WO2021039808A1 - Decorative film and decorative molded product - Google Patents

Decorative film and decorative molded product Download PDF

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Publication number
WO2021039808A1
WO2021039808A1 PCT/JP2020/032076 JP2020032076W WO2021039808A1 WO 2021039808 A1 WO2021039808 A1 WO 2021039808A1 JP 2020032076 W JP2020032076 W JP 2020032076W WO 2021039808 A1 WO2021039808 A1 WO 2021039808A1
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Prior art keywords
decorative film
acrylate
meth
decorative
resin composition
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PCT/JP2020/032076
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French (fr)
Japanese (ja)
Inventor
圭亮 後藤
西　秀樹
隆久 矢野
Original Assignee
大倉工業株式会社
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Application filed by 大倉工業株式会社 filed Critical 大倉工業株式会社
Priority to CN202080059779.8A priority Critical patent/CN114364722A/en
Priority to KR1020227008375A priority patent/KR20220049017A/en
Priority to JP2021510486A priority patent/JP6913838B1/en
Publication of WO2021039808A1 publication Critical patent/WO2021039808A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/26—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer which influences the bonding during the lamination process, e.g. release layers or pressure equalising layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C3/00—Processes, not specifically provided for elsewhere, for producing ornamental structures
    • B44C3/02—Superimposing layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C5/00—Processes for producing special ornamental bodies
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/244—All polymers belonging to those covered by group B32B27/36
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • B32B2307/7163—Biodegradable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2310/00—Treatment by energy or chemical effects
    • B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
    • B32B2310/0806—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation
    • B32B2310/0831—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation using UV radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a decorative film applied to a decorative use of a molded product and a decorative molded product decorated by the decorative film.
  • molded products such as mobile information terminal devices such as smartphones, notebook computers, home appliances, and interior / exterior parts of automobiles have been decorated on the surface by painting or printing. Further, in order to protect the surface, the molded product is provided with a hard coat layer on the surface by spray coating or dipping coating.
  • a conventional decoration method it is difficult to perform decoration with a high degree of design. There is also a drawback in productivity. For this reason, as an alternative method, a method of decorating the surface of a resin molded product by using a decorative film in which a pattern or a hard coat layer is provided on a base film has become widespread.
  • a method of using a decorative film a method of laminating a decorative film on the surface of a pre-molded molded product, or a method of injecting an injection molding resin to be decorated into a decorative film set in a mold, and resin.
  • a method of integrating the molded product and the decorative film the decorative film can be premolded prior to injection of the injection molding resin.
  • thermoplastic resin containing a polycarbonate resin as a main component is preferable because it is necessary to ensure moldability, heat resistance when the injection resin is injected, and adhesion to the injection resin. It is used.
  • a molded product decorated with a decorative film containing a polycarbonate resin as a main component has a problem that the surface hardness is not sufficient and the scratch resistance is inferior. Further, the polycarbonate resin has a problem that it is easily affected by chemicals and is inferior in chemical resistance. Therefore, a hard coat layer made of an acrylic resin composition is formed on the surface of a decorative film containing a polycarbonate resin as a main component to improve scratch resistance and chemical resistance. (Patent Document 2)
  • the hard coat layer made of the conventional acrylic resin composition has insufficient scratch resistance and chemical resistance.
  • the hard coat layer made of the above acrylic resin composition have a surface hardness that can withstand the decorative use, it is necessary to make a thick film of about 20 ⁇ m, but when the hard coat layer becomes thick, the decorative film becomes thicker.
  • the present invention has been made in view of such a problem, and an object of the present invention is to provide a decorative film having excellent scratch resistance, chemical resistance and moldability.
  • a cured resin composition layer and a polycarbonate-based resin obtained by reacting a bifunctional urethane (meth) acrylate-based oligomer (A) having a weight average molecular weight of 1,000 to 10,000 with a reactive diluent monomer (B).
  • a decorative film characterized by being a laminate composed of layers.
  • the bifunctional urethane (meth) acrylate-based oligomer (A) is an oligomer obtained by the reaction of (poly) alkylene glycol (a1), aliphatic cyclic diisocyanate (a2) and hydroxyl (meth) acrylate (a3).
  • the decorative film according to (1) is provided.
  • a decorative molded product in which the decorative film according to any one of (1) to (4) is bonded to the surface.
  • the decorative film of the present invention can be applied to decorative applications of molded products for vehicle interiors such as electronic devices and automobiles, and is useful as a decorative film having excellent scratch resistance and chemical resistance and suitable for molding processing. ..
  • FIG. 1 is a schematic view showing an example of a method for producing the decorative film of the present invention.
  • the resin component constituting the polycarbonate-based resin layer of the decorative film of the present invention is not particularly limited as long as it contains the polycarbonate-based resin as the main component, and is not particularly limited as long as it contains a styrene-based resin or a styrene / acrylonitrile-based resin, if necessary. , Acrylic resin and the like may be included.
