Method for manufacturing a film laminate with a printed layer

Abstract

The present invention provides a simple manufacturing method of a film laminate (100) with a printed layer having high pencil hardness and suppressed curling. The manufacturing method of the film laminate with a printed layer of the present invention includes: forming a hard coat layer (20) on one side of a base film (10); forming a printed layer (30) on the other side of the base film; laminating a protective film (40) having a heat shrinkage rate in the conveying direction of 0.1% or less on the surface of the hard coat layer; and heat-drying the printed layer in a state where the protective film is laminated.

Description

TECHNICAL FIELD

[0001] The present application relates to a method for manufacturing a film laminate with a printed layer. BACKGROUND

[0002] As a method for improving the design of various products, a decorative film (film with a printed layer) has been used. For example, as one of the methods for improving the design of an image display device (for example, masking of a non-display region without using a frame for a wiring or the like), it has been proposed to provide a colored layer, a pattern design layer, or a decorative layer or the like in a portion (typically, a peripheral portion) corresponding to a non-display region of a front panel (for example, Patent Documents 1 and 2). However, in order to form a printed layer, long-time heating and drying are required, and as a result, there is a problem that the film with a printed layer is curled.

[0003] PRIOR ART DOCUMENTS

[0004] PATENT DOCUMENTS

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 2011-194799

[0006] Patent Document 2: Japanese Patent Application Laid-Open No. 2017-126003 SUMMARY

[0007] PROBLEMS TO BE SOLVED BY THE INVENTION

[0008] The present application has been achieved in order to solve the above-described conventional problems, and has an object to provide a simple method for manufacturing a film laminate with a printed layer, which has high pencil hardness and in which curling is suppressed.

[0009] MEANS FOR SOLVING THE PROBLEMS

[0010] The method for manufacturing a film laminate with a printed layer of the present application includes:

[0011] forming a hard coat layer on one side of a base film;

[0012] forming a printed layer on the other side of the base film;

[0013] stacking a protective film having a heat shrinkage rate in a stacking direction of 0.1% or less on a surface of the hard coat layer; and

[0014] performing heating and drying on the printed layer in a state in which the protective film is stacked.

[0015] In one embodiment, the heating and drying of the printed layer is performed at 40°C or higher for 20 minutes or more.

[0016] In one embodiment, the protective film is stacked on the hard coat layer surface of the laminate of the base film and the hard coat layer by roll-to-roll.

[0017] In one embodiment, the above-mentioned printed layer is formed after the above-mentioned protective film is laminated.

[0018] In one embodiment, the above-mentioned manufacturing method further includes cutting the laminate of the above-mentioned base film, the above-mentioned hard coat layer and the protective film into a given size and a given shape, between the lamination of the above-mentioned protective film and the formation of the above-mentioned printed layer.

[0019] In one embodiment, the above-mentioned hard coat layer is formed by forming a coating layer by applying a coating liquid for hard coat layer formation containing a (meth)acrylate of active energy ray-curable type, and curing the coating layer by irradiating active energy rays thereto.

[0020] According to another aspect of the present application, there is provided a manufacturing method of an image display device. The manufacturing method includes laminating an optical film and a film laminate with a printed layer obtained by the above-mentioned manufacturing method on a visible side of an image display unit, after laminating the above-mentioned optical film.

[0021] In one embodiment, the above-mentioned manufacturing method includes peeling off the above-mentioned protective film, after laminating the above-mentioned optical film and the above-mentioned film laminate with a printed layer.

[0022] According to another aspect of the present application, there is provided a manufacturing method of an image display device. The manufacturing method includes laminating an optical film and a film laminate with a printed layer obtained by the above-mentioned manufacturing method on a visible side of an image display unit, after laminating the above-mentioned optical film.

[0023] In one embodiment, the above-mentioned manufacturing method includes peeling off the above-mentioned protective film, after laminating the above-mentioned optical film and the above-mentioned film laminate with a printed layer.

[0024] Another image display device of the present application includes laminating the optical laminate obtained by the above-mentioned manufacturing method on a visible side of an image display unit.

[0025] In one embodiment, the above-mentioned manufacturing method includes peeling off the above-mentioned protective film, after laminating the above-mentioned optical laminate.

[0026] Effects of the Invention

[0027] According to the embodiment of the present application, by heating and drying the printed layer in the state that the protective film having a heat shrinkage of a given value or less in a given direction is laminated in the manufacturing method of the film laminate with a printed layer, the film laminate with a printed layer having a high pencil hardness and a curling being suppressed can be easily manufactured. Further, according to the embodiment of the present application, since the protective film is peeled off after laminating the optical film on the side opposite to the hard coat layer of the base film in the film laminate with a printed layer, the base film can be surely laminated to the optical film without a curling. BRIEF DESCRIPTION OF DRAWINGS

[0028] Figure 1 is a cross-sectional view of an optical laminate of a printed film laminate obtained by the manufacturing method of the present embodiment.

