Laminated film, method for manufacturing the same, and article

Abstract

To provide a laminated film which achieves both excellent designability and high air releasability.SOLUTION: A laminated film includes a protective film (C), a clear layer (B), a base material layer (A), an adhesive layer (D), and a release liner (E), wherein the protective film (C) has a surface development area ratio (Sdr) of a surface contacting the clear layer (B) of less than 2.8*10^(-3), the release liner (E) contains a support base material composed of a thermoplastic resin, and has such an uneven shape that roof-like projections continuously connected from one end to the other end are provided in a lattice shape on the surface of a surface contacting the adhesive layer (D), and in the uneven shape, the average pitch of the projection is 50 μm or more and 320 μm or less, and the average height of the projection is 10 μm or more and 20 μm or less.SELECTED DRAWING: Figure 1

Description

Technical Field

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

Background Art

[0002] Coating replacement adhesive sheets, decorative adhesive sheets, surface protection adhesive sheets, etc. that are attached to the exterior of vehicles such as automobiles and motorcycles and building materials for housing generally have a relatively large attachment area and require designability in appearance. Therefore, by forming grooves on the surface of the adhesive layer and using these grooves to form a flow path for discharging fluid (typically a gas such as air) to the outside when the adhesive sheet is attached to the adherend, it is possible to prevent the phenomenon that the gas trapped during the attachment forms bubbles and remains, thereby degrading the appearance quality. A technique for this is known.

[0003] As a preferable method for forming grooves on the surface of the adhesive layer, there is a method of forming a groove shape on a release liner for protecting the adhesive layer until the adhesive sheet is used (when attached to the adherend) and transferring this groove shape to the adhesive layer (for example, Patent Document 1).

[0004] However, the uneven shape of the release liner may be visually recognized as protruding from the surface of the adhesive sheet. If the uneven shape of the release liner is visually recognized as protruding from the surface of the adhesive sheet, there is a risk of impairing the designability such as the distinctness of image, which is not preferable.

[0005] Patent Document 2 discloses an adhesive sheet having a base material layer, an adhesive layer, and a release liner in this order in the lamination direction, and having an uneven shape formed on the surface of the release liner on the adhesive layer side, wherein the 60-degree specular glossiness measured in accordance with JIS Z 8741 on one surface on the base material layer side is 30% or less. This suppresses the uneven shape from protruding to the surface by suppressing the glossiness of the surface on the base material layer side, so it cannot be used to obtain a characteristic appearance with high gloss.

Prior Art Documents

Patent Document

[0006]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

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

Means for Solving the Problems

[0008] The present invention sequentially includes 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 substrate made of a thermoplastic resin. The surface of the adhesive layer (D) has a concavo - convex shape with ridge - like protrusions continuously connected from one end to the other end in a grid pattern. In the concavo - convex 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. The present invention relates to a laminated film characterized by this.

[0009] Preferably, 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).

[0010] Preferably, 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). 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 development area ratio (Sdr) of 2.0*10^(-3) or more on the surface that does not contact the adhesive layer (D).

[0011] The release liner (E) consists of a support substrate and a resin layer formed by a polyolefin-based resin composition on at least the surface of the support substrate on the side of the adhesive layer (D). The resin layer is preferably one that has been 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 is a method for manufacturing the above-mentioned laminated film, characterized by including a step (I) of pressing the protective film (C) or the substrate layer (A) while the clear layer (B) is not fully cured, and then fully curing it. The method for manufacturing the laminated film preferably further includes a step (II) of forming the adhesive layer (D) on the surface of the release liner (E) having an uneven shape and laminating the adhesive layer (D) on the side opposite to the side where the clear layer (B) of the substrate layer (A) is provided.

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

Effects of the Invention

[0014] According to the present invention, by providing a specific uneven shape on the adhesive layer, it is possible to obtain a laminated film having excellent design properties, with high air permeability and a high gloss, and the uneven shape is difficult to be visually recognized from the front side.

Brief Description of the Drawings

[0015]

Figure 1

Figure 2

Mode for Carrying Out the Invention

[0016] Hereinafter, the present invention will be described in detail. In a laminated film, if a large uneven shape is provided to impart sufficient air permeability, the uneven shape is visually recognized and leads to a deterioration in appearance. On the other hand, if the uneven shape is made small to maintain the appearance, the air permeability becomes insufficient, and swelling on the film surface or inconvenience during construction occurs. In particular, when the front side has a very high glossiness of 85 / 60° gloss or more, the uneven shape is likely to float on the film surface and be visually recognized from the front side, or the shape of the adhesive layer is deformed and visually recognized by finger pressure from the front side, and there has been a problem that good air permeability cannot be ensured.

[0017] The present invention has achieved a laminated film with excellent workability without deteriorating the appearance quality even with a high gloss by specifying an uneven shape that can achieve both excellent air permeability and design.

[0018] Hereinafter, the laminated film of the present invention will be described in detail. (Layer Structure) The laminated film of the present invention sequentially includes a protective film (C), a clear layer (B), a base material layer (A), an adhesive layer (D), and a release liner (E) (see FIG. 1). By adhering the film having such a configuration to an adherend, a layer is formed. Thereafter, the protective film (C) may be peeled off. Also, the protective film (C) may be peeled off before adhering to the adherend.

