  • the tensile elongation is measured in accordance with JIS K6781.
  • a method for manufacturing a film laminate with a print layer is typically to form a hard coat layer on one surface of a base film; on the other surface of the base film. It includes forming a print layer; laminating a protective film on the surface of the hard coat layer; and heating and drying the print layer with the protective film laminated. A typical embodiment of the manufacturing method will be described below.
  • the hard coat layer is typically formed by applying a coating liquid for forming a hard coat layer to form a coating layer, and irradiating the coating layer with active energy rays (for example, ultraviolet rays) to cure the coating layer.
  • the coating liquid for forming a hard coat layer contains the active energy ray-curable (meth) acrylate according to the above item A-3 as a base resin.
  • the coating liquid may further contain any suitable additive depending on the purpose. Additives include, for example, photopolymerization initiators, leveling agents, blocking inhibitors, dispersion stabilizers, rockers, antioxidants, UV absorbers, defoamers, thickeners, dispersants, surfactants, etc. Examples thereof include catalysts, fillers, lubricants, and antistatic agents.
  • the type, combination, content, etc. of the additives contained can be appropriately set according to the purpose and desired characteristics.
  • Active energy ray (e.g., ultraviolet) irradiation amount is, for example, 150mJ / cm 2 ⁇ 400mJ / cm 2.
  • the coating layer may be heated before irradiation with active energy rays.
  • the heating temperature is, for example, 70 ° C to 100 ° C.
  • the heating time is, for example, 1 minute to 4 minutes.
  • the protective film can be typically laminated on the surface of the hard coat layer of the laminate of the base film / hard coat layer by roll-to-roll. As described above, the protective film has the larger heat shrinkage of the heat shrinkage rate in the first direction (typically, the transport direction) and the heat shrinkage rate in the second direction (typically, the width direction).
  • the rate (typically, the heat shrinkage rate in the transport direction) is 0.1% or less, preferably 0.08% or less, more preferably 0.06% or less, still more preferably 0.05. % Or less.
  • the print layer can typically be formed after laminating the protective film. More specifically, the print layer may be formed after the laminate of the base film / hard coat layer / protective film is cut into a predetermined size and shape. As described above, the print layer is formed by gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, or the like. In this way, a film laminate with a print layer can be produced.
  • the final film laminate with a print layer can be obtained. That is, the heat-drying of the print layer is performed in a state where the protective films are laminated. Curling can be remarkably suppressed by heating and drying the print layer in a state where the protective films are laminated.
  • Heat drying is typically performed at 40 ° C. or higher for 20 minutes or longer.
  • the heating temperature is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and even more preferably 70 ° C. or higher.
  • the upper limit of the heating temperature can be, for example, 95 ° C.
  • the heating time is preferably 30 minutes or more, more preferably 40 minutes or more, still more preferably 50 minutes or more, and particularly preferably 60 minutes or more.
  • the upper limit of the heating time can be, for example, 90 minutes. If the heating temperature is too high and / or the heating time is too long, the curl of the film laminate with the print layer becomes large, and / or the film laminate with the print layer softens or melts due to heat and breaks. There is. If the heating temperature is too low and / or the heating time is too short, the print layer may not be sufficiently formed.
  • the process protection film is temporarily attached to the print layer and the surface of the base film of the obtained film laminate with the print layer so as to be peelable.
  • the film laminate with a print layer to which the process protection film is temporarily attached is used for alignment cutting, pre-shipment inspection, and the like.
  • the protective film and the process protective film are peeled off and removed.
  • the protective film is stripped off (substantially at the end) after the process protective film.
  • FIG. 2 is a schematic cross-sectional view of an optical laminate according to one embodiment of the present invention.
  • the optical laminate 200 of the illustrated example has a film laminate 100 with a print layer and an optical film 120.
  • the optical film 120 is arranged on the side opposite to the hard coat layer 20 of the base film 10 in the film laminate 100 with a print layer.
  • the optical film 120 is typically laminated on the film laminate 100 with a print layer via an adhesive layer 140.
  • the adhesive layer is composed of any suitable adhesive or adhesive depending on the purpose.
  • the film laminate 100 with a print layer is as described in item A above.
  • optical film 120 examples include any suitable optical film.
  • the optical film may be a film composed of a single layer or a laminated body.