[0029] Figure 2 is a cross-sectional view of an optical laminate of a printed film laminate obtained by the manufacturing method of the present embodiment. Figure 1

[0030] Explanation of symbols

[0031] 10 base film

[0032] 20 hard coat layer

[0033] 30 printed layer

[0034] 40 protective film

[0035] 100 printed film laminate

[0036] 120 optical film

[0037] 200 optical laminate DETAILED DESCRIPTION

[0038] Hereinafter, representative embodiments of the present application will be described, but the present application is not limited to these embodiments.

[0039] A. Manufacturing method of printed film laminate

[0040] The manufacturing method of a printed film laminate according to the present embodiment includes: forming a hard coat layer on one side of a base film; forming a printed layer on the other side of the base film; laminating a protective film having a heat shrinkage rate in the conveyance direction of 0.1% or less on the surface of the hard coat layer; and heat-drying the printed layer in a state in which the protective film is laminated.

[0041] A-1. Overall configuration of obtained printed film laminate

[0042] In order to facilitate understanding of the manufacturing method, first, the overall configuration and constituent elements of the printed film laminate obtained by the manufacturing method will be simply described. Figure 1 ​A cross-sectional view of a printed film laminate obtained by the production method of the present application is shown in FIG. 1. The printed film laminate 100 shown in the figure has a base film 10, a hard coat layer 20 formed on one surface of the base film 10, a printed layer 30 formed on the other surface of the base film 10, and a protective film 40 laminated on the surface of the hard coat layer 20. The protective film 40 comprises a base film (resin film) and an adhesive layer. The protective film 40 is laminated on the surface of the hard coat layer 20 in a peelable manner via the adhesive layer. If necessary, a color phase adjusting layer (not shown) can be provided between the base film 10 and the printed layer 30. In actual use, other protective films (sometimes referred to as process protective films, not shown) can be temporarily attached to the printed layer 30 and the surface of the base film 10 in a peelable manner.

[0043] A-2. Base film

[0044] The base film 10 can be composed of any appropriate material. As specific examples of the composition material, the following can be mentioned: polyethylene terephthalate-based resins, polyethylene naphthalate-based resins, acetate-based resins, polyether sulfone-based resins, polycarbonate-based resins, polyamide-based resins, polyimide-based resins, polyamide-imide-based resins, polyolefin-based resins, (meth)acrylic-based resins, polyvinyl chloride-based resins, polyvinylidene chloride-based resins, polystyrene-based resins, polyvinyl alcohol-based resins, polyarylate-based resins, polyphenylene sulfide-based resins, and the like. These resins can be used alone or in combination of two or more. Polyamide-based resins, polyimide-based resins, polyamide-imide-based resins, polyethylene naphthalate-based resins, and polycarbonate-based resins are preferred. The reason is that they are excellent in durability and mechanical strength. Polyimide-based resins are further preferred.

[0045] The base film can contain fine particles incorporated in the above-mentioned composition material. More specifically, the base film can be a so-called nanocomposite film in which fine particles of nanometer scale are dispersed in the matrix of the above-mentioned composition material. If composed in this way, very excellent hardness and scratch resistance can be imparted. The average particle diameter of the fine particles is, for example, about 1 nm to 100 nm. Typically, the fine particles are formed of inorganic oxides. The surface of the fine particles is preferably modified with a given functional group. As the inorganic oxides constituting the fine particles, the following can be mentioned: zirconium oxide, zirconium oxide to which yttrium oxide is added, lead zirconate, strontium titanate, tin titanate, tin oxide, bismuth oxide, niobium oxide, tantalum oxide, potassium tantalate, tungsten oxide, cerium oxide, lanthanum oxide, gallium oxide, and the like, silicon dioxide, aluminum oxide, titanium oxide, zirconium oxide, barium titanate.

[0046] The thickness of the base film is preferably 40 μm to 100 μm, and more preferably 50 μm to 80 μm. If the thickness is in this range, the balance among thinness, handleability, and mechanical strength is excellent.

[0047] The pencil hardness of the base film is preferably B or more, more preferably F or more, and further preferably H or more.

[0048] A-3. Formation of Hard Coat Layer

[0049] Typically, the hard coat layer 20 can be formed by coating a coating liquid for hard coat layer formation to form a coated layer, and irradiating the coated layer with active energy rays (e.g., ultraviolet rays) to cure it. The coating liquid for hard coat layer formation contains an active energy ray-curable (meth)acrylate as a base resin. As the active energy ray-curable (meth)acrylate, for example, ultraviolet ray-curable (meth)acrylate, electron beam-curable (meth)acrylate can be listed. The ultraviolet ray-curable (meth)acrylate is preferred. The reason is that they can efficiently form a hard coat layer by a simple processing operation. The ultraviolet ray-curable (meth)acrylate contains a monomer, an oligomer, a polymer, or the like that is ultraviolet ray-curable. The ultraviolet ray-curable (meth)acrylate includes a monomer component and an oligomer component that have preferably two or more, more preferably three to six, ultraviolet ray-polymerizable functional groups. Typically, a photopolymerization initiator is incorporated in the ultraviolet ray-curable (meth)acrylate. The curing mode can be either a radical polymerization mode or a cationic polymerization mode. In one embodiment, an organic-inorganic hybrid material in which a silica particle, a polysilsesquioxane compound, or the like is incorporated in the (meth)acrylate can be used. The constituent material and the formation method of the hard coat layer are described in, for example, Japanese Patent Application Publication No. 2011-237789. The description of this publication is incorporated herein by reference. Note that, in the present specification, the (meth)acrylate refers to an acrylate and / or a methacrylate.