[0019] In addition, the laminated film of the present invention may be provided with a design layer (F), an adhesion layer, etc. as required. When the design layer (F) is provided, it may be located between the clear layer (B) and the base material layer (A) (see Fig. 2). Further, the design layer (F) may be located between the base material layer (A) and the adhesive layer (D). Hereinafter, each layer constituting the laminated film of the present invention will be described in detail.

[0020] (Release liner (E)) The release liner (E) is detachably disposed on the surface of the adhesive layer. As the structure of the release liner, for example, a structure including a support substrate is preferable, and a structure having a resin layer on the support substrate and the surface on the adhesive layer side of the support substrate is preferable, and a three-layer structure having a resin layer on the back surface side is more preferable. Further, an intermediate layer may be disposed between the layers as required.

[0021] As the support substrate, when paper is used as the support substrate when the laminated film has a high gloss, the texture of the paper may protrude on the surface. For this reason, a support substrate made of a thermoplastic resin is preferable. 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, since the bending rigidity is high, the support substrate is preferably a polyethylene terephthalate film. The polyethylene terephthalate film is preferably biaxially stretched because it is difficult to shrink and has high bending rigidity. Further, as the polyethylene terephthalate film, after producing an unstretched resin film by a known method such as T-die extrusion molding, a film produced using a known method such as sequential biaxial stretching or simultaneous biaxial stretching can be used.

[0022] The resin layers on the adhesive layer side surface and the back side surface are not particularly limited. For example, they can be provided in layers by applying a polyolefin-based resin composition in a heated and melted state. The polyolefin-based resin compositions for forming the resin layers on the adhesive layer side surface and the back side surface may be the same or different, but it is preferable that they are the same.

[0023] The polyolefin-based resin composition can be, for example, a polypropylene-based resin (PP resin) composition having a propylene-based polymer as a base polymer. Here, the concept of the "propylene-based polymer" includes a homopolymer of propylene (homopolypropylene, typically isotactic polypropylene), a copolymer of propylene and other olefins (for example, one or more selected from α-olefins having 2 to 10 carbon atoms), and a copolymer of propylene and other olefins and / or monomers other than olefins. The copolymer may be a random copolymer (random polypropylene) or a block copolymer. Further, a PP resin composition containing two or more kinds of propylene-based polymers (for example, a combination of homopolypropylene and random polypropylene, a combination of two kinds of random polypropylenes having different copolymerization compositions, etc.) in an arbitrary ratio may also be used.

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

[0025] The above polyolefin resin composition can contain various components generally known as additives for polyolefin resin compositions as required, as long as 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, it can be a PP composition having a composition containing a pigment such as TiO2 in a proportion of about 5 to 20 parts by mass with respect to 100 parts by mass of the propylene-based polymer.

[0026] It is preferable that the resin layer on the adhesive layer side of the above release liner is subjected to a release treatment with a release agent. The release agent (also referred to as a mold release agent) can be 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. Examples of the release agent preferable for the present invention include thermosetting silicone-based release agents. As the thermosetting silicone-based release agent, both addition-curing type and condensation-curing type can be used, but among them, an addition-curing type silicone-based release treatment agent is preferable. In this type of release treatment agent, generally, a platinum (Pt) catalyst or a rhodium (Rh) catalyst is used as a curing catalyst. From the viewpoint of ease of curing, etc., usually, a platinum catalyst is more preferably used.

[0027] The above release liner has an uneven shape on the surface on the adhesive layer side (the surface in contact with the adhesive layer). By laminating this release liner with the adhesive layer, the uneven shape of the release liner is transferred to the adhesive layer. In the present invention, the above uneven shape is a shape having ridge-like protrusions continuously connected from one end of the film to the other end in a lattice pattern, and 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.

[0028] In the above uneven shape, if the average projection 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 average projection 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 escape 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 the shape of the adhesive layer is deformed and visible when finger pressure is applied from the front side. The average protrusion height is preferably 12 μm or more and 18 μm or less.

[0030] The projections of the uneven shape are measured by the following method. The height difference and the distance between the protrusion tips are calculated using a laser microscope VK-X3100 (Keyence non-contact three-dimensional surface shape measuring device) with a 10x objective lens and 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 uneven shapes when the release liner is viewed in plan may be either regular or irregular, but are preferably regular in the form of parallel lines or a lattice pattern.

[0032] The cross-sectional shape of the unevenness when cut in the thickness direction may vary depending on the cut surface and cannot be generally specified, but examples include polygons such as triangles and quadrangles (including rectangles, squares, and trapezoids); shapes in which some or all of the corners of the polygon are slightly rounded; semicircular shapes such as semiellipses 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 surface of the adhesive layer side to transfer the shape engraved on the circumferential surface of the embossing roll to the surface of the layer. Further, for example, by using a printing technique such as screen printing, an uneven shape can be formed on the layer before it becomes a layer using the same material as the layer.

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

[0035] Examples of the adhesive for forming the adhesive layer include polyester urethane resin, acrylic urethane resin, acrylic resin, and silicone resin.

