WO2024062589A1 - Laminate having excellent chemical resistance, and transfer film for manufacturing same - Google Patents

Laminate having excellent chemical resistance, and transfer film for manufacturing same Download PDF

Info

Publication number
WO2024062589A1
WO2024062589A1 PCT/JP2022/035323 JP2022035323W WO2024062589A1 WO 2024062589 A1 WO2024062589 A1 WO 2024062589A1 JP 2022035323 W JP2022035323 W JP 2022035323W WO 2024062589 A1 WO2024062589 A1 WO 2024062589A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
laminate
transfer film
resin
thickness
Prior art date
Application number
PCT/JP2022/035323
Other languages
French (fr)
Japanese (ja)
Inventor
勝也 岩崎
朋也 前川
大介 宮地
Original Assignee
株式会社麗光
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社麗光 filed Critical 株式会社麗光
Priority to PCT/JP2022/035323 priority Critical patent/WO2024062589A1/en
Publication of WO2024062589A1 publication Critical patent/WO2024062589A1/en

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
    • B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
    • B44C1/17—Dry transfer

Definitions

  • the present invention relates to a laminate having excellent chemical resistance and a transfer film from which the same can be obtained.
  • transfer films have been used in which a release layer, functional layers (protective layer, colored layer, printing layer, hard coat layer, antireflection layer, metal thin film layer, etc.), and adhesive layer are sequentially formed on a plastic film. Then, the above-mentioned functional layer and adhesive layer (hereinafter collectively referred to as the transfer layer) formed on the release layer of the transfer film are applied to the surface of the transferred object from above the release layer of the transfer film.
  • a transfer layer is formed on the surface of the transferred object by transfer processing, and it is widely used to obtain a laminate that has various functions such as metallic luster, design such as patterns, hard coating properties, and antireflection properties. It is used.
  • the laminate is used as various products such as home appliances, automobile parts, miscellaneous goods, paper cartons, and labels.
  • Patent Document 1 discloses a transfer sheet (transfer sheet) with less foil burrs (a phenomenon in which all or part of the transfer layer in the transferred area in the vicinity of the transfer area peels off from the base sheet while remaining connected to the transfer layer).
  • the film has a structure in which a release layer, a protective layer, a design layer (decoration layer), and an adhesive layer are sequentially formed on a base sheet (plastic film), and the protective layer is made of polyol compound and isocyanurate.
  • a transfer sheet characterized by comprising a modified isocyanate compound is disclosed. This transfer sheet is intended to reduce the occurrence of foil burrs.
  • the protective layer is composed of a conventionally common polyol compound and an isocyanurate-modified isocyanate compound, there is less occurrence of foil burrs during transfer processing. Moreover, a laminate can be obtained relatively inexpensively.
  • the laminate obtained using the transfer film described in Patent Document 1 does not have a strong layer because the protective layer is composed of a conventional general polyol compound and an isocyanurate-modified isocyanate compound. Although it is possible to obtain certain surface properties such as scratch resistance, when the laminate is subjected to a chemical resistance test, the test agent penetrates from the surface of the transfer layer, causing blisters and cracks in the entire transfer layer and the base material.
  • an object of the present invention is to provide a laminate that solves all of the above problems, and a transfer film suitable for manufacturing the laminate.
  • the transfer film and laminate of the present invention that solve the above problems include the following configurations.
  • a transfer film in which at least a functional layer and an adhesive layer are sequentially formed on a plastic film, A transfer film characterized in that at least the thickness of the functional layer that satisfies conditions a, b, and c below is 3 ⁇ m or more and 8 ⁇ m or less.
  • the transfer film according to Item 1 wherein the functional layer includes at least a protective layer, an intermediate layer, and a decorative layer.
  • the decoration layer comprises at least one layer among a metal base layer, a metal thin film layer, a colored layer, and a printing layer.
  • the decoration layer includes a metal base layer and a metal thin film layer.
  • a laminate in which at least an adhesive layer and a functional layer are sequentially formed on a base material A laminate characterized in that at least the thickness of the functional layer that satisfies conditions a, b, and c below is 3 ⁇ m or more and 8 ⁇ m or less.
  • the laminate of the present invention is characterized in that the thickness of the functional layer that satisfies conditions a, b, and c below is 3 ⁇ m or more and 8 ⁇ m or less.
  • a) Consisting of at least a polyol compound and a polyisocyanate compound b) The hydroxyl value of the polyol compound is 20 mgKOH/g or more and 60 mgKOH/g or less c) Isocyanate groups contained in the polyisocyanate compound relative to the total number of hydroxyl groups contained in the polyol compound The ratio of the total number of ([NCO]/[OH] ratio) is 0.5 or more and 3.0 or less
  • the functional layer By making the functional layer have the above composition, a transfer layer that is difficult to be penetrated by various components used in chemical resistance tests can be obtained. As a result, in the laminate of the present invention, after the chemical resistance test, the overall transfer layer and the base material are less likely to suffer from deterioration in appearance due to damage such as blistering or crack formation.
  • the transfer film of the present invention includes a functional layer having the above-mentioned composition
  • the laminate of the present invention obtained using the transfer film of the present invention suffers from damage such as swelling and significant crack formation after a chemical resistance test. Deterioration of appearance due to this is less likely to occur. Further, the functional layer of the present invention is easily broken at the boundary between the transfer portion and the transferred portion, and foil burrs are less likely to occur during transfer processing. Therefore, the transfer film of the present invention is the most suitable transfer film for producing the laminate of the present invention.
  • FIG. 1 is a schematic diagram of a cross-sectional structure of one embodiment of a transfer film of the present invention, in which a release layer, a protective layer, an intermediate layer, a metal base layer, a metal thin film layer, and an adhesive layer are sequentially formed on a plastic film.
  • FIG. 2 is a schematic diagram of a cross-sectional structure of one embodiment of the laminate of the present invention, in which an adhesive layer, a metal thin film layer, a metal base layer, an intermediate layer, and a protective layer are sequentially formed on a base material.
  • FIG. 1 is a schematic diagram of a cross-sectional structure of one embodiment of a transfer film of the present invention, in which a release layer, a protective layer, an intermediate layer, a metal base layer, a metal thin film layer, and an adhesive layer are sequentially formed on a plastic film.
  • FIG. 2 is a schematic diagram of a cross-sectional structure of one embodiment of the laminate of the present invention, in which an adhesive layer, a metal thin film layer
  • FIG. 2 is a schematic diagram of a cross-sectional structure of one embodiment of the transfer film of the present invention, in which a release layer, a protective layer, an intermediate layer, and an adhesive layer are sequentially formed on a plastic film.
  • FIG. 2 is a schematic diagram of a cross-sectional structure of one embodiment of the laminate of the present invention, in which an adhesive layer, an intermediate layer, and a protective layer are sequentially formed on a base material.
  • the plastic film used in the transfer film of the present invention is not particularly limited as long as it is a plastic film generally used for transfer films, and various types such as polyethylene terephthalate film, polycarbonate film, polyethylene film, polypropylene film, polyamide film, etc. can be used. Conventionally known plastic films can be used.
  • the plastic film may be unstretched, uniaxially stretched, or biaxially stretched, and may contain various additives such as antistatic agents, colorants, and heat stabilizers.
  • the type of plastic film may be appropriately selected depending on the desired use and purpose.
  • the surface of the plastic film (the surface on which the release layer will be formed) may be subjected to hairline processing, matte processing, embossing, etc.
  • the surface may be textured.
  • the thickness of the plastic film used in the transfer film of the present invention is not particularly limited, but is preferably 12 to 250 ⁇ m. If the thickness of the plastic film is thinner than 12 ⁇ m, it will not only be more likely to curl, but also more likely to crease and wrinkle when forming a release layer etc. on the plastic film or when handling the transfer film of the present invention. This is not preferable because it may become difficult to handle. If the thickness of the plastic film is more than 250 ⁇ m, the so-called stiffness will become strong, and when performing a transfer process using the transfer film of the present invention, it will be difficult to place it on the surface of the substrate that is the transferred object, etc. This is not preferred as it may become difficult to handle.
  • the transfer film of the present invention may have a release layer formed thereon. As long as the protective layer described below satisfies the mold releasability, the mold release layer may not be formed.
  • the release layer is formed on a plastic film for the purpose of making it easier to peel off the transfer layer from the release layer of the transfer film of the present invention when performing transfer processing using the transfer film of the present invention. This is the layer in which people live. Furthermore, during the transfer process, the release layer is not transferred or formed on the surface of the object to be transferred, but is removed from the object together with the plastic film.
  • the release layer is a layer made of a resin.
  • resins such as polyethylene-based resins, polypropylene-based resins, polystyrene-based resins, vinyl chloride-based resins, polyester-based resins, acrylic-based resins, urethane-based resins, melamine-based resins, and epoxy-based resins can be used. Any one of these resins or a mixture of two or more of them may be used, and the resin may be selected appropriately according to the purpose.
  • the thickness of the release layer may be appropriately selected within a range that can achieve the above objective, and is preferably in the range of 0.5 to 5 ⁇ m.
  • conventionally known coating methods such as gravure coating method, reverse coating method, die coating method, reverse gravure coating method, bar coating method, etc. can be used, and can be selected as appropriate depending on the purpose. do it.
  • the functional layer of the present invention is formed so that the thickness of the layer satisfying the following conditions is 3 ⁇ m or more and 8 ⁇ m or less.
  • a) Consisting of at least a polyol compound and a polyisocyanate compound b) The hydroxyl value of the polyol compound is 20 mgKOH/g or more and 60 mgKOH/g or less c) The isocyanate group contained in the polyisocyanate compound relative to the total number of hydroxyl groups contained in the polyol compound The ratio of the total number of ([NCO]/[OH] ratio) is 0.5 or more and 3.0 or less
  • the above-mentioned polyol compound is not particularly limited, and for example, acrylic polyol, polyester polyol, polyether polyol, hydroxyl group-containing fluororesin, etc. may be used alone or in any combination of multiple types. can. In particular, it is most desirable to use an acrylic polyol compound from the viewpoint of imparting not only chemical resistance but also weather resistance.
  • the above-mentioned isocyanate compound is not particularly limited, but for example, aromatic diisocyanate compounds such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), etc.
  • a resin that satisfies the above conditions will be expressed as a resin that is a feature of the present invention.
  • the functional layer may include a layer that does not meet the above conditions, and its materials include polyethylene resin, polypropylene resin, polystyrene resin, vinyl chloride resin, polyester resin, acrylic resin, urethane resin, etc.
  • resins such as resins, melamine resins, and epoxy resins can be used, and any one of these resins or a mixture of two or more resins may be used, and the resins may be selected as appropriate depending on the purpose of forming the layer. do it.
  • a curing agent such as an isocyanate compound may be included.
  • the hydroxyl value of the polyol compound in the resin is 20 mgKOH/g or more and 60 mgKOH/g or less. If it is less than 20 mgKOH/g, sufficient crosslinking density will not be obtained and chemical resistance will deteriorate. Moreover, if it is larger than 60 mgKOH/g, foil burrs are likely to occur. Further, the ratio of the total number of isocyanate groups contained in the polyisocyanate to the total number of hydroxyl groups contained in the polyol ([NCO]/[OH] ratio) is preferably 0.5 or more and 3.0 or less, preferably less than 0.5.
  • the total thickness of the layer made of resin which is a feature of the present invention, is preferably 3 ⁇ m or more and 8 ⁇ m or less. If it is thinner than 3 ⁇ m, the test agent will easily penetrate in the chemical resistance test, and the appearance will tend to deteriorate. Further, if the thickness is greater than 8 ⁇ m, foil burrs are likely to occur during transfer processing.
  • Examples of the structure of the functional layer of the present invention include the following combinations.
  • the layers shown in parentheses are layers located above and below the example functional layer in the thickness direction.
  • any combination of layers other than this can be applied depending on the desired purpose. Any combination of these layers may be made of the resin that is a feature of the present invention.
  • the layer may be made of a specific resin that is a feature of the present invention, and other layers may be a combination of resins other than the resin that is a feature of the present invention. Even in any combination, chemical resistance can be obtained as long as the total thickness of the resin layers, which is a feature of the present invention, is 3 ⁇ m or more.
  • the protective layer of the present invention is formed on the plastic film or release layer on the transfer layer side for the purpose of stabilizing the releasability of the transfer film of the present invention.
  • the protective layer is peeled off at the interface between the plastic film or release layer and the protective layer.
  • the transfer layer is transferred and formed on the surface of the transfer object, and the transfer layer of the obtained laminate is protected.
  • the resins described in the functional layer above can be used. Furthermore, one or more types of various additives such as antistatic agents, ultraviolet absorbers, heat stabilizers, and hardening agents may be added to the protective layer as necessary, and the amounts of the various additives may be determined depending on the purpose. It may be selected as appropriate.
  • the resin which is a feature of the present invention, as a protective layer, it is desirable to provide the above-mentioned release layer from the viewpoint of releasability. If no mold release layer is provided or if the mold release layer alone does not provide stable releasability, the resin that is a feature of the present invention may not be usable from the viewpoint of releasability.
  • Resins with good mold release properties may have poor chemical resistance, but in that case, the thickness of the protective layer should be 1 ⁇ m or less, and the resin that is a feature of the present invention should be used for the intermediate layer, etc., which will be described later. By doing so, deterioration of the appearance can be suppressed to an extent that does not pose a problem in actual use.
  • the thickness of the protective layer may be appropriately selected within a range that can achieve the above objective, and is preferably in the range of 0.5 to 5 ⁇ m.
  • conventionally known coating methods such as gravure coating method, reverse coating method, die coating method, reverse gravure coating method, bar coating method, etc. can be used, and the method should be selected as appropriate depending on the purpose. Bye.
  • the intermediate layer of the transfer film of the present invention is a layer formed on the protective layer for the purpose of supplementing the chemical resistance of functional layers other than the intermediate layer. That is, when the functional layers other than the intermediate layer are made of resin, which is a feature of the present invention, and have chemical resistance, the intermediate layer does not need to be formed. Furthermore, if the thickness of the layer made of resin, which is a feature of the present invention, in a functional layer other than the intermediate layer is insufficient, chemical resistance can be obtained by providing an intermediate layer made of resin, which is a feature of the present invention. .
  • the above-mentioned or below-mentioned protective layer, metal base layer, colored layer, or printing layer cannot use the above-mentioned resin having the characteristics of the present invention in view of its purpose, it is made of the resin having the characteristics of the present invention.
  • the layer thickness 3 ⁇ m or more it is preferable to form an intermediate layer.
  • the resin that characterizes the present invention as described in the functional layer above can be used.
  • various additives such as antistatic agents, ultraviolet absorbers, heat stabilizers, and hardening agents may be added to the intermediate layer as necessary, and the amounts of the various additives may be determined depending on the purpose. It may be selected as appropriate.
  • the thickness of the intermediate layer may be appropriately selected within a range that allows the above-mentioned object to be achieved, and is preferably in the range of 0.5 to 5 ⁇ m.
  • the intermediate layer may be formed by any of the conventional coating methods such as gravure coating, reverse coating, die coating, reverse gravure coating, and bar coating, which may be appropriately selected depending on the purpose.
  • the transfer film of the present invention may include a colored layer using a coloring agent, a printed layer, and a metal thin film layer formed for the purpose of imparting design to the transferred object.
  • the colored layer is a layer formed by adding a pigment or dye to a resin and forming it on the entire surface or a desired part of the transfer film of the present invention.
  • the printed layer is a layer in which colored portions are formed in a desired pattern.
  • the resins described above for the functional layer can be used for the colored layer and the printing layer.
  • a resin, which is a feature of the present invention may be used for the colored layer and the printing layer.
  • one or more types of various additives such as antistatic agents, ultraviolet absorbers, heat stabilizers, and hardening agents may be added, and the amount of each additive to be added should be selected as appropriate depending on the purpose. Bye.
  • the thickness of the colored layer and printed layer may be any thickness that can obtain the desired effect of the colored layer and printed layer, and is preferably in the range of 0.5 to 5 ⁇ m, respectively. It may be selected as appropriate depending on the purpose of forming.
  • the colored layer and the printed layer can be formed using conventionally known coating methods such as gravure coating, reverse coating, die coating, reverse gravure coating, bar coating, screen printing, and offset printing. can be selected as appropriate depending on the purpose.
  • the metal underlayer is a layer formed for the purpose of adhering a protective layer, intermediate layer, colored layer or printed layer to a metal thin film layer when the metal thin film layer described below is formed on the transfer film of the present invention.
  • the resin described in the above functional layer can be used for the metal base layer.
  • the ratio of the total number of isocyanate groups contained in the polyisocyanate compound to the total number of hydroxyl groups contained in the polyol compound is 1. It is more preferable to use a resin with a particle size of .0 or more as the metal base layer, as this will strengthen the adhesion with the metal thin film layer.
  • the resin that is a feature of the present invention cannot be used for the metal base layer, it is preferable to provide an intermediate layer made of a resin that is a feature of the present invention.
  • one or more types of various additives such as antistatic agents, ultraviolet absorbers, heat stabilizers, and curing agents may be added, and the amount of each additive to be added may be selected as appropriate depending on the purpose. good.
  • the thickness of the metal base layer may be appropriately selected within a range that can achieve the above objective, and is preferably in the range of 0.5 to 2 ⁇ m.
  • conventionally known coating methods such as gravure coating, reverse coating, die coating, reverse gravure coating, and bar coating can be used, and can be selected as appropriate depending on the purpose. do it.
  • the metal thin film layer is a layer formed mainly for the purpose of imparting metallic luster to the transferred object, and is a layer that is transferred and formed on the surface of the transferred object together with the adhesive layer when a transfer process is performed. Further, by using a metal compound described below in the metal thin film layer, properties such as barrier properties and conductivity may be imparted in addition to or in place of metallic luster.
  • the metals used for the metal thin film layer include various conventionally known metals such as aluminum, chromium, tin, gold, silver, copper, zinc, silicon, nickel, and indium, or oxides, sulfides, and nitrides of the above conventionally known metals.
  • Metal compounds such as metal compounds can be used, and may be appropriately selected depending on the desired purpose.
  • the metal thin film layer may be one layer or multiple layers of two or more layers, and when the metal thin film layer is two or more layers, the metal used for each layer is different between each layer. They may be of the same species.
  • the thickness of the metal thin film layer is preferably in the range of 10 to 200 nm. If it is thinner than 10 nm, it may not be possible to impart the desired metallic luster to the transfer film of the present invention, so it is not preferable, and if it is thicker than 200 nm, it may be difficult to heat or transfer during the formation of the metal thin film layer. This is not preferable because there is a risk that the plastic film may be deformed or deteriorated by the heat of the process, and it may become impossible to impart the desired metallic luster or the like to the transfer film of the present invention.
  • the method for forming the metal thin film layer can be any conventional method for forming a metal thin film layer, such as vacuum deposition, sputtering, or chemical vapor deposition (CVD), and can be appropriately selected depending on the purpose.
  • CVD chemical vapor deposition
  • the types and order of the metal thin film layer, colored layer, printing layer, and metal base layer to be formed may be appropriately selected depending on the purpose. good.
  • the metal thin film layer, colored layer, printing layer, metal base layer, and adhesive layer described below may be formed on the entire surface of the protective layer or partially, and the positions where they are formed may be , may be selected as appropriate depending on the purpose.
  • the adhesive layer formed on the transfer film of the present invention is not particularly limited as long as it is a thermoplastic resin generally used for transfer films, such as acrylic resin, polyethylene resin, polypropylene resin, polystyrene resin, chloride resin, etc.
  • a thermoplastic resin generally used for transfer films such as acrylic resin, polyethylene resin, polypropylene resin, polystyrene resin, chloride resin, etc.
  • Conventionally known resins such as vinyl resins, polyester resins, urethane resins, and vinyl acetate resins can be used, and any one of these resins, a mixed resin of two or more types, or a copolymer resin of two or more of these resins can be used. It may be selected as appropriate depending on the transfer target to be used. Further, it is preferable to use a resin that has good compatibility with the resin used for the object to be transferred.
  • the thickness of the adhesive layer may be appropriately selected within a range that can achieve the above objective, and is preferably in the range of 0.5 to 10 ⁇ m.
  • conventionally known coating methods such as gravure coating method, reverse coating method, die coating method, reverse gravure coating method, bar coating method, etc. can be used, and the method should be selected as appropriate depending on the purpose. Bye.
  • the laminate of the present invention can be obtained by sequentially forming the above-mentioned layers on a substrate which is a transfer target. Furthermore, in order to obtain the laminate of the present invention, it is optimal to form each layer on a base material using the transfer film of the present invention.
  • the base material may be acrylic resin, polyethylene resin, polypropylene resin, polystyrene resin, vinyl chloride resin, polyester resin, urethane resin, vinyl acetate resin, ABS resin, polycarbonate resin, etc. , conventionally known materials can be used, and it may be any one of these, a mixed resin of two or more of these, or a copolymer resin of two or more of these. Further, these base materials may be transparent or colored.
  • Step 1 A thermosetting acrylic melamine resin was coated on a polyethylene terephthalate film with a thickness of 25 ⁇ m using a bar coating method to form a release layer with a thickness of 0.5 ⁇ m.
  • Step 2 A thermoplastic acrylic resin was coated on the release layer using a bar coating method to form a protective layer with a thickness of 1 ⁇ m.
  • Step 3 On the above protective layer, An intermediate layer was formed by mixing an acrylic polyol resin and an HDI polyisocyanate compound and coating the mixture using a bar coating method. At this time, the hydroxyl value of the acrylic polyol, the ratio of the total number of isocyanate groups contained in the polyisocyanate compound to the total number of hydroxyl groups contained in the polyol compound ([NCO]/[OH] ratio), and the thickness of the intermediate layer are shown in Table 1. It was as follows. (Step 4) On the intermediate layer, A copolymer resin of acrylic resin and vinyl acetate resin was coated using a bar coating method to form an adhesive layer with a thickness of 2 ⁇ m.
  • the obtained transfer film was placed on an ABS base material with the adhesive layer facing the base material side, and pressure and heating were applied from the plastic film side using a roll transfer machine to a transfer temperature of 200°C. After performing transfer processing at a transfer speed of 50 mm/sec, the plastic film containing the release layer was immediately peeled off to obtain a laminate.
  • Step 1 A thermosetting acrylic melamine resin was coated on a polyethylene terephthalate film having a thickness of 25 ⁇ m by a bar coating method to form a release layer having a thickness of 0.5 ⁇ m.
  • Step 2 A thermoplastic acrylic resin was coated on the release layer by a bar coating method to form a protective layer having a thickness of 1 ⁇ m.
  • Step 3 On the protective layer, An acrylic polyol resin having a hydroxyl value of 24 mgKOH/g and an HDI-based polyisocyanate compound were mixed so that the ratio of the total number of isocyanate groups contained in the polyisocyanate compound to the total number of hydroxyl groups contained in the polyol compound ([NCO]/[OH] ratio) was 0.8, and the mixture was coated by a bar coating method to form an intermediate layer having a thickness of 2 ⁇ m.
  • Step 4 On the intermediate layer, An acrylic polyol resin having a hydroxyl value of 24 mgKOH/g and an HDI-based polyisocyanate compound were mixed so that the ratio of the total number of isocyanate groups contained in the polyisocyanate compound to the total number of hydroxyl groups contained in the polyol compound ([NCO]/[OH] ratio) was 2.0, and the mixture was coated by a bar coating method to form a metal undercoat layer having a thickness of 1 ⁇ m.
  • Step 5 On the metal underlayer, Chromium was deposited by vacuum deposition to form a thin chromium layer having a thickness of 50 nm.
  • Step 6 A copolymer resin of an acrylic resin and a vinyl acetate resin was coated on the chromium thin film layer by a bar coating method to form an adhesive layer having a thickness of 2 ⁇ m.
  • [Creation of Laminate] The above steps were carried out, and using the resulting transfer film, a laminate was obtained in the same manner as in Example 1.
  • Step 1 A thermosetting acrylic melamine resin was coated on a polyethylene terephthalate film with a thickness of 25 ⁇ m using a bar coating method to form a release layer with a thickness of 0.5 ⁇ m.
  • Step 2 A thermoplastic acrylic resin was coated on the above mold release layer by a bar coating method to form a protective layer having a thickness of 1 ⁇ m.
  • Step 3 On the above protective layer, The ratio of the total number of isocyanate groups contained in the polyisocyanate compound to the total number of hydroxyl groups contained in the polyol compound ([NCO]/[OH] ratio) is 0.8 and coated using a bar coating method to form an intermediate layer with a thickness of 3 ⁇ m.
  • Step 4 A copolymer resin of an acrylic resin and a vinyl acetate resin was coated on the intermediate layer by a bar coating method to form an adhesive layer with a thickness of 2 ⁇ m.
  • [Creation of laminate] A laminate was obtained in the same manner as in Example 1 using the transfer film obtained by carrying out the above steps.
  • Step 1 A thermosetting acrylic melamine resin was coated on a polyethylene terephthalate film having a thickness of 25 ⁇ m by a bar coating method to form a release layer having a thickness of 0.5 ⁇ m.
  • Step 2 A thermoplastic acrylic resin was coated on the release layer by a bar coating method to form a protective layer having a thickness of 1 ⁇ m.
  • Step 3 On the protective layer, An acrylic polyol resin having a hydroxyl value of 24 mgKOH/g and an HDI-based polyisocyanate compound were mixed so that the ratio of the total number of isocyanate groups contained in the polyisocyanate compound to the total number of hydroxyl groups contained in the polyol compound ([NCO]/[OH] ratio) was 0.8, and a black pigment was added in an amount of 10% by weight relative to the resin, and the mixture was coated by a bar coating method to form a colored layer having a thickness of 3 ⁇ m.
  • Step 4 A copolymer resin of an acrylic resin and a vinyl acetate resin was coated on the colored layer by a bar coating method to form an adhesive layer having a thickness of 2 ⁇ m.
  • [Creation of Laminate] The above steps were carried out, and using the resulting transfer film, a laminate was obtained in the same manner as in Example 1.
  • Step 1 A thermosetting acrylic melamine resin was coated on a polyethylene terephthalate film with a thickness of 25 ⁇ m using a bar coating method to form a release layer with a thickness of 0.5 ⁇ m.
  • Step 2 A thermoplastic acrylic resin was coated on the release layer using a bar coating method to form a protective layer with a thickness of 1 ⁇ m.
  • Step 3 On the above protective layer, The ratio of the total number of isocyanate groups contained in the polyisocyanate compound to the total number of hydroxyl groups contained in the polyol compound ([NCO]/[OH] ratio) is 2.0 and coated using a bar coating method to form a metal base layer with a thickness of 3 ⁇ m.
  • Step 4 On the metal base layer, Chromium was formed by vacuum evaporation to form a chromium thin film layer with a thickness of 50 nm.
  • Step 5 A copolymer resin of acrylic resin and vinyl acetate resin was coated on the chromium thin film layer by a bar coating method to form an adhesive layer with a thickness of 2 ⁇ m.
  • [Creation of laminate] A laminate was obtained in the same manner as in Example 1 using the transfer film obtained by carrying out the above steps.
  • Step 1 A thermosetting acrylic melamine resin was coated on a polyethylene terephthalate film with a thickness of 25 ⁇ m using a bar coating method to form a release layer with a thickness of 0.5 ⁇ m.
  • Step 2 On the above mold release layer, The ratio of the total number of isocyanate groups contained in the polyisocyanate compound to the total number of hydroxyl groups contained in the polyol compound ([NCO]/[OH] ratio) is 0.8 and coated using a bar coating method to form a protective layer with a thickness of 1 ⁇ m.
  • Step 3 On the above protective layer, The ratio of the total number of isocyanate groups contained in the polyisocyanate compound to the total number of hydroxyl groups contained in the polyol compound ([NCO]/[OH] ratio) is 0.8, and then coated with a black pigment added in a weight ratio of 10% to the resin using a bar coating method to form a colored layer with a thickness of 1 ⁇ m.
  • Step 4 On the colored layer, The ratio of the total number of isocyanate groups contained in the polyisocyanate compound to the total number of hydroxyl groups contained in the polyol compound ([NCO]/[OH] ratio) is 2.0 and coated using a bar coating method to form a metal base layer with a thickness of 1 ⁇ m.
  • Step 5 On the metal base layer, Chromium was formed by vacuum evaporation to form a chromium thin film layer with a thickness of 50 nm.
  • Step 6 A copolymer resin of acrylic resin and vinyl acetate resin was coated on the chromium thin film layer by a bar coating method to form an adhesive layer with a thickness of 2 ⁇ m.
  • [Creation of laminate] A laminate was obtained in the same manner as in Example 1 using the transfer film obtained by carrying out the above steps.
  • Step 1 A thermosetting acrylic melamine resin was coated on a polyethylene terephthalate film with a thickness of 25 ⁇ m using a bar coating method to form a release layer with a thickness of 0.5 ⁇ m.
  • Step 2 On the above mold release layer, The ratio of the total number of isocyanate groups contained in the polyisocyanate compound to the total number of hydroxyl groups contained in the polyol compound ([NCO]/[OH] ratio) is 0.8 and coated using a bar coating method to form a protective layer with a thickness of 1 ⁇ m.
  • Step 3 On the above protective layer, The ratio of the total number of isocyanate groups contained in the polyisocyanate compound to the total number of hydroxyl groups contained in the polyol compound ([NCO]/[OH] ratio) is 2.0 and coated using a bar coating method to form a metal base layer with a thickness of 1 ⁇ m.
  • Step 4 On the metal base layer, Chromium was formed by vacuum evaporation to form a chromium thin film layer with a thickness of 50 nm.
  • Step 5 A copolymer resin of acrylic resin and vinyl acetate resin was coated on the metal thin film layer by a bar coating method to form an adhesive layer with a thickness of 2 ⁇ m.
  • [Creation of laminate] A laminate was obtained in the same manner as in Example 1 using the transfer film obtained by carrying out the above steps.
  • Example 17 to 20 [Preparation of transfer film and laminate] A laminate was obtained in the same manner as in Example 1, except that the polyol compounds and the polyisocyanate compounds in step 3 of Example 1 were combined as shown in Table 3.
  • the hydroxyl value of the acrylic polyol, the ratio of the total number of isocyanate groups contained in the polyisocyanate compound to the total number of hydroxyl groups contained in the polyol compound ([NCO]/[OH] ratio), and the thickness of each layer are as shown in Table 3. And so. However, a layer described as having a thickness of 0 ⁇ m does not form that layer.
  • the same thermoplastic acrylic resin as in Step 2 (protective layer) of Example 1 was used.
  • Comparative Example 9 a thermoplastic acrylic resin was used as the intermediate layer, and an intermediate layer having a thickness of 1 ⁇ m was formed by a bar coating method. moreover.
  • thermoplastic acrylic resin to which a black pigment was added in an amount of 10% by weight based on the resin was used, and a colored layer having a thickness of 6 ⁇ m was formed by a bar coating method.
  • Al, Cr, and In in the table represent aluminum, chromium, and indium, respectively, and the metal thin film layers were all formed to a thickness of 50 nm by a vacuum evaporation method.
  • a commercially available sunscreen cosmetic with SPF 50 was used.
  • ⁇ No change in appearance such as swelling, cracks, or discoloration.
  • ⁇ There are slight changes in appearance such as blisters, cracks, and discoloration, but this does not pose a problem in actual use.
  • ⁇ There are changes in appearance such as swelling, cracks, and discoloration.
  • ⁇ There is a significant change in appearance such as blisters, cracks, and discoloration.
  • ⁇ In any of the tests (1) to (3), there is a slight change in appearance such as blistering, cracking, or discoloration, but this does not pose a problem in actual use. ⁇ : In any of the tests (1) to (3), there is a change in appearance such as blistering, cracking, or discoloration. ⁇ : In any of the tests (1) to (3), there is a significant change in appearance such as blistering, cracking, or discoloration.
  • foil burr evaluation When creating a laminate using a transfer film, it was evaluated whether or not foil burrs were generated. ⁇ : No foil burrs occur. ⁇ : Slight burrs occur in the foil, but there is no problem in actual use. ⁇ : Foil burrs occur.