[0050] A sliding ring material can be incorporated in the ultraviolet-curable (meth)acrylate. By incorporating the sliding ring material, good flexibility can be imparted. As a representative example of the sliding ring material, a polyrotaxane can be cited. Typically, a polyrotaxane has a structure in which a cyclodextrin (CD) ring molecule slides on a straight-chain polyethylene glycol (PEG) main chain. The both ends of the PEG main chain are modified with adamantyl amine to prevent the CD ring molecule from falling off. In the polyrotaxane, the CD ring molecule is preferably chemically modified to be imparted with a radical polymerizable group. In the case of using a sliding ring material, as the ultraviolet-curable (meth)acrylate, it is preferable to use a radical polymerizable monomer having a radical polymerizable group. As the radical polymerizable group, (meth)acryloyl group, (meth)acryloyloxy group, and the like can be cited. The reason is that they are excellent in compatibility with the polyrotaxane, and a variety of materials can be selected. When the polyrotaxane (essentially a polymerizable group of the CD ring molecule) is cured by reacting with the ultraviolet-curable component of the ultraviolet-curable (meth)acrylate, a hard coat layer in which the crosslinking points are movable even after curing can be obtained. As a result, the stress at the time of bending can be mitigated, and the bending durability can be improved. The polyrotaxane and the curing mechanism are described in, for example, Japanese Patent Application Publication No. 2015-155530. The description of this publication is incorporated herein by reference.

[0051] A nanofiber and / or a nanocrystal can be incorporated in the ultraviolet-curable (meth)acrylate. As representative examples of the nanofiber, cellulose nanofiber, chitin nanofiber, chitosan nanofiber can be cited. By incorporating these nanofibers, a hard coat layer excellent in flexibility, pencil hardness, scratch resistance, and wear resistance while maintaining excellent transparency can be obtained. The nanofiber and / or the nanocrystal (total of these in the case of being used in combination) can be incorporated at a ratio of preferably 0.1 to 40% by mass with respect to the entire hard coat layer. The average fiber diameter of the nanofiber is, for example, 1 to 100 nm, and the average fiber length is, for example, 10 to 1000 nm. The hard coat layer containing the nanofiber is described in, for example, Japanese Patent Application Publication No. 2012-131201, Japanese Patent Application Publication No. 2012-171171. The description of these publications is incorporated herein by reference.

[0052] The coating liquid can further contain any appropriate additive as necessary. As the additive, photopolymerization initiator, leveling agent, anti-blocking agent, dispersion stabilizer, thixotropic agent, antioxidant, ultraviolet absorber, defoaming agent, tackifier, dispersant, surfactant, catalyst, filler, lubricant, antistatic agent, and the like can be cited. The kind, combination, content, and the like of the additive contained can be appropriately set according to the purpose, desired properties.

[0053] The amount of irradiation of the active energy ray (for example, ultraviolet ray) (cumulative light amount) is, for example, 150 mJ / cm2 ~ 400 mJ / cm 2 If necessary, the coated layer can be heated before irradiation with active energy rays. The heating temperature is, for example, from 70°C to 100°C. The heating time is, for example, from 1 minute to 4 minutes.

[0054] The thickness of the formed hard coat layer is preferably from 3 μm to 20 μm, more preferably from 3 μm to 15 μm. If the thickness is within such a range, excellent surface hardness and flexibility and / or foldability can be achieved while curling is favorably suppressed.

[0055] A-4. Lamination of the protective film

[0056] Typically, the protective film 40 can be laminated to the surface of the hard coat layer of the laminate of the base material film / hard coat layer by roll-to-roll. The heat shrinkage ratio of the protective film in the first direction and the heat shrinkage ratio in the second direction orthogonal to the first direction, whichever is larger, is 0.1% or less, preferably 0.08% or less, more preferably 0.06% or less, and further preferably 0.05% or less. The smaller the heat shrinkage ratio, the more preferable it is. The lower limit of the heat shrinkage ratio can be, for example, 0.01%. If the heat shrinkage ratio is within such a range, curling of the film laminate with the print layer (particularly, curling caused by heating during formation of the print layer) can be significantly suppressed. The first direction is typically the conveyance direction of the protective film.

