Non-oriented film

Abstract

To provide a film that can be used for transfer foil, which is applicable to polypropylene resin parts, polyethylene resin parts, and ABS resin that are widely used as automotive exterior parts, and which achieves both formability in low-temperature regions and surface gloss.SOLUTION: There is provided a non-oriented film comprising a B layer, an A layer, and a B layer in that order. The A layer comprises a resin component primarily composed of at least one resin selected from the group consisting of polypropylene-based resins and polyethylene-based resins, and the thickness of the A layer is 10 to 200 μm. The B layer primarily composed of a cycloolefin copolymer, and the thickness of the B layer is 0.1 to 10 μm. The B layer contains at least one type of particles in an amount of 1 to 20 mass % relative to the total mass of the B layer. The value obtained by dividing the thickness of the B layer by the average particle diameter of the particles is 0.1 to 3.0.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a non-oriented film. [Background technology]

[0002] In recent years, as efforts to reduce environmental impact in the manufacturing industry have progressed, there has been a growing trend to reduce or even eliminate paint booths in the automotive exterior process. As an alternative to the spray painting that was previously carried out in paint booths, a decorative method using film is available.

[0003] A known method of decorating three-dimensional automotive parts with this film is to laminate a design layer onto a thermoplastic resin film and transfer a functional layer including the design layer simultaneously with molding. Films containing polyolefin resins have also been proposed for this type of decoration. However, when polyolefin resin films are used for decorative purposes, the quality of the surface appearance is poor, and various attempts have been made to improve and commercialize them.

[0004] For example, Patent Document 1 discloses a design that provides excellent fingerprint wiping properties for product components by applying a laminated film containing a cyclic olefin resin as a main component. Also, Patent Document 2 discloses a film design that contains a cyclic olefin resin and has excellent anti-blocking properties as a film for protecting a transparent film.

[0005] Patent Document 3 discloses a design that achieves both excellent dimensional stability during processing and moldability at high temperatures by using a laminated film in which each layer of the laminated film contains a cyclic olefin resin as the main component. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2016 / 006448 [Patent Document 2] Japanese Patent Publication No. 2020-105285 [Patent Document 3] International Publication No. 2013 / 027547 Summary of the Invention [Problem to be solved by the invention]

[0007] The technology of Patent Document 1 mentioned above does not provide a sufficient surface gloss for automotive exterior parts, which require high gloss. Furthermore, Patent Document 2 provides a high surface smoothness of the film, but it is primarily a protective film for transparent films, and its formability is insufficient for use as a film for molding. The technology of Patent Document 3 is difficult to apply to resin parts that are widely used for automotive exteriors and have a relatively low deformation temperature, and has issues with formability in the low-temperature range.

[0008] Therefore, the problem to be solved by the present invention is to provide a film that can be used for transfer foils that combine low-temperature formability with surface gloss, and that can be applied to polypropylene resin parts, polyethylene resin parts, and ABS resins, which are widely used as exterior parts for automobiles. [Means for solving the problem]

[0009] The present inventors have found that the above problems can be solved mainly by the following configuration. (1) Layer B, Layer A and Layer B in this order; the layer A is mainly composed of a resin component composed of at least one selected from the group consisting of polypropylene-based resins and polyethylene-based resins, The thickness of the layer A is 10 to 200 μm, The layer B is composed mainly of a cycloolefin copolymer, The thickness of the layer B is 0.1 to 10 μm, the layer B contains at least one type of particles in an amount of 1 to 20% by mass based on the entire layer B, A non-oriented film in which the value obtained by dividing the thickness of the layer B by the average particle size of the particles is 0.1 to 3.0. (2) The surface gloss of at least one surface is greater than 50% and less than or equal to 100%, and The non-oriented film according to (1), having a surface roughness Ra of 1 to 500 nm. (3) The tensile elongation at break in the longitudinal direction of the non-oriented film and the tensile elongation at break in the width direction perpendicular to the longitudinal direction of the non-oriented film are both 600 to 1500%, and The non-oriented film according to (1) or (2), wherein the tensile breaking strength of the non-oriented film in the longitudinal direction and the tensile breaking strength of the non-oriented film in the width direction perpendicular to the longitudinal direction are both 1 to 12 N / mm2. (4) The non-oriented film according to any one of (1) to (3), wherein the heat shrinkage rate of the non-oriented film in the longitudinal direction and the heat shrinkage rate of the non-oriented film in the width direction perpendicular to the longitudinal direction are both −1 to 3%. (5) The non-oriented film according to any one of (1) to (4), wherein the surface roughness Ra of the non-oriented film when stretched by 100 to 600% simultaneously in both the longitudinal direction and the width direction perpendicular to the longitudinal direction at a temperature of 80°C or higher and 160°C or lower is 0.01 to 0.50 μm. (6) A film roll comprising the non-oriented film according to any one of (1) to (5), A film roll in which the length of the width direction perpendicular to the longitudinal direction of the non-oriented film is 400 mm or more and 2000 mm or less, and the surface gloss values ​​of the non-oriented film measured continuously over a 1000 m section in the longitudinal direction of the non-oriented film are all within the range of 0.9 to 1.1 times the average surface gloss of the entire non-oriented film. (7) A decorative film having, in this order, the non-oriented film according to any one of (1) to (5), an anchor coat layer, an ink layer, and an adhesive layer, wherein the screen ruling of the ink layer is 133 lines / inch or more and 200 lines / inch or less. (8) A decorative film having, in this order, a non-oriented film, an anchor coat layer, an ink layer, and an adhesive layer provided in the film roll described in (6), and the screen line count of the ink layer is 133 lines / inch or more and 280 lines / inch or less. (9) A decorative transfer foil for automobile exteriors, comprising the decorative film according to (7) or (8). [Effects of the Invention]