[0036] From the viewpoint that the adhesive layer ensures adhesion to the object and exhibits a peeling force that can be peeled off as needed, the adhesive layer preferably contains an acrylic resin and an isocyanate compound.

[0037] From the viewpoint that the adhesive layer ensures adhesion to the object and exhibits a peeling force that can be peeled off as needed, the peeling force of the adhesive layer with respect to the object is preferably 4.0 N to 25.0 N / 25 mm.

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

[0039] A commercially available product may be used for the adhesive layer. Examples of commercially available products of the adhesive layer include the product name "SK Dine (registered trademark)" manufactured by Synthetics Chemical Co., Ltd., and the product name "NS-S9T5" manufactured by Toyobo Co., Ltd.

[0040] (Base material layer (A)) The base material layer (A) is a member that serves as the base material for the clear layer, adhesive layer, and optional design layer of the laminated film.

[0041] The base material layer (A) is not particularly limited, and conventionally known resin base materials can be used. Examples of the resin base material 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, acrylic films, and the like. The resin base material is preferably a thermoplastic polyurethane resin (TPU) film.

[0042] Commercially available products may be used as the resin base material. Examples of commercially available products of the resin base material include the product name "Unipile (registered trademark)" manufactured by Unitika Ltd., the product name "Lumirror (registered trademark) S-10" manufactured by Toray Industries, Inc., the product name "Purex A54" manufactured by Teijin Film Solutions Co., Ltd., the product name "PET Separator TF-535" manufactured by Nippa Co., Ltd., the product name "Film Biner (registered trademark) NT-2" manufactured by Fujimori Kogyo Co., Ltd., the product name "Cerapil WZS" manufactured by Toray Film Processing Co., Ltd., the product names "SP4030" and "SP4035" manufactured by Toyo Cross Co., Ltd., the product name "RF1·CS006" manufactured by Aim Co., Ltd., the product names "PET238" and "Esmer URS PX98#" manufactured by Nippon Mat Tai Co., Ltd., the product name "Silkron SNY-90" manufactured by Okura Kogyo Co., Ltd., the product name "SHG2393" manufactured by Seedam Co., Ltd., and the like.

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

[0044] The base material layer (A) may be surface-modified by corona treatment, low-temperature plasma treatment, or the like. Further, the base material layer (A) may contain additives such as antistatic agents and ultraviolet absorbers.

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

[0046] As the paint for the clear layer for forming the clear layer, a conventionally known paint for the clear layer can be used. The paint for the clear layer contains, for example, a resin component and a solvent.

[0047] Examples of the resin component of the paint for the clear layer include acrylic resin, polyester resin, alkyd resin, fluororesin, epoxy resin, polyurethane resin, polyether resin, polyolefin resin, and the like. Further, as the resin component, for example, a hydroxyl group-containing acrylic resin (c-1), a non-aqueous dispersion type acrylic resin (c-2), a diol resin (c-3), a polyisocyanate compound (c-4), etc. described in JP-A-2020-100783 may be used. Also, as the resin component, for example, a polyurethane acrylate (B1) described in JP-A-2015-145103, a urethane resin (D1) described in JP-A-2017-007109, etc. may be used.

[0048] In one embodiment, the resin component of the paint for the clear layer contains a thermosetting resin. In another embodiment, the resin component of the paint for the clear layer contains a thermosetting resin and a photocurable resin. In yet another embodiment, the resin component of the paint for the clear layer is only a thermosetting resin.

[0049] From the viewpoint of performance such as weather resistance, an acrylic resin is preferable as the resin component of the paint for the clear layer. Also, it is preferable to use a mixture of a resin component and an isocyanate compound for the paint for the clear layer.

[0050] The weight average molecular weight of the acrylic resin of the paint for the clear layer 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 in the paint for the clear layer is, for example, 10 to 100 °C, preferably 20 to 60 °C. In one embodiment, the Tg of the acrylic resin in the paint for the clear layer 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 in the paint for the clear layer is 60 °C or lower, 50 °C or lower, 40 °C or lower, or 30 °C or lower.

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

[0053] The SP value of the acrylic resin in the paint for the clear layer is, for example, from 8.00 to 11.50, preferably from 9.50 to 10.80. In one embodiment, the SP value of the acrylic resin in the paint 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 paint 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 plurality of acrylic resins are mixed and used, it refers to the SP value obtained by weighted average based on the SP values and blending ratios of the individual acrylic resins.

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

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

[0056] Examples of the polyisocyanate include aromatic ones 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; monomers thereof; and multimers such as burette type, nurate type, and adduct type. Among them, from the viewpoint of ensuring extensibility after curing, it is preferable to use HDI nurate type and allophanate type.

[0057] Examples of the commercially available products include R-271 (Nippon Paint Automotive Coatings), Cross Nate UV (Dainichi Seika Chemicals), D-178N (Mitsui Chemicals), Sumidule N-3400 (Sumitomo Bayer Urethane), and the like.

[0058] As the isocyanate compound, a blocked isocyanate compound in which the isocyanate group is blocked with a blocking agent can also be used. Thereby, the reactivity of the isocyanate can be suppressed, the storage stability can be improved, and the handling in the reaction process can be facilitated.

