Laminated film, method for producing same, and article

Abstract

Provided is a laminated film that combines excellent designability with high air permeability. This laminated film includes, in the following order, a protective film (C), a clear layer (B), a base material layer (A), a pressure-sensitive adhesive layer (D), and a release liner (E). The protective film (C) has a surface development area ratio (Sdr) of a surface in contact with the clear layer (B) of less than 2.8 * 10 ^ (-3). The release liner (E) includes a support base material made of a thermoplastic resin and has an uneven shape having ridge-like protrusions continuously arranged in a lattice shape from one end to the other end on a surface in contact with the pressure-sensitive adhesive layer (D). In the uneven shape, an average protrusion pitch is 50-320 μm, and an average protrusion height is 10-20 μm.

Description

Laminated film, its manufacturing method, and article

[0001] The present invention relates to a laminated film, a method for producing the same, and an article.

[0002] Paint-replacement adhesive sheets, decorative adhesive sheets, surface-protecting adhesive sheets, etc., which are attached to the exteriors of vehicles such as automobiles and motorcycles, or to building materials for housing, generally require a relatively large application area and are required to have an aesthetically pleasing appearance. Therefore, a known technology involves forming grooves on the surface of the adhesive layer, and using these grooves to form circulation paths for releasing fluid (typically gas such as air) to the outside when the adhesive sheet is attached to an adherend, thereby preventing gas trapped during the attachment from remaining as bubbles and degrading the appearance quality.

[0003] One preferred method for forming grooves on the surface of a pressure-sensitive adhesive layer is to form a groove pattern in a release liner that protects the pressure-sensitive adhesive layer until the pressure-sensitive adhesive sheet is used (when attached to an adherend), and then transfer this groove pattern to the pressure-sensitive adhesive layer (e.g., Patent Document 1).

[0004] However, the uneven shape of the release liner may be visually recognized as standing out on the surface of the PSA sheet, which is undesirable because it may impair the design properties such as image clarity.

[0005] Patent Document 2 discloses a PSA sheet having a base layer, a pressure-sensitive adhesive layer, and a release liner in this order in the lamination direction, with a concave-convex shape formed on the surface of the release liner facing the pressure-sensitive adhesive layer, wherein one surface facing the base layer has a 60-degree specular gloss of 30% or less as measured in accordance with JIS Z 8741. This is because the gloss of the surface facing the base layer is reduced to prevent the concave-convex shape from protruding to the surface, and therefore cannot be used to obtain a characteristic high-gloss appearance.

[0006] Japanese Patent No. 5244072 JP 2022-43551 A

[0007] In view of the above, an object of the present invention is to provide a laminated film that combines excellent design and high air release properties.

[0008] The present invention relates to a laminated film comprising, in order, a protective film (C), a clear layer (B), a base layer (A), an adhesive layer (D), and a release liner (E), wherein the protective film (C) has a surface developed area ratio (Sdr) of less than 2.8*10^(-3) on the side in contact with the clear layer (B), and the release liner (E) includes a supporting base made of a thermoplastic resin, and the surface on the side in contact with the adhesive layer (D) has an uneven shape with ridge-like protrusions that are continuously connected from one end to the other end in a lattice pattern, and the uneven shape has an average protrusion pitch of 50 μm or more and 320 μm or less and an average protrusion height of 10 μm or more and 20 μm or less.

[0009] The protective film (C) preferably has a surface developed area ratio (Sdr) of less than 2.0*10^(-3) on the surface in contact with the clear layer (B).

[0010] The clear layer (B) preferably has a surface developed area ratio (Sdr) of less than 2.0*10^(-3) on the surface in contact with the protective film (C). The protective film (C) preferably has an average thickness of 25 μm or more and 100 μm or less. The protective film (C) preferably contains polyethylene terephthalate. The release liner (E) preferably has a surface developed area ratio (Sdr) of 2.0*10^(-3) or more on the surface not in contact with the adhesive layer (D).

[0011] The release liner (E) comprises a support substrate and a resin layer formed of a polyolefin resin composition on at least the surface of the support substrate facing the pressure-sensitive adhesive layer (D), and the resin layer is preferably subjected to a release treatment with a silicone-based release agent. The laminated film may further include a design layer (F).

[0012] The present invention also relates to the method for producing the laminate film described above, which comprises a step (I) of pressing a protective film (C) or a base layer (A) onto the clear layer (B) in a state where the clear layer (B) is not completely cured, and then completely curing the clear layer (B). The method for producing the laminate film preferably further comprises a step (II) of forming an adhesive layer (D) on the uneven surface of the release liner (E) and laminating the adhesive layer (D) onto the side of the base layer (A) opposite to the side on which the clear layer (B) is formed.

[0013] The present invention also relates to an article comprising the above-mentioned laminated film attached to an adherend. The adherend may be an automobile body or an automobile part.

[0014] According to the present invention, by providing a specific uneven shape in the adhesive layer, it is possible to obtain a laminated film having excellent design properties, in which the uneven shape is difficult to see from the front side even when it is highly glossy, while having high air release properties.

[0015] 1 is a diagram showing the layer structure of a laminate film according to the present invention. 2 is a diagram showing the layer structure of a laminate film according to the present invention.

[0016] The present invention will be described in detail below. When large irregularities are provided in a laminated film to provide sufficient air release properties, the irregularities are visible, leading to a deterioration in appearance. On the other hand, when the irregularities are made small to maintain the appearance, the air release properties are insufficient, resulting in swelling of the film surface and other inconveniences during application. In particular, when the front side has a very high gloss, such as 85 / 60° gloss or higher, the irregularities tend to rise to the surface of the film and be visible from the front side, or the shape of the adhesive layer is deformed and visible by finger pressure from the front side, making it difficult to ensure good air release properties.

[0017] By specifying a concave-convex shape that can achieve both excellent air release properties and design, the present invention has led to the completion of a laminated film that is highly glossy but does not reduce appearance quality and is also easy to apply.

[0018] The laminate film of the present invention will be described in detail below. (Layer structure) The laminate film of the present invention comprises, in order, a protective film (C), a clear layer (B), a substrate layer (A), an adhesive layer (D), and a release liner (E) (see FIG. 1). A film having this structure is adhered to an adherend to form a layer. Thereafter, the protective film (C) may be peeled off. Alternatively, the protective film (C) may be peeled off before adhering to the adherend.

[0019] Furthermore, the laminate film of the present invention may include a design layer (F), an adhesive layer, etc., as necessary. When the design layer (F) is included, it may be located between the clear layer (B) and the substrate layer (A) (see FIG. 2). Furthermore, the design layer (F) may be located between the substrate layer (A) and the adhesive layer (D). Each layer constituting the laminate film of the present invention will be described in detail below.

[0020] (Release Liner (E)) The release liner (E) is releasably disposed on the surface of the adhesive layer. The release liner may be configured, for example, as a structure including a support substrate, preferably a structure having a resin layer on the support substrate and the adhesive layer side surface of the support substrate, and more preferably a three-layer structure having a resin layer on the back side surface as well. Furthermore, an intermediate layer may be disposed between each layer as necessary.