[0057] With respect to the heat shrinkage ratio of the protective film, typically, the heat shrinkage ratio in the conveyance direction is larger than the heat shrinkage ratio in the direction orthogonal to the conveyance direction (width direction). The characteristics of the protective film related to such a heat shrinkage ratio can be achieved by lowering the glass transition temperature or by increasing the linear expansion coefficient.

[0058] The protective film can be composed of any appropriate material that can achieve the heat shrinkage ratio as described above. As specific examples of the composition material, polyester-based resins such as polyethylene terephthalate, cycloolefin-based resins such as norbornene-based resins, polyamide-based resins, polycarbonate-based resins, copolymer resins thereof, and the like can be listed. The polyester-based resins are preferred, and polyethylene terephthalate is more preferred.

[0059] The thickness of the protective film is preferably from 30 μm to 140 μm, and preferably from 35 μm to 135 μm. If the thickness is within such a range, based on the synergistic effect of the characteristics related to the heat shrinkage ratio described above, curling of the film laminate with the print layer can be significantly suppressed. Note that the protective film, as described above, includes a base film (resin film) and an adhesive layer, and the thickness of the protective film is the total thickness of the base film and the adhesive layer.

[0060] The elastic modulus of the protective film is preferably from 2.2 kN / mm 2 ~ 4.8 kN / mm 2The elastic modulus of the protective film is preferably in the range of 0.5 to 5 MPa. When the elastic modulus of the protective film is in this range, the curling of the film laminate with the printed layer can be suppressed. Note that the elastic modulus can be measured based on JIS K6781.

[0061] The tensile elongation at break of the protective film is preferably 90 to 170%. When the tensile elongation at break of the protective film is in this range, the film is less likely to break during transport. Note that the tensile elongation at break can be measured based on JIS K6781.

[0062] A-5. Formation of the printed layer

[0063] Typically, the printed layer 30 can be formed after the laminate of the protective film is formed. More specifically, the printed layer can be formed after the laminate of the base film / hard coat layer / protective film is cut to a given size and a given shape. As for the cutting, for example, in the case where the laminate is cut into a rectangle, the laminate can be cut into a rectangle with the length direction (transport direction) of the laminate as the long side direction, or can be cut into a rectangle with the short side direction.

[0064] The printed layer can be formed by any appropriate printing method using any appropriate ink or paint. As specific examples of the printing method, gravure printing, offset printing, screen printing, and transfer printing from a transfer sheet can be given.

[0065] Typically, the ink or paint used contains a binder, a colorant, a solvent, and any appropriate additive that can be used as needed. As the binder, chlorinated polyolefin (e.g., chlorinated polyethylene, chlorinated polypropylene), polyester-based resin, urethane-based resin, acrylic-based resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer, and cellulose-based resin can be given. The binder resin can be used alone or in combination with two or more. In one embodiment, the binder resin is a thermopolymerizable resin. A thermopolymerizable resin requires a smaller amount of use than a photopolymerizable resin, and thus the amount of use of the colorant (the content of the colorant in the colored layer) can be increased. As a result, particularly in the case where a black colored layer is formed, a colored layer with very small total light transmittance and excellent hiding property can be formed. In one embodiment, the binder resin is a (meth)acrylic-based resin, and preferably a (meth)acrylic-based resin containing a multifunctional monomer (e.g., pentaerythritol tri(meth)acrylate) as a copolymerization component. By using a (meth)acrylic-based resin containing a multifunctional monomer as a copolymerization component, a printed layer with an appropriate elastic modulus can be formed. In addition, a height difference due to the thickness of the printed layer is also formed, which can function effectively in terms of anti-blocking.

[0066] As the colorant, any appropriate colorant can be used depending on the purpose and the desired color. As specific examples of the colorant, inorganic pigments such as titanium white, zinc white, carbon black, iron black, red iron oxide, molybdenum chrome red, ultramarine blue, cobalt blue, chrome yellow, titanium yellow, and the like; organic pigments or dyes such as phthalocyanine blue, indanthrone blue, isoindolinone yellow, benzidine yellow, quinacridone red, disazo red, perylene red, aniline black, and the like; metallic pigments including flaky foils of aluminum, brass, and the like; and pearlescent pigments (pearl pigments) including flaky foils of titanium dioxide-coated mica, basic lead carbonate, and the like can be listed. In the case of forming a colored layer that is black, carbon black, iron black, and aniline black can be appropriately used. In this case, it is preferable to use a combination of colorants. The reason for this is that they can form a colored layer that uniformly absorbs visible light in a wide range without color, that is, a completely black colored layer. For example, in addition to the above-described colorants, an azo compound and / or a quinone compound can be used. In one embodiment, the colorant contains carbon black as a main component and another colorant (for example, an azo compound and / or a quinone compound). If such a configuration is adopted, a colored layer that is colorless and has excellent stability over time can be formed. In the case of forming a colored layer that is black, the colorant can be used in a proportion of preferably 50 parts by weight to 200 parts by weight, with respect to 100 parts by weight of the binder resin. In this case, the proportion of carbon black in the colorant is preferably 80% to 100%. By using the colorant (particularly, carbon black) in such a proportion, a colored layer that has a very small total light transmittance and has excellent stability over time can be formed.