[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 diols at both ends such as polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol phenol; diols such as ethylene glycol, propylene glycol, and 1,4-butanediol; polyester-type polyols at both ends 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; lactams represented by ε-caprolactam and γ-butyrolactam, and the like.

[0060] Examples of commercially available block isocyanate compounds include, for example, products with the trade names "Durate 17B-60PX" and "TPA-B80E" manufactured by Asahi Kasei Corporation.

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

[0062] The amount of the resin component of the paint for the clear layer may be adjusted as appropriate. For example, it is 10 to 80% by mass, preferably 20 to 60% by mass, based on the total mass of the paint for the clear layer including solvents and the like.

[0063] Examples of solvents for the clear layer paint include water and organic solvents. Examples of organic solvents 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); glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, pentamethylene glycol, and 1,3-octylene glycol; amides such as formamide, N-methylformamide, dimethylformamide (DMF), dimethylacetamide, dimethyl sulfoxide (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 dichloromethane. The solvents may be used alone or in combination of two or more.

[0064] The clear layer paint may be an aqueous paint or a solvent-based paint. In the present invention, an aqueous paint refers to a paint in which water is the most abundant dispersion medium in the paint, while a solvent-based paint refers to a paint in which a solvent is the most abundant dispersion medium in the paint.

[0065] In addition to the resin component and the solvent, the clear layer paint may be blended with conventionally known additives used in the clear layer paint. Examples of such additives include ultraviolet absorbers, light stabilizers, crosslinking agents, curing agents, pigments, surface modifiers, defoamers, conductive fillers, hindered amine light stabilizers, antioxidants, and catalysts.

[0066] The viscosity of the paint for the clear layer may be adjusted as appropriate. For example, it is 5 to 5,000 mPa·s, preferably 10 to 1,000 mPa·s. In one embodiment, the viscosity of the paint for the clear layer 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 paint for the clear layer 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 as appropriate. For example, it is 10 to 60 μm, preferably 20 to 50 μm.

[0068] The surface on the protective film side of the clear layer after removing the protective film preferably has good surface smoothness. The smaller the height of the unevenness on the coating film surface, the smaller the angle of the unevenness with respect to the film plane, and the larger the period, the better the surface smoothness, and the higher the design quality of the laminated film. On the other hand, the larger the height of the unevenness on the coating film surface, the larger the angle of the unevenness with respect to the film plane, and the smaller the period, the lower the surface smoothness, and the lower the design quality of the laminated film.

[0069] In the present invention, as an index of the surface smoothness of the coating film, the surface development area ratio (Sdr) that summarizes the above parameters is used. The surface development area ratio (Sdr) is a parameter that represents how much the surface area (development area) reflecting the actual unevenness in the measurement area increases with respect to the area of the flat surface without unevenness in the measurement area when measured based on ISO 25178, and is represented by the following formula. The smaller this Sdr, the smoother the surface, and the Sdr of a completely flat surface is 0. The Sdr in the present invention is a value obtained by performing surface analysis using a Keyence VK-X3100 with an objective lens magnification of 10 times so that the measurement area area is 1511358 μm 2 Surface analysis was performed at 10 locations, and the number average value thereof was taken as the average Sdr. Surface development area ratio (Sdr) = (A - B) / B A: Surface area (developed area) reflecting actual unevenness in the measurement area B: Area of a flat surface without unevenness in the measurement area

[0070] It is preferable that the surface development area ratio (Sdr) of the surface on the protective film (C) side (the surface in contact with the protective film (C)) of the clear layer (B) is less than 2.8×10^(-3). When the Sdr is within this range, it is considered that the surface smoothness after peeling the protective film is good and the design property is enhanced. The Sdr is more preferably less than 2.0×10^(-3), still more preferably less than 3.5×10^(-4), and even more preferably less than 3.5×10^(-5). The Sdr of the surface on the protective film (C) side of the clear layer can be made substantially the same value as the Sdr of the surface on the clear layer side of the protective film by pressing the protective film before the clear layer is completely cured.

[0071] (Protective film (C)) The protective film has the function of protecting the clear layer and any design layer of the laminated film until use. The protective film of the laminated film according to the present invention preferably has good surface smoothness on the surface on the clear layer side. Specifically, for the protective film (C), the surface development area ratio (Sdr) of the surface on the clear layer (B) side (the surface in contact with the clear layer (B)) is less than 2.8×10^(-3). When the Sdr is 2.8×10^(-3) or more, fine unevenness is transferred to the clear layer (B), and gloss and DOI decrease. 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] In addition, it is preferable that the surface development area ratio (Sdr) of the surface of the protective film (C) that does not contact the clear layer (B) is 2.0×10^(-3) or more. When the Sdr is 2.0×10^(-3) or more, blocking between the protective film (C) and the opposite surface side of the adhesive layer (D) of the release liner (E) can be prevented. The above Sdr is more preferably 1.0*10^(-2) or more, and even more preferably 5.0*10^(-2) or more.

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

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

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

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

[0077] Examples of the polyolefin film include a polyethylene film, a polypropylene film, an unstretched polypropylene film (CPP film), and a biaxially stretched polypropylene film (OPP film).