[0021] When the laminated film has a high gloss, if paper is used as the support substrate, the texture of the paper may appear on the surface. For this reason, a support substrate made of a thermoplastic resin is preferred. The thermoplastic resin is not particularly limited, and examples thereof include plastic films such as polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyolefin films such as polypropylene and polyethylene. Among these, a polyethylene terephthalate film is preferred as the support substrate due to its high bending rigidity. Polyethylene terephthalate films are preferably biaxially stretched because they are less likely to shrink and have high bending rigidity. Furthermore, polyethylene terephthalate films can be produced by producing an unstretched resin film using a known method such as T-die extrusion molding, followed by known methods such as sequential biaxial stretching and simultaneous biaxial stretching.

[0022] The resin layers on the pressure-sensitive adhesive layer side surface and the back surface side surface are not particularly limited, and can be applied in layer form, for example, by applying a polyolefin-based resin composition in a heated and molten state. The polyolefin-based resin compositions forming the resin layers on the pressure-sensitive adhesive layer side surface and the back surface side surface may be the same or different, but are preferably the same.

[0023] The polyolefin resin composition may be, for example, a polypropylene resin (PP resin) composition using a propylene polymer as the base polymer. The term "propylene polymer" encompasses a homopolymer of propylene (homopolypropylene, typically isotactic polypropylene), a copolymer of propylene with another olefin (e.g., one or more α-olefins having 2, 4 to 10 carbon atoms), and a copolymer of propylene with another olefin and / or a monomer other than an olefin. The copolymer may be a random copolymer (random polypropylene) or a block copolymer. The polyolefin resin composition may also be a PP resin composition containing two or more propylene polymers in any proportion (e.g., a combination of homopolypropylene and random polypropylene, a combination of two random polypropylenes with different copolymerization compositions, etc.).

[0024] The polyolefin resin composition may also be a polyethylene resin (PE resin) composition having an ethylene polymer as the base polymer. The ethylene polymer may be a homopolymer of ethylene, a copolymer of ethylene and another olefin (e.g., one or more α-olefins having 3 to 10 carbon atoms), or a copolymer of ethylene and another olefin and / or a monomer other than an olefin (e.g., one or more ethylenically unsaturated monomers selected from vinyl acetate, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, etc.). The ethylene polymer may be any of so-called low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), etc.

[0025] The polyolefin resin composition may contain, as needed, various components generally known as additives for polyolefin resin compositions, provided that the effects of the present invention are not significantly impaired. Examples of such components include antioxidants, neutralizing agents, heat stabilizers, light stabilizers, ultraviolet absorbers, antistatic agents, slip agents, antiblocking agents, colorants (pigments, dyes, etc.). For example, TiO ２ The PP composition may have a composition containing a pigment such as the above in a proportion of about 5 to 20 parts by mass.

[0026] The resin layer on the adhesive layer side of the release liner is preferably treated with a release agent. The release agent (also referred to as a release agent) may be any of various conventionally known release agents, such as silicone-based release agents, fluorine-based release agents, long-chain alkyl-based release agents, fatty acid amide-based release agents, and silica powder. A preferred release agent for the present invention is a thermosetting silicone-based release agent. While both addition-curing and condensation-curing types of thermosetting silicone-based release agents can be used, addition-curing silicone-based release agents are preferred. In this type of release agent, a platinum (Pt) catalyst or a rhodium (Rh) catalyst is generally used as the curing catalyst. From the viewpoint of ease of curing, etc., a platinum catalyst is usually more preferably used.

[0027] The release liner has an uneven shape on the surface of the adhesive layer (the surface in contact with the adhesive layer). By laminating this release liner to the adhesive layer, the uneven shape of the release liner is transferred to the adhesive layer. In the present invention, the uneven shape has a lattice-like shape of ridge-like protrusions that are continuously connected from one end of the film to the other end, and is characterized in that the average protrusion pitch is 50 μm or more and 320 μm or less and the average protrusion height is 10 μm or more and 20 μm or less.

[0028] In the above-mentioned uneven shape, if the average protrusion pitch is less than 50 μm, it is difficult to form a film, and if it exceeds 320 μm, the uneven shape is visually recognized and is judged to be poor in appearance. The above-mentioned average protrusion pitch is preferably 100 μm or more and 300 μm or less.

[0029] In the uneven shape, if the average protrusion height is less than 10 μm, sufficient air release properties cannot be obtained. On the other hand, if the average protrusion height exceeds 20 μm, the grooves in the adhesive layer become large, and when finger pressure is applied from the front side, the shape of the adhesive layer is deformed and becomes visible. The average protrusion height is preferably 12 μm or more and 18 μm or less.

[0030] The uneven protrusions are measured by the following method. A laser microscope VK-X3100 (a non-contact three-dimensional surface shape measuring device manufactured by KEYENCE) with a 10x objective lens is used to calculate the height difference and the distance between the protrusion tips using a line roughness profile. The height difference is measured at 10 locations, and the number average value is taken as the average protrusion height. The distance between the protrusion tips is measured at 10 locations, and the number average value is taken as the average protrusion pitch.

[0031] The uneven shape when the release liner is viewed in plan is preferably continuous from one side to the other side of the release liner. The various shapes that can be taken as unevenness when the release liner is viewed in plan may be present regularly or irregularly, but are preferably present regularly in a pattern such as parallel lines or a lattice.

[0032] The cross-sectional shape of the unevenness when cut in the thickness direction cannot be generally specified because it may vary depending on the cut surface, but examples include polygons such as triangles and quadrilaterals (including rectangles, squares, and trapezoids); shapes in which some or all of the corners of the polygon are slightly rounded; semicircular shapes such as semi-circles, semi-ellipses, and U-shapes; and the like.

[0033] The uneven shape can be formed, for example, by pressing an embossing roll against the resin layer on the adhesive layer side surface and transferring the shape engraved on the circumferential surface of the embossing roll to the surface of the layer. Alternatively, the uneven shape can be formed on a pre-formed layer using the same material as the layer by using a printing technique such as screen printing.

[0034] (Adhesive Layer (D)) The adhesive layer has a function of adhering the laminated film to an object to be decorated. The adhesive layer is not particularly limited, and conventionally known adhesive layers, double-sided tapes, and adhesives can be used.

[0035] Examples of adhesives that form the adhesive layer include polyester urethane resin, acrylic urethane resin, acrylic resin, and silicone resin.

[0036] From the viewpoint of ensuring the adhesiveness of the adhesive layer to the object and exhibiting a peeling force that enables peeling as needed, the adhesive layer preferably contains an acrylic resin and an isocyanate compound.

[0037] From the viewpoint of ensuring adhesion of the adhesive layer to the object and exhibiting a peeling force that enables peeling as needed, it is preferable that the peeling force of the adhesive layer from the object be 4.0 N to 25.0 N / 25 mm.