  • Specific examples of the optical film composed of a single layer include a polarizer and a retardation film.
  • Specific examples of the optical film configured as a laminate include a polarizing plate (typically, a laminate of a polarizing element and a protective film), a conductive film for a touch panel, a surface treatment film, and a single layer thereof.
  • Examples thereof include a laminated body (for example, a circular polarizing plate for antireflection, a polarizing plate with a conductive layer for a touch panel) in which an optical film formed as an optical film and / or an optical film formed as a laminated body is appropriately laminated according to a purpose.
  • a laminated body for example, a circular polarizing plate for antireflection, a polarizing plate with a conductive layer for a touch panel
  • an optical film formed as an optical film and / or an optical film formed as a laminated body is appropriately laminated according to a purpose.
  • the optical laminate 200 can be produced by laminating the optical film 120 on the side opposite to the hard coat layer 20 of the base film 10 in the film laminate 100 with a print layer. After laminating the optical film 120, the protective film 40 is peeled off.
  • an embodiment of the present invention includes an image display device using such a film laminate with a print layer or an optical laminate.
  • the image display device include a liquid crystal display device and an electroluminescence (EL) display device (for example, an organic EL display device and an inorganic EL display device).
  • the image display device typically includes a film laminate with a print layer or an optical laminate on the visual side of the image display cell.
  • the image display device is preferably an organic EL display device.
  • the image display device has a curved shape (substantially a curved display screen) and / or is bendable or bendable. More preferably, the image display device is foldable.
  • the image display device can be manufactured by laminating the optical film 120 and the film laminate 100 with a print layer on the visual side of the image display cell (not shown). After laminating the optical film 120 and the film laminate 100 with a print layer, the protective film 40 is peeled off.
  • the image display device can be manufactured by laminating the optical laminate 200 on the visual side of the image display cell (not shown). After laminating the optical laminate 200, the protective film 40 is peeled off.
  • the measurement method of each characteristic is as follows. (1) Thickness Measured with a micro gauge type thickness gauge manufactured by Mitutoyo. The thickness of the base film / hard coat layer laminate was measured, and the thickness of the hard coat layer was calculated by subtracting the thickness of the base film. (2) Heat Shrinkage Rate of Protective Film The protective film used in Examples and Comparative Examples was cut into sizes of 100 mm in the long direction and 100 mm in the width direction to prepare test samples. The initial dimensions of this test sample were measured using an image measuring machine "QVA606-PRO_AE10" manufactured by Mitutoyo. The test sample was then heated at 70 ° C.
  • Example 1 1.
  • coating liquid for forming hard coat layer 100 parts by mass of ultraviolet curable polyfunctional acrylate (manufactured by Aika Kogyo Co., Ltd., product name "Z-850-16") as base resin, leveling agent (manufactured by DIC Co., Ltd., product name: GRANDIC) PC-4100) 5 parts by mass and 3 parts by mass of a photopolymerization initiator (manufactured by Ciba Japan, trade name: Irgacure 907) are mixed and diluted with methylisobutylketone so that the solid content concentration becomes 50% by mass. To prepare a coating liquid for forming a hard coat layer.
  • ultraviolet curable polyfunctional acrylate manufactured by Aika Kogyo Co., Ltd., product name "Z-850-16
  • leveling agent manufactured by DIC Co., Ltd., product name: GRANDIC
  • a photopolymerization initiator manufactured by Ciba Japan, trade name: Irgacure 907
  • the weight average molecular weight of the acrylic polymer (A) was 600,000, and the Tg was ⁇ 50 ° C.
  • Acrylic polymer (A) solution (30% by weight) is diluted to 20% by weight with ethyl acetate, and an epoxy-based cross-linking agent (Mitsubishi Gas) is used as a cross-linking agent for 100 parts by weight (solid content) of the acrylic polymer in this solution.
  • 11 parts by weight of TETRAD-C) manufactured by Kagaku Co., Ltd. was added, and the mixture was mixed and stirred for about 1 minute at about 25 ° C. to prepare an acrylic pressure-sensitive adhesive composition.
  • the acrylic pressure-sensitive adhesive composition is applied to one side of a polyethylene terephthalate (PET) base material (thickness 110 ⁇ m) and heated at 140 ° C. for 60 seconds to form a pressure-sensitive adhesive layer having a thickness of 20 ⁇ m. A thickness of 130 ⁇ m) was produced. The heat shrinkage of the obtained protective film was 0.04%.