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

[0079] Examples of the polystyrene resin film include a polystyrene film, an AS resin film, and an ABS resin film. As the protective film, those containing polyethylene terephthalate (PET) are particularly preferred. When polyethylene terephthalate is contained, when laminated so that the surface that does not contact the adhesive layer of the release liner (E) and the surface that does not contact the clear layer (B) of the protective film (C) contact each other in a state where the clear layer (B) is not fully cured, it is possible to sufficiently prevent the surface roughness of the surface that does not contact the clear layer (B) of the protective film (C) from being transferred to the clear layer (B) through the protective film (C).

[0080] The thickness of the protective film may be adjusted as appropriate. For example, it is preferably 25 μm or more and 100 μm or less in average thickness. When the average thickness is 25 μm or more, when laminated so that the surface that does not contact the adhesive layer of the release liner (E) and the surface that does not contact the clear layer (B) of the protective film (C) contact each other in a state where the clear layer (B) is not fully cured, it is possible to sufficiently prevent the surface roughness of the surface that does not contact the clear layer (B) of the protective film (C) 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, it is possible to sufficiently prevent film displacement due to the difference between the inner and outer circumferences and the protective film (C) from floating from the clear layer (B). More preferably, 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 surfaces, such as the surface on the clear layer side and the surface on the side opposite to the clear layer side. The protective film may be subjected to surface modification treatments such as corona treatment or low-temperature plasma treatment. Further, the protective film may contain additives such as an antistatic agent and an ultraviolet inhibitor.

[0082] Commercially available products may be used as the protective film. Examples of commercially available products of the protective film include products with the trade name "Unipile (registered trademark)" manufactured by Unitika Ltd., products with the trade names "Lumirror (registered trademark) S-10, T-60, U-40, Serapile (registered trademark) WZ" manufactured by Toray Industries, Inc., products with the trade name "Purex A54" manufactured by Teijin Film Solutions Co., Ltd., products with the trade names "PET Separator TF-535, PET38X1-TR3" manufactured by Nippa Co., Ltd., products with the trade names "Film Bina (registered trademark) NT-2, NSP-5" manufactured by Fujimori Kogyo Co., Ltd., products with the trade name "PLD38X" manufactured by Lintec Corporation, products with the trade names "SP4030", "SP4035" manufactured by Toyo Boseki Co., Ltd., products with the trade name "RF1·CS006" manufactured by AIM Co., Ltd., products with the trade name "PET238" manufactured by Nippon Mattei Co., Ltd., products with the trade name "Cosmo Shine (registered trademark) A4160" manufactured by Toyobo Co., Ltd., and the like.

[0083] (Design layer (F)) The design layer is a coating film of a paint for the design layer and is the layer that bears the main design property of the laminated film. As the design layer, a conventionally known base layer of a topcoat film for automobiles, a design layer or a colored layer of a decorative laminate can be used.

[0084] As the paint for the design layer for forming the design layer, a conventionally known paint for the design layer or a paint for the base coating film can be used. The paint for the design 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 in the above paint for the clear layer.

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

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

[0088] The resin component of the paint for the design layer and the resin component of the paint for the clear layer may be the same or different. However, from the perspective 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, similar to the paint for the clear layer. As the acrylic resin and the isocyanate compound, those described for the paint for the clear layer can be preferably used.

[0089] The pigment for the paint for the design layer is not particularly limited, and known pigments can be used. Examples of the pigment include inorganic pigments, organic pigments, etc. Examples of the pigment include metals such as aluminum, copper, zinc, iron, nickel, tin, aluminum oxide; alloys thereof; pearlescent pigments such as interference mica, white mica, graphite, glass flakes, alumina flakes; and pearlescent pigments in which these metals, alloys, interference mica, white mica, graphite, glass flakes or alumina flakes are coated with a metal oxide (e.g., titanium oxide, titanium dioxide, iron oxide) or a metal (e.g., gold, silver). In addition, for example, the alumina flake pigment (a) described in JP-A No. 2016-221473; pearlescent pigments in which a metal substrate or a glass flake substrate is coated with a metal oxide or a metal; pearlescent pigments in which a coloring pigment is chemisorbed on 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-shaped iron oxide pigments; pearlescent pigments in which the surfaces of interference mica, graphite or silica flakes are coated with titanium dioxide; plate-shaped iron oxide pigments, etc. are included.

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

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

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

[0093] In addition to the resin component and the solvent, conventionally known additives used in the paint for the design layer may be blended in the paint for the design layer. Examples of such additives include the additives exemplified for the above-mentioned clear layer paint.

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

[0095] In one embodiment, the viscosity of the paint for the clear layer is 10 to 1000 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, it is 5 to 35 μm, preferably 15 to 30 μm.