[0038] The adhesive layer is laminated on the uneven surface of the release liner. The thickness of the adhesive layer is not particularly limited, but in order to stably laminate the adhesive layer and the base layer (A) and to obtain sufficient adhesion, the dry film thickness is preferably the height of the projections of the uneven surface + 4 μm or more.

[0039] The adhesive layer may be a commercially available product, such as "SK Dyne (registered trademark)" manufactured by Soken Chemical & Engineering Co., Ltd. or "NS-S9T5" manufactured by Toyobo Co., Ltd.

[0040] (Substrate Layer (A)) The substrate layer (A) is a member that functions as a substrate for the clear layer, adhesive layer and any design layer of the laminated film.

[0041] The substrate layer (A) is not particularly limited, and a conventionally known resin substrate can be used. Examples of the resin substrate include polyolefin film, modified polyolefin film, polyester film, polystyrene resin film, polyurethane film, urethane nylon film, polyamide film, polyvinyl chloride film, polyvinylidene chloride film, polymethylpentene film, and acrylic film. The resin substrate is preferably a thermoplastic polyurethane resin (TPU) film.

[0042] The resin substrate may be a commercially available product. Examples of commercially available resin substrates include Unitika Ltd.'s trade name "Unipeel (registered trademark)", Toray Industries, Inc.'s trade name "Lumirror (registered trademark) S-10", Teijin Film Solutions Ltd.'s trade name "Purex A54", Nippa Corporation's trade name "PET Separator TF-535", Fujimori Industries Co., Ltd.'s trade name "Filmbyna (registered trademark) NT-2", Toray Film Processing Co., Ltd.'s trade name "Cerapeel WZS", Toyo Cross Co., Ltd.'s trade names "SP4030", "SP4035", Aim Co., Ltd.'s trade name "RF1 CS006", Nippon Matai Co., Ltd.'s trade name "PET238", "Esmar URS PX98#", Okura Industries Co., Ltd.'s trade name "Silkron SNY-90", and Seedam Co., Ltd.'s trade name "SHG2393".

[0043] The thickness of the substrate layer (A) may be adjusted as appropriate, and is, for example, 25 to 300 μm, preferably 50 to 200 μm, and particularly preferably 80 to 150 μm.

[0044] The substrate layer (A) may be subjected to a surface modification treatment such as a corona treatment or a low-temperature plasma treatment, and may also contain additives such as an antistatic agent and an ultraviolet protection agent.

[0045] (Clear layer (B)) The clear layer is a coating film of a paint for a clear layer, and has the function of protecting the laminate film after removing the protective film (C). As the clear layer, a clear layer of a conventionally known top coat coating film for an automobile or a clear layer of a decorative laminate can be used.

[0046] The clear layer may be formed using a conventional clear layer paint, which may contain, for example, a resin component and a solvent.

[0047] Examples of resin components of the clear layer paint include acrylic resins, polyester resins, alkyd resins, fluororesins, epoxy resins, polyurethane resins, polyether resins, and polyolefin resins. Examples of resin components that may be used include hydroxyl group-containing acrylic resins (c-1), non-aqueous dispersion-type acrylic resins (c-2), diol resins (c-3), and polyisocyanate compounds (c-4) described in JP 2020-100783 A. Examples of resin components that may be used include polyurethane acrylates (B1) described in JP 2015-145103 A and urethane resins (D1) described in JP 2017-007109 A.

[0048] In one embodiment, the resin component of the clear layer coating material includes a thermosetting resin. In another embodiment, the resin component of the clear layer coating material includes a thermosetting resin and a photocurable resin. In yet another embodiment, the resin component of the clear layer coating material is only a thermosetting resin.

[0049] From the viewpoint of performance such as weather resistance, the resin component of the clear layer paint is preferably an acrylic resin, and the clear layer paint preferably contains a mixture of a resin component and an isocyanate compound.

[0050] The weight average molecular weight of the acrylic resin in the clear layer coating is, for example, 1,000 to 200,000, and preferably 3,000 to 100,000.

[0051] The glass transition temperature (Tg) of the acrylic resin of the clear layer paint is, for example, 10 to 100° C., and preferably 20 to 60° C. In one embodiment, the Tg of the acrylic resin of the clear layer paint is 20° C. or higher, 30° C. or higher, 40° C. or higher, or 50° C. or higher. In another embodiment, the Tg of the acrylic resin of the clear layer paint is 60° C. or lower, 50° C. or lower, 40° C. or lower, or 30° C. or lower.

[0052] The solid content of the acrylic resin in the clear layer paint solids is, for example, 30% by mass or more, preferably 40 to 70% by mass. In one embodiment, the solid content of the acrylic resin in the clear layer paint is 40% by mass or more, 50% by mass or more, or 60% by mass or more. In another embodiment, the solid content of the acrylic resin in the clear layer paint is 70% by mass or less, 60% by mass or less, 50% by mass or less, or 40% by mass or less.

[0053] The SP value of the acrylic resin in the clear layer coating material is, for example, 8.00 to 11.50, and preferably 9.50 to 10.80. In one embodiment, the SP value of the acrylic resin in the coating material for the clear layer is 8.00 or more, 8.10 or more, 8.20 or more, 8.30 or more, 8.40 or more, 8.50 or more, 8.60 or more, 8.70 or more, 8.80 or more, 8.90 or more, 9.00 or more, 9.10 or more, 9.20 or more, 9.30 or more, 9.40 or more, 9.50 or more, 9.60 or more, 9.70 or more, 9.80 or more, 9.90 or more, 10.00 or more, 10.10 or more, 10.20 or more, 10.30 or more, 10.40 or more, 10.50 or more, 10.60 or more, 10.70 or more, 10.80 or more, 10.90 or more, 11.00 or more, 11.10 or more, 11.20 or more, 11.30 or more, or 11.40 or more. In another embodiment, the SP value of the acrylic resin in the coating material for the clear layer is 11.50 or less, 11.40 or less, 11.30 or less, 11.20 or less, 11.10 or less, 11.00 or less, 10.90 or less, 10.80 or less, 10.70 or less, 10.60 or less, 10.50 or less, 10.40 or less, 10.30 or less, 10.20 or less, 10.10 or less, 10.00 or less, 9.90 or less, 9.80 or less, 9.70 or less, 9.60 or less, 9.50 or less, 9.40 or less, 9.30 or less, 9.20 or less, 9.10 or less, 9.00 or less, 8.90 or less, 8.80 or less, 8.70 or less, 8.60 or less, 8.50 or less, 8.40 or less, 8.30 or less, 8.20 or less, or 8.10 or less. When a mixture of multiple acrylic resins is used, the SP value refers to the weighted average SP value calculated based on the SP values ​​of the individual acrylic resins and their blending ratios.

[0054] The isocyanate compound used in the clear layer coating material is not particularly limited as long as it is a compound having one or more isocyanate groups. For example, known isocyanates such as monoisocyanates having one isocyanate group and polyisocyanates having two or more isocyanate groups, or isocyanate-based curing agents can be used.