  • PET polyethylene terephthalate
  • the protective film obtained in 1) was laminated by roll-to-roll to prepare a film laminate.
  • the obtained film laminate was cut into sizes of 100 mm in the long direction and 100 mm in the width direction, and black ink was printed on the peripheral edge thereof by gravure printing to form a flat printing layer (black colored layer).
  • the width of the print layer was 12 mm and the thickness was 10 ⁇ m. In this way, a film laminate with a print layer was produced.
  • the formulation of the black ink was as follows: 100 parts of binder resin (acrylic resin: manufactured by Kyoeisha Chemical Co., Ltd., trade name: light acrylate PE-3A), 100 parts of carbon black, solvent for adjusting viscosity ( Methyl ethyl ketone: MEK) 200 parts. These mixtures were subjected to a high dispersion treatment by ultrasonic waves to improve diffusivity.
  • binder resin acrylic resin: manufactured by Kyoeisha Chemical Co., Ltd., trade name: light acrylate PE-3A
  • MEK Methyl ethyl ketone
  • Example 2 A film laminate with a print layer was obtained in the same manner as in Example 1 except that the base film was changed to another transparent polyimide film (manufactured by KOLON, product name “CPITMC_50”, thickness 50 ⁇ m). The obtained film laminate with a print layer was subjected to the same evaluation as in Example 1. The results are shown in Table 1.
  • Example 3 A film laminate with a print layer was obtained in the same manner as in Example 1 except that the thickness of the hard coat layer was 3 ⁇ m. The obtained film laminate with a print layer was subjected to the same evaluation as in Example 1. The results are shown in Table 1.
  • Example 4 A film laminate with a print layer was obtained in the same manner as in Example 1 except that the thickness of the hard coat layer was 8 ⁇ m. The obtained film laminate with a print layer was subjected to the same evaluation as in Example 1. The results are shown in Table 1.
  • Example 5 A film laminate with a print layer was obtained in the same manner as in Example 1 except that the thickness of the hard coat layer was 13 ⁇ m. The obtained film laminate with a print layer was subjected to the same evaluation as in Example 1. The results are shown in Table 1.
  • Example 6> A film laminate with a print layer was obtained in the same manner as in Example 1 except that the thickness of the hard coat layer was 20 ⁇ m. The obtained film laminate with a print layer was subjected to the same evaluation as in Example 1. The results are shown in Table 1.
  • Example 7 A film laminate with a print layer in the same manner as in Example 1 except that the protective film was changed to another polyethylene terephthalate film (manufactured by Nitto Denko Corporation, product name "IP300F", thickness 38 ⁇ m, heat shrinkage rate 0.07%). Got The obtained film laminate with a print layer was subjected to the same evaluation as in Example 1. The results are shown in Table 1.
  • Example 1 A film laminate with a print layer was prepared in the same manner as in Example 1 except that the protective film was changed to a polyethylene film (manufactured by Toray Film Processing Co., Ltd., product name "Tretec 7832C", thickness 30 ⁇ m, heat shrinkage rate 0.87%). Obtained. The obtained film laminate with a print layer was subjected to the same evaluation as in Example 1. The results are shown in Table 1.
  • Example 2 A film laminate with a print layer was prepared in the same manner as in Example 2 except that the protective film was changed to a polyethylene film (manufactured by Toray Film Processing Co., Ltd., product name "Tretec 7832C", thickness 30 ⁇ m, heat shrinkage rate 0.87%). Obtained. The obtained film laminate with a print layer was subjected to the same evaluation as in Example 1. The results are shown in Table 1.
  • the film laminate with a print layer of the present invention can be suitably used as a window film of an image display device.
  • the optical laminate of the present invention can be suitably used as a visible side member of an image display device.
  • Base film 20 Hard coat layer 30 Printing layer 40 Protective film 100 Film laminate with printing layer 120 Optical film 200 Optical laminate

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PCT/JP2020/024373 2019-10-07 2020-06-22 印刷層付フィルム積層体、該印刷層付フィルム積層体を含む光学積層体、およびこれらを用いた画像表示装置 WO2021070424A1 (ja)

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