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

[0098] (DOI) Evaluation after bonding to the adherend is conducted as follows. The protective film (C) and the release liner (E) of the laminated film are peeled off, and the surface of the adhesive layer (D) is bonded to a smooth glass plate at a linear pressure of 2 kg / 10 cm using a rubber roller. The bonded article is placed at a position where the distance from the fluorescent lamp is 1.8 m, the angle formed by the straight line connecting the central point of the fluorescent lamp and the central point of the article, and the perpendicular line to the ground is 20 degrees, with the clear layer (B) side facing the fluorescent lamp. Then, the image of the fluorescent lamp is visually observed from a position where the angle formed by the straight line connecting the central point of the fluorescent lamp and the central point of the article, and the straight line connecting the central point of the article and the observer's eye is 40 degrees, and the distance between the central point of the article and the observer's eye is 50 cm, and the determination is made according to the following criteria. Good: There is almost no distortion or blurring of the outer shape of the fluorescent lamp, and it can be clearly seen. Fair: The outer shape of the fluorescent lamp can be recognized, but it appears distorted or blurred. Poor: It is difficult to recognize the outer shape of the fluorescent lamp.

[0099] Evaluation before bonding to the adherend is conducted as follows. The laminated film with the protective film (C) peeled off is placed at a position where the distance from the fluorescent lamp is 1.8 m, the angle formed by the straight line connecting the central point of the fluorescent lamp and the central point of the film, and the perpendicular line to the ground is 20 degrees, with the clear layer (B) side facing the fluorescent lamp. Then, the image of the fluorescent lamp is visually observed from a position where the angle formed by the straight line connecting the central point of the fluorescent lamp and the central point of the film, and the straight line connecting the central point of the film and the observer's eye is 40 degrees, and the distance between the central point of the film and the observer's eye is 50 cm, and the determination is made according to the following criteria. Good: There is almost no distortion or blurring of the outer shape of the fluorescent lamp, and it can be clearly seen. Fair: The outer shape of the fluorescent lamp can be recognized, but it appears distorted or blurred. Poor: It is difficult to recognize the outer shape of the fluorescent lamp.

[0100] In order for the uneven shape imparted to the adhesive layer (D) not to have an adverse effect on the appearance quality, it is desirable that there is no difference between the determination before bonding to the adherend and the determination after bonding to the adherend.

[0101] (Method for manufacturing laminated film) For each layer other than the protective film (C) and the base material layer (A) constituting the laminated film of the present invention, a coating composition in which the components constituting each layer are dissolved in a solvent is prepared, applied directly onto the base material layer (A) and dried, and then the protective film (C) and the release liner (E) are laminated onto the laminate thus formed to obtain a laminated structure, or a coating composition in which the components constituting the adhesive layer are dissolved in a solvent is applied and dried onto the release liner (E), and the base material layer (A) laminated with the clear layer (B) or the like 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 manufacturing method preferably includes a step (I) of pressing the protective film (C) or the base material layer (A) against the clear layer (B) in a state where the clear layer (B) is not fully cured, and then fully curing the clear layer (B). The fully cured state means that the residual ratio of thermosetting reactive groups such as isocyanate groups and epoxy groups is less than 10%, and the residual ratio of photocurable reactive groups such as acryloyl groups is less than 50%. The non-fully cured state means that the residual ratio of thermosetting reactive groups such as isocyanate groups and epoxy groups is 10% or more, and the residual ratio of photocurable reactive groups such as acryloyl groups is 50% or more. The residual ratio of thermosetting reactive groups and the residual ratio 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 the reaction in infrared spectroscopy (IR).

[0103] For example, (1) a step of applying a coating for the clear layer onto the protective film (C), drying to form a film, pressing the base material layer (A) or the surface having the design layer (F) of the base material layer (A) in a state where the clear layer (B) is not fully cured, and then fully curing; (2) a step of applying a coating for the clear layer onto the base material layer (A) or the surface having the design layer (F) of the base material layer (A), drying to form a film, pressing the protective film (C) in a state where the clear layer (B) is not fully cured, and then fully curing, etc. can be mentioned. The fully curing step is preferably a heat curing step of curing at 40 degrees 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 surface of the release liner (E) having an uneven shape and laminating the adhesive layer (D) on the opposite side of the clear layer (B) of the base material layer (A). By the above step, the uneven shape previously imparted to the release liner (E) is transferred to the surface of the adhesive layer (D) on the release liner (E) side. The paint for the adhesive layer is preferably applied so that the dry film thickness is 4 μm or more greater than the height of the protrusions of the uneven shape. Also, the surface of the adhesive layer (D) on the opposite side of the release liner (E) may be covered with an arbitrary cover film as necessary, and while peeling off the cover film, it may be laminated on the opposite side of the clear layer (B) of the base material layer (A).

[0105] The coating method of each coating composition is not particularly limited, and a conventionally known coating method can be used. Examples of the coating method include spraying, applicator, die coater, bar coater, roll coater, comma coater, roller, brush, spatula, etc. After applying each coating composition, drying may be performed by heating or at room temperature as necessary. When heating, for example, the temperature may be 60 to 130 °C for 1 to 20 minutes.

[0106] Regarding the adhesive layer (D), it may be formed by a method of applying and drying the paint for the adhesive layer, or it may be adhered by a lamination method. That is, it may be formed by a method of preparing a film formed by the adhesive layer (D) and adhering it by lamination.