[0055] Examples of monoisocyanates include methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, lauryl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, and tolylene isocyanate.

[0056] Examples of polyisocyanates include aromatic isocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, and metaxylylene diisocyanate; aliphatic isocyanates such as hexamethylene diisocyanate; alicyclic isocyanates such as isophorone diisocyanate; and monomers thereof and multimers thereof such as biuret type, nurate type, and adduct type. Of these, from the viewpoint of ensuring stretchability after curing, it is preferable to use HDI nurate type and allophanate type.

[0057] Commercially available products include R-271 (Nippon Paint Automotive Coatings), Crossnate UV (Dainichiseika Color & Chemicals Mfg. Co., Ltd.), D-178N (Mitsui Chemicals), and Sumidur N-3400 (Sumitomo Bayer Urethane).

[0058] The isocyanate compound may be a blocked isocyanate compound in which the isocyanate group is blocked with a blocking agent, which suppresses the reactivity of the isocyanate, improves storage stability, and makes it easier to handle during the reaction process.

[0059] Examples of the sealant include monohydric alkyl alcohols and aromatic alcohols such as n-butanol, n-hexyl alcohol, 2-ethylhexanol, lauryl alcohol, phenol carbinol, and methylphenyl carbinol; cellosolves such as ethylene glycol monohexyl ether and ethylene glycol mono-2-ethylhexyl ether; polyether-type both-terminal diols such as polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol phenol; diols such as ethylene glycol, propylene glycol, and 1,4-butanediol; polyester-type both-terminal polyols obtained from dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, suberic acid, and sebacic acid; phenols such as para-t-butylphenol and cresol; oximes such as dimethyl ketoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, methyl amyl ketoxime, and cyclohexanone oxime; and lactams represented by ε-caprolactam and γ-butyrolactam.

[0060] Commercially available blocked isocyanate compounds include, for example, products manufactured by Asahi Kasei Corporation under the trade names "Duranate 17B-60PX" and "TPA-B80E."

[0061] The resin component of the clear layer coating material may be used alone or in combination of two or more.

[0062] The amount of the resin component in the clear layer coating may be adjusted as appropriate, for example, from 10 to 80% by mass, preferably from 20 to 60% by mass, based on the total mass of the clear layer coating including the solvent.

[0063] Examples of the solvent for the clear layer coating material include water and organic solvents. Examples of the organic solvent include alcohols such as methanol, ethanol, 2-propanol, and 1-butanol; esters such as ethyl acetate, butyl acetate, isobutyl acetate, ethyl propionate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; ethers such as diethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, dioxane, and tetrahydrofuran (THF); and ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol. Examples of suitable solvents include glycols such as ethanol, 1,3-butylene glycol, pentamethylene glycol, and 1,3-octylene glycol; amides such as formamide, N-methylformamide, dimethylformamide (DMF), dimethylacetamide, dimethylsulfoxide (DMSO), and N-methylpyrrolidone (NMP); ketones such as acetone, methyl ethyl ketone (MEK), methyl propyl ketone, methyl isobutyl ketone, acetylacetone, and cyclohexanone; aliphatic hydrocarbons such as mineral spirits and kerosene; aromatic hydrocarbons such as toluene, xylene, mesitylene, and dodecylbenzene; and halogenated solvents such as chloroform and dichloromethylene. These solvents may be used alone or in combination of two or more.

[0064] The clear layer paint may be either a water-based paint or a solvent-based paint. In the present invention, a paint in which the dispersion medium contained in the largest amount in water is called a water-based paint, while a paint in which the dispersion medium contained in the largest amount in a solvent is called a solvent-based paint.

[0065] In addition to the resin component and solvent, the clear layer coating material may contain conventionally known additives used in clear layer coating materials, such as ultraviolet absorbers, light stabilizers, crosslinking agents, curing agents, pigments, surface conditioners, antifoaming agents, conductive fillers, hindered amine light stabilizers, antioxidants, and catalysts.

[0066] The viscosity of the clear layer paint may be adjusted appropriately and is, for example, 5 to 5,000 mPa·s, preferably 10 to 1,000 mPa·s. In one embodiment, the viscosity of the clear layer paint is 10 mPa·s or more, 30 mPa·s or more, 50 mPa·s or more, 200 mPa·s or more, or 500 mPa·s or more. In another embodiment, the viscosity of the clear layer paint is 1,000 mPa·s or less, 500 mPa·s or less, 200 mPa·s or less, 50 mPa·s or less, 30 mPa·s or less, or 20 mPa·s or less.

[0067] The thickness of the clear layer may be adjusted appropriately, for example, to 10 to 60 μm, preferably 20 to 50 μm.

[0068] It is preferable that the surface of the clear layer on the protective film side after removing the protective film has good surface smoothness. The smaller the height of the unevenness on the coating film surface, the smaller the angle of the unevenness relative to the film plane, and the larger the period, the better the surface smoothness and the higher the design of the laminate film. On the other hand, the greater the height of the unevenness on the coating film surface, the larger the angle of the unevenness relative to the film plane, and the smaller the period, the lower the surface smoothness and the lower the design of the laminate film.

[0069] In the present invention, the surface developed area ratio (Sdr), which is a summary of the above parameters, is used as an index of the surface smoothness of a coating film. The surface developed area ratio (Sdr) is a parameter that indicates how much the surface area (developed area) reflecting the actual irregularities in the measurement area increases relative to the area of ​​a flat surface without irregularities in the measurement area when measured in accordance with ISO 25178, and is expressed by the following formula. The smaller this Sdr is, the smoother the surface is, and the Sdr of a completely flat surface is 0. The Sdr in the present invention was measured using a Keyence VK-X3100 with an objective lens magnification of 10x and a measurement area area of ​​1511358 μm ２ This is the value obtained by performing surface analysis so that the average Sdr is 10 points. Measurements are taken at 10 locations, and the average value is the average Sdr. Surface developed area ratio (Sdr) = (A - B) / B A: Surface area (developed area) reflecting the actual unevenness in the measurement area B: Flat area without unevenness in the measurement area

[0070] The clear layer (B) preferably has a surface development area ratio (Sdr) of the protective film (C) side surface (surface in contact with the protective film (C)) of less than 2.8*10^(-3). When the Sdr is within this range, the surface smoothness after peeling off the protective film is good, and it is thought that the designability is enhanced. The Sdr is more preferably less than 2.0*10^(-3), more preferably less than 3.5*10^(-4), and even more preferably less than 3.5*10^(-5). The Sdr of the protective film (C) side surface of the clear layer can be made approximately the same value as the Sdr of the clear layer side surface of the protective film by crimping the protective film before the clear layer is completely cured.