[0010] The film of the present invention provides excellent surface appearance for product components when used for decoration, and can achieve good formability that can follow complex three-dimensional shapes, including deep-draw shapes, in various molding methods such as vacuum forming, compressed air forming, press molding, and TOM molding.Therefore, it is possible to provide a film that can be used as a transfer foil that combines formability in the low temperature range with surface gloss, and is applicable to polypropylene resin parts, polyethylene resin parts, and ABS resin, which are widely used as exterior parts for automobiles. DETAILED DESCRIPTION OF THE INVENTION

[0011] It is important that the non-oriented film of the present invention (hereinafter, sometimes simply referred to as the film of the present invention) is non-oriented. By forming the film as a non-oriented film, it is possible to reduce stress when the film is stretched when used as a decorative transfer foil, and excellent moldability is possible even for molded parts that require deep drawing. Here, the term "non-oriented film" refers to a film having a planar orientation coefficient (fn) in the range of 0.00 to 0.05. One way to obtain a film with a planar orientation coefficient (fn) of 0.00 to 0.05 is to use a non-stretched film. Even in the case of non-stretched films, drafting may occur during film formation, causing the film to be slightly oriented in the longitudinal direction. Therefore, in order to achieve a planar orientation coefficient (fn) of 0.00 to 0.05, it is important to suppress orientation even in the case of non-stretching. If the planar orientation coefficient (fn) exceeds 0.05, the formability in the longitudinal direction and the width direction may differ during molding. fn is more preferably in the range of 0.00 to 0.03, and even more preferably in the range of 0.00 to 0.02. The plane orientation coefficient (fn) is a value calculated from the refractive indexes (Nx, Ny, Nz) in the longitudinal, transverse, and thickness directions of the film measured using an Abbe refractometer or the like, using the following formula: Plane orientation coefficient: fn={(Nx+Ny) / 2}-Nz Here, when the longitudinal direction and width direction of the film are unknown, the plane orientation coefficient (fn) can be calculated by defining the direction having the maximum refractive index in the film plane as the longitudinal direction, the direction perpendicular to the longitudinal direction in the film plane as the width direction, and the direction perpendicular to the film plane as the thickness direction. The direction of the maximum refractive index in the film plane may be determined by measuring the refractive index in all in-plane directions using an Abbe refractometer, or by determining the direction as the slow axis direction using, for example, a retardation measurement device (birefringence measurement device).

[0012] The non-oriented film of the present invention has a surface layer (B layer) mainly composed of a cycloolefin copolymer disposed on both sides of an intermediate layer (A layer) mainly composed of a resin component composed of at least one selected from the group consisting of polypropylene-based resins and polyethylene-based resins. That is, the non-oriented film of the present invention has a B layer, an A layer, and a B layer in this order. Furthermore, by using a layer (B layer) mainly composed of a cycloolefin copolymer as the surface layer of the non-oriented film, the surface appearance of the non-oriented film of the present invention is improved. On the other hand, by using a layer mainly composed of at least one resin component selected from the group consisting of polypropylene-based resins and polyethylene-based resins as the intermediate layer (A layer), the formability of the non-oriented film of the present invention is improved. Furthermore, compared to a single-layer film composed of only a cycloolefin copolymer, the production cost is reduced, improving productivity and enabling use in a wide range of applications.

[0013] Here, it is important that the thickness of the intermediate layer (layer A) is 10 to 200 μm. By setting the thickness within this range, it is possible to maintain good handleability when using the non-oriented film of the present invention in molding processes, etc., while imparting good releasability when used as a transfer foil. It is also important that the thickness of the surface layer (layer B) is 0.1 to 14 μm, and that the ratio of this thickness to the average particle size of the particles contained in the surface layer (layer B) (the value obtained by dividing the thickness of the surface layer by the average particle size of the particles) is 0.1 to 3.0. This allows the particles contained in the surface layer to be uniformly dispersed within the surface layer (layer B), making it possible to impart a uniform uneven state to the surface of the film of the present invention, and as a result, the surface gloss of the non-oriented film of the present invention is good.