[0107] (Usage method) The laminated film of the present invention can be used, for example, by laminating it on an adherend, for an article comprising the adherend and the laminated film laminated on the adherend. When decorating an adherend using the laminated film of the present invention, it may be carried out in the same manner as a conventionally known method, and is not particularly limited. That is, the laminated film is pressure-bonded and decorated so that the adhesive layer faces the surface of the adherend and the laminated film is adhered closely. Further, in the case of the multilayer film having the layer structure shown in FIGS. 1 and 2, the protective film (C) may be peeled off after pressure bonding, or may be peeled off before adhering to the surface of the adherend.

[0108] The adherend that can be suitably decorated with the laminated 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 above laminated film is not particularly limited, and examples thereof include automotive exterior parts such as automobile bodies, bumpers, front under spoilers, rear under spoilers, side under skirts, side garnishes, and door mirrors, automotive 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 washbasin dressing tables.

Examples

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

[0110] Details of the protective film used in the examples are as follows. A-50: Cosmo Shine A4160, thickness 50 μm A-38: Equivalent to A-50 with a thickness of 38 μm, and the surface roughness parameters are Sa = 0.133 μm, Sdr = 2.1×10^(-5), Sal = 178.662 μm, and Sq = 0.007, respectively. A-25: Equivalent to a product with a thickness of 25 μm between A-25 and A-50, and the surface roughness parameters are Sa = 0.127 μm, Sdr = 1.9×10^(-5), Sal = 181.543 μm, and Sq = 0.006 respectively B-38: Film Binder 38E-0010 NSP-5 with a thickness of 38 μm C-38: PLD38X with a thickness of 38 μm D-38: PET38X1-TR3 with a thickness of 38 μm E-38: Serapil WZ with a thickness of 38 μm F-50: Lumirror T-60 with a thickness of 50 μm G-40: Trephan BO40-2500 with a thickness of 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 forming the PE layer, a cooling roll having an embossed shape was pressed against one of the molten surfaces to obtain a release liner having convex portions. The shape of the convex portions was such that the height was 15 μm and the pitch of the convex portions was 100 μm. As the LDPE, a product of Sumitomo Chemical Co., Ltd., trade name "Sumikasen CE4009" (LDPE not containing a phosphorus-based antioxidant) was used. Next, a release treatment was performed on the treated surface having the convex portion shape. Specifically, a commercially available addition-curing type silicone-based release agent (using a platinum catalyst, solvent-free type) was applied to the above-mentioned treated surface so that the coating amount was about 1.0 g / m 2 and cured by heating at 125 °C for 1 minute. Supporter films were made by replacing the polyethylene terephthalate film with a high-quality paper having a thickness of 100 μm, and by changing the height and pitch of the convex portions respectively.

[0112] (Preparation of Coating 1 for Clear Layer) 30 parts by mass of Acrylic Resin 1 (trade name "LR2671" manufactured by Mitsubishi Chemical Corporation, Tg 23°C, SP value 10.5, Mw 11000, solid content 61%), 28 parts by mass of 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%), 9 parts by mass of polycarbonate diol (trade name T5650E manufactured by Asahi Kasei Corporation), and 33 parts by mass of Hardener 1 (trade name "H1200", isocyanate compound manufactured by Nippon Paint Automotive Coatings Co., Ltd.) were mixed, and further diluted with methyl ethyl ketone as necessary to adjust the viscosity, thereby preparing Coating 1 for the clear layer (viscosity: 20 mPa·s).

[0113] (Preparation of Coating 1 for the design layer) 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 Co., Ltd.), 14 parts by mass of Rheology Control Agent 1 (trade name "PBC-212 D Paste" manufactured by Nippon Paint Automotive Coatings Co., Ltd.), 20 parts by mass of Hardener 2 (trade name "H1250" manufactured by Nippon Paint Automotive Coatings Co., Ltd.), and 5 parts by mass of MEK were mixed to prepare Coating 1 for the design layer (viscosity: 400 mPa·s).

[0114] (Preparation of the composition for the adhesive layer) 100 parts by mass of Main Agent 1 for Adhesive (trade name "SK Dyn 1811L" manufactured by Soken Chemical & Engineering Co., Ltd.) and 0.2 parts by mass of Hardener 1 for Adhesive (trade name "TD-75" manufactured by Soken Chemical & Engineering Co., Ltd.) were mixed to prepare the composition for the adhesive layer.

[0115] (Example 1) On one surface of the base material layer (A), the design paint 1 was applied with an applicator so that the dry film thickness became 20 μm to 30 μm, and then heated at 115 °C for 2 minutes to laminate the design layer (F). Next, the clear layer paint 1 was applied with an applicator on the surface of the design layer (F) opposite to the base material layer (A) so that the dry film thickness became 25 to 35 μm, and then heated at 115 °C for 3 minutes. After that, the protective film (C) was laminated by laminating while pressing the above laminated film and the protective film (C). Then, it was cured completely by curing at 60 degrees for 3 days. Next, the adhesive layer composition was applied with an applicator on the surface of the peeling liner (E) on the side having the ridge-shaped protrusion so that the dry film thickness including the ridge-shaped protrusion became 20 to 30 μm, and then heated at 100 °C for 3 minutes, and laminated while pressing on the surface of the base material layer (A) opposite to the design layer (F) to laminate the adhesive layer (D) and the peeling liner (E). Then, it was cured completely by curing at 50 degrees for 2 days. By the above, a laminated film including, in order, the protective film (C), the clear layer (B) (Sdr: 1.9*10^(-5) of the surface in contact with the protective film (C)), the design layer (F), the base material layer (A), the adhesive layer (D), and the peeling liner (E) was obtained.