[0071] (Protective Film (C)) The protective film functions to protect the clear layer and any design layer of the laminate film until use. The protective film of the laminate film according to the present invention preferably has good surface smoothness on the clear layer side surface. Specifically, the protective film (C) has a surface developed area ratio (Sdr) of the clear layer (B) side surface (the surface in contact with the clear layer (B)) of less than 2.8*10^(-3). If the Sdr is 2.8*10^(-3) or more, fine irregularities are transferred to the clear layer (B), resulting in reduced gloss and image clarity. The Sdr is preferably less than 2.0*10^(-3), more preferably less than 3.5*10^(-4), and even more preferably less than 3.5*10^(-5).

[0072] Furthermore, the protective film (C) preferably has a surface development area ratio (Sdr) of 2.0*10^(-3) or more on the side not in contact with the clear layer (B). When the Sdr is 2.0*10^(-3) or more, blocking between the protective film (C) and the side opposite the adhesive layer (D) of the release liner (E) can be prevented. The Sdr is more preferably 1.0*10^(-2) or more, and even more preferably 5.0*10^(-2) or more.

[0073] Furthermore, the release liner (E) also preferably has a surface developed area ratio (Sdr) of 2.0*10^(-3) or more on the side not in contact with the adhesive layer (D). When the Sdr is 2.0*10^(-3) or more, blocking between the release liner (E) and the side of the protective film (C) opposite the clear layer (B) can be prevented. The Sdr is more preferably 1.0*10^(-2) or more, and even more preferably 5.0*10^(-2) or more.

[0074] The protective film (C) preferably has an arithmetic mean height (Sa) of 0.7 μm or less, more preferably 0.4 μm or less, and even more preferably 0.3 μm or less, on the surface in contact with the clear layer (B). The protective film (C) preferably has a minimum autocorrelation length (Sal) of 40 μm or more, more preferably 100 μm or more, on the surface in contact with the clear layer (B). The protective film (C) preferably has a root mean square slope (Sdq) of 0.3 or less, more preferably 0.06 or less, on the surface in contact with the clear layer (B).

[0075] As the protective film, a cover film and a protective film of a conventionally known laminated film can be used.

[0076] Examples of protective films include polyolefin films, modified polyolefin films, polyester films, polystyrene-based resin films, polyurethane films, urethane nylon films, polyamide films, polyvinyl chloride films, polyvinylidene chloride films, polymethylpentene films, and acrylic films.

[0077] Examples of polyolefin films include polyethylene films, polypropylene films, non-oriented polypropylene films (CPP films), and biaxially oriented polypropylene films (OPP films).

[0078] Examples of polyester films include polyethylene terephthalate (PET), unstretched polyethylene terephthalate, biaxially stretched polyethylene terephthalate, polycarbonate, and polylactic acid.

[0079] Examples of polystyrene resin films include polystyrene films, AS resin films, and ABS resin films. The protective film is particularly preferably one containing polyethylene terephthalate (PET). Compared with films made solely of soft materials such as polyethylene or polypropylene, the inclusion of polyethylene terephthalate makes it possible to sufficiently prevent the surface roughness of the surface of the protective film (C) that does not contact the clear layer (B) from being transferred to the clear layer (B) via the protective film (C) when the surface of the protective film (C) that does not contact the clear layer (B) is laminated so that the surface of the release liner (E) that does not contact the adhesive layer is in contact with the surface of the protective film (C) that does not contact the clear layer (B) in a state where the clear layer (B) is not completely cured.

[0080] The thickness of the protective film may be adjusted as appropriate, and for example, the average thickness is preferably 25 μm or more and 100 μm or less. When the average thickness is 25 μm or more, when the clear layer (B) is not completely cured, and the surface of the protective film (C) that does not contact the clear layer (B) is laminated so that the surface of the release liner (E) that does not contact the adhesive layer is in contact with the surface of the protective film (C) that does not contact the clear layer (B), the surface roughness of the surface of the protective film (C) that does not contact the clear layer (B) can be sufficiently prevented from being transferred to the clear layer (B) through the protective film (C). When the average thickness is 100 μm or less, when the laminated film of the present invention is wound into a roll, the film slippage due to the difference in inner and outer circumferences and the protective film (C) floating from the clear layer (B) can be sufficiently prevented. It is more preferable that the average thickness is 30 μm or more and 50 μm or less.

[0081] The protective film may have a release agent applied to one or both of the surfaces, for example, the surface on the clear layer side and the surface opposite the clear layer side. The protective film may have been subjected to a surface modification treatment such as corona treatment or low-temperature plasma treatment. The protective film may also contain additives such as antistatic agents and ultraviolet inhibitors.

[0082] The protective film may be a commercially available product. Examples of commercially available protective films include those manufactured by Unitika Ltd. under the trade name "Uni-Peel (registered trademark)", those manufactured by Toray Industries, Inc. under the trade names "Lumirror (registered trademark) S-10, T-60, U-40, Therapeel (registered trademark) WZ", those manufactured by Teijin Film Solutions Co., Ltd. under the trade name "Purex A54", those manufactured by Nippa Corporation under the trade name "PET Separator TF-535, PET38X1-TR3", those manufactured by Fujimori Kogyo Co., Ltd. under the trade name "Filmbyna (registered trademark) NT-2, NSP-5", those manufactured by Lintec Corporation under the trade name "PLD38X", those manufactured by Toyo Cross Co., Ltd. under the trade name "SP4030" and "SP4035", those manufactured by Aim Co., Ltd. under the trade name "RF1-CS006", those manufactured by Nihon Matai Co., Ltd. under the trade name "PET238", and those manufactured by Toyobo Co., Ltd. under the trade name "Cosmoshine (registered trademark) A4160".

[0083] (Design Layer (F)) The design layer is a coating film of a paint for a design layer, and is the layer that mainly provides the design of the laminate film. As the design layer, a base layer of a conventionally known top coat paint for an automobile, or a design layer or colored layer of a decorative laminate can be used.

[0084] The paint for the decorative layer that forms the decorative layer can be a conventionally known paint for a decorative layer or a paint for a base coating film. The paint for the decorative layer contains, for example, a resin component, a pigment, and a solvent.

[0085] Examples of the resin component of the paint for the design layer include the resin components exemplified above for the paint for the clear layer.

[0086] In one embodiment, the resin component of the decorative layer paint includes a thermosetting resin. In another embodiment, the resin component of the decorative layer paint includes a thermosetting resin and a photocurable resin. In yet another embodiment, the resin component of the decorative layer paint is only a thermosetting resin.

[0087] The resin component of the paint for the decorative layer may be used alone or in combination of two or more.

[0088] The resin components of the paint for the design layer and the paint for the clear layer may be the same or different, but from the viewpoint of performance such as weather resistance, it is preferable to use a mixture of an acrylic resin and an isocyanate compound as the resin component, as in the paint for the clear layer. The acrylic resin and isocyanate compound described in the paint for the clear layer can be suitably used.