[0014] From the viewpoints of handling ease and peelability when using the non-oriented film of the present invention as a molding transfer foil, the thickness of the intermediate layer is more preferably 20 to 150 μm, and even more preferably 30 to 120 μm. The thickness of Layer B is more preferably 0.1 to 10 μm, and even more preferably 0.1 to 5 μm.

[0015] Here, "mainly composed of a cycloolefin copolymer" means that the total of all components forming the surface layer (layer B) is 100% by weight, and the cycloolefin monomer-derived component is 50% by weight to 100% by weight. Similarly, "mainly composed of a resin component consisting of at least one resin selected from the group consisting of polypropylene-based resins and polyethylene-based resins" means that the total of all components forming the intermediate layer (layer A) is 100% by weight, and the resin selected from the group consisting of polypropylene-based resins and polyethylene-based resins is 50% by weight to 100% by weight.

[0016] The surface layer (layer B) also contains at least one type of particle, the content of which is 1 to 20% by mass of the entire surface layer (layer B). When the content of the particles in the surface layer (layer B) is 1% by mass or more, the film will have an excellent roll shape when wound into a roll, while when the content is 20% by mass or less, the film will have an excellent roll shape when wound into a roll. From this perspective, the content is preferably 3 to 15% by mass, and more preferably 4 to 10% by mass.

[0017] The cycloolefin copolymer in the present invention may also be a resin obtained by copolymerizing a cycloolefin monomer and a chain olefin monomer. The cycloolefin copolymer is not particularly limited, but from the viewpoint of productivity, a cycloolefin copolymer obtained by copolymerizing norbornene and ethylene with a metallocene catalyst is preferably used.

[0018] The polypropylene resin of the present invention refers to a polymer in which the total amount of ethylene-derived components is 50% by weight or more and 100% by weight or less, based on 100% by weight of the polymer. The polypropylene resin of the present invention refers to a polymer in which the total amount of propylene-derived components is 50% by weight or more and 100% by weight or less, based on 100% by weight of the polymer.

[0019] Furthermore, among polyethylene-based resins and polypropylene-based resins, polyethylene-based resins are preferably used from the viewpoint of compatibility with cycloolefin copolymers, and high-density polyethylene and linear low-density polyethylene are particularly preferably used, with linear low-density polyethylene being most preferably used.

[0020] When the non-oriented film of the present invention is used as a molding transfer foil for automobile exteriors, from the viewpoint of imparting a good appearance and surface gloss to the automobile exterior, the surface gloss of at least one side of the film is preferably greater than 50% and less than 100%, more preferably 70% to 100%, and even more preferably 85% to 100%. If the gloss of the film is 50% or less, when the film of the present invention is used as a molding transfer foil, the surface of the part decorated with the foil cannot be imparted with gloss, and the appearance may be deteriorated. The method for achieving a surface gloss of 50% to 100% in the non-oriented film of the present invention is not particularly limited, but examples include a method in which the resin used as the raw material for the non-oriented film is extruded through a T-die and then cooled and solidified using a pair of metal shaping rolls at 20°C to 60°C and a roll made of a material such as silicone, rubber, or metal. In this case, by setting the surface roughness Ra of the pair of rolls to 0.001 μm or more and 0.1 μm or less, and selecting the temperature setting conditions, film take-up tension, and conveying speed, the gloss of both surfaces of the film of the present invention can be made greater than 50% and less than 100%.

[0021] The film of the present invention is preferably a film having a surface roughness Ra of 1 nm or more and 500 nm or less on at least one side thereof, from the viewpoint of improving the surface design of the product component after a design layer is printed on the film to form a molding transfer foil, the molding transfer foil is transferred to a molding component (adherend), and only the molding film is peeled off. A surface roughness Ra of 500 nm or less is preferable because unevenness does not appear on the design layer provided on the surface of the film of the present invention, improving the surface design of the product component. Furthermore, a film surface roughness Ra of 1 nm or more ensures the surface smoothness of the surface on which the design layer is applied when providing the design layer on the film of the present invention, and prevents wrinkles and other defects from occurring when the film is wound into a roll, thereby maintaining productivity. The surface roughness Ra of the film of the present invention is more preferably 1 nm or more and 400 nm or less, and particularly preferably 1 nm or more and 300 nm or less.