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

[0117] Examples 8 to 9, Comparative Examples 3 to 11 A laminated film was obtained in the same manner as in Example 1 except that the peeling liner (E) in Example 1 was replaced with the peeling liner (E) having the physical properties shown in Table 2, respectively.

[0118] A laminate having a length of 15 cm and a width of 7 cm was cut out from the laminate of each example and comparative example, the protective film (C) and the peeling liner (E) were peeled off, and the adhesive layer (D) was bonded to a smooth glass plate with a line pressure of 2 kg / 10 cm using a rubber roller. A laminate having an adhesive layer (D), a base material layer (A), a design layer (F), and a clear layer (B) was arranged adjacent to each other in order from the surface side of the glass plate. In addition, the surface development area ratio (Sdr) of the surface of the peeled protective film (C) that contacts the clear layer (B) was measured by the method described above. Also, the arithmetic mean height (Sa), the minimum autocorrelation length (Sal), and the root mean square slope (Sdq) were measured in the same manner.

[0119] (20° gloss, 60° gloss) It was measured in accordance with JIS Z 8741.

[0120] (DOI) The laminated film before and after being bonded to the adherend was visually observed and evaluated according to the following criteria. Good or acceptable is considered a pass. Good: There is almost no distortion or blurring of the outer shape of the fluorescent lamp, and it can be clearly seen. Acceptable: The outer shape of the fluorescent lamp can be visually recognized, but it appears distorted or blurred. Unacceptable: It is difficult to visually recognize the outer shape of the fluorescent lamp.

[0121] (Back surface pressure bonding test) Each protective film (C) was bonded to the clear layer (B) that was not fully cured, and before fully curing, the side opposite to the adhesive layer (D) layer of the release liner (E) used in Example 1 (Sdr = 0.8312) was brought into contact with the opposite side of the (B) layer of each protective film (C), and while maintaining the state of applying a uniform force of 10 kg / 25 cm in the vertical direction to the film plane of the laminated film in this state, it was stored at room temperature for 1 day. 2 It was stored at room temperature for 1 day while maintaining the state of applying a uniform force of 10 kg / 25 cm in the vertical direction to the film plane of the laminated film in this state.

[0122] (Δ20° gloss, Δ60° gloss before and after the back surface pressure bonding test) The laminated film before and after the back surface pressure bonding test was fully cured by curing at 60°C for 3 days. The protective film (C) of each laminated film was peeled off, and Δ20° gloss and Δ60° gloss were measured respectively. The smaller the absolute value of the gloss difference (Δ gloss) before and after the backside pressure bonding test for each of Δ20° gloss and Δ60° gloss, the smaller the appearance deterioration when the laminated film is wound into a roll state with the clear layer (B) not fully cured, and it can be judged to be good.

[0123] (Air permeability) The air permeability of the laminated film after being bonded to the adherend was evaluated according to the following criteria. 5: Air of 1 mm in size can escape without applying force. 4: Air of 1 mm in size can escape by using a specific jig or a specific way of applying force. 3: It is difficult for air of 1 mm in size to escape, and air of 3 mm or more can escape by using a specific jig or a specific way of applying force. 2: It is difficult for air of 3 mm or more to escape. 1: No air can escape at all (qualified if 4 or more).

[0124] (Appearance) The laminated film after being bonded to the adherend was visually observed, and the appearance (visually recognizing the shape of the adhesive layer), appearance (visually recognizing the deformation during finger pressure), and appearance (visually recognizing the texture of the support film) were evaluated according to the following criteria. 5: It cannot be visually recognized at all. 4: It can hardly be visually recognized. 3: It can be visually recognized when stared at. 2: It can be visually recognized without staring. 1: It can be visually recognized even from a distance (qualified if 4 or more).

[0125]

Table 1

[0126]

Table 2

[0127] ※1 A film with a uniform adhesive surface cannot be obtained.

[0128] The laminated film obtained in the examples had few convexities and concavities that lifted, showed no decrease in vividness before and after lamination, and was shown to be a laminated film that achieved both excellent design and high air permeability.

Industrial Applicability

[0129] The laminated film of the present invention can be suitably used for decoration of automobile bodies, automobile exterior parts, interior decoration of houses, etc.

Explanation of Signs

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

Claims

1. It sequentially includes 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 side that contacts the adhesive layer (D) has an uneven shape having ridge-like protrusions 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 this.

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 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 laminated film according to Claim 1 or 2, wherein the resin layer has been subjected to a release treatment with a silicone-based release agent.

8. Furthermore, the laminated film according to Claim 1 or 2, which includes 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. Furthermore, a step (II) of forming an adhesive layer (D) on a surface having an uneven shape of a release liner (E) and laminating the adhesive layer (D) on the opposite side of the clear layer (B) of the base material layer (A) is included. The method for manufacturing a laminated film according to claim 9.

11. An article including 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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