[0089] The pigment for the decorative layer paint is not particularly limited, and known pigments can be used. Examples of pigments include inorganic pigments and organic pigments. Examples of pigments include metals such as aluminum, copper, zinc, iron, nickel, tin, and aluminum oxide; alloys thereof; luster pigments such as interference mica, white mica, graphite, glass flakes, and alumina flakes; and scaly luster pigments in which these metals, alloys, interference mica, white mica, graphite, glass flakes, or alumina flakes are coated with metal oxides (e.g., titanium oxide, titanium dioxide, iron oxide) or metals (e.g., gold and silver). Other examples include alumina flake pigments (a) described in JP 2016-221473 A; scaly luster pigments in which a metal substrate or a glass flake substrate is coated with a metal oxide or a metal; scaly luster pigments in which a colored pigment is chemically adsorbed onto the surface of a metal substrate or a glass flake substrate; aluminum pigments in which an aluminum oxide layer is formed on the surface of an aluminum substrate; aluminum solid-solution plate-like iron oxide pigments; scaly luster pigments in which the surface of interference mica, graphite, or silica flakes is coated with titanium dioxide; and plate-like iron oxide pigments.

[0090] The amount of pigment in the paint for the design layer may be adjusted as appropriate, for example, from 1 to 70% by mass, preferably from 3 to 60% by mass, based on the total mass of the paint for the design layer including the solvent.

[0091] Examples of the solvent for the paint for the design layer include the solvents exemplified above for the paint for the clear layer, etc. The solvents may be used alone or in combination of two or more.

[0092] The paint for the design layer may be a water-based paint or a solvent-based paint.

[0093] In addition to the resin component and the solvent, the paint for the decorative layer may contain conventionally known additives used in paints for the decorative layer, such as the additives exemplified above for the paint for the clear layer.

[0094] The viscosity of the paint for the decorative layer may be adjusted as appropriate, and is, for example, 100 to 7,000 mPa·s, and preferably 300 to 4,000 mPa·s.

[0095] In one embodiment, the viscosity of the paint for the clear layer is 10 to 1,000 mPa·s, and the viscosity of the paint for the design layer is 300 to 4,000 mPa·s.

[0096] The thickness of the design layer may be adjusted as appropriate, for example, from 5 to 35 μm, preferably from 15 to 30 μm.

[0097] The design layer may be formed from two or more design layers. For example, a first design layer and a second design layer having different resin components, paint materials such as pigments, thicknesses, etc. may be combined to form a design layer.

[0098] (Image clarity) Evaluation after application to an adherend is performed as follows. The protective film (C) and release liner (E) of the laminate film are peeled off, and the surface of the adhesive layer (D) is applied to a smooth glass plate using a rubber roller at a linear pressure of 2 kg / 10 cm. The applied article is placed 1.8 m from the fluorescent lamp, at a position where the angle between the line connecting the center of the fluorescent lamp and the center of the article and the perpendicular to the ground is 20 degrees, with the clear layer (B) facing the fluorescent lamp. Next, the image of the fluorescent lamp is visually observed from a position where the angle between the line connecting the center of the fluorescent lamp and the center of the article and the line connecting the center of the article and the observer's eye is 40 degrees, and the distance between the center of the article and the observer's eye is 50 cm, and the image is evaluated according to the following criteria. Good: The outline of the fluorescent light is clearly visible with almost no distortion or blurring. Fair: The outline of the fluorescent light is visible, but appears distorted or blurred. Poor: It is difficult to see the outline of the fluorescent light.

[0099] Evaluation before attachment to an adherend is carried out as follows. The laminated film with the protective film (C) peeled off is placed 1.8 m from the fluorescent lamp, with the clear layer (B) facing the fluorescent lamp, at a position where the angle between the line connecting the center of the fluorescent lamp and the center of the film and the perpendicular to the ground is 20 degrees. Next, the image of the fluorescent lamp is visually observed from a position where the angle between the line connecting the center of the fluorescent lamp and the center of the film and the line connecting the center of the film and the observer's eye is 40 degrees, and the distance between the center of the film and the observer's eye is 50 cm, and the image is judged according to the following criteria: Good: The outline of the fluorescent lamp is clearly visible with almost no distortion or blurring. Fair: The outline of the fluorescent lamp is visible, but appears distorted or blurred. Poor: The outline of the fluorescent lamp is difficult to see.

[0100] In order to prevent the uneven shape imparted to the pressure-sensitive adhesive layer (D) from adversely affecting the appearance quality, it is desirable that there is no difference between the judgment before and after lamination to the adherend.

[0101] (Method for manufacturing laminated film) For each layer other than the protective film (C) and base layer (A) constituting the laminated film of the present invention, a coating composition is prepared by dissolving the components constituting each layer in a solvent, and this is directly applied and dried on the base layer (A), and then the protective film (C) and release liner (E) are laminated on the laminate thus formed to obtain a laminated structure, or a coating composition is applied and dried on the release liner (E) in which the components constituting the adhesive layer are dissolved in a solvent, and then the base layer (A) on which the clear layer (B) and the like are laminated is laminated to obtain a laminated structure. Thereafter, the laminated film of the present invention can be obtained by performing heat curing or energy ray curing.

[0102] The above-mentioned manufacturing method preferably includes a step (I) of pressing a protective film (C) or a substrate layer (A) onto the clear layer (B) while the clear layer (B) is not completely cured, and then completely curing the clear layer (B). A completely cured state means that the residual rate of thermosetting reactive groups such as isocyanate groups and epoxy groups is less than 10%, and the residual rate of photocurable reactive groups such as acryloyl groups is less than 50%. A completely incurable state means that the residual rate of thermosetting reactive groups such as isocyanate groups and epoxy groups is 10% or more, and the residual rate of photocurable reactive groups such as acryloyl groups is 50% or more. The residual rate of thermosetting reactive groups and the residual rate of photocurable reactive groups can be calculated, for example, by the absorption peak intensity ratio (after reaction / before reaction * 100) of each functional group before and after reaction in infrared spectroscopy (IR).

[0103] For example, examples include (1) a process in which a clear layer paint is applied to a protective film (C), dried to form a film, and while the clear layer (B) is not completely cured, the clear layer (B) is pressed onto the substrate layer (A) or the surface of the substrate layer (A) having the design layer (F), and then completely cured, or (2) a process in which a clear layer paint is applied to the substrate layer (A) or the surface of the substrate layer (A) having the design layer (F), dried to form a film, and while the clear layer (B) is not completely cured, the clear layer paint is pressed onto the protective film (C), and then completely cured. The completely curing process is preferably a heat curing process in which the clear layer is cured at 40 to 60 degrees for 2 to 7 days.

[0104] Furthermore, it is preferable to include a step (II) of forming an adhesive layer (D) on the uneven surface of the release liner (E) and laminating the adhesive layer (D) on the opposite side of the substrate layer (A) to the side where the clear layer (B) is provided. By the above step, the uneven surface previously provided on the release liner (E) is transferred to the release liner (E) side surface of the adhesive layer (D). It is preferable that the adhesive layer coating material is applied so that the dry film thickness is at least 4 μm above the height of the protrusions of the uneven surface. Furthermore, if necessary, the surface of the adhesive layer (D) opposite to the release liner (E) may be covered with an arbitrary cover film, and the cover film may be peeled off while the adhesive layer (D) is laminated on the opposite side of the substrate layer (A) to the side where the clear layer (B) is provided.