[0022] Furthermore, the non-oriented film of the present invention preferably has a surface gloss of more than 50% and not more than 100% on at least one side of the film, and a surface roughness Ra of 1 to 500 nm. These characteristics provide the non-oriented film of the present invention with superior design properties. In particular, when the non-oriented film of the present invention is used as a transfer foil for molding, it can impart a glossy, shiny, and excellent appearance surface to the molded part.

[0023] In order to allow the film of the present invention to easily conform to the shape of a molded part when used as a molding transfer foil, the film has a longitudinal tensile breaking elongation of 600% or more and a widthwise breaking elongation of 1500% or less in the temperature range of 50°C or more and 200°C or less, which is the temperature range in which the film is used as a molding transfer foil for automotive exteriors to be molded for decorative molding onto exterior parts, and the film has a longitudinal tensile breaking strength of 1 N / mm 2 More than 12N / mm 2 Preferably, the breaking strength is 2 N / mm or less. 2 More than 11M / mm 2 Preferably, 3N / mm 2 More than 10N / mm 2 It is even more preferable if it is less than this.

[0024] In the film of the present invention, the method for adjusting the breaking elongation and breaking strength within the above ranges is not particularly limited, but examples thereof include a method of adjusting the glass transition temperature or molecular weight of the raw materials used in producing the film.

[0025] When forming a design layer on the surface of the film of the present invention, if heating is performed to dry and cure paint, ink, etc., from the viewpoint of improving the dimensional stability and flatness of the film, the heat shrinkage rate of the film of the present invention in the longitudinal direction and in the width direction perpendicular to the longitudinal direction is preferably -1% to 3%, more preferably -1% to 2%, and most preferably -1% to 1%, in the temperature range of 50°C to 130°C, which is the temperature range in which paint, ink, etc. are dried and cured. Here, the longitudinal direction refers to the direction in which the film travels during film production, and the width direction refers to the direction parallel to the film transport plane and perpendicular to the longitudinal direction.

[0026] In the film of the present invention, the method for setting the heat shrinkage rate to between -1% and 3% is not particularly limited, but an example thereof is a method in which the tension applied in the longitudinal direction during film production is reduced while maintaining the film length in the width direction.

[0027] When the film of the present invention is used as a molding transfer foil, from the viewpoint of improving the design of the surface of the product component after transferring the molding transfer foil to a molding component (adherend) and peeling off only the molding film, when the film of the present invention is stretched simultaneously in both the longitudinal direction and the width direction perpendicular to the longitudinal direction by 100% to 600% at a temperature in the range of 80°C to 160°C, the film surface roughness Ra is preferably 0.01 μm to 0.5 μm, more preferably 0.01 μm to 0.4 μm, and most preferably 0.01 μm to 0.3 μm.

[0028] The method for controlling the surface roughness of the stretched film within the above-mentioned range is not particularly limited, but examples include a masterbatch method in which a masterbatch is used in which the film raw materials that form the B layer are pre-compounded, and then diluted, in order to uniformly disperse the particles contained in the surface layer (B layer) of the film of the present invention.

[0029] When a film roll of the present invention having a width direction length of 400 mm to 2000 mm is wound up, and a length of 1000 m is unwound from the film roll in the longitudinal direction and the surface gloss is measured continuously, it is preferable that all values ​​are within the range of 0.9 to 1.1 times the average surface gloss of the entire film of the present invention. When a design layer is formed on the surface of the film of the present invention, by controlling the gloss in the longitudinal direction of the film wound into a roll within the above range, it is possible to impart excellent long-term storage stability to the film of the present invention.

[0030] One method for controlling the surface gloss of a film roll wound with the film of the present invention within the above-mentioned range is to use a cylindrical winding core made of plastic or paper that is less susceptible to expansion and contraction due to temperature and humidity and less deformed by winding pressure.

[0031] When the film of the present invention or a film taken out of the film roll of the present invention is used as a transfer foil for molding, the surface of the film has an anchor coat layer, an ink layer, and an adhesive layer in this order, and the screen ruling when the ink layer is formed by printing is preferably 133 lines / inch or more and 200 lines / inch or less, more preferably 133 lines / inch or more and 175 lines / inch or less. By using such a configuration, the design of a decorative film using the film of the present invention will be more excellent.

[0032] By setting the line count of the ink layer within the above-mentioned range, when a film having an anchor coat layer, an ink layer, and an adhesive layer formed on the surface of the film of the present invention is used as a transfer foil, it is possible to impart excellent design to the decorated product component.

[0033] One method for controlling the line count of the ink layer within the aforementioned range is to use a screen printing machine or offset printing machine with a roll-to-roll transport system to prevent the edges of the film from lifting or bending during printing.