Abstract

[Problem] To obtain a laminate having improved chemical resistance, and a transfer film for creating the laminate while suppressing the occurrence of foil burr. [Solution] Provided is a transfer film 11 in which a release layer 2, a protective layer 3, an intermediate layer 4, a metal base layer 5, a metal thin film layer 6, and an adhesive layer 7 are formed in the stated order on a substrate 1, wherein the transfer film is characterized in that, from among functional layers 10 such as the protective layer 3, the intermediate layer 4, the metal base layer 5, the metal thin film layer 6, etc., the thickness of layers that satisfy conditions a, b, and c in the thickness of the functional layers 10 is 3-8 µm. a): Comprising at least a polyol compound and polyisocyanate compound. b): The hydroxyl value of the polyol compound is 20-60 mg KOH/g. c): The ratio ([NCO]/[OH]) of the total number of isocyanate groups included in the polyisocyanate compound with respect to the total number of hydroxyl groups included in the polyol compound is 0.5-3.0.

Description

耐薬品性に優れる積層体およびそれを製造するための転写フイルムLaminate with excellent chemical resistance and transfer film for manufacturing it
本発明は耐薬品性に優れる積層体およびそれを得ることができる転写フイルムに関する。 The present invention relates to a laminate having excellent chemical resistance and a transfer film from which the same can be obtained.
従来から、プラスチックフイルム上に、離型層、機能層（保護層、着色層、印刷層、ハードコート層、反射防止層、金属薄膜層等）、及び接着層が順次形成された転写フイルムを使用し、該転写フイルムの離型層上に形成された上記、機能層、及び接着層（以下、これらの層をまとめて転写層という。）を、転写フイルムの離型層上から被転写物表面に転写加工することで、被転写物表面に転写層が形成され、金属光沢や図柄等の意匠性、ハードコート性、反射防止性等の各種機能が付与された積層体を得る方法が広く一般に使用されている。
そして、該積層体は、家電製品や自動車の部品、雑貨、紙器、ラベル等の各種製品として利用されている。 Traditionally, transfer films have been used in which a release layer, functional layers (protective layer, colored layer, printing layer, hard coat layer, antireflection layer, metal thin film layer, etc.), and adhesive layer are sequentially formed on a plastic film. Then, the above-mentioned functional layer and adhesive layer (hereinafter collectively referred to as the transfer layer) formed on the release layer of the transfer film are applied to the surface of the transferred object from above the release layer of the transfer film. A transfer layer is formed on the surface of the transferred object by transfer processing, and it is widely used to obtain a laminate that has various functions such as metallic luster, design such as patterns, hard coating properties, and antireflection properties. It is used.
The laminate is used as various products such as home appliances, automobile parts, miscellaneous goods, paper cartons, and labels.
積層体を自動車内外装用途に適用する場合、一般的に耐薬品性、例えば日焼け止め化粧料やガソリンといった試験剤を積層体表面に塗布し、８０℃の高温下で１０分間静置する耐薬品性試験を実施しても外観に不具合を生じない、といった性能を求められる。また、自動車メーカーは耐薬品性について各社独自の規格を設定しており、それらのいずれにも対応可能な優れた耐薬品性を備えることがより望ましい。 When applying a laminate to the interior and exterior of automobiles, chemical resistance is generally tested by applying a test agent such as sunscreen cosmetics or gasoline to the surface of the laminate and allowing it to stand for 10 minutes at a high temperature of 80°C. Performance is required such that there will be no defects in appearance even if a test is conducted. Furthermore, automobile manufacturers have set their own standards for chemical resistance, and it is more desirable to have excellent chemical resistance that can meet all of them.
特許文献１には、箔バリ（転写部分との近傍における被転写部分の転写層の全部または一部が、転写層と接続したまま基材シートから剥離してしまう現象）の少ない転写シート（転写フイルム）として、基材シート（プラスチックフイルム）上に、離型層、保護層、意匠層（加飾層）、および接着層が順次形成された構成からなり、保護層が、ポリオール化合物とイソシアヌレート変性イソシアネート化合物とからなることを特徴とする転写シートが開示されている。この転写シートは箔バリの発生を少なくすることを目的としたものである。 Patent Document 1 discloses a transfer sheet (transfer sheet) with less foil burrs (a phenomenon in which all or part of the transfer layer in the transferred area in the vicinity of the transfer area peels off from the base sheet while remaining connected to the transfer layer). The film has a structure in which a release layer, a protective layer, a design layer (decoration layer), and an adhesive layer are sequentially formed on a base sheet (plastic film), and the protective layer is made of polyol compound and isocyanurate. A transfer sheet characterized by comprising a modified isocyanate compound is disclosed. This transfer sheet is intended to reduce the occurrence of foil burrs.
特開２００３－１５４７９４号公報Japanese Patent Application Publication No. 2003-154794
特許文献１に記載の転写フイルムを使用して積層体を得る場合、保護層が従来から一般的な、ポリオール化合物とイソシアヌレート変性イソシアネート化合物とからなる為、転写加工時に箔バリの発生が少なく、また、比較的安価に積層体が得られる。しかしながら、特許文献１に記載の転写フイルムを使用して得られた積層体は、保護層が、従来の一般的なポリオール化合物とイソシアヌレート変性イソシアネート化合物とからなるため強靭な層とならず、耐擦傷性などの一定の表面物性を得ることができるものの、該積層体に耐薬品性試験を実施した際に、転写層表面から試験剤が浸透し、転写層全体および基材に膨れや亀裂が生じ、外観が悪くなる問題点があった。特に、この問題点は試験剤に日焼け止め化粧料やガソリンを使用した場合に顕著であった。以上のことから、本発明は上記の問題点のすべてを解決する積層体および、その製造に適した転写フイルムの提供を課題とする。 When obtaining a laminate using the transfer film described in Patent Document 1, since the protective layer is composed of a conventionally common polyol compound and an isocyanurate-modified isocyanate compound, there is less occurrence of foil burrs during transfer processing. Moreover, a laminate can be obtained relatively inexpensively. However, the laminate obtained using the transfer film described in Patent Document 1 does not have a strong layer because the protective layer is composed of a conventional general polyol compound and an isocyanurate-modified isocyanate compound. Although it is possible to obtain certain surface properties such as scratch resistance, when the laminate is subjected to a chemical resistance test, the test agent penetrates from the surface of the transfer layer, causing blisters and cracks in the entire transfer layer and the base material. There was a problem that the appearance deteriorated. This problem was particularly noticeable when sunscreen cosmetics or gasoline were used as test agents. In light of the above, an object of the present invention is to provide a laminate that solves all of the above problems, and a transfer film suitable for manufacturing the laminate.
本発明者らは、鋭意検討した結果、転写フイルムの離型層上（転写層側）に特定の組成の熱硬化性樹脂からなる機能層を設けることにより、耐薬品性を向上するとともに、箔バリの発生を抑制し得ることを見出し、本発明を完成させた。すなわち上記課題を解決する本発明の転写フイルムおよび積層体には以下の構成を含む。 As a result of extensive studies, the present inventors have found that by providing a functional layer made of a thermosetting resin with a specific composition on the release layer of the transfer film (transfer layer side), it is possible to improve the chemical resistance of the transfer film and to The present invention was completed based on the discovery that the occurrence of burrs can be suppressed. That is, the transfer film and laminate of the present invention that solve the above problems include the following configurations.
［項１］
プラスチックフイルム上に、少なくとも、機能層および接着層が順次形成されている転写フイルムにおいて、
少なくとも、機能層の厚さのうち、下記ａ、ｂおよびｃの条件を満たす厚さが３μｍ以上８μｍ以下であることを特徴とする転写フイルム。
ａ）少なくとも、ポリオール化合物とポリイソシアネート化合物とからなる
ｂ）ポリオール化合物の水酸基価が２０ｍｇＫＯＨ／ｇ以上６０ｍｇＫＯＨ／ｇ以下である
ｃ）ポリオール化合物に含まれる水酸基の総数に対するポリイソシアネート化合物に含まれるイソシアネート基の総数の比率（［ＮＣＯ］／［ＯＨ］比）が０．５以上３．０以下である
［項２］
機能層が、少なくとも、保護層と中間層とからなる、項１に記載の転写フイルム。
［項３］
機能層が、少なくとも、保護層と中間層と加飾層とからなる、項１に記載の転写フイルム。
［項４］
加飾層が、金属下地層、金属薄膜層、着色層および印刷層のうち少なくとも１層からなる項３に記載の転写フイルム。
［項５］
加飾層が、金属下地層と金属薄膜層とからなる、項４に記載の転写フイルム。
［項６］
項１から項５に記載の転写フイルムを基材に転写して得られることを特徴とする積層体。
［項７］
基材上に、少なくとも、接着層、および機能層が順次形成されている積層体であって、
少なくとも、機能層の厚さのうち、下記ａ、ｂおよびｃの条件を満たす厚さが３μｍ以上８μｍ以下であることを特徴とする積層体。
ａ）少なくとも、ポリオール化合物とポリイソシアネート化合物とからなる
ｂ）ポリオール化合物の水酸基価が２０ｍｇＫＯＨ／ｇ以上６０ｍｇＫＯＨ／ｇ以下である
ｃ）ポリオール化合物に含まれる水酸基の総数に対するポリイソシアネート化合物に含まれるイソシアネート基の総数の比率（［ＮＣＯ］／［ＯＨ］比）が０．５以上３．０以下である
［項８］
機能層が、少なくとも、保護層と中間層とからなる項７に記載の積層体。
［項９］
機能層が、少なくとも、保護層と中間層と加飾層とからなる項７に記載の積層体。
［項１０］
加飾層が、金属下地層、金属薄膜層、着色層および印刷層のうち少なくとも１層からなる項９に記載の積層体。
［項１１］
加飾層が、金属下地層と金属薄膜層とからなる、項１０に記載の積層体。 [Section 1]
In a transfer film in which at least a functional layer and an adhesive layer are sequentially formed on a plastic film,
A transfer film characterized in that at least the thickness of the functional layer that satisfies conditions a, b, and c below is 3 μm or more and 8 μm or less.
a) Consisting of at least a polyol compound and a polyisocyanate compound b) The hydroxyl value of the polyol compound is 20 mgKOH/g or more and 60 mgKOH/g or less c) The isocyanate group contained in the polyisocyanate compound relative to the total number of hydroxyl groups contained in the polyol compound The ratio of the total number of ([NCO]/[OH] ratio) is 0.5 or more and 3.0 or less [Item 2]
Item 2. The transfer film according to Item 1, wherein the functional layer consists of at least a protective layer and an intermediate layer.
[Section 3]
Item 2. The transfer film according to Item 1, wherein the functional layer includes at least a protective layer, an intermediate layer, and a decorative layer.
[Section 4]
4. The transfer film according to item 3, wherein the decoration layer comprises at least one layer among a metal base layer, a metal thin film layer, a colored layer, and a printing layer.
[Section 5]
Item 5. The transfer film according to Item 4, wherein the decoration layer includes a metal base layer and a metal thin film layer.
[Section 6]
A laminate obtained by transferring the transfer film according to Items 1 to 5 onto a base material.
[Section 7]
A laminate in which at least an adhesive layer and a functional layer are sequentially formed on a base material,
A laminate characterized in that at least the thickness of the functional layer that satisfies conditions a, b, and c below is 3 μm or more and 8 μm or less.
a) Consisting of at least a polyol compound and a polyisocyanate compound b) The hydroxyl value of the polyol compound is 20 mgKOH/g or more and 60 mgKOH/g or less c) Isocyanate groups contained in the polyisocyanate compound relative to the total number of hydroxyl groups contained in the polyol compound The ratio of the total number of ([NCO]/[OH] ratio) is 0.5 or more and 3.0 or less [Section 8]
Item 8. The laminate according to Item 7, wherein the functional layer includes at least a protective layer and an intermediate layer.
[Section 9]
Item 8. The laminate according to Item 7, wherein the functional layer includes at least a protective layer, an intermediate layer, and a decorative layer.
[Section 10]
Item 10. The laminate according to Item 9, wherein the decorative layer comprises at least one layer selected from a metal base layer, a metal thin film layer, a colored layer, and a printed layer.
[Section 11]
Item 11. The laminate according to Item 10, wherein the decorative layer includes a metal base layer and a metal thin film layer.
本発明の積層体は機能層の厚さのうち、下記ａ、ｂおよびｃの条件を満たす厚さが３μｍ以上８μｍ以下であることを特徴とする。
ａ）少なくとも、ポリオール化合物とポリイソシアネート化合物とからなる
ｂ）ポリオール化合物の水酸基価が２０ｍｇＫＯＨ／ｇ以上６０ｍｇＫＯＨ／ｇ以下である
ｃ）ポリオール化合物に含まれる水酸基の総数に対するポリイソシアネート化合物に含まれるイソシアネート基の総数の比率（［ＮＣＯ］／［ＯＨ］比）が０．５以上３．０以下である The laminate of the present invention is characterized in that the thickness of the functional layer that satisfies conditions a, b, and c below is 3 μm or more and 8 μm or less.
a) Consisting of at least a polyol compound and a polyisocyanate compound b) The hydroxyl value of the polyol compound is 20 mgKOH/g or more and 60 mgKOH/g or less c) Isocyanate groups contained in the polyisocyanate compound relative to the total number of hydroxyl groups contained in the polyol compound The ratio of the total number of ([NCO]/[OH] ratio) is 0.5 or more and 3.0 or less
機能層を上記の組成とすることで、耐薬品性試験で用いられる種々の成分に対し浸透されにくい転写層が得られる。結果、本発明の積層体は耐薬品性試験後に、転写層全体および基材に、膨れや亀裂の生成といった損傷が発生することによる外観の悪化の発生が少ない。 By making the functional layer have the above composition, a transfer layer that is difficult to be penetrated by various components used in chemical resistance tests can be obtained. As a result, in the laminate of the present invention, after the chemical resistance test, the overall transfer layer and the base material are less likely to suffer from deterioration in appearance due to damage such as blistering or crack formation.
本発明の転写フイルムは上記の組成からなる機能層を備えるため、本発明の転写フイルムを用いて得られる本発明の積層体は耐薬品性試験後の膨潤や著しい亀裂の生成といった損傷が発生することによる外観の悪化が発生しにくい。また、本発明の機能層は転写部と被転写部の境界での破断が容易であり、転写加工時に箔バリが発生しにくい。
従って、本発明の転写フイルムは、本発明の積層体を製造するために最適な転写フイルムである。 Since the transfer film of the present invention includes a functional layer having the above-mentioned composition, the laminate of the present invention obtained using the transfer film of the present invention suffers from damage such as swelling and significant crack formation after a chemical resistance test. Deterioration of appearance due to this is less likely to occur. Further, the functional layer of the present invention is easily broken at the boundary between the transfer portion and the transferred portion, and foil burrs are less likely to occur during transfer processing.
Therefore, the transfer film of the present invention is the most suitable transfer film for producing the laminate of the present invention.