[0105] The method for applying each coating composition is not particularly limited, and any conventionally known coating method can be used. Examples of application methods include spraying, applicators, die coaters, bar coaters, roll coaters, comma coaters, rollers, brushes, and spatulas. After applying each coating composition, heating or drying at room temperature may be performed as necessary. When heating is performed, for example, the temperature may be 60 to 130°C for 1 to 20 minutes.

[0106] The adhesive layer (D) may be formed by applying and drying a coating material for the adhesive layer, or may be bonded by a lamination method. That is, the adhesive layer (D) may be formed by preparing a film formed by the adhesive layer (D) and bonding it by lamination.

[0107] (Method of Use) The laminate film of the present invention can be used for an article comprising an adherend and a laminate film attached to the adherend, for example, by being attached to the adherend. When decorating an adherend using the laminate film of the present invention, it can be carried out in the same manner as a conventionally known method, and is not particularly limited. That is, the laminate film is pressure-bonded to the adherend so that the adhesive layer faces the adherend surface and the laminate film is in close contact with the adherend, and decoration is performed. In addition, in the case of a multilayer film having the layer structure shown in Figures 1 and 2, the protective film (C) may be peeled off after pressure bonding, or may be peeled off before adhering to the adherend surface.

[0108] The adherend that can be suitably decorated with the laminate film of the present invention is not particularly limited, and may be, for example, the surface of a metal product such as a steel plate, or the surface of a plastic product. The article decorated with the laminate film is not particularly limited, and examples thereof include automobile exterior parts such as automobile bodies, bumpers, front under spoilers, rear under spoilers, side under skirts, side garnishes, and door mirrors, automobile interior parts such as instrument panels, center consoles, and door switch panels, housings of home appliances such as mobile phones, audio products, refrigerators, fan heaters, and lighting fixtures, and bathroom vanities.

[0109] The present invention will be described below with reference to examples. In the examples, parts and % used in the formulations mean parts by mass and % by mass unless otherwise specified. The present invention is not limited to the examples shown below.

[0110] Details of the protective films used in the examples are as follows. A-50: Cosmoshine A4160, thickness 50 μm A-38: Equivalent to A-50 with a thickness of 38 μm, with surface roughness parameters Sa = 0.133 μm, Sdr = 2.1 x 10^(-5), Sal = 178.662 μm, Sdq = 0.007 A-25: Equivalent to A-50 with a thickness of 25 μm, with surface roughness parameters Sa = 0.127 μm, Sdr = 1.9 x 10^(-5), Sal = 181.543 μm, Sdq = 0.006 B-38: Film Bina 38E-0010 NSP-5, thickness 38 μm C-38: PLD38X, thickness 38 μm D-38: PET38X1-TR3 Thickness 38 μm E-38: Therapeel WZ Thickness 38 μm F-50: Lumirror T-60 Thickness 50 μm G-40: Torayfan BO40-2500 Thickness 40 μm

[0111] (Method for manufacturing a release liner) Linear low-density polyethylene (LDPE) was melt-extrusion laminated at 140°C on both sides of a polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name: Lumirror T60, thickness 100 μm) to form a PE layer, while pressing an embossed cooling roll against one of the molten surfaces to obtain a release liner with convex portions. The convex portions had a height of 15 μm and a pitch of 100 μm. The LDPE used was "Sumikathen CE4009" (LDPE containing no phosphorus-based antioxidant), a product of Sumitomo Chemical Co., Ltd. Next, a release treatment was performed on the convex-shaped treated surface. Specifically, a commercially available addition-curing type silicone-based release agent (using a platinum catalyst, solventless) was applied at approximately 1.0 g / m to the treated surface. ２ The coating amount was then cured by heating at 125° C. for 1 minute. The support film was changed to polyethylene terephthalate film or 100 μm thick fine paper, and the height and pitch of the convex portions were changed.

[0112] (Preparation of clear layer paint 1) Acrylic resin 1 (trade name "LR2671" manufactured by Mitsubishi Chemical Corporation, Tg 23 ° C., SP value 10.5, Mw 11000, solid content 61%) 30 parts by mass, acrylic resin 2 (trade name "ACS-1268" manufactured by Nippon Paint Automotive Coatings Co., Ltd., Tg 16 ° C., SP value 10.2, Mw 8600, solid content 64%) 28 parts by mass, polycarbonate diol (trade name T5650E manufactured by Asahi Kasei Corporation) 9 parts by mass, curing agent 1 (trade name "H1200" manufactured by Nippon Paint Automotive Coatings Co., Ltd., isocyanate compound) 33 parts by mass were mixed, and further diluted with methyl ethyl ketone as necessary to adjust the viscosity, and clear layer paint 1 was prepared (viscosity: 20 mPa s).

[0113] (Preparation of Design Layer Coating 1) 11 parts by mass of acrylic resin 3 (trade name "A-200" manufactured by Mitsubishi Chemical Corporation), 50 parts by mass of pigment dispersion paste 1 (trade name "PBC-212 204 Black A" manufactured by Nippon Paint Automotive Coatings), 14 parts by mass of rheology control agent 1 (trade name "PBC-212 D Paste" manufactured by Nippon Paint Automotive Coatings), 20 parts by mass of curing agent 2 (trade name "H1250" manufactured by Nippon Paint Automotive Coatings), and 5 parts by mass of MEK were mixed to prepare design layer coating 1 (viscosity: 400 mPa s).

[0114] (Preparation of adhesive layer composition) A composition for adhesive layer was prepared by mixing 100 parts by mass of adhesive base agent 1 (manufactured by Soken Chemical & Engineering Co., Ltd. under the trade name "SK Dyne 1811L") and 0.2 parts by mass of adhesive curing agent 1 (manufactured by Soken Chemical & Engineering Co., Ltd. under the trade name "TD-75").

[0115] (Example 1) Design paint 1 was applied to one surface of the base layer (A) with an applicator to a dry film thickness of 20 μm to 30 μm, and then heated at a temperature of 115°C for 2 minutes, and the design layer (F) was laminated. Next, clear layer paint 1 was applied to the surface of the design layer (F) opposite the base layer (A) with an applicator to a dry film thickness of 25 to 35 μm, and then heated at a temperature of 115°C for 3 minutes, and then the laminate film and protective film (C) were laminated while being pressed together, thereby laminating the protective film (C). Then, the product was cured at 60°C for 3 days to allow it to fully cure. Next, the adhesive layer composition was applied with an applicator to the surface of the release liner (E) having the ridge-like protrusions, so that the dry film thickness, including the ridge-like protrusions, was 20 to 30 μm. The composition was then heated at 100°C for 3 minutes, and the adhesive layer (D) and the release liner (E) were laminated by laminating them while pressing them onto the surface of the base layer (A) opposite the design layer (F). The resulting laminate was then cured at 50°C for 2 days to allow complete curing. This resulted in a laminated film comprising, in order, the protective film (C), the clear layer (B) (Sdr: 1.9*10^(-5) on the surface contacting the protective film (C)), the design layer (F), the base layer (A), the adhesive layer (D), and the release liner (E).