[0034] Furthermore, when a film roll comprising the film of the present invention meets the requirement that the surface gloss measured continuously over a length of 1000 m unwound from the film roll in the longitudinal direction is in the range of 0.9 to 1.1 times the average surface gloss of the entire film of the present invention, it is preferable that the decorative film further meets the requirement that the film roll comprises a non-oriented film, an anchor coat layer, an ink layer, and an adhesive layer in this order, and that the screen line frequency of the ink layer is 175 lines / inch or more and 280 lines / inch or less. Having such characteristics makes the decorative film more stable for long periods of time.

[0035] Furthermore, the decorative film can be suitably used as a decorative transfer foil for automobile exteriors, and it is preferable to use the film of the present invention as a decorative transfer foil for automobile exteriors. [Example]

[0036] The measurement methods commonly used in the present invention will be summarized below.

[0037] (1) Film Thickness and Layer Thickness The film of the present invention or a film taken out of the film roll of the present invention is used as a sample. When measuring the overall thickness of the laminate film, a dial gauge is used to measure the thickness at any five locations on a specimen cut out from the sample, and the average value is used as the film thickness of the sample. When measuring the layer thickness of each layer of the laminate film, a Leica DMLM metallurgical microscope manufactured by Leica Microsystems is used to photograph the cross section of the film under transmitted light at a magnification of 100x, and the layer thickness of each layer of the laminate film is measured at any five locations for each layer, and the average value is used as the layer thickness of each layer of the sample.

[0038] (2) Average particle size The film of the present invention or a film taken from a film roll of the present invention is used as a sample. The cycloolefin copolymer is removed from the sample using a low-temperature plasma ashing method (for example, Yamato Scientific PR-503 model) to expose the particles. The processing conditions are selected so that the cycloolefin copolymer is ashed but the particles are not damaged. The sample is observed using a scanning electron microscope (SEM), and the particle images (light shading caused by the particles) are connected to an image analyzer. The observation location is changed and the following numerical processing is performed on 5,000 or more particles, and the number-average particle diameter D obtained is used as the average particle diameter of the sample. D=ΣD / N Here, D is the equivalent circle diameter of the particle, and N is the number of particles.

[0039] (3) Particle content The film of the present invention or a film taken out of the film roll of the present invention is used as a sample. A solvent that dissolves the cycloolefin copolymer but not the particles is selected, and the particles are separated by centrifugation from the cycloolefin copolymer. The particle content of the sample is determined as the ratio (wt%) of the particles to the total weight. In some cases, infrared spectroscopy may also be used in combination.

[0040] (4) Surface gloss The film of the present invention or a film taken out of a film roll containing the film of the present invention was used as a sample. Based on JIS Z8741 (1997), the surface gloss of the surface (layer B) of the film of the present invention was measured using a digital variable-angle gloss watch UGV-5D manufactured by Suga Test Instruments Co., Ltd., under the condition of an inlet / outlet angle of 60° (unit: %). The same measurement was carried out five times for the same sample, and the average value of the obtained surface gloss values ​​was used as the surface gloss of the sample.

[0041] (5) Surface roughness Ra The film of the present invention or a film taken out of a film roll containing the film of the present invention is used as a sample. The center line average roughness Ra of the sample is measured using a stylus surface roughness meter under the following conditions. The sample is scanned 20 times in the film width direction, and the average value of the obtained results is taken as the surface roughness Ra of the sample. Measurement equipment: Kosaka Laboratory's high-precision thin film step measuring instrument ET-10 ·Stylus tip radius: 0.5μm Stylus load: 5mg ·Measurement length: 1mm Cutoff value: 0.08 mm ·Measurement environment: Temperature 23℃ Humidity 65%RH (6) Tensile elongation and tensile strength The film of the present invention or a film taken out from a film roll containing the film of the present invention was used as a sample. According to JIS K 7127 (1999, test piece type 2), a film strength and elongation measuring device (AMF / RTA-100) manufactured by Orientec Co., Ltd. was used to measure at 100°C. The sample was cut into a size of 15 cm in the measurement direction and 1 cm in the direction perpendicular to the measurement direction, and elongated to an original length of 50 mm at a pulling speed of 300 m / min to measure the tensile breaking elongation (unit: %) and tensile breaking strength (unit: N / mm 2 When measuring the tensile breaking elongation and tensile breaking strength in the longitudinal direction of the film, the sample was prepared so that the longitudinal length was 15 cm, and when measuring the tensile breaking elongation and tensile breaking strength in the width direction of the film, the sample was prepared so that the width direction was 15 cm.

[0042] The same measurement was carried out five times for the same sample, and the average values ​​of the obtained tensile elongation at break and tensile strength at break were taken as the tensile elongation at break and tensile strength at break, respectively, of the sample.