プラスチックフイルム上に、離型層、保護層、中間層、金属下地層、金属薄膜層および接着層が順次形成されている本発明の転写フイルムの一形態の断面構造の模式図である。FIG. 1 is a schematic diagram of a cross-sectional structure of one embodiment of a transfer film of the present invention, in which a release layer, a protective layer, an intermediate layer, a metal base layer, a metal thin film layer, and an adhesive layer are sequentially formed on a plastic film. 基材上に、接着層、金属薄膜層、金属下地層、中間層および保護層が順次形成されている本発明の積層体の一形態の断面構造の模式図であるFIG. 2 is a schematic diagram of a cross-sectional structure of one embodiment of the laminate of the present invention, in which an adhesive layer, a metal thin film layer, a metal base layer, an intermediate layer, and a protective layer are sequentially formed on a base material. プラスチックフイルム上に、離型層、保護層、中間層および接着層が順次形成されている本発明の転写フイルムの一形態の断面構造の模式図であるFIG. 2 is a schematic diagram of a cross-sectional structure of one embodiment of the transfer film of the present invention, in which a release layer, a protective layer, an intermediate layer, and an adhesive layer are sequentially formed on a plastic film. 基材上に、接着層、中間層および保護層が順次形成されている本発明の積層体の一形態の断面構造の模式図であるFIG. 2 is a schematic diagram of a cross-sectional structure of one embodiment of the laminate of the present invention, in which an adhesive layer, an intermediate layer, and a protective layer are sequentially formed on a base material.
以下に本発明の転写フイルムについて説明する。 The transfer film of the present invention will be explained below.
（プラスチックフイルム）
本発明の転写フイルムに使用するプラスチックフイルムは、一般に転写フイルムに使用するプラスチックフイルムであれば、特に制限すること無く使用でき、ポリエチレンテレフタレートフイルム、ポリカーボネートフイルム、ポリエチレンフイルム、ポリプロピレンフイルム、ポリアミドフイルム等、各種従来公知のプラスチックフイルムが使用できる。 (Plastic film)
The plastic film used in the transfer film of the present invention is not particularly limited as long as it is a plastic film generally used for transfer films, and various types such as polyethylene terephthalate film, polycarbonate film, polyethylene film, polypropylene film, polyamide film, etc. can be used. Conventionally known plastic films can be used.
プラスチックフイルムは、無延伸、一軸延伸、二軸延伸の何れでもよく、また、帯電防止剤、着色剤、熱安定剤等の各種添加剤を含んでいても構わない。プラスチックフイルムの種類は、所望の用途、目的に応じて適宜選択すればよい。 The plastic film may be unstretched, uniaxially stretched, or biaxially stretched, and may contain various additives such as antistatic agents, colorants, and heat stabilizers. The type of plastic film may be appropriately selected depending on the desired use and purpose.
さらに、プラスチックフイルムには、本発明の転写フイルムを意匠性に富んだものとする目的で、プラスチックフイルムの表面（離型層を形成する側の面）に、ヘアライン加工、マット加工、エンボス加工等の凹凸加工が施されていてもよい。 Furthermore, in order to make the transfer film of the present invention rich in design, the surface of the plastic film (the surface on which the release layer will be formed) may be subjected to hairline processing, matte processing, embossing, etc. The surface may be textured.
本発明の転写フイルムに使用するプラスチックフイルムの厚さは、特に限定されないが、１２～２５０μｍであるのが好ましい。プラスチックフイルムの厚さが１２μｍよりも薄いと、プラスチックフイルム上に離型層等を形成する場合や、本発明の転写フイルムを取り扱う場合に、カールしやすくなるだけでなく、折れシワが発生しやすくなり、取り扱いにくくなるおそれがある為、好ましくない。プラスチックフイルムの厚さが２５０μｍよりも厚いと、いわゆるコシが強くなり、本発明の転写フイルムを使用し転写加工を行なう場合に、被転写物である基材の表面に載置しにくくなる等、取り扱いにくくなる場合がある為、好ましくない。 The thickness of the plastic film used in the transfer film of the present invention is not particularly limited, but is preferably 12 to 250 μm. If the thickness of the plastic film is thinner than 12 μm, it will not only be more likely to curl, but also more likely to crease and wrinkle when forming a release layer etc. on the plastic film or when handling the transfer film of the present invention. This is not preferable because it may become difficult to handle. If the thickness of the plastic film is more than 250 μm, the so-called stiffness will become strong, and when performing a transfer process using the transfer film of the present invention, it will be difficult to place it on the surface of the substrate that is the transferred object, etc. This is not preferred as it may become difficult to handle.
（離型層）
本発明の転写フイルムは離型層が形成されていてもよい。後述の保護層が離型性を満足するものであれば、離型層は形成されなくともよい。離型層は、本発明の転写フイルムを使用して転写加工を行う場合に、本発明の転写フイルムの離型層上から、転写層を剥離させやすくする目的で、プラスチックフイルム上に形成されている層である。また、離型層は、転写加工時に、被転写物表面に転写、形成されず、被転写物からプラスチックフイルムとともに除去される。 (Release layer)
The transfer film of the present invention may have a release layer formed thereon. As long as the protective layer described below satisfies the mold releasability, the mold release layer may not be formed. The release layer is formed on a plastic film for the purpose of making it easier to peel off the transfer layer from the release layer of the transfer film of the present invention when performing transfer processing using the transfer film of the present invention. This is the layer in which people live. Furthermore, during the transfer process, the release layer is not transferred or formed on the surface of the object to be transferred, but is removed from the object together with the plastic film.
前記離型層は、樹脂からなる層である。離型層に使用する樹脂は、上記目的を達成することができるものであれば特に制限なく、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリスチレン系樹脂、塩化ビニル系樹脂、ポリエステル系樹脂、アクリル系樹脂、ウレタン系樹脂、メラミン系樹脂、エポキシ系樹脂等、従来公知の樹脂が使用でき、これらのいずれか１種、または２種以上の混合樹脂としてもよく、目的に応じて適宜選択すればよい。 The release layer is a layer made of a resin. There are no particular limitations on the resin used for the release layer as long as it can achieve the above-mentioned purpose, and conventionally known resins such as polyethylene-based resins, polypropylene-based resins, polystyrene-based resins, vinyl chloride-based resins, polyester-based resins, acrylic-based resins, urethane-based resins, melamine-based resins, and epoxy-based resins can be used. Any one of these resins or a mixture of two or more of them may be used, and the resin may be selected appropriately according to the purpose.
離型層の厚さは、前記目的を達成することができる範囲で、適宜選択すればよく、０．５～５μｍの範囲とすることが好ましい。
また、離型層を形成する方法は、グラビアコート法、リバースコート法、ダイコート法、リバースグラビアコート法、バーコート法等、従来公知のコーティング方法を使用することができ、目的に応じて適宜選択すればよい。 The thickness of the release layer may be appropriately selected within a range that can achieve the above objective, and is preferably in the range of 0.5 to 5 μm.
In addition, as a method for forming the release layer, conventionally known coating methods such as gravure coating method, reverse coating method, die coating method, reverse gravure coating method, bar coating method, etc. can be used, and can be selected as appropriate depending on the purpose. do it.
（機能層）
本発明の機能層は下記の条件を満たす層の厚さが３μｍ以上８μｍ以下となるよう形成される。
ａ）少なくとも、ポリオール化合物とポリイソシアネート化合物とからなる
ｂ）ポリオール化合物の水酸基価が２０ｍｇＫＯＨ／ｇ以上６０ｍｇＫＯＨ／ｇ以下である
ｃ）ポリオール化合物に含まれる水酸基の総数に対するポリイソシアネート化合物に含まれるイソシアネート基の総数の比率（［ＮＣＯ］／［ＯＨ］比）が０．５以上３．０以下である (Functional layer)
The functional layer of the present invention is formed so that the thickness of the layer satisfying the following conditions is 3 μm or more and 8 μm or less.
a) Consisting of at least a polyol compound and a polyisocyanate compound b) The hydroxyl value of the polyol compound is 20 mgKOH/g or more and 60 mgKOH/g or less c) The isocyanate group contained in the polyisocyanate compound relative to the total number of hydroxyl groups contained in the polyol compound The ratio of the total number of ([NCO]/[OH] ratio) is 0.5 or more and 3.0 or less
上記ポリオール化合物としては、特に限定されるものではなく、例えばアクリルポリオール、ポリエステルポリオール、ポリエーテルポリオール、水酸基含有フッ素系樹脂等を、それぞれ単独で、若しくは複数種類を任意に混合して使用することができる。特に耐薬品性に加え、さらに耐候性も付与する観点からはアクリルポリオール化合物を使用することが最も望ましい。 The above-mentioned polyol compound is not particularly limited, and for example, acrylic polyol, polyester polyol, polyether polyol, hydroxyl group-containing fluororesin, etc. may be used alone or in any combination of multiple types. can. In particular, it is most desirable to use an acrylic polyol compound from the viewpoint of imparting not only chemical resistance but also weather resistance.
上記イソシアネート化合物としては、特に限定されるものではないが、例えばトリレンジイソシアネート（ＴＤＩ）、ジフェニルメタンジイソシアネート（ＭＤＩ）、キシリレンジイソシアネート（ＸＤＩ）等の芳香族ジイソシアネート化合物や、ヘキサメチレンジイソシアネート（ＨＤＩ）等の脂肪族ジイソシアネート化合物、イソホロンジイソシアネート（ＩＰＤＩ）、水素添加ジフェニルメタンジイソシアネート（水添ＭＤＩ）、水素添加キシリレンジイソシアネート（水添ＸＤＩ）等の脂環式ジイソシアネート化合物等を、それぞれ単独で、若しくは複数種類を任意に混合して使用することができる。上記の条件を満たす樹脂を以下の明細書内では、本発明の特徴である樹脂と表現する。 The above-mentioned isocyanate compound is not particularly limited, but for example, aromatic diisocyanate compounds such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), etc. Aliphatic diisocyanate compounds, isophorone diisocyanate (IPDI), hydrogenated diphenylmethane diisocyanate (hydrogenated MDI), hydrogenated xylylene diisocyanate (hydrogenated XDI), and other alicyclic diisocyanate compounds, each singly or in combination They can be used in any combination. In the following specification, a resin that satisfies the above conditions will be expressed as a resin that is a feature of the present invention.
また、機能層には上記の条件を満たさない層が含まれてもよく、その材料としてはポリエチレン系樹脂、ポリプロピレン系樹脂、ポリスチレン系樹脂、塩化ビニル系樹脂、ポリエステル系樹脂、アクリル系樹脂、ウレタン系樹脂、メラミン系樹脂、エポキシ系樹脂等、従来公知の樹脂が使用でき、これらのいずれか１種、または２種以上の混合樹脂としてもよく、当該層を形成する目的に応じて、適宜選択すればよい。さらにイソシアネート化合物等の硬化剤が含まれていてもよい。 In addition, the functional layer may include a layer that does not meet the above conditions, and its materials include polyethylene resin, polypropylene resin, polystyrene resin, vinyl chloride resin, polyester resin, acrylic resin, urethane resin, etc. Conventionally known resins such as resins, melamine resins, and epoxy resins can be used, and any one of these resins or a mixture of two or more resins may be used, and the resins may be selected as appropriate depending on the purpose of forming the layer. do it. Furthermore, a curing agent such as an isocyanate compound may be included.
上記本発明の特徴である樹脂におけるポリオール化合物の水酸基価が２０ｍｇＫＯＨ／ｇ以上６０ｍｇＫＯＨ／ｇ以下であることが好ましい。２０ｍｇＫＯＨ/ｇより小さいと十分な架橋密度が得られず、耐薬品性が悪くなる。また６０ｍｇＫＯＨ/ｇより大きいと箔バリが生じやすくなる。また、ポリオールに含まれる水酸基の総数に対するポリイソシアネートに含まれるイソシアネート基の総数の比率（［ＮＣＯ］／［ＯＨ］比）が０．５以上３．０以下であることが好ましい、０．５より小さいと十分な架橋密度が得られず、耐薬品性が悪くなる。また３．０より大きくても耐薬品性が悪くなる場合がある。また機能層のうち本発明の特徴である樹脂からなる層の総厚さは３μｍ以上８μｍ以下であることが好ましい。３μｍより薄いと、耐薬品性試験で試験剤が浸透しやすくなり、外観の悪化を起こしやすくなる。また８μｍより厚いと、転写加工を行った際に箔バリが発生しやすくなる。 It is preferable that the hydroxyl value of the polyol compound in the resin, which is a feature of the present invention, is 20 mgKOH/g or more and 60 mgKOH/g or less. If it is less than 20 mgKOH/g, sufficient crosslinking density will not be obtained and chemical resistance will deteriorate. Moreover, if it is larger than 60 mgKOH/g, foil burrs are likely to occur. Further, the ratio of the total number of isocyanate groups contained in the polyisocyanate to the total number of hydroxyl groups contained in the polyol ([NCO]/[OH] ratio) is preferably 0.5 or more and 3.0 or less, preferably less than 0.5. If it is too small, sufficient crosslinking density cannot be obtained, resulting in poor chemical resistance. Moreover, even if it is larger than 3.0, chemical resistance may deteriorate. Further, among the functional layers, the total thickness of the layer made of resin, which is a feature of the present invention, is preferably 3 μm or more and 8 μm or less. If it is thinner than 3 μm, the test agent will easily penetrate in the chemical resistance test, and the appearance will tend to deteriorate. Further, if the thickness is greater than 8 μm, foil burrs are likely to occur during transfer processing.
本発明の機能層の構成として、例として以下のような組み合わせが挙げられる。
（離型層）／保護層／中間層／（接着層）、
（離型層）／保護層／着色層／（接着層）、
（離型層）／保護層／中間層／着色層／（接着層）、
（離型層）／保護層／中間層／金属下地層／金属薄膜層／（接着層）、
（離型層）／保護層／中間層／着色層／金属下地層／金属薄膜層／（接着層）
上記の例示では括弧内に示される層は例示された機能層の厚み方向の上下に位置する層を示すものである。もちろんこれ以外の組み合わせであっても所望の目的に応じて、任意の層を適用することができる。これら層のうち任意の組み合わせの層が、本発明の特徴である樹脂からなってよい。例えば、保護層と中間層とが本発明の特徴である樹脂からなる層であり、他の層が本発明の特徴である樹脂でない樹脂からなる組み合わせ、あるいは着色層と金属下地層とが本発明の特徴である特定の樹脂からなる層であり、他の層が、本発明の特徴である樹脂でない樹脂からなる組み合わせであってもよい。任意の組み合わせであっても本発明の特徴である樹脂からなる層の厚さが合計で３μｍ以上であれば、耐薬品性を得ることができる。 Examples of the structure of the functional layer of the present invention include the following combinations.
(Release layer) / Protective layer / Intermediate layer / (Adhesive layer),
(Release layer) / Protective layer / Colored layer / (Adhesive layer),
(Release layer) / Protective layer / Intermediate layer / Colored layer / (Adhesive layer),
(Release layer) / Protective layer / Intermediate layer / Metal base layer / Metal thin film layer / (Adhesive layer),
(Release layer) / Protective layer / Intermediate layer / Colored layer / Metal base layer / Metal thin film layer / (Adhesive layer)
In the above examples, the layers shown in parentheses are layers located above and below the example functional layer in the thickness direction. Of course, any combination of layers other than this can be applied depending on the desired purpose. Any combination of these layers may be made of the resin that is a feature of the present invention. For example, a combination in which the protective layer and the intermediate layer are made of a resin, which is a feature of the present invention, and the other layer is made of a resin other than the resin, which is a feature of the present invention, or a combination in which a colored layer and a metal base layer are made of a resin, which is a feature of the present invention. The layer may be made of a specific resin that is a feature of the present invention, and other layers may be a combination of resins other than the resin that is a feature of the present invention. Even in any combination, chemical resistance can be obtained as long as the total thickness of the resin layers, which is a feature of the present invention, is 3 μm or more.
（保護層）
本発明の保護層は本発明の転写フイルムの離型性を安定させる目的で転写層側のプラスチックフイルムまたは離型層上に形成される。転写時には、プラスチックフイルムまたは離型層と、保護層との界面で剥離する。その結果、被転写物表面に転写、形成され、得られた積層体の転写層を保護する。 (protective layer)
The protective layer of the present invention is formed on the plastic film or release layer on the transfer layer side for the purpose of stabilizing the releasability of the transfer film of the present invention. During transfer, the protective layer is peeled off at the interface between the plastic film or release layer and the protective layer. As a result, the transfer layer is transferred and formed on the surface of the transfer object, and the transfer layer of the obtained laminate is protected.