[0067] The printed layer formed is a colored layer that is colored by printing depending on the purpose and the desired design. As the color of the printed layer, for example, black, brown, white, dark blue, red, gold, and silver can be listed. The printed layer can be a pattern design layer in which a given design is implemented, or can be a solid colored layer. The printed layer is preferably a solid colored layer, and more preferably a black colored layer. By making the printed layer a black colored layer, the wiring, the terminal, the backlight, and other components can be shielded in the non-display region. That is, the printed layer can function as a shielding layer. The printed layer can be formed in any appropriate pattern corresponding to the purpose. In one embodiment, the printed layer can be formed at a position corresponding to the bezel. If such a configuration is adopted, the non-display region can be shielded without using a bezel, and thus, an image display device that does not use a bezel can be implemented. As a result, an image display device that has excellent appearance without a height difference at the top surface can be provided.

[0068] The thickness of the printed layer formed is preferably 3 μm to 15 μm. Further, the total light transmittance of the printed layer at a thickness of 3 μm to 15 μm is preferably 0.01% or less, and more preferably 0.008% or less. When the total light transmittance is in such a range, the non-display region of the image display device can be well shielded without using a bezel.

[0069] As described above, the film laminate with a printed layer can be produced.

[0070] A-6. Heat drying of the printed layer

[0071] Next, by heat drying the printed layer of the film laminate with a printed layer, a final film laminate with a printed layer can be obtained. That is, the heat drying of the printed layer can be performed in a state where the protective film is laminated. By heat drying the printed layer in a state where the protective film is laminated, curling can be significantly suppressed. Typically, the heat drying is performed at 40°C or higher for 20 minutes or more. The heat temperature is preferably 50°C or higher, more preferably 60°C or higher, and further preferably 70°C or higher. The upper limit of the heat temperature can be, for example, 95°C. The heat time is preferably 30 minutes or more, more preferably 40 minutes or more, further preferably 50 minutes or more, and particularly preferably 60 minutes or more. The upper limit of the heat time can be, for example, 90 minutes. When the heat temperature is too high and / or the heat time is too long, the film laminate with a printed layer can be significantly curled and / or the film laminate with a printed layer can be softened or melted by heat and then broken. When the heat temperature is too low and / or the heat time is too short, the printed layer can not be sufficiently formed.

[0072] A-7. Others

[0073] In practice, the process protective film can be temporarily attached to the printed layer and the substrate film surface of the obtained film laminate with a printed layer in a peelable manner. The film laminate with a printed layer to which the process protective film is temporarily attached can be supplied to an alignment cut, pre-shipment inspection, and the like. In practice, the protective film and the process protective film will be peeled off and removed from the film laminate with a printed layer. Typically, the protective film is peeled off and removed last after the process protective film.

[0074] A-8. Characteristics of the obtained film laminate with a printed layer

[0075] The film laminate with a printed layer has a warpage of 19 mm or less, preferably 15 mm or less, more preferably 10 mm or less, and further preferably 7 mm or less, after being left in an environment of 70°C for 60 minutes. The warpage is more preferably smaller. The lower limit of the warpage can be, for example, 2 mm. According to the embodiment of the present application, the warpage (curling) can be suppressed to a very small level in the film laminate with a printed layer. As a result, the film laminate with a printed layer can be reliably and favorably laminated to an optical film or an image display unit.

[0076] The visual side surface (essentially the hard coat surface) of the film laminate with a printed layer preferably has a pencil hardness of 2H or more, more preferably 3H or more, further preferably 4H or more. When the pencil hardness is in this range, the film laminate with a printed layer can function well as a window film. The pencil hardness can be measured based on JIS K 5400-5-4. Furthermore, the visual side surface has scratch resistance that does not produce a scratch even after reciprocating rubbing of preferably 300 times, more preferably 500 times, further preferably 1000 times under a load of 1000 g. Note that the scratch resistance can be evaluated based on the state of the scratch when a steel wool #0000 is used to rub the surface a given number of times under a given load (e.g., 500 g / cm 2 , 1000 g / cm 2 ).

[0077] The film laminate with a printed layer has a bending property that enables bending of preferably 50,000 times, more preferably 100,000 times, further preferably 200,000 times with a radius of curvature of 3 mm or less (e.g., 3 mm, 2 mm, 1 mm). By providing the film laminate with a printed layer with such a bending property, in the case of applying the film laminate with a printed layer to an image display device, it is possible to realize an image display device that can be bent or folded. The bending property test is performed by bending with the hard coat on the inside. Specifically, the bending property test is performed as follows: the film laminate with a printed layer is cut into a long strip of 100 mm x 20 mm, as a measurement sample, and the measurement sample is set in a tester (CL09-type D01-FMC90, manufactured by Yuasa System Co., Ltd.) so that the hard coat side becomes the inside of the bend, under the following conditions. Evaluation of the bending property can be determined by visually observing the state of peeling of the bent portion of the sample after the test.