[0116] Examples 2 to 7, Comparative Examples 1 and 2 Laminated films were obtained in the same manner as in Example 1, except that the protective film (C) in Example 1 was replaced with a protective film (C) having the physical properties shown in Table 1.

[0117] Examples 8 to 9 and Comparative Examples 3 to 11 Laminated films were obtained in the same manner as in Example 1, except that the release liner (E) in Example 1 was replaced with a release liner (E) having the physical properties shown in Table 2.

[0118] A laminate of 15 cm in length and 7 cm in width was cut out from the laminate of each Example and Comparative Example, the protective film (C) and the release liner (E) were peeled off, and the adhesive layer (D) was attached to a glass plate with a smooth surface using a rubber roller at a linear pressure of 2 kg / 10 cm. A laminate having an adhesive layer (D), a base layer (A), a design layer (F), and a clear layer (B) was arranged adjacently from the surface side of the glass plate. The surface development area ratio (Sdr) of the surface of the peeled protective film (C) in contact with the clear layer (B) was measured by the method described above. The arithmetic mean height (Sa), minimum autocorrelation length (Sal), and root mean square slope (Sdq) were also measured in the same manner.

[0119] (20° gloss, 60° gloss) Measurement was carried out in accordance with JIS Z 8741.

[0120] (Image clarity) The laminated film was visually observed before and after being attached to the adherend, and evaluated according to the following criteria. Good or fair is acceptable. Good: The outline of the fluorescent lamp is clearly visible with almost no distortion or blurring. Fair: The outline of the fluorescent lamp is visible, but appears distorted or blurred. Poor: The outline of the fluorescent lamp is difficult to see.

[0121] (Backside pressure test) Each protective film (C) was attached to an incompletely cured clear layer (B), and before being completely cured, the side (Sdr=0.8312) opposite to the adhesive layer (D) of the release liner (E) used in Example 1 was brought into contact with the side opposite to the layer (B) of each protective film (C), and a pressure of 10 kg / 25 cm was applied from above and below the film plane of the laminated film in this state. ２ The sample was stored at room temperature for one day while maintaining the state in which a uniform force of 1000 W was applied.

[0122] (Δ20° gloss and Δ60° gloss before and after back pressure bonding test) The laminated films before and after the back pressure bonding test were each aged at 60°C for 3 days to be completely cured. The protective film (C) of each laminated film was peeled off, and the Δ20° gloss and Δ60° gloss were measured. The smaller the absolute value of the gloss difference (Δgloss) between before and after the back pressure bonding test for each of the Δ20° gloss and Δ60° gloss, the less deterioration in appearance occurs when the laminated film is wound into a roll in a state where the clear layer (B) is not completely cured, and the better it can be judged to be.

[0123] (Air Release) The air release of the laminated film after being attached to the adherend was evaluated according to the following criteria: 5: 1 mm air releases without applying force 4: 1 mm air releases with a specific tool or by applying force 3: 1 mm air is difficult to release, but 3 mm or larger air is released with a specific tool or by applying force 2: 3 mm or larger air is difficult to release 1: No air release at all (4 or higher is pass)

[0124] (Appearance) After being attached to the adherend, the laminated film was visually observed, and the appearance (visible shape of adhesive layer), appearance (visible deformation upon finger pressure), and appearance (visible formation of support film) were evaluated according to the following criteria: 5: Not visible at all, 4: Almost not visible, 3: Visible when closely watched, 2: Visible without closely watched, 1: Visible even from a long distance (4 or above is pass).

[0125]

[0126]

[0127] *1 Unable to obtain a film with a uniform adhesive surface

[0128] The laminated film obtained in the examples showed little lifting of the uneven shape and no decrease in image clarity before and after lamination, demonstrating that the laminated film combines excellent design and high air release properties.

[0129] The laminated film of the present invention can be suitably used for decorating automobile bodies, automobile exterior parts, residential interior parts, and the like.

[0130] REFERENCE SIGNS LIST 1 Protective film (C) 2 Clear layer (B) 3 Base layer (A) 4 Adhesive layer (D) 5 Release liner (E) 6 Design layer (F)

Claims

1. It includes, in order, a protective film (C), a clear layer (B), a base material layer (A), an adhesive layer (D), and a release liner (E). The surface development area ratio (Sdr) of the surface of the protective film (C) that contacts the clear layer (B) is less than 2.8*10^(-3). The release liner (E) includes a support base material made of a thermoplastic resin. The surface of the adhesive layer (D) that contacts the release liner (E) has an uneven shape with ridge-shaped protrusions that are continuously connected from one end to the other end in a grid pattern. In the uneven shape, the average pitch of the protrusions is 50 μm or more and 320 μm or less, and the average height of the protrusions is 10 μm or more and 20 μm or less. A laminated film characterized by the above.

2. The laminated film according to claim 1, wherein the surface development area ratio (Sdr) of the surface of the protective film (C) that contacts the clear layer (B) is less than 2.0*10^(-3).

3. The laminated film according to claim 1 or 2, wherein the surface development area ratio (Sdr) of the surface of the clear layer (B) that contacts the protective film (C) is less than 2.0*10^(-3).

4. The laminated film according to claim 1 or 2, wherein the protective film (C) has an average thickness of 25 μm or more and 100 μm or less.

5. The laminated film according to claim 1 or 2, wherein the protective film (C) contains polyethylene terephthalate.

6. The laminated film according to claim 1 or 2, wherein the surface development area ratio (Sdr) of the surface of the release liner (E) that does not contact the adhesive layer (D) is 2.0*10^(-3) or more.

7. The laminated film according to claim 1 or 2, wherein the release liner (E) consists of a support base material and a resin layer formed by a polyolefin-based resin composition on at least the surface of the support base material on the adhesive layer (D) side. The resin layer has been subjected to a release treatment with a silicone-based release agent.

8. The laminated film according to claim 1 or 2, further including a design layer (F).

9. A method for manufacturing the laminated film according to claim 1 or 2, characterized by including a step (I) of pressing the protective film (C) or the base material layer (A) in a state where the clear layer (B) is not fully cured, and then fully curing it.

10. The method for manufacturing a laminated film according to claim 9, further including a step (II) of forming the adhesive layer (D) on the surface of the release liner (E) having the uneven shape and laminating the adhesive layer (D) on the side of the base material layer (A) opposite to the side where the clear layer (B) is provided.

11. An article comprising the laminated film according to claim 1 or 2 adhered to an adherend.

12. The article according to claim 11, wherein the adherend is an automobile body or an automobile part.

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