保護層には上記機能層で説明した樹脂を使用することができる。さらに、保護層は、必要に応じて、帯電防止剤、紫外線吸収剤、熱安定剤、硬化剤等の各種添加剤を１種類以上添加してもよく、各種添加剤の添加量は、目的に応じて適宜選択すればよい。本発明の特徴である樹脂を保護層として用いる場合、上述の離型層を設けることが、剥離性の観点から望ましい。離型層を設けない場合または離型層のみでは剥離性が安定しない場合、本発明の特徴である樹脂が剥離性の観点から使用できない場合がある。その際は本発明の特徴である樹脂でない離型性の良い樹脂を使用することができる。離型性の良い樹脂は耐薬品性が悪い場合があるが、その際は保護層の厚さを１μｍ以下となるようにするとともに、後述する中間層等に本発明の特徴である樹脂を使用することで、外観の劣化を実使用上支障ない程度に抑制することができる。 For the protective layer, the resins described in the functional layer above can be used. Furthermore, one or more types of various additives such as antistatic agents, ultraviolet absorbers, heat stabilizers, and hardening agents may be added to the protective layer as necessary, and the amounts of the various additives may be determined depending on the purpose. It may be selected as appropriate. When using the resin, which is a feature of the present invention, as a protective layer, it is desirable to provide the above-mentioned release layer from the viewpoint of releasability. If no mold release layer is provided or if the mold release layer alone does not provide stable releasability, the resin that is a feature of the present invention may not be usable from the viewpoint of releasability. In that case, it is possible to use a resin with good mold releasability other than the resin that is a feature of the present invention. Resins with good mold release properties may have poor chemical resistance, but in that case, the thickness of the protective layer should be 1 μm or less, and the resin that is a feature of the present invention should be used for the intermediate layer, etc., which will be described later. By doing so, deterioration of the appearance can be suppressed to an extent that does not pose a problem in actual use.
保護層の厚さは、前記目的を達成することができる範囲で、適宜選択すればよく、０．５～５μｍの範囲とすることが好ましい。
また、保護層を形成する方法は、グラビアコート法、リバースコート法、ダイコート法、リバースグラビアコート法、バーコート法等、従来公知のコーティング方法を使用することができ、目的に応じて適宜選択すればよい。 The thickness of the protective layer may be appropriately selected within a range that can achieve the above objective, and is preferably in the range of 0.5 to 5 μm.
Furthermore, as a method for forming the protective layer, conventionally known coating methods such as gravure coating method, reverse coating method, die coating method, reverse gravure coating method, bar coating method, etc. can be used, and the method should be selected as appropriate depending on the purpose. Bye.
（中間層）
本発明の転写フイルムの中間層は、中間層以外の機能層の耐薬品性を補完する目的で保護層上に形成される層である。すなわち、中間層以外の機能層が本発明の特徴である樹脂からなり、耐薬品性を備える場合には中間層は形成される必要はない。また中間層以外の機能層における本発明の特徴である樹脂からなる層の厚さが不十分である場合、本発明の特徴である樹脂からなる中間層を設けて耐薬品性を得ることができる。上記あるいは下記される保護層、金属下地層、着色層、または印刷層がその目的に照らして、前記の本発明の特徴のある樹脂を使用できない場合には、本発明の特徴である樹脂からなる層の厚さを３μｍ以上とするために、中間層を形成することが好ましい。 (middle class)
The intermediate layer of the transfer film of the present invention is a layer formed on the protective layer for the purpose of supplementing the chemical resistance of functional layers other than the intermediate layer. That is, when the functional layers other than the intermediate layer are made of resin, which is a feature of the present invention, and have chemical resistance, the intermediate layer does not need to be formed. Furthermore, if the thickness of the layer made of resin, which is a feature of the present invention, in a functional layer other than the intermediate layer is insufficient, chemical resistance can be obtained by providing an intermediate layer made of resin, which is a feature of the present invention. . If the above-mentioned or below-mentioned protective layer, metal base layer, colored layer, or printing layer cannot use the above-mentioned resin having the characteristics of the present invention in view of its purpose, it is made of the resin having the characteristics of the present invention. In order to make the layer thickness 3 μm or more, it is preferable to form an intermediate layer.
中間層には上記機能層で説明した本発明の特徴である樹脂を使用することができる。
さらに、中間層は、必要に応じて、帯電防止剤、紫外線吸収剤、熱安定剤、硬化剤等の各種添加剤を１種類以上添加してもよく、各種添加剤の添加量は、目的に応じて適宜選択すればよい。 For the intermediate layer, the resin that characterizes the present invention as described in the functional layer above can be used.
Furthermore, one or more types of various additives such as antistatic agents, ultraviolet absorbers, heat stabilizers, and hardening agents may be added to the intermediate layer as necessary, and the amounts of the various additives may be determined depending on the purpose. It may be selected as appropriate.
中間層の厚さは、前記目的を達成することができる範囲で、適宜選択すればよく、０．５～５μｍの範囲とすることが好ましい。
また、中間層を形成する方法は、グラビアコート法、リバースコート法、ダイコート法、リバースグラビアコート法、バーコート法等、従来公知のコーティング方法を使用することができ、目的に応じて適宜選択すればよい。 The thickness of the intermediate layer may be appropriately selected within a range that allows the above-mentioned object to be achieved, and is preferably in the range of 0.5 to 5 μm.
The intermediate layer may be formed by any of the conventional coating methods such as gravure coating, reverse coating, die coating, reverse gravure coating, and bar coating, which may be appropriately selected depending on the purpose.
（加飾層）
本発明の転写フイルムは、被転写物に意匠性を付与する目的で形成される着色剤を使用した着色層、印刷層および金属薄膜層が形成されていても構わない。 (Decoration layer)
The transfer film of the present invention may include a colored layer using a coloring agent, a printed layer, and a metal thin film layer formed for the purpose of imparting design to the transferred object.
（着色層および印刷層）
着色層は、樹脂に顔料あるいは染料を添加して、本発明の転写フイルムの全面あるいは一部の所望の部位に形成した層である。印刷層は同様に着色部を所望の図柄状に形成した層である。着色層および印刷層には上記機能層で説明した樹脂を使用することができる。着色層および印刷層には本発明の特徴である樹脂を用いてもよい。また、着色層および印刷層には本発明の特徴である樹脂を用いることができない場合、本発明の特徴である樹脂からなる中間層を設けることが好ましい。さらに必要に応じて、帯電防止剤、紫外線吸収剤、熱安定剤、硬化剤等の各種添加剤を１種類以上添加してもよく、各種添加剤の添加量は、目的に応じて適宜選択すればよい。 (Colored layer and printing layer)
The colored layer is a layer formed by adding a pigment or dye to a resin and forming it on the entire surface or a desired part of the transfer film of the present invention. Similarly, the printed layer is a layer in which colored portions are formed in a desired pattern. The resins described above for the functional layer can be used for the colored layer and the printing layer. A resin, which is a feature of the present invention, may be used for the colored layer and the printing layer. Furthermore, when the resin that is a feature of the present invention cannot be used for the colored layer and the printing layer, it is preferable to provide an intermediate layer made of a resin that is a feature of the present invention. Furthermore, if necessary, one or more types of various additives such as antistatic agents, ultraviolet absorbers, heat stabilizers, and hardening agents may be added, and the amount of each additive to be added should be selected as appropriate depending on the purpose. Bye.
着色層および印刷層の厚さは、所望する着色層および印刷層の効果を得ることができる厚さであればよく、それぞれ０.５～５μｍの範囲とすることが好ましく、着色層および印刷層を形成する目的に応じて、適宜選択すればよい。また、着色層および印刷層を形成する方法は、グラビアコート法、リバースコート法、ダイコート法、リバースグラビアコート法、バーコート法、スクリーン印刷法、オフセット印刷法等、従来公知のコーティング方法を使用することができ、目的に応じて適宜選択すればよい。 The thickness of the colored layer and printed layer may be any thickness that can obtain the desired effect of the colored layer and printed layer, and is preferably in the range of 0.5 to 5 μm, respectively. It may be selected as appropriate depending on the purpose of forming. The colored layer and the printed layer can be formed using conventionally known coating methods such as gravure coating, reverse coating, die coating, reverse gravure coating, bar coating, screen printing, and offset printing. can be selected as appropriate depending on the purpose.
（金属下地層）
金属下地層は本発明の転写フイルムに後述する金属薄膜層を形成する構成とする際に、保護層、中間層、着色層あるいは印刷層と、金属薄膜層とを密着させる目的で形成される層である。 (Metal Undercoat Layer)
The metal underlayer is a layer formed for the purpose of adhering a protective layer, intermediate layer, colored layer or printed layer to a metal thin film layer when the metal thin film layer described below is formed on the transfer film of the present invention.
金属下地層には上記機能層で説明した樹脂を使用することができる。
また、金属下地層に本発明の特徴のある樹脂を用いる場合、ポリオール化合物に含まれる水酸基の総数に対するポリイソシアネート化合物に含まれるイソシアネート基の総数の比率（［ＮＣＯ］／［ＯＨ］比）を１．０以上とした樹脂を金属下地層とすることで、金属薄膜層との密着が強くなりより好ましい。また、金属下地層には本発明の特徴である樹脂を用いることができない場合、本発明の特徴である樹脂からなる中間層を設けることが好ましい。必要に応じて、帯電防止剤、紫外線吸収剤、熱安定剤、硬化剤等の各種添加剤を１種類以上添加してもよく、各種添加剤の添加量は、目的に応じて適宜選択すればよい。 The resin described in the above functional layer can be used for the metal base layer.
In addition, when using the characteristic resin of the present invention for the metal base layer, the ratio of the total number of isocyanate groups contained in the polyisocyanate compound to the total number of hydroxyl groups contained in the polyol compound ([NCO]/[OH] ratio) is 1. It is more preferable to use a resin with a particle size of .0 or more as the metal base layer, as this will strengthen the adhesion with the metal thin film layer. Further, when the resin that is a feature of the present invention cannot be used for the metal base layer, it is preferable to provide an intermediate layer made of a resin that is a feature of the present invention. If necessary, one or more types of various additives such as antistatic agents, ultraviolet absorbers, heat stabilizers, and curing agents may be added, and the amount of each additive to be added may be selected as appropriate depending on the purpose. good.
金属下地層の厚さは、前記目的を達成することができる範囲で、適宜選択すればよく、０．５～２μｍの範囲とすることが好ましい。
また、金属下地層を形成する方法は、グラビアコート法、リバースコート法、ダイコート法、リバースグラビアコート法、バーコート法等、従来公知のコーティング方法を使用することができ、目的に応じて適宜選択すればよい。 The thickness of the metal base layer may be appropriately selected within a range that can achieve the above objective, and is preferably in the range of 0.5 to 2 μm.
In addition, as a method for forming the metal base layer, conventionally known coating methods such as gravure coating, reverse coating, die coating, reverse gravure coating, and bar coating can be used, and can be selected as appropriate depending on the purpose. do it.
（金属薄膜層）
前記金属薄膜層は、被転写物に主に金属光沢を付与する目的で形成される層であり、転写加工を行なった場合に、接着層とともに被転写物表面に転写、形成される層である。さらに金属薄膜層に後述の金属化合物を用いることで、金属光沢に加え、あるいは金属光沢に代えて、バリア性や導電性等の特性を付与してもよい。 (metal thin film layer)
The metal thin film layer is a layer formed mainly for the purpose of imparting metallic luster to the transferred object, and is a layer that is transferred and formed on the surface of the transferred object together with the adhesive layer when a transfer process is performed. . Further, by using a metal compound described below in the metal thin film layer, properties such as barrier properties and conductivity may be imparted in addition to or in place of metallic luster.
金属薄膜層に使用する金属は、アルミニウム、クロム、錫、金、銀、銅、亜鉛、珪素、ニッケル、インジウム等の従来公知の各種金属または、上記従来公知の金属の酸化物、硫化物、窒化物等の金属化合物を使用することができ、所望の目的により適宜選択すればよい。
また、金属薄膜層は、１層であっても２層以上の複数層としても構わず、金属薄膜層を２層以上の複数層とする場合には、各層に使用する金属は各層間で異なっていてもよく同種であってもよい。 The metals used for the metal thin film layer include various conventionally known metals such as aluminum, chromium, tin, gold, silver, copper, zinc, silicon, nickel, and indium, or oxides, sulfides, and nitrides of the above conventionally known metals. Metal compounds such as metal compounds can be used, and may be appropriately selected depending on the desired purpose.
In addition, the metal thin film layer may be one layer or multiple layers of two or more layers, and when the metal thin film layer is two or more layers, the metal used for each layer is different between each layer. They may be of the same species.
金属薄膜層の厚さは、１０～２００ｎｍの範囲が好ましい。１０ｎｍよりも薄いと、本発明の転写フイルムに所望の金属光沢等を付与することができなくなるおそれがある為、好ましくなく、２００ｎｍよりも厚いと、金属薄膜層を形成する際の熱や転写加工時の熱によってプラスチックフイルムが変形、変質してしまうおそれがあり、本発明の転写フイルムに所望の金属光沢等を付与することができなくなるおそれがある為、好ましくない。 The thickness of the metal thin film layer is preferably in the range of 10 to 200 nm. If it is thinner than 10 nm, it may not be possible to impart the desired metallic luster to the transfer film of the present invention, so it is not preferable, and if it is thicker than 200 nm, it may be difficult to heat or transfer during the formation of the metal thin film layer. This is not preferable because there is a risk that the plastic film may be deformed or deteriorated by the heat of the process, and it may become impossible to impart the desired metallic luster or the like to the transfer film of the present invention.
金属薄膜層を形成する方法は、真空蒸着法、スパッタリング法、化学気相蒸着法（ＣＶＤ法）等、従来公知の金属薄膜層を形成する方法が使用でき、目的に応じて適宜選択すればよい。 The method for forming the metal thin film layer can be any conventional method for forming a metal thin film layer, such as vacuum deposition, sputtering, or chemical vapor deposition (CVD), and can be appropriately selected depending on the purpose.
そして、本発明の転写フイルムに、加飾層を形成する場合に、形成する金属薄膜層、着色層、印刷層、金属下地層の種類、形成される順序は、目的に応じて適宜選択すればよい。また、金属薄膜層、着色層、印刷層、金属下地層、及び後述する接着層は、保護層上の全面に形成されていても部分的に形成されていても構わず、形成される位置は、目的に応じて適宜選択すればよい。 When forming a decorative layer on the transfer film of the present invention, the types and order of the metal thin film layer, colored layer, printing layer, and metal base layer to be formed may be appropriately selected depending on the purpose. good. In addition, the metal thin film layer, colored layer, printing layer, metal base layer, and adhesive layer described below may be formed on the entire surface of the protective layer or partially, and the positions where they are formed may be , may be selected as appropriate depending on the purpose.
（接着層）