[0078] Environmental conditions: 25°C, 55% RH

[0079] Test speed: 60 rpm

[0080] The light transmittance of the film laminate with a printed layer (excluding the printed layer) is preferably 85% or more, more preferably 87% or more, further preferably 90% or more. The haze of the film laminate with a printed layer (excluding the printed layer) is preferably 1.5% or less, more preferably 1.2% or less, further preferably 1.0% or less. When the light transmittance and / or the haze are in this range, in the case of applying the film laminate with a printed layer to an image display device, it is possible to realize good visual recognition.

[0081] The film laminate with a printed layer can be suitably used, for example, as a window film for an image display device, a front panel for an automotive navigation system, a de-dusting cover for a head-up display system.

[0082] B. Optical laminate

[0083] The film laminate with a printed layer can be used to construct an optical laminate by laminating an optical film. Figure 2 is an optical laminate of a film laminate with a printed layer including Figure 1 A cross-sectional schematic view of the optical laminate of the film laminate with a printed layer including

[0084] The film laminate with a printed layer 100 is as described in the above item A.

[0085] As the optical film 120, any appropriate optical film can be given. The optical film can be a film composed of a single layer, or can be a laminate. As specific examples of the optical film composed of a single layer, a polarizing plate, a phase difference film can be given. As specific examples of the optical film composed in the form of a laminate, a polarizing plate (typically, a laminate of a polarizing plate and a protective film), a conductive film for a touch panel, a surface treatment film, and a laminate in which these optical films composed of a single layer and / or optical films composed in the form of a laminate are appropriately laminated according to the purpose (for example, a circularly polarizing plate for anti-reflection, a polarizing plate with a conductive layer for a touch panel) can be given.

[0086] The optical laminate 200 can be produced by laminating the optical film 120 on the opposite side of the substrate film 10 to the hard coat layer 20 in the film laminate with a printed layer 100. After the optical film 120 is laminated, the protective film 40 is peeled off.

[0087] C. Image display device

[0088] The film laminate with a printed layer described in the above item A and the optical laminate described in the above item B can be applied to an image display device. As representative examples of the image display device, a liquid crystal display device, an electroluminescence (EL) display device (for example, an organic EL display device, an inorganic EL display device) can be given. Typically, the image display device has the film laminate with a printed layer or the optical laminate on the visual side of the image display unit. The image display device is preferably an organic EL display device. In one embodiment, the image display device has a curved shape (substantially a curved display screen), and / or is capable of being curved or capable of being bent. More preferably, the image display device is capable of being folded.

[0089] The image display device can be produced by laminating the optical film 120 and the film with a printed layer laminate 100 on the visual side of an image display unit (not shown). After the optical film 120 and the film with a printed layer laminate 100 are laminated, the protective film 40 is peeled off. Alternatively, the image display device can be produced by laminating the optical laminate 200 on the visual side of an image display unit (not shown). After the optical laminate 200 is laminated, the protective film 40 is peeled off.

[0090] Examples

[0091] Hereinafter, the present application will be specifically described by way of examples, but the present application is not limited to these examples. The measuring method of each property is described below.

[0092] (1) Thickness

[0093] The measurement was performed by a micrometer thickness gauge manufactured by Mitsutoyo. The thickness of the laminate of the substrate film / hard coat layer was measured, and the thickness of the substrate film was subtracted, thereby calculating the thickness of the hard coat layer.

[0094] (2) Heat shrinkage of protective film

[0095] The protective film used in the examples and comparative examples was cut out to a size of 100 mm in length and 100 mm in width, and used as a test sample. The initial size of the test sample was measured using an image measuring machine "QVA606-PRO_AE10" manufactured by Mitutoyo G. Next, the size was measured again after the test sample was heated at 70°C for 60 minutes. The heat shrinkage was calculated by the following equation. Note that the size measurement was performed with respect to the size in the direction corresponding to the length direction.

[0096] Heat shrinkage (%) = {(initial size - size after heating) / (initial size)} x 100

[0097] (3) Warpage

[0098] The final (after drying) film with a printed layer laminate obtained in the examples and comparative examples was left on a flat surface, and the height of each of the four corners with respect to the flat surface was measured. The height of the corner having the largest height was taken as the warpage.

[0099] (4) Pencil hardness

[0100] The pencil hardness of the surface of the hard coat layer formed in the examples and comparative examples was measured based on the pencil hardness test of JIS K 5600-5-4 (in which the load was 750 g).