[0043] (7) Heat shrinkage rate The film of the present invention or a film taken from a film roll containing the film of the present invention was used as a sample. To measure the thermal shrinkage in the longitudinal direction, a sample measuring 250 mm in the longitudinal direction and 10 mm in the width direction perpendicular to the longitudinal direction was cut out from the sample, a 200 mm long gauge line was marked on the sample, and a 3 g load was attached to the sample, which was then heat-treated at 80°C for 5 minutes in a hot air circulation oven. The thermal shrinkage of the film in the longitudinal direction was calculated according to the following formula. The same measurement was performed five times on the same sample, and the average of the obtained thermal shrinkage values ​​was used as the thermal shrinkage of the sample in the longitudinal direction.

[0044] When cutting out the sample, the longitudinal direction and the width direction were reversed to obtain the thermal shrinkage rate in the width direction in the same manner.

[0045] (8) Surface gloss of the film in a 1000m section A film was unwound from a film roll having a width of 400 mm or more and 2000 mm or less and a length of 1000 m or more in the longitudinal direction, and the surface gloss of the film was measured at 20 points every 50 m, and the average value was used as the average surface gloss of the roll.

[0046] Rolls where the surface glossiness at all 20 measured points was within the range of 0.9 to 1.1 times the average value were rated as ◯, and rolls where even one point was outside the range were rated as ×.

[0047] (9) Screen ruling A decorative film having an anchor coat layer, an ink layer, and an adhesive layer, in that order, on the surface of the non-oriented film of the present invention is used as a sample. The screen line frequency is measured using a screen line frequency gauge. The screen line frequency gauge is placed on the decorative film, and only the screen line frequency gauge is rotated. A four-cornered diamond appears on the screen line frequency gauge. The line frequency passing through the center of this diamond represents the screen line frequency of the sample. The same measurement was performed five times on the same sample, and the resulting screen line frequency was used as the screen line frequency of that sample.

[0048] (10) Appearance of molded product after decoration with transfer foil The decorative film using the film of the present invention was molded onto a flat plate-shaped part made of ABS resin using the TOM method, and then the non-oriented film was peeled off. After peeling, the part was placed under a fluorescent lamp, and the surface of the anchor coat layer transferred onto the part was observed with the naked eye and the appearance was judged according to the following criteria. The fluorescent light was reflected on the surface of the molded product as if it were a mirror: Yes Depending on the observation angle, slight fluctuations (yellow peel) were observed: × The present invention will be described with reference to the following examples, in which the extrusion rate of the polymer was adjusted to a predetermined value in order to obtain a film of the desired thickness, unless otherwise specified.

[0049] Example 1 The following resins were prepared: Cycloolefin copolymer: Polyplastics Co., Ltd. "TOPAS" (registered trademark) 8007F-04 Polyethylene resin: Prime Polymer's "Evolue" (registered trademark) SP2540 Ethylene-α-olefin elastomer: "ESPRENE" (registered trademark) SPO manufactured by Sumitomo Chemical Particles: Substantially spherical silica particles resulting from colloidal silica.

[0050] The compositions and configurations of Layers A and B were as shown in Table 1. Each resin was fed into a single-screw extruder (L / D = 30), passed through a 400-mesh single-plate filter, and then laminated in a feed block installed above the nozzle so that it formed Layer B / Layer A / Layer B. The resin was then extruded through a slit nozzle heated to 240°C and cast onto a drum (=casting drum, cast drum; CD) heated to 40°C. Hot air was blown onto the non-drum side of the film using an air knife to adhere the film tightly, and the film was molded into a sheet to obtain an unoriented film.

[0051] After corona discharge treatment of the surface of the obtained unoriented film, an anchor coat layer of urethane acrylate resin was formed by screen printing, and then a waterless lithographic printing plate precursor with a screen ruling of 175 lines was attached to an offset printing machine (Komori Sprint 4-color press) to print a red ink layer. Then, "Mold Fit 50" (registered trademark) manufactured by Nichiei Shinka Co., Ltd. was laminated on top of the ink layer. In this way, a decorative film consisting of unoriented film / anchor coat layer / ink layer / adhesive layer was formed.

[0052] Using a TOM molding machine (NGF0406-T, manufactured by Fuse Vacuum Co., Ltd.), the film was set so that the adhesive layer side of the decorative film faced the decorated surface of the part to be decorated, and molding was carried out under the following conditions to produce a decorated molded body. Molding temperature (equipment setting temperature): 80℃ Heater output: 200% for rapid heating, 80% for normal heating Rapid heating time: 10 seconds Vacuum pressure: 0kPa Compressed air pressure: 300kPa Compressed air time: 15 seconds Slight release: 0 seconds (at 0% molding), 2 seconds (at 150% molding) The molded article to be decorated was a flat plate-shaped resin molded article made of ABS resin and measuring 250 mm in length, 100 mm in width, and 3 mm in thickness.

[0053] Next, after peeling off only the non-oriented film from the obtained decorated molding, the surface appearance of the decorated molding was evaluated. As a result, the surface gloss was high and the design was excellent.