本発明の転写フイルムに形成されている接着層は、一般に転写フイルムに使用される熱可塑性の樹脂であれば特に制限はなく、アクリル系樹脂、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリスチレン系樹脂、塩化ビニル系樹脂、ポリエステル系樹脂、ウレタン系樹脂、酢酸ビニル系樹脂等、従来公知の樹脂が使用でき、これらのいずれか１種、または２種以上の混合樹脂や、これら２種以上の共重合樹脂であってもよく、使用する被転写物に応じて適宜選択すれば良い。また、被転写物に使用する樹脂と相溶性の良い樹脂を使用すれば被転写物との相性もよく好ましい。 (Adhesive layer)
The adhesive layer formed on the transfer film of the present invention is not particularly limited as long as it is a thermoplastic resin generally used for transfer films, such as acrylic resin, polyethylene resin, polypropylene resin, polystyrene resin, chloride resin, etc. Conventionally known resins such as vinyl resins, polyester resins, urethane resins, and vinyl acetate resins can be used, and any one of these resins, a mixed resin of two or more types, or a copolymer resin of two or more of these resins can be used. It may be selected as appropriate depending on the transfer target to be used. Further, it is preferable to use a resin that has good compatibility with the resin used for the object to be transferred.
接着層の厚さは、前記目的を達成することができる範囲で、適宜選択すればよく、０．５～１０μｍの範囲とすることが好ましい。
また、接着層を形成する方法は、グラビアコート法、リバースコート法、ダイコート法、リバースグラビアコート法、バーコート法等、従来公知のコーティング方法を使用することができ、目的に応じて適宜選択すればよい。 The thickness of the adhesive layer may be appropriately selected within a range that can achieve the above objective, and is preferably in the range of 0.5 to 10 μm.
In addition, as a method for forming the adhesive layer, conventionally known coating methods such as gravure coating method, reverse coating method, die coating method, reverse gravure coating method, bar coating method, etc. can be used, and the method should be selected as appropriate depending on the purpose. Bye.
本発明の積層体は被転写物である基材上に上記の各層を順次形成して得ることができる。
また、本発明の積層体を得るには本発明の転写フイルムを用いて基材上に各層を形成する方法が最適である。 The laminate of the present invention can be obtained by sequentially forming the above-mentioned layers on a substrate which is a transfer target.
Furthermore, in order to obtain the laminate of the present invention, it is optimal to form each layer on a base material using the transfer film of the present invention.
（基材）
基材は所望の目的に応じて、アクリル系樹脂、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリスチレン系樹脂、塩化ビニル系樹脂、ポリエステル系樹脂、ウレタン系樹脂、酢酸ビニル系樹脂、ＡＢＳ樹脂、ポリカーボネート樹脂等、従来公知の材料を用いることができ、これらのいずれか１種、または２種以上の混合樹脂や、これら２種以上の共重合樹脂であってもよい。またこれらの基材は透明であってもよく、着色されていてもよい。 (Base material)
Depending on the desired purpose, the base material may be acrylic resin, polyethylene resin, polypropylene resin, polystyrene resin, vinyl chloride resin, polyester resin, urethane resin, vinyl acetate resin, ABS resin, polycarbonate resin, etc. , conventionally known materials can be used, and it may be any one of these, a mixed resin of two or more of these, or a copolymer resin of two or more of these. Further, these base materials may be transparent or colored.
以下に実施例および比較例を挙げて本発明をさらに具体的に説明するが、本発明はこれら実施例に限定されるものではない。 The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
［実施例１～１１・比較例１～８］
［転写フイルムの作成］
以下の工程１～４を順に行い、ポリエチレンテレフタレートフイルム上に、離型層、保護層、中間層、および接着層が順次形成された転写フイルムを得た。
（工程１）厚さ２５μｍのポリエチレンテレフタレートフイルム上に、熱硬化型アクリルメラミン樹脂をバーコート法でコーティングして厚さ０．５μｍの離型層を形成した。
（工程２）上記離型層上に、熱可塑性アクリル樹脂をバーコート法でコーティングして
厚さ１μｍの保護層を形成した。
（工程３）上記保護層上に、
アクリルポリオール樹脂とＨＤＩ系ポリイソシアネート化合物を混合しバーコート法でコーティングし中間層を形成した。
この際、アクリルポリオールの水酸基価、ポリオール化合物に含まれる水酸基の総数に対するポリイソシアネート化合物に含まれるイソシアネート基の総数の比率（［ＮＣＯ］／［ＯＨ］比）、および中間層の厚さは表１の通りとした。
（工程４）上記中間層上に、 
アクリル系樹脂と酢酸ビニル系樹脂との共重合樹脂をバーコート法でコーティングし、厚さ２μｍの接着層を形成した。
［積層体の作成］
上記工程を行い、得られた転写フイルムをＡＢＳ基材上に接着層が基材側となるよう載置し、プラスチックフイルム側からロール転写機を用いて加圧および加熱を行い、転写温度２００℃、転写速度５０ｍｍ/秒で転写加工を行った後、速やかに離型層を含むプラスチックフイルムを剥離し、積層体を得た。 [Examples 1 to 11/Comparative Examples 1 to 8]
[Creation of transfer film]
The following steps 1 to 4 were performed in order to obtain a transfer film in which a release layer, a protective layer, an intermediate layer, and an adhesive layer were sequentially formed on a polyethylene terephthalate film.
(Step 1) A thermosetting acrylic melamine resin was coated on a polyethylene terephthalate film with a thickness of 25 μm using a bar coating method to form a release layer with a thickness of 0.5 μm.
(Step 2) A thermoplastic acrylic resin was coated on the release layer using a bar coating method to form a protective layer with a thickness of 1 μm.
(Step 3) On the above protective layer,
An intermediate layer was formed by mixing an acrylic polyol resin and an HDI polyisocyanate compound and coating the mixture using a bar coating method.
At this time, the hydroxyl value of the acrylic polyol, the ratio of the total number of isocyanate groups contained in the polyisocyanate compound to the total number of hydroxyl groups contained in the polyol compound ([NCO]/[OH] ratio), and the thickness of the intermediate layer are shown in Table 1. It was as follows.
(Step 4) On the intermediate layer,
A copolymer resin of acrylic resin and vinyl acetate resin was coated using a bar coating method to form an adhesive layer with a thickness of 2 μm.
[Creation of laminate]
After carrying out the above steps, the obtained transfer film was placed on an ABS base material with the adhesive layer facing the base material side, and pressure and heating were applied from the plastic film side using a roll transfer machine to a transfer temperature of 200°C. After performing transfer processing at a transfer speed of 50 mm/sec, the plastic film containing the release layer was immediately peeled off to obtain a laminate.
［実施例１２］
［転写フイルムの作成］
以下の工程１～６を順に行い、ポリエチレンテレフタレートフイルム上に、離型層、保護層、中間層、金属下地層、金属薄膜層および接着層が順次形成された転写フイルムを得た。
（工程１）厚さ２５μｍのポリエチレンテレフタレートフイルム上に、熱硬化型アクリルメラミン樹脂をバーコート法でコーティングして厚さ０．５μｍの離型層を形成した。
（工程２）上記離型層上に、熱可塑性アクリル樹脂をバーコート法でコーティングして
厚さ１μｍの保護層を形成した。
（工程３）上記保護層上に、
水酸基価 ２４ｍｇＫＯＨ／ｇであるアクリルポリオール樹脂とＨＤＩ系ポリイソシアネート化合物を、ポリオール化合物に含まれる水酸基の総数に対するポリイソシアネート化合物に含まれるイソシアネート基の総数の比率（［ＮＣＯ］／［ＯＨ］比）が０．８となるよう混合しバーコート法でコーティングし、厚さ２μｍの中間層を形成した。
（工程４）上記中間層上に、 
水酸基価 ２４ｍｇＫＯＨ／ｇであるアクリルポリオール樹脂とＨＤＩ系ポリイソシアネート化合物を、ポリオール化合物に含まれる水酸基の総数に対するポリイソシアネート化合物に含まれるイソシアネート基の総数の比率（［ＮＣＯ］／［ＯＨ］比）が２．０となるよう混合しバーコート法でコーティングし、厚さ１μｍの金属下地層を形成した。
（工程５）上記金属下地層上に、
クロムを真空蒸着法で形成し、厚さ５０ｎｍのクロム薄膜層を形成した。
（工程６）上記クロム薄膜層上に
アクリル系樹脂と酢酸ビニル系樹脂との共重合樹脂をバーコート法でコーティングし、厚さ２μｍの接着層を形成した。
［積層体の作成］
上記工程を行い、得られた転写フイルムを用いて実施例１と同様にして積層体を得た。 [Example 12]
[Creating transfer film]
The following steps 1 to 6 were carried out in order to obtain a transfer film having a release layer, a protective layer, an intermediate layer, a metal underlayer, a metal thin film layer and an adhesive layer formed in that order on a polyethylene terephthalate film.
(Step 1) A thermosetting acrylic melamine resin was coated on a polyethylene terephthalate film having a thickness of 25 μm by a bar coating method to form a release layer having a thickness of 0.5 μm.
(Step 2) A thermoplastic acrylic resin was coated on the release layer by a bar coating method to form a protective layer having a thickness of 1 μm.
(Step 3) On the protective layer,
An acrylic polyol resin having a hydroxyl value of 24 mgKOH/g and an HDI-based polyisocyanate compound were mixed so that the ratio of the total number of isocyanate groups contained in the polyisocyanate compound to the total number of hydroxyl groups contained in the polyol compound ([NCO]/[OH] ratio) was 0.8, and the mixture was coated by a bar coating method to form an intermediate layer having a thickness of 2 μm.
(Step 4) On the intermediate layer,
An acrylic polyol resin having a hydroxyl value of 24 mgKOH/g and an HDI-based polyisocyanate compound were mixed so that the ratio of the total number of isocyanate groups contained in the polyisocyanate compound to the total number of hydroxyl groups contained in the polyol compound ([NCO]/[OH] ratio) was 2.0, and the mixture was coated by a bar coating method to form a metal undercoat layer having a thickness of 1 μm.
(Step 5) On the metal underlayer,
Chromium was deposited by vacuum deposition to form a thin chromium layer having a thickness of 50 nm.
(Step 6) A copolymer resin of an acrylic resin and a vinyl acetate resin was coated on the chromium thin film layer by a bar coating method to form an adhesive layer having a thickness of 2 μm.
[Creation of Laminate]
The above steps were carried out, and using the resulting transfer film, a laminate was obtained in the same manner as in Example 1.
［実施例１３］
［転写フイルムの作成］
以下の工程１～４を順に行い、ポリエチレンテレフタレートフイルム上に、離型層、保護層、中間層、および接着層が順次形成された転写フイルムを得た。
（工程１）厚さ２５μｍのポリエチレンテレフタレートフイルム上に、熱硬化型アクリルメラミン樹脂をバーコート法でコーティングして厚さ０．５μｍの離型層を形成した。
（工程２）上記離型層上に、熱可塑性アクリル樹脂をバーコート法でコーティングして
厚さ１μｍの保護層を形成した。
（工程３）上記保護層上に、
水酸基価 ２４ｍｇＫＯＨ／ｇであるアクリルポリオール樹脂とＨＤＩ系ポリイソシアネート化合物を、ポリオール化合物に含まれる水酸基の総数に対するポリイソシアネート化合物に含まれるイソシアネート基の総数の比率（［ＮＣＯ］／［ＯＨ］比）が０．８となるよう混合しバーコート法でコーティングし、厚さ３μｍの中間層を形成した。
（工程４）上記中間層上に
アクリル系樹脂と酢酸ビニル系樹脂との共重合樹脂をバーコート法でコーティングし、厚さ２μｍの接着層を形成した。
［積層体の作成］
上記工程を行い、得られた転写フイルムを用いて実施例１と同様にして積層体を得た。 [Example 13]
[Creation of transfer film]
The following steps 1 to 4 were performed in order to obtain a transfer film in which a release layer, a protective layer, an intermediate layer, and an adhesive layer were sequentially formed on a polyethylene terephthalate film.
(Step 1) A thermosetting acrylic melamine resin was coated on a polyethylene terephthalate film with a thickness of 25 μm using a bar coating method to form a release layer with a thickness of 0.5 μm.
(Step 2) A thermoplastic acrylic resin was coated on the above mold release layer by a bar coating method to form a protective layer having a thickness of 1 μm.
(Step 3) On the above protective layer,
The ratio of the total number of isocyanate groups contained in the polyisocyanate compound to the total number of hydroxyl groups contained in the polyol compound ([NCO]/[OH] ratio) is 0.8 and coated using a bar coating method to form an intermediate layer with a thickness of 3 μm.
(Step 4) A copolymer resin of an acrylic resin and a vinyl acetate resin was coated on the intermediate layer by a bar coating method to form an adhesive layer with a thickness of 2 μm.
[Creation of laminate]
A laminate was obtained in the same manner as in Example 1 using the transfer film obtained by carrying out the above steps.
［実施例１４］
［転写フイルムの作成］
以下の工程１～４を順に行い、ポリエチレンテレフタレートフイルム上に、離型層、保護層、着色層、および接着層が順次形成された転写フイルムを得た。
（工程１）厚さ２５μｍのポリエチレンテレフタレートフイルム上に、熱硬化型アクリルメラミン樹脂をバーコート法でコーティングして厚さ０．５μｍの離型層を形成した。
（工程２）上記離型層上に、熱可塑性アクリル樹脂をバーコート法でコーティングして
厚さ１μｍの保護層を形成した。
（工程３）上記保護層上に、
水酸基価 ２４ｍｇＫＯＨ／ｇであるアクリルポリオール樹脂とＨＤＩ系ポリイソシアネート化合物を、ポリオール化合物に含まれる水酸基の総数に対するポリイソシアネート化合物に含まれるイソシアネート基の総数の比率（［ＮＣＯ］／［ＯＨ］比）が０．８となるよう混合し、さらに黒色顔料を樹脂に対して重量比で１０％添加したものをバーコート法でコーティングし、厚さ３μｍの着色層を形成した。
（工程４）上記着色層上に
アクリル系樹脂と酢酸ビニル系樹脂との共重合樹脂をバーコート法でコーティングし、厚さ２μｍの接着層を形成した。
［積層体の作成］
上記工程を行い、得られた転写フイルムを用いて実施例１と同様にして積層体を得た。 [Example 14]
[Creating transfer film]
The following steps 1 to 4 were carried out in order to obtain a transfer film having a release layer, a protective layer, a colored layer, and an adhesive layer formed in that order on a polyethylene terephthalate film.
(Step 1) A thermosetting acrylic melamine resin was coated on a polyethylene terephthalate film having a thickness of 25 μm by a bar coating method to form a release layer having a thickness of 0.5 μm.
(Step 2) A thermoplastic acrylic resin was coated on the release layer by a bar coating method to form a protective layer having a thickness of 1 μm.
(Step 3) On the protective layer,
An acrylic polyol resin having a hydroxyl value of 24 mgKOH/g and an HDI-based polyisocyanate compound were mixed so that the ratio of the total number of isocyanate groups contained in the polyisocyanate compound to the total number of hydroxyl groups contained in the polyol compound ([NCO]/[OH] ratio) was 0.8, and a black pigment was added in an amount of 10% by weight relative to the resin, and the mixture was coated by a bar coating method to form a colored layer having a thickness of 3 μm.
(Step 4) A copolymer resin of an acrylic resin and a vinyl acetate resin was coated on the colored layer by a bar coating method to form an adhesive layer having a thickness of 2 μm.
[Creation of Laminate]
The above steps were carried out, and using the resulting transfer film, a laminate was obtained in the same manner as in Example 1.
［実施例１５］
［転写フイルムの作成］
以下の工程１～５を順に行い、ポリエチレンテレフタレートフイルム上に、離型層、保護層、金属下地層、金属薄膜層および接着層が順次形成された転写フイルムを得た。
（工程１）厚さ２５μｍのポリエチレンテレフタレートフイルム上に、熱硬化型アクリルメラミン樹脂をバーコート法でコーティングして厚さ０．５μｍの離型層を形成した。
（工程２）上記離型層上に、熱可塑性アクリル樹脂をバーコート法でコーティングして
厚さ１μｍの保護層を形成した。
（工程３）上記保護層上に、
水酸基価 ２４ｍｇＫＯＨ／ｇであるアクリルポリオール樹脂とＨＤＩ系ポリイソシアネート化合物を、ポリオール化合物に含まれる水酸基の総数に対するポリイソシアネート化合物に含まれるイソシアネート基の総数の比率（［ＮＣＯ］／［ＯＨ］比）が２．０となるよう混合しバーコート法でコーティングし、厚さ３μｍの金属下地層を形成した。
（工程４）上記金属下地層上に、
クロムを真空蒸着法で形成し、厚さ５０ｎｍのクロム薄膜層を形成した。
（工程５）上記クロム薄膜層上に
アクリル系樹脂と酢酸ビニル系樹脂との共重合樹脂をバーコート法でコーティングし、厚さ２μｍの接着層を形成した。
［積層体の作成］
上記工程を行い、得られた転写フイルムを用いて実施例１と同様にして積層体を得た。 [Example 15]
[Creation of transfer film]
The following steps 1 to 5 were performed in order to obtain a transfer film in which a release layer, a protective layer, a metal base layer, a metal thin film layer, and an adhesive layer were sequentially formed on a polyethylene terephthalate film.
(Step 1) A thermosetting acrylic melamine resin was coated on a polyethylene terephthalate film with a thickness of 25 μm using a bar coating method to form a release layer with a thickness of 0.5 μm.
(Step 2) A thermoplastic acrylic resin was coated on the release layer using a bar coating method to form a protective layer with a thickness of 1 μm.
(Step 3) On the above protective layer,