[0101] Example 1

[0102] 1. Preparation of coating liquid for hard coat layer formation

[0103] A hard coat layer forming coating liquid was prepared by mixing 100 parts by mass of an ultraviolet-curable multifunctional acrylate (product name "Z-850-16" manufactured by Aica Kogyo Co., Ltd.) as a base resin, 5 parts by mass of a leveling agent (product name: GRANDIC PC-4100 manufactured by DIC Corporation), and 3 parts by mass of a photopolymerization initiator (product name: IRGACURE 907 manufactured by Ciba Japan Co., Ltd.), and diluting the mixture with methyl isobutyl ketone so that the solid content concentration would be 50% by mass.

[0104] 2. Production of protective film

[0105] An acrylic polymer (A) solution (30% by mass) was prepared by adding 90 parts by mass of butyl acrylate (BA), 10 parts by mass of acrylic acid (AA), and 0.2 parts by mass of 2,2'-azobisisobutyronitrile as a polymerization initiator to a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser, and introducing nitrogen gas while slowly stirring, and performing a polymerization reaction for about 7 hours while maintaining the liquid temperature in the flask at about 63°C. The weight average molecular weight of the acrylic polymer (A) was 600,000, and the Tg was -50°C. The acrylic polymer (A) solution (30% by mass) was diluted to 20% by mass with ethyl acetate, and 11 parts by mass of an epoxy crosslinking agent (TETRAD-C manufactured by Mitsubishi Gas Chemical Co., Inc.) was added as a crosslinking agent with respect to 100 parts by mass of the acrylic polymer (solid content) of the solution, and mixed and stirred for about 1 minute while maintaining the temperature at about 25°C, to prepare an acrylic adhesive composition.

[0106] The above-described acrylic adhesive composition was applied to one side of a polyethylene terephthalate (PET) substrate (thickness: 110 μm), and heated at 140°C for 60 seconds to form an adhesive layer having a thickness of 20 μm, thereby producing a protective film (thickness: 130 μm). The heat shrinkage of the obtained protective film was 0.04%.

[0107] 3. Production of film laminate with printed layer

[0108] A transparent polyimide film (product name "CPITMC_80" manufactured by KOLON Co., Ltd., thickness: 80 μm) was used as a substrate film. While the substrate film was roll-fed, the above-described hard coat layer forming coating liquid was applied to one side of the substrate film to form a coating layer, and the coating layer was heated at 90°C for 2 minutes together with the transparent polyimide film. Next, the coating layer was irradiated with a high-pressure mercury lamp at a cumulative light quantity of 300 mJ / cm 2The hard coat layer was formed by irradiation of ultraviolet rays. The thickness of the formed hard coat layer was 10 μm. Next, the protective film obtained in the above-mentioned 2. was layered on the hard coat layer surface of the substrate film / hard coat layer laminate by roll-to-roll, and a film laminate was produced. The obtained film laminate was cut to a size of 100 mm in length and 100 mm in width, and a black ink was printed on the peripheral portion thereof by gravure printing, and a flat printed layer (black colored layer) was formed. The width of the printed layer was 12 mm, and the thickness was 10 μm. In this way, a film laminate with a printed layer was produced. Note that the prescription of the black ink was as follows: binder resin (acrylic resin: manufactured by Kyoeisha Chemical Co., Ltd., trade name: LIGHT ACRYLATE PE-3A) 100 parts, carbon black 100 parts, solvent (methyl ethyl ketone: MEK) for adjusting viscosity 200 parts. The mixture was subjected to high dispersion treatment using ultrasonic waves, and the dispersibility was improved.

[0109] The obtained film laminate with a printed layer (essentially the printed layer) was dried at 70°C for 60 minutes, and a final film laminate with a printed layer was obtained. The obtained film laminate with a printed layer was subjected to the evaluations of (3) and (4) described above. The results are shown in Table 1.

[0110] <Example 2>

[0111] Drying was performed at 60°C for 50 minutes, and otherwise, a film laminate with a printed layer was obtained in the same manner as in Example 1. The obtained film laminate with a printed layer was subjected to the same evaluation as in Example 1. The results are shown in Table 1.

[0112] <Example 3>

[0113] Drying was performed at 50°C for 40 minutes, and otherwise, a film laminate with a printed layer was obtained in the same manner as in Example 1. The obtained film laminate with a printed layer was subjected to the same evaluation as in Example 1. The results are shown in Table 1.

[0114] <Example 4>

[0115] Drying was performed at 40°C for 30 minutes, and otherwise, a film laminate with a printed layer was obtained in the same manner as in Example 1. The obtained film laminate with a printed layer was subjected to the same evaluation as in Example 1. The results are shown in Table 1.

[0116] <Example 5>

[0117] The substrate film was changed to another transparent polyimide film (manufactured by KOLON, product name "CPITMC_50", thickness 50 μm), and otherwise the same as in Example 1, a film laminate with a printed layer was obtained. The film laminate with a printed layer obtained was subjected to the same evaluation as in Example 1. The results are shown in Table 1.