[0054] (Examples 2 and 3) A decorative film was produced in the same manner as in Example 1, except that the composition of Layer A, the composition of Layer B, and the lamination ratio of Layer A and Layer B were as shown in Table 1, and parts were decorated using a TOM molding machine. After peeling off only the non-oriented film from the resulting decorated molded body, the surface appearance of the decorated molded body was evaluated, and it was found to have high surface gloss and excellent design.

[0055] Examples 4 to 6 A decorative film was produced in the same manner as in Example 1, except that the composition of Layer A and Layer B, the lamination ratio of Layer A and Layer B, and the polypropylene resin: Prime Polypro (registered trademark) J106 manufactured by Prime Polymer Co., Ltd. were used, as shown in Table 2, and parts were decorated using a TOM molding machine. After peeling off only the non-oriented film from the resulting decorated molded body, the surface appearance of the decorated molded body was evaluated, and it was found to have high surface gloss and excellent design.

[0056] (Comparative Example 1) Layer A composition: Cyclic olefin resin A: 65% by weight of "TOPAS" (registered trademark) 8007F-04 manufactured by Polyplastics Co., Ltd. Cyclic olefin resin B: 30% by weight of "TOPAS" (registered trademark) 6013F-04 manufactured by Polyplastics Co., Ltd. Polyethylene resin: 5% by weight of Prime Polymer's "Evolue" (registered trademark) SP2540 B layer composition: Polyplastics Co., Ltd. "TOPAS" (registered trademark) 8007F-04: 67% by weight, Polyplastics Co., Ltd. "TOPAS" (registered trademark) 6013F-04: 30% by weight, Prime Polymer Co., Ltd. "Evolue" (registered trademark) SP2540: 3% by weight.

[0057] Each resin was fed into a single-screw extruder (L / D = 30), melted at a feed temperature of 230 ° C and then at 240 ° C. After filtering through a leaf disc filter with a filtration accuracy of 30 μm, the mixture was laminated in a feed block installed above the die so that the layer ratio of B / A / B was 15 μm / 70 μm / 15 μm. It was then extruded into a sheet form from a T-die (lip spacing: 0.4 mm) onto a matte metal forming roll (surface roughness Ra: 0.9 μm) temperature-controlled at 40 ° C. The mixture was then nipped with a matte rubber forming roll temperature-controlled at 30 ° C (surface roughness Ra: 1.7 μm, nip pressure: 0.2 MPa) to obtain a molding film with a film thickness of 100 μm. The evaluation results of the obtained molding film and the molding transfer foil and molding parts using it are shown in Table 1. After peeling off only the molding film from the resulting decorated molded body, the surface appearance of the decorated molded body was evaluated, and it was found that the surface gloss was low and the body could not be used as an exterior part for an automobile, etc. As described above, the evaluation results of Comparative Example 1 were different from those of Examples 1 to 3. This is because the molding film of Comparative Example 1 has a cyclic olefin resin as the main component of Layer A and a high glass transition temperature, so when molded at a relatively low temperature such as around 80°C, the film does not conform well to the part and wrinkles easily, and the surface smoothness of the film is insufficient.

[0058] (Comparative Example 2) Using a φ32mm single-screw extruder, a cycloolefin copolymer (Polyplastics Co., Ltd.) cyclic olefin resin and a Septon series styrene elastomer (Kuraray Co., Ltd.) were mixed (screw speed 150 rpm) to a styrene elastomer content of 2% by weight and a styrene content of 60% by weight in the styrene elastomer. The mixture was extruded (extrusion temperature 310°C, output rate 20 kg / hr) through a coat hanger die (300mm width, gap 1.3mm) and wound onto a roll to obtain an 80μm thick protective film. The evaluation results of the resulting film and the molding transfer foil and molding parts using it are shown in Table 1. The film broke during molding, and the design layer could not be transferred satisfactorily to the molded product. As described above, the evaluation results of Comparative Example 2 were different from those of Examples 1 to 3. This is because the molding film of Comparative Example 2 was composed of a high content of cyclic olefin resin, which has a particularly high glass transition temperature, and the elongation of the film was insufficient when molded at a relatively low temperature, such as around 80°C.

[0059] (Comparative Example 3) A layer: Cyclic olefin resin A: 38% by weight of "TOPAS 8007F-04" manufactured by Polyplastics Co., Ltd. Cyclic olefin resin B: 57% by weight of "TOPAS 6013F-04" manufactured by Polyplastics Co., Ltd. Polyethylene resin: 5% by weight of Prime Polymer's "Evolue SP2540" B layer: Cyclic olefin resin A: 30% by weight of "TOPAS 8007F-04" manufactured by Polyplastics Co., Ltd. Cyclic olefin resin B: 69.9% by weight of "TOPAS 6013F-04" manufactured by Polyplastics Co., Ltd. Antioxidant: 0.1% by weight of "Irganox 1010" manufactured by BASF Japan.