The ratio of the total number of isocyanate groups contained in the polyisocyanate compound to the total number of hydroxyl groups contained in the polyol compound ([NCO]/[OH] ratio) is 2.0 and coated using a bar coating method to form a metal base layer with a thickness of 3 μm.
(Step 4) On the metal base layer,
Chromium was formed by vacuum evaporation to form a chromium thin film layer with a thickness of 50 nm.
(Step 5) A copolymer resin of acrylic resin and vinyl acetate resin was coated on the chromium thin film layer by a bar coating method to form an adhesive layer with a thickness of 2 μm.
[Creation of laminate]
A laminate was obtained in the same manner as in Example 1 using the transfer film obtained by carrying out the above steps.
［実施例１６］
［転写フイルムの作成］
以下の工程１～６を順に行い、ポリエチレンテレフタレートフイルム上に、離型層、保護層、着色層、金属下地層、金属薄膜層および接着層が順次形成された転写フイルムを得た。
（工程１）厚さ２５μｍのポリエチレンテレフタレートフイルム上に、熱硬化型アクリルメラミン樹脂をバーコート法でコーティングして厚さ０．５μｍの離型層を形成した。
（工程２）上記離型層上に、
水酸基価 ２４ｍｇＫＯＨ／ｇであるアクリルポリオール樹脂とＨＤＩ系ポリイソシアネート化合物を、ポリオール化合物に含まれる水酸基の総数に対するポリイソシアネート化合物に含まれるイソシアネート基の総数の比率（［ＮＣＯ］／［ＯＨ］比）が０．８となるよう混合しバーコート法でコーティングし、厚さ１μｍの保護層を形成した。
（工程３）上記保護層上に、
水酸基価 ２４ｍｇＫＯＨ／ｇであるアクリルポリオール樹脂とＨＤＩ系ポリイソシアネート化合物を、ポリオール化合物に含まれる水酸基の総数に対するポリイソシアネート化合物に含まれるイソシアネート基の総数の比率（［ＮＣＯ］／［ＯＨ］比）が０．８となるよう混合し、さらに黒色顔料を樹脂に対して重量比で１０％添加したものをバーコート法でコーティングし、厚さ１μｍの着色層を形成した。
（工程４）上記着色層上に、
水酸基価 ２４ｍｇＫＯＨ／ｇであるアクリルポリオール樹脂とＨＤＩ系ポリイソシアネート化合物を、ポリオール化合物に含まれる水酸基の総数に対するポリイソシアネート化合物に含まれるイソシアネート基の総数の比率（［ＮＣＯ］／［ＯＨ］比）が２．０となるよう混合しバーコート法でコーティングし、厚さ１μｍの金属下地層を形成した。
（工程５）上記金属下地層上に、
クロムを真空蒸着法で形成し、厚さ５０ｎｍのクロム薄膜層を形成した。
（工程６）上記クロム薄膜層上に
アクリル系樹脂と酢酸ビニル系樹脂との共重合樹脂をバーコート法でコーティングし、厚さ２μｍの接着層を形成した。
［積層体の作成］
上記工程を行い、得られた転写フイルムを用いて実施例１と同様にして積層体を得た。 [Example 16]
[Creation of transfer film]
The following steps 1 to 6 were performed in order to obtain a transfer film in which a release layer, a protective layer, a colored layer, a metal base layer, a metal thin film layer, and an adhesive layer were sequentially formed on a polyethylene terephthalate film.
(Step 1) A thermosetting acrylic melamine resin was coated on a polyethylene terephthalate film with a thickness of 25 μm using a bar coating method to form a release layer with a thickness of 0.5 μm.
(Step 2) On the above mold release layer,
The ratio of the total number of isocyanate groups contained in the polyisocyanate compound to the total number of hydroxyl groups contained in the polyol compound ([NCO]/[OH] ratio) is 0.8 and coated using a bar coating method to form a protective layer with a thickness of 1 μm.
(Step 3) On the above protective layer,
The ratio of the total number of isocyanate groups contained in the polyisocyanate compound to the total number of hydroxyl groups contained in the polyol compound ([NCO]/[OH] ratio) is 0.8, and then coated with a black pigment added in a weight ratio of 10% to the resin using a bar coating method to form a colored layer with a thickness of 1 μm.
(Step 4) On the colored layer,
The ratio of the total number of isocyanate groups contained in the polyisocyanate compound to the total number of hydroxyl groups contained in the polyol compound ([NCO]/[OH] ratio) is 2.0 and coated using a bar coating method to form a metal base layer with a thickness of 1 μm.
(Step 5) On the metal base layer,
Chromium was formed by vacuum evaporation to form a chromium thin film layer with a thickness of 50 nm.
(Step 6) A copolymer resin of acrylic resin and vinyl acetate resin was coated on the chromium thin film layer by a bar coating method to form an adhesive layer with a thickness of 2 μm.
[Creation of laminate]
A laminate was obtained in the same manner as in Example 1 using the transfer film obtained by carrying out the above steps.
［比較例７］
［転写フイルムの作成］
以下の工程１～５を順に行い、ポリエチレンテレフタレートフイルム上に、離型層、保護層、金属下地層、金属薄膜層および接着層が順次形成された転写フイルムを得た。
（工程１）厚さ２５μｍのポリエチレンテレフタレートフイルム上に、熱硬化型アクリルメラミン樹脂をバーコート法でコーティングして厚さ０．５μｍの離型層を形成した。
（工程２）上記離型層上に、
水酸基価 ２４ｍｇＫＯＨ／ｇであるアクリルポリオール樹脂とＨＤＩ系ポリイソシアネート化合物を、ポリオール化合物に含まれる水酸基の総数に対するポリイソシアネート化合物に含まれるイソシアネート基の総数の比率（［ＮＣＯ］／［ＯＨ］比）が０．８となるよう混合しバーコート法でコーティングし、厚さ１μｍの保護層を形成した。
（工程３）上記保護層上に、
水酸基価 ２４ｍｇＫＯＨ／ｇであるアクリルポリオール樹脂とＨＤＩ系ポリイソシアネート化合物を、ポリオール化合物に含まれる水酸基の総数に対するポリイソシアネート化合物に含まれるイソシアネート基の総数の比率（［ＮＣＯ］／［ＯＨ］比）が２．０となるよう混合しバーコート法でコーティングし、厚さ１μｍの金属下地層を形成した。
（工程４）上記金属下地層上に、
クロムを真空蒸着法で形成し、厚さ５０ｎｍのクロム薄膜層を形成した。
（工程５）上記金属薄膜層上に
アクリル系樹脂と酢酸ビニル系樹脂との共重合樹脂をバーコート法でコーティングし、厚さ２μｍの接着層を形成した。
［積層体の作成］
上記工程を行い、得られた転写フイルムを用いて実施例１と同様にして積層体を得た。 [Comparative Example 7]
[Creation of transfer film]
The following steps 1 to 5 were performed in order to obtain a transfer film in which a release layer, a protective layer, a metal base layer, a metal thin film layer, and an adhesive layer were sequentially formed on a polyethylene terephthalate film.
(Step 1) A thermosetting acrylic melamine resin was coated on a polyethylene terephthalate film with a thickness of 25 μm using a bar coating method to form a release layer with a thickness of 0.5 μm.
(Step 2) On the above mold release layer,
The ratio of the total number of isocyanate groups contained in the polyisocyanate compound to the total number of hydroxyl groups contained in the polyol compound ([NCO]/[OH] ratio) is 0.8 and coated using a bar coating method to form a protective layer with a thickness of 1 μm.
(Step 3) On the above protective layer,
The ratio of the total number of isocyanate groups contained in the polyisocyanate compound to the total number of hydroxyl groups contained in the polyol compound ([NCO]/[OH] ratio) is 2.0 and coated using a bar coating method to form a metal base layer with a thickness of 1 μm.
(Step 4) On the metal base layer,
Chromium was formed by vacuum evaporation to form a chromium thin film layer with a thickness of 50 nm.
(Step 5) A copolymer resin of acrylic resin and vinyl acetate resin was coated on the metal thin film layer by a bar coating method to form an adhesive layer with a thickness of 2 μm.
[Creation of laminate]
A laminate was obtained in the same manner as in Example 1 using the transfer film obtained by carrying out the above steps.
［実施例１７～２０］
［転写フイルムおよび積層体の作成］
実施例１の工程３におけるポリオール化合物およびポリイソシアネート化合物を表３のように組み合わせた以外は実施例１と同様に積層体を得た。 [Examples 17 to 20]
[Preparation of transfer film and laminate]
A laminate was obtained in the same manner as in Example 1, except that the polyol compounds and the polyisocyanate compounds in step 3 of Example 1 were combined as shown in Table 3.
［実施例２１～２９・比較例８～１４］
［転写フイルムの作成］
本発明の機能層（保護層、中間層、着色層、金属下地層、金属薄膜層）について、表３のように組み合わせて積層し、転写フイルムを作成した。なお積層順はプラスチックフイルム／離型層／保護層／中間層／着色層／金属下地層／金属薄膜層／接着層の順である。すなわち、表４に示される本発明の機能層を構成する各層は表の左側から順に形成した。各層の形成方法は実施例１～１６に準じ、転写フイルムを作成した。この際、アクリルポリオールの水酸基価、ポリオール化合物に含まれる水酸基の総数に対するポリイソシアネート化合物に含まれるイソシアネート基の総数の比率（［ＮＣＯ］／［ＯＨ］比）、および各層の厚みは表３の通りとした。但し、厚さが０μｍと記載される層は当該層を形成していないものである。実施例２１～２５、比較例８～１２および比較例１４の保護層は実施例１の工程２（保護層）と同じ熱可塑性アクリル樹脂を使用した。比較例９では中間層として、熱可塑性アクリル樹脂を用い、バーコート法で厚さ１μｍの中間層を形成した。さらに。着色層として、熱可塑性アクリル樹脂に、黒色顔料を樹脂に対して重量比で１０％添加したものを用い、バーコート法で厚さ６μｍの着色層を形成した。表中のＡｌ、Ｃｒ、Ｉｎはそれぞれアルミニウム、クロム、インジウムを示し、金属薄膜層はいずれも真空蒸着法で、厚さ５０ｎｍとなるよう形成した。
［積層体の作成］
上記のように得られた転写フイルムを用いて、実施例１と同様に積層体を得た。 [Examples 21 to 29/Comparative Examples 8 to 14]
[Creation of transfer film]
The functional layers of the present invention (protective layer, intermediate layer, colored layer, metal base layer, metal thin film layer) were combined and laminated as shown in Table 3 to create a transfer film. The lamination order is plastic film/release layer/protective layer/intermediate layer/colored layer/metal base layer/metal thin film layer/adhesive layer. That is, each layer constituting the functional layer of the present invention shown in Table 4 was formed in order from the left side of the table. Transfer films were prepared by forming each layer in accordance with Examples 1 to 16. At this time, the hydroxyl value of the acrylic polyol, the ratio of the total number of isocyanate groups contained in the polyisocyanate compound to the total number of hydroxyl groups contained in the polyol compound ([NCO]/[OH] ratio), and the thickness of each layer are as shown in Table 3. And so. However, a layer described as having a thickness of 0 μm does not form that layer. For the protective layers of Examples 21 to 25, Comparative Examples 8 to 12, and Comparative Example 14, the same thermoplastic acrylic resin as in Step 2 (protective layer) of Example 1 was used. In Comparative Example 9, a thermoplastic acrylic resin was used as the intermediate layer, and an intermediate layer having a thickness of 1 μm was formed by a bar coating method. moreover. As a colored layer, a thermoplastic acrylic resin to which a black pigment was added in an amount of 10% by weight based on the resin was used, and a colored layer having a thickness of 6 μm was formed by a bar coating method. Al, Cr, and In in the table represent aluminum, chromium, and indium, respectively, and the metal thin film layers were all formed to a thickness of 50 nm by a vacuum evaporation method.
[Creation of laminate]
A laminate was obtained in the same manner as in Example 1 using the transfer film obtained as described above.
［各転写フイルムおよび積層体の評価］
実施例１～２９および比較例１～１４で得た転写フイルムとそれを用いて得た積層体について、下記の耐薬品性評価および、箔バリ性の評価を行った。結果を表１～３に示す。
［耐薬品性試験（日焼け止め化粧料）］
上記で得られた積層体の表面(保護層面)に対して、縦５０ｍｍ×横５０ｍｍの部分に市販の日焼け止め化粧料０．１５ｇを均一に塗布した。これを５５℃の恒温槽内に２４時間放置した。積層体を取り出し、洗浄液で日焼け止め化粧料を洗い流した後、日焼け止め化粧料を塗布した部分（試験表面）の状態を目視で観察して、以下の基準で評価した。日焼け止め化粧料は、市販のＳＰＦ５０のものを使用した。
◎：膨れ、亀裂、変色など外観に変化が無い。
〇：膨れ、亀裂、変色など外観にわずかな変化があるが、実使用上支障ない。
△：膨れ、亀裂、変色など外観に変化がある。
×：膨れ、亀裂、変色など外観に著しい変化がある。 [Evaluation of each transfer film and laminate]
The transfer films obtained in Examples 1 to 29 and Comparative Examples 1 to 14 and the laminates obtained using the same were evaluated for chemical resistance and foil burr resistance as described below. The results are shown in Tables 1 to 3.
[Chemical resistance test (sunscreen cosmetics)]
On the surface (protective layer side) of the laminate obtained above, 0.15 g of a commercially available sunscreen cosmetic was evenly applied to a 50 mm long x 50 mm wide area. This was left in a constant temperature bath at 55°C for 24 hours. After the laminate was taken out and the sunscreen cosmetic was washed away with a cleaning solution, the condition of the area (test surface) to which the sunscreen cosmetic was applied was visually observed and evaluated using the following criteria. A commercially available sunscreen cosmetic with SPF 50 was used.
◎: No change in appearance such as swelling, cracks, or discoloration.
○: There are slight changes in appearance such as blisters, cracks, and discoloration, but this does not pose a problem in actual use.
△: There are changes in appearance such as swelling, cracks, and discoloration.
×: There is a significant change in appearance such as blisters, cracks, and discoloration.
［耐薬品性試験（ガソリン）］
以下の３種類の条件で耐薬品試験を実施した。いずれもガソリンはＪＩＳ－Ｋ－２２０２に規定される自動車用レギュラーガソリンを使用した。
（１）積層体の表面(保護層側)に対して、２５℃の条件下、０．１ｍｌ滴下し揮発後５分間経過後のガソリンを滴下した部分（試験表面）外観を評価した。
（２）（１）の試験後、さらにそこから８０℃の恒温槽内に静置し、１０分間経過した後のガソリンを滴下した部分（試験表面）外観を評価した。
（３）２５℃の条件下で浸漬させ、３０分経過した後の、試験表面の外観を評価した。
◎：（１）～（３）のいずれの試験でも、膨れ、亀裂、変色など外観に変化が無い。
○：（１）～（３）のいずれかの試験で、膨れ、亀裂、変色など外観にわずかな変化があるが、実使用上支障ない。
△：（１）～（３）のいずれかの試験で、膨れ、亀裂、変色など外観に変化がある。
×：（１）～（３）のいずれかの試験で、膨れ、亀裂、変色など外観に著しい変化がある。 [Chemical resistance test (gasoline)]
A chemical resistance test was conducted under the following three conditions. In both cases, regular gasoline for automobiles specified in JIS-K-2202 was used.
(1) 0.1 ml of gasoline was dropped onto the surface of the laminate (protective layer side) at 25° C., and 5 minutes after volatilization, the appearance of the portion (test surface) where gasoline was dropped was evaluated.
(2) After the test in (1), the test piece was further placed in a constant temperature bath at 80°C, and after 10 minutes, the appearance of the portion (test surface) onto which gasoline had been dropped was evaluated.
(3) The appearance of the test surface was evaluated after 30 minutes of immersion at 25°C.
◎: No change in appearance such as blistering, cracking, or discoloration in any of the tests (1) to (3).
○: In any of the tests (1) to (3), there is a slight change in appearance such as blistering, cracking, or discoloration, but this does not pose a problem in actual use.
Δ: In any of the tests (1) to (3), there is a change in appearance such as blistering, cracking, or discoloration.
×: In any of the tests (1) to (3), there is a significant change in appearance such as blistering, cracking, or discoloration.
［箔バリ性評価］
転写フイルムを用いて積層体を作成する際に、箔バリの発生があるかどうか評価した。
◎：箔バリが生じない。
〇：箔バリがわずかに生じるが、実使用上支障ない。
×：箔バリが生じる。 [Foil burr evaluation]
When creating a laminate using a transfer film, it was evaluated whether or not foil burrs were generated.
◎: No foil burrs occur.
○: Slight burrs occur in the foil, but there is no problem in actual use.
×: Foil burrs occur.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
以上のように、本発明の転写フイルムによれば、箔バリの発生の少なく、耐薬品性の良い積層体を得ることができる。 As described above, according to the transfer film of the present invention, a laminate with less occurrence of foil burrs and good chemical resistance can be obtained.
１           プラスチックフイルム
２           離型層
３           保護層
４           中間層
５           金属下地層
６           金属薄膜層
７　       接着層
８           基材
１０       転写層
１１　　転写フイルム
１２       積層体
  1 Plastic film 2 Release layer 3 Protective layer 4 Intermediate layer 5 Metal base layer 6 Metal thin film layer 7 Adhesive layer 8 Base material 10 Transfer layer 11 Transfer film 12 Laminated body