  • the polycarbonate-based resin is not particularly limited as long as it has a carbonate structure in its structure, but for example, an aromatic polycarbonate resin having a bisphenol A structure can be preferably used.
  • the styrene resin is a homopolymer or copolymer of a styrene compound such as styrene or ⁇ -methylstyrene, or a mixed resin thereof.
  • the styrene / acrylonitrile resin is a resin composed of a copolymer of styrene and acrylonitrile.
  • the acrylic resin is a homopolymer or copolymer of various acrylic monomers, or a mixed resin thereof.
  • the bifunctional urethane (meth) acrylate-based oligomer (A) having a weight average molecular weight of 1,000 to 10,000 used in the present invention has two or more radically polymerizable (meth) acryloyl groups and urethane bonds in the molecule. It is a compound that has.
  • (meth) acrylate includes both acrylate and methacrylate.
  • the (poly) alkylene glycol includes both alkylene glycol and polyalkylene glycol.
  • the bifunctional urethane (meth) acrylate-based oligomer (A) used in the present invention can be obtained by reacting various types of monomers in combination, and is not particularly limited, but for example, (poly) alkylene glycol (poly) alkylene glycol ( A urethane (meth) acrylate obtained by reacting a1) with an aliphatic cyclic diisocyanate (a2) and a hydroxyl (meth) acrylate (a3) is preferable.
  • the weight average molecular weight of the bifunctional urethane (meth) acrylate-based oligomer (A) is 1,000 to 10,000, preferably 2,500 to 7,000.
  • the weight average molecular weight of the bifunctional urethane (meth) acrylate-based oligomer (A) is less than 1,000, the molecular weight of the cured product becomes small, the cohesive force becomes low, the curing shrinkage becomes large, and when it exceeds 10,000, the viscosity becomes high. It is unsuitable because it has difficulty in properties, crosslinkability is lowered, and heat resistance is also lowered.
  • the number of functional groups of the bifunctional urethane (meth) acrylate-based oligomer (A) is preferably bifunctional, and if it is trifunctional or higher, the number of cross-linked points increases and the flexibility decreases, resulting in low moldability.
  • Examples of the (poly) alkylene glycol (a1) include (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene ether glycol, hexaethylene glycol, 1,3- (poly) butylene glycol, and 1,4-.
  • (poly) ethylene glycol having many ether bond points and high flexibility is preferable.
  • Examples of the aliphatic cyclic diisocyanate (a2) include isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, hydrogenated xylylene diisocyanate, methylcyclohexylene diisocyanate, and 6-norbornane diisocyanate, which are used alone. You may use two or more kinds together. Among these, isophorone diisocyanate, which can improve the rigidity, is preferable.
  • Examples of the hydroxyl (meth) acrylate (a3) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-.
  • 2-hydroxypropyl acrylate and 2-hydroxyethyl acrylate are preferable in terms of suppressing crystallization and gelation of the synthesized resin.
  • the blending amount of the bifunctional urethane (meth) acrylate-based oligomer (A) with respect to the total solid content of the bifunctional urethane (meth) acrylate-based oligomer (A) and the reactive diluted monomer (B) is preferably 35 to 75% by weight. It is more preferably 40 to 70% by weight. When it is 35% by weight or more, sufficient cohesive force and film strength can be secured, and when it is 75% by weight or less, the viscosity of the composition can be appropriately controlled and good workability can be ensured.
  • the reactive diluting monomer (B) used in the present invention is a main material that dilutes the bifunctional urethane (meth) acrylate-based oligomer (A) and improves the curing reactivity to form a resin film.
  • the reactive diluting monomer (B) include alkyl-based (meth) acrylates, aromatic (meth) acrylates, and (meth) acrylates containing polar groups such as hydroxyl groups and amino groups in these (meth) acrylates. Can be mentioned.
  • Alkyl-based (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, and octyl (meth) acrylate.
  • aromatic (meth) acrylates include phenoxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, methylphenoxyethyl acrylate, phenoxydiethylene glycol acrylate, and phenoxypolyethylene glycol acrylate.
  • aromatic (meth) acrylates include 2-hydroxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, methylphenoxyethyl acrylate, phenoxydiethylene glycol acrylate, and phenoxypolyethylene glycol acrylate.
  • Examples of the (meth) acrylate containing a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like. ..
  • Examples of the (meth) acrylate containing an amino group include acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, acryloyl morpholine and the like. These monomers may be used alone or in combination of two or more.
  • the viscosity of the reactive diluent monomer (B) used in the present invention is preferably 10,000 mPa ⁇ s or less so that the viscosity of the formulation can be easily adjusted. Further, the reactive diluting monomer (B) is preferably monofunctional in order to suppress curing shrinkage and increase the elongation rate.
  • the reactive diluting monomer (B) used in the present invention is preferably a highly polar (meth) acrylate (1) because of its compatibility with the bifunctional urethane (meth) acrylate-based oligomer (A), and has a small C number (meth).
  • Acrylate (1-1) and (meth) acrylate having a polar group (1-2) can be mentioned.