[0118] Example 6

[0119] The thickness of the hard coat layer was set to 3 μm, and otherwise the same as in Example 1, a film laminate with a printed layer was obtained. The film laminate with a printed layer obtained was subjected to the same evaluation as in Example 1. The results are shown in Table 1.

[0120] Example 7

[0121] The thickness of the hard coat layer was set to 8 μm, and otherwise the same as in Example 1, a film laminate with a printed layer was obtained. The film laminate with a printed layer obtained was subjected to the same evaluation as in Example 1. The results are shown in Table 1.

[0122] Example 8

[0123] The thickness of the hard coat layer was set to 13 μm, and otherwise the same as in Example 1, a film laminate with a printed layer was obtained. The film laminate with a printed layer obtained was subjected to the same evaluation as in Example 1. The results are shown in Table 1.

[0124] Example 9

[0125] The thickness of the hard coat layer was set to 20 μm, and otherwise the same as in Example 1, a film laminate with a printed layer was obtained. The film laminate with a printed layer obtained was subjected to the same evaluation as in Example 1. The results are shown in Table 1.

[0126] Example 10

[0127] The protective film was changed to another polyethylene terephthalate film (manufactured by Nippon Electric Glass Co., Ltd., product name "IP300F", thickness 38 μm, heat shrinkage 0.07%), and otherwise the same as in Example 1, a film laminate with a printed layer was obtained. The film laminate with a printed layer obtained was subjected to the same evaluation as in Example 1. The results are shown in Table 1.

[0128] Comparative Example 1

[0129] A protective film was changed to a polyethylene film (manufactured by Toyobo Film Process Co., Ltd., product name "TORETEC 7832C", thickness 30 μm, heat shrinkage 0.87%), and otherwise, a film laminate with a print layer was obtained in the same manner as in Example 1. The film laminate with a print layer obtained was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0130] <Comparative Example 2>

[0131] A protective film was changed to a polyethylene film (manufactured by Toyobo Film Process Co., Ltd., product name "TORETEC 7832C", thickness 30 μm, heat shrinkage 0.87%), and otherwise, a film laminate with a print layer was obtained in the same manner as in Example 5. The film laminate with a print layer obtained was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0132] <Comparative Example 3>

[0133] A protective film was not laminated, and otherwise, a film laminate with a print layer was obtained in the same manner as in Example 1. The film laminate with a print layer obtained was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0134]

[0135] <Evaluation>

[0136] As is clear from Table 1, the film laminate with a print layer of the Examples of the present application significantly suppressed the amount of warpage (curl) while maintaining high pencil hardness.

[0137] Industrial Applicability

[0138] The film laminate with a print layer of the present application can be suitably used as a window film for an image display device. The optical layer of the present application can be suitably used as a visual side member for an image display device.

Claims

1. A method for manufacturing a film laminate with a printed layer, the method comprising: forming a hard coat layer on one side of a base film; directly forming a printed layer on the other side of the base film; stacking a protective film having a heat shrinkage rate in a stacking direction of 0.1% or less on the surface of the hard coat layer; and heat-drying the printed layer with the protective film stacked thereon, the heat-drying of the printed layer being performed at 40°C or higher for 20 minutes or more, the base film having a thickness of 40 μm to 100 μm, the protective film having a thickness of 35 μm to 140 μm, the hard coat layer having a thickness of 3 μm to 20 μm.

2. The method for manufacturing according to claim 1, wherein the protective film is stacked on the hard coat layer surface of the laminate of the base film and the hard coat layer by roll-to-roll.

3. The method for manufacturing according to claim 1, wherein the printed layer is formed after the protective film is stacked.

4. The method for manufacturing according to claim 3, wherein cutting the laminate of the base film, the hard coat layer and the protective film into a given size and a given shape is further included between the stacking of the protective film and the formation of the printed layer.

5. The method for manufacturing according to claim 1, wherein the hard coat layer is formed by forming a coating layer with a coating solution for forming a hard coat layer containing a (meth)acrylate ester which is curable with active energy rays, and curing the coating layer by irradiating active energy rays thereto.

6. A method for manufacturing an optical laminate, the method comprising: stacking an optical film on the side of the base film of the film laminate with a printed layer obtained by the method for manufacturing according to any one of claims 1 to 5, which is opposite to the hard coat layer.

7. The method for manufacturing according to claim 6, the method comprising: peeling off the protective film after the optical film is stacked.

8. A method for manufacturing an image display device, the method comprising: stacking an optical film and a film laminate with a printed layer obtained by the method for manufacturing according to any one of claims 1 to 5 on the visual side of an image display unit.

9. The method for manufacturing according to claim 8, the method comprising: peeling off the protective film after the optical film and the film laminate with a printed layer are stacked.

10. A method for manufacturing an image display device, the method comprising: stacking an optical laminate obtained by the method for manufacturing according to claim 6 or 7 on the visual side of an image display unit.

11. The method for manufacturing according to claim 10, the method comprising: peeling off the protective film after the optical laminate is stacked.

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