Claims (11)

  1. プラスチックフイルム上に、少なくとも、機能層および接着層が順次形成されている転写フイルムにおいて、
    少なくとも、機能層の厚さのうち、下記ａ、ｂおよびｃの条件を満たす厚さが３μｍ以上８μｍ以下であることを特徴とする転写フイルム。
    ａ）少なくとも、ポリオール化合物とポリイソシアネート化合物とからなる
    ｂ）ポリオール化合物の水酸基価が２０ｍｇＫＯＨ／ｇ以上６０ｍｇＫＯＨ／ｇ以下である
    ｃ）ポリオール化合物に含まれる水酸基の総数に対するポリイソシアネート化合物に含まれるイソシアネート基の総数の比率（［ＮＣＯ］／［ＯＨ］比）が０．５以上３．０以下である     In a transfer film in which at least a functional layer and an adhesive layer are sequentially formed on a plastic film,
    A transfer film characterized in that at least the thickness of the functional layer that satisfies conditions a, b, and c below is 3 μm or more and 8 μm or less.
    a) Consisting of at least a polyol compound and a polyisocyanate compound b) The hydroxyl value of the polyol compound is 20 mgKOH/g or more and 60 mgKOH/g or less c) The isocyanate group contained in the polyisocyanate compound relative to the total number of hydroxyl groups contained in the polyol compound The ratio of the total number of ([NCO]/[OH] ratio) is 0.5 or more and 3.0 or less
  2. 機能層が、少なくとも、保護層と中間層とからなる、請求項１に記載の転写フイルム。 The transfer film according to claim 1, wherein the functional layer comprises at least a protective layer and an intermediate layer.
  3. 機能層が、少なくとも、保護層と中間層と加飾層とからなる、請求項１に記載の転写フイルム。 The transfer film according to claim 1, wherein the functional layer includes at least a protective layer, an intermediate layer, and a decorative layer.
  4. 加飾層が、金属下地層、金属薄膜層、着色層および印刷層のうち少なくとも１層からなる請求項３に記載の転写フイルム。 4. The transfer film according to claim 3, wherein the decorative layer comprises at least one layer among a metal base layer, a metal thin film layer, a colored layer, and a printing layer.
  5. 加飾層が、金属下地層と金属薄膜層とからなる、請求項４に記載の転写フイルム。 The transfer film according to claim 4, wherein the decoration layer comprises a metal base layer and a metal thin film layer.
  6. 請求項１から請求項５に記載の転写フイルムを基材に転写して得られることを特徴とする積層体。 A laminate obtained by transferring the transfer film according to claim 1 to a base material.
  7. 基材上に、少なくとも、接着層、および機能層が順次形成されている積層体であって、
    少なくとも、機能層の厚さのうち、下記ａ、ｂおよびｃの条件を満たす厚さが３μｍ以上８μｍ以下であることを特徴とする積層体。
    ａ）少なくとも、ポリオール化合物とポリイソシアネート化合物とからなる
    ｂ）ポリオール化合物の水酸基価が２０ｍｇＫＯＨ／ｇ以上６０ｍｇＫＯＨ／ｇ以下である
    ｃ）ポリオール化合物に含まれる水酸基の総数に対するポリイソシアネート化合物に含まれるイソシアネート基の総数の比率（［ＮＣＯ］／［ＯＨ］比）が０．５以上３．０以下である     A laminate in which at least an adhesive layer and a functional layer are sequentially formed on a base material,
    A laminate characterized in that at least the thickness of the functional layer that satisfies conditions a, b, and c below is 3 μm or more and 8 μm or less.
    a) Consisting of at least a polyol compound and a polyisocyanate compound b) The hydroxyl value of the polyol compound is 20 mgKOH/g or more and 60 mgKOH/g or less c) The isocyanate group contained in the polyisocyanate compound relative to the total number of hydroxyl groups contained in the polyol compound The ratio of the total number of ([NCO]/[OH] ratio) is 0.5 or more and 3.0 or less
  8. 機能層が、少なくとも、保護層と中間層とからなる請求項７に記載の積層体。 The laminate according to claim 7, wherein the functional layer comprises at least a protective layer and an intermediate layer.
  9. 機能層が、少なくとも、保護層と中間層と加飾層とからなる請求項７に記載の積層体。 The laminate according to claim 7, wherein the functional layer includes at least a protective layer, an intermediate layer, and a decorative layer.
  10. 加飾層が、金属下地層、金属薄膜層、着色層および印刷層のうち少なくとも１層からなる請求項９に記載の積層体。 The laminate according to claim 9, wherein the decorative layer comprises at least one of a metal base layer, a metal thin film layer, a colored layer, and a printed layer.
  11. 加飾層が、金属下地層と金属薄膜層とからなる、請求項１０に記載の積層体。
          The laminate according to claim 10, wherein the decorative layer consists of a metal base layer and a metal thin film layer.
PCT/JP2022/035323 2022-09-22 2022-09-22 Laminate having excellent chemical resistance, and transfer film for manufacturing same WO2024062589A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2022/035323 WO2024062589A1 (en) 2022-09-22 2022-09-22 Laminate having excellent chemical resistance, and transfer film for manufacturing same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2022/035323 WO2024062589A1 (en) 2022-09-22 2022-09-22 Laminate having excellent chemical resistance, and transfer film for manufacturing same