[0060] The above composition and configuration were mixed and fed into a single-screw extruder (L / D = 30). The mixture was melted at a temperature of 250°C in the feed section and 260°C thereafter. After passing through a leaf disc filter with a filtration accuracy of 30 μm, the mixture was laminated in a feed block installed above the die to form a layer B / layer A / layer B (lamination thickness: 25 μm / 50 μm / 25 μm). It was then extruded into a sheet form from a T-die (lip spacing: 0.4 mm) onto a mirror-finished drum (surface roughness: 0.2 μs) temperature-controlled at 100°C. The mixture was then nipped with an elastic metal roll (nip pressure: 0.2 MPa) to obtain a molding film with a thickness of 100 μm. The film broke during molding, and the design layer could not be transferred properly to the molded product. As described above, the evaluation results of Comparative Example 3 were different from those of Examples 1 to 3. This is because the molding film of Comparative Example 3 has a structure in which the main component of Layer A is a cyclic olefin resin and has a high glass transition temperature. Therefore, when molding is performed at a relatively low temperature such as around 80°C, the film does not conform well to the part and wrinkles easily occur, and the surface smoothness of the film is insufficient.

[0061] The structures of the non-oriented films of Examples 1 to 3 are shown in Table 1, the structures of the non-oriented films of Examples 4 to 6 are shown in Table 2, the structures of the non-oriented films of Comparative Examples 1 to 3 are shown in Table 3, the properties and evaluation results of the non-oriented films of Examples 1 to 3 are shown in Table 4, the properties and evaluation results of the non-oriented films of Examples 4 to 6 are shown in Table 4, and the properties and evaluation results of the non-oriented films of Comparative Examples 1 to 3 are shown in Table 5.

[0062] [Table 1]

[0063] [Table 2]

[0064] [Table 3]

[0065]

Table 4

[0066]

Table 5

Claims

1. The laminated ... the layer A is mainly composed of a resin component composed of at least one resin selected from the group consisting of polypropylene-based resins and polyethylene-based resins, The thickness of the layer A is 10 to 200 μm, The layer B contains a cycloolefin copolymer as a main component, The thickness of the layer B is 0.1 to 10 μm, the layer B contains at least one type of particles in an amount of 1 to 20% by mass based on the entire layer B, A non-oriented film, wherein the value obtained by dividing the thickness of the layer B by the average particle size of the particles is 0.1 to 3.

0.

2. The surface gloss of at least one surface is greater than 50% and less than 100%, and 2. The non-oriented film according to claim 1, wherein the surface roughness Ra is 1 to 500 nm.

3. The tensile elongation at break in the longitudinal direction of the non-oriented film and the tensile elongation at break in the width direction perpendicular to the longitudinal direction of the non-oriented film are both 600 to 1500%, and The non-oriented film according to claim 1 or 2, wherein the tensile breaking strength in the longitudinal direction of the non-oriented film and the tensile breaking strength in the width direction perpendicular to the longitudinal direction of the non-oriented film are both 1 to 12 N / mm 2.

4. The non-oriented film according to claim 1 or 2, wherein the heat shrinkage rate of the non-oriented film in the longitudinal direction and the heat shrinkage rate of the non-oriented film in the width direction perpendicular to the longitudinal direction are both -1 to 3%.

5. 3. The non-oriented film according to claim 1, wherein the non-oriented film has a surface roughness Ra of 0.01 to 0.50 μm when stretched by 100 to 600% simultaneously in both the longitudinal direction of the non-oriented film and the width direction perpendicular to the longitudinal direction at a temperature of 80° C. or higher and 160° C. or lower.

6. A film roll comprising the non-oriented film according to claim 1 or 2, The length of the non-oriented film in the width direction perpendicular to the longitudinal direction is 400 mm or more and 2000 mm or less, The surface gloss values ​​of the non-oriented film continuously measured in a section of 1000 m in the longitudinal direction of the non-oriented film are all within the range of 0.9 to 1.1 times the average value of the surface gloss of the entire non-oriented film.

7. A non-oriented film according to claim 1 or 2, an anchor coat layer, an ink layer, and an adhesive layer in this order, The decorative film, wherein the screen ruling of the ink layer is 133 lines / inch or more and 280 lines / inch or less.

8. The film roll according to claim 6 has a non-oriented film, an anchor coat layer, an ink layer, and an adhesive layer in this order, The decorative film, wherein the screen ruling of the ink layer is 133 lines / inch or more and 280 lines / inch or less.

9. A decorative transfer foil for automobile exteriors, comprising the decorative film according to claim 7 or 8.

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