Publications (1)

Publication Number Publication Date
WO2024062589A1 true WO2024062589A1 (en) 2024-03-28

Family

ID=90454011

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/035323 WO2024062589A1 (en) 2022-09-22 2022-09-22 Laminate having excellent chemical resistance, and transfer film for manufacturing same

Country Status (1)

Country Link
WO (1) WO2024062589A1 (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1148695A (en) * 1997-07-30 1999-02-23 Dainippon Printing Co Ltd Transfer sheet and method for transferring curved surface using the same
JP2000328010A (en) * 1999-05-17 2000-11-28 Sekisui Chem Co Ltd Preparation of surface decorative member
JP2006056183A (en) * 2004-08-23 2006-03-02 Fujicopian Co Ltd Transfer sheet and manufacturing method for decorative material using the same
JP2020163760A (en) * 2019-03-29 2020-10-08 大日本印刷株式会社 Decorative sheet and method of manufacturing resin molding article using the same
JP2021037651A (en) * 2019-08-30 2021-03-11 大日本印刷株式会社 Thermal transfer sheet, intermediate transfer medium, printed object produced using thermal transfer sheet or intermediate transfer medium, printed object production method, and printed object production system
JP2021160355A (en) * 2020-03-31 2021-10-11 大日本印刷株式会社 Transfer sheet, decorative material and manufacturing method of decorative material

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1148695A (en) * 1997-07-30 1999-02-23 Dainippon Printing Co Ltd Transfer sheet and method for transferring curved surface using the same
JP2000328010A (en) * 1999-05-17 2000-11-28 Sekisui Chem Co Ltd Preparation of surface decorative member
JP2006056183A (en) * 2004-08-23 2006-03-02 Fujicopian Co Ltd Transfer sheet and manufacturing method for decorative material using the same
JP2020163760A (en) * 2019-03-29 2020-10-08 大日本印刷株式会社 Decorative sheet and method of manufacturing resin molding article using the same
JP2021037651A (en) * 2019-08-30 2021-03-11 大日本印刷株式会社 Thermal transfer sheet, intermediate transfer medium, printed object produced using thermal transfer sheet or intermediate transfer medium, printed object production method, and printed object production system
JP2021160355A (en) * 2020-03-31 2021-10-11 大日本印刷株式会社 Transfer sheet, decorative material and manufacturing method of decorative material

Similar Documents

Publication Publication Date Title
JP6597305B2 (en) Transfer film and transfer molded product using the same
JP4155651B2 (en) Hard coat film
JP5668475B2 (en) Decorative can body and manufacturing method thereof
CN106457881B (en) Transfer film and transfer molded article using the same
KR20150090050A (en) Transfer film
WO2014119271A1 (en) Transfer film for decoration
JP6969146B2 (en) Mirror label and its manufacturing method
KR101458290B1 (en) Metallic decoration sheet, method of making the same, and resin molded product
CN100469570C (en) Laminated resin sheet, embossed sheet and covered substrate
WO2024062589A1 (en) Laminate having excellent chemical resistance, and transfer film for manufacturing same
KR20080014269A (en) High glossy sheet having aluminum foil
WO2019043542A1 (en) Decorative sheet, structure including a decorative sheet and method for producing a decorative sheet
EP2814653B1 (en) Low-gloss soft-touch thermoformable paint film laminate
KR101364237B1 (en) Ornamental films
CN115320193A (en) Multilayer film and method for manufacturing multilayer film with surface touch and used for in-mold transfer printing
JP3960021B2 (en) Transfer sheet
CN112622382A (en) Multilayer film, manufacturing method and application thereof
JP3936260B2 (en) Multilayer resin sheet
JP3885980B2 (en) Transfer sheet
CN218876535U (en) Multilayer film, automotive interior and plastic part surface structure
JP7307398B2 (en) laminated film
JPH02108600A (en) Transfer foil
CN215397493U (en) Multilayer film and material surface decoration applied to automobile interior decoration
CN116547155A (en) Transfer film and method for producing the same
JP2004167828A (en) Transfer sheet and facing material