  • the highly polar (meth) acrylate has an SP value (solubility parameter) of 9 to 12, and for example, methyl methacrylate is preferable as the acrylate (1-1) having a small C number, and it has an amino group as a polar group (meth).
  • the reactive diluent monomer (B) contains a highly polar (meth) acrylate (1) having an SP value of 9 to 12, it is preferably the main component of the reactive diluent monomer (B).
  • the fingerprint visibility of the decorative film will be described here.
  • a decorative film is used for decorating vehicle interior materials such as electronic devices and automobiles, it is normal for a person to touch the surface of the decorative film, and when the surface of the decorative film is touched by a finger pad or the like. Fingerprints are attached to the surface of the decorative film, and the traces of the fingerprints are clearly left.
  • a calm atmosphere is preferred, so monotone color tones such as black and gray are often used inside the vehicle. If fingerprints are clearly left on the surface of the interior material decorated in monotone, the cleanliness will be impaired. Therefore, it is difficult to see the fingerprints (not noticeable), which makes the interior material aesthetically pleasing. Very important to maintain.
  • the blending amount of the reactive diluted monomer (B) with respect to the total solid content of the bifunctional urethane (meth) acrylate-based oligomer (A) and the reactive diluted monomer (B) is preferably 25 to 65% by weight, preferably 30 to 60% by weight. Is more preferable. When it is 25% by weight or more, quick curing property can be obtained, and when it is 65% by weight or less, the curing shrinkage rate can be controlled to be small.
  • the cured resin composition layer of the decorative film of the present invention is other than the bifunctional urethane (meth) acrylate-based oligomer (A) and the reactive diluent monomer (B) of the present invention as long as the effects of the present invention can be obtained. It may further contain the component of. Examples of such other components include active energy ray-curable oligomers, polymerization initiators, additives, and solvents.
  • the polymerization initiator is mainly used for the purpose of improving the initiation efficiency of the polymerization reaction that proceeds by irradiation with active energy rays such as ultraviolet rays and electron beams.
  • active energy rays such as ultraviolet rays and electron beams.
  • a photoradical polymerization initiator which is a compound having a property of generating radicals by light is generally used, and a known photoradical polymerization initiator can be used as long as the effect of the present invention can be obtained. ..
  • As the polymerization initiator one type may be used alone, or two or more types may be mixed and used.
  • photoradical polymerization initiator examples include benzophenone, 2,4,6-trimethylbenzophenone, 4,4-bis (diethylamino) benzophenone, 4-phenylbenzophenone, methyl orthobenzoylbenzoate, thioxanthone, diethylthioxanthone, isopropylthioxanthone, and chloro.
  • the content of these polymerization initiators in the cured resin composition layer of the decorative film of the present invention is 100 parts by weight in total of the bifunctional urethane (meth) acrylate-based oligomer (A) and the reactive diluted monomer (B). It is preferably 10 parts by weight or less, and more preferably 5 parts by weight or less. When the content of the polymerization initiator is 10 parts by weight or less, the mechanical strength is unlikely to be lowered by the decomposition product of the initiator, which is preferable.
  • a photosensitizer may be added to the cured resin composition layer of the decorative film of the present invention in addition to the photoradical polymerization initiator as long as the effects of the present invention can be obtained.
  • the photosensitizer can be used for the same purpose as the polymerization initiator.
  • One type of photosensitizer may be used alone, or two or more types may be mixed and used.
  • known photosensitizers can be used as long as the effects of the present invention can be obtained.
  • Examples of the photosensitizer include ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, and 4-. Examples thereof include dimethylaminoacetophenone.
  • the content of the photosensitizer in the cured resin composition layer of the decorative film of the present invention is 100 parts by weight in total of the bifunctional urethane (meth) acrylate-based oligomer (A) and the reactive diluted monomer (B). It is preferably 10 parts by weight or less, and more preferably 5 parts by weight or less. When the content of the photosensitizer is 10 parts by weight or less, the mechanical strength is unlikely to decrease due to the decrease in the crosslink density, which is preferable.
  • Additives to be blended in the cured resin composition layer of the decorative film of the present invention include antioxidants, ultraviolet absorbers, (near) infrared absorbers, fluorescent whitening agents, flame retardants, fillers, organic fine particles, and the like. Inorganic fine particles, dispersants, silane coupling agents, leveling agents, defoaming agents, surfactants, anti-fingerprint agents, antistatic agents, antibacterial agents, anti-virus agents, polymerization inhibitors, pigments, dyes, pigments and other colorants , Plasticizers and the like.
  • the decorative film of the present invention may be provided with a layer other than the cured resin composition layer and the polycarbonate-based resin layer as long as the effects of the present invention are not impaired. Further, on the surface of the decorative film, a printing layer such as a pattern or characters, an adhesive layer, an adhesive layer, or the like can be provided as needed. Generally, the printing layer, the adhesive layer, or the adhesive layer is provided on the surface of the polycarbonate resin layer on the side to be bonded to the molded body.
  • the thickness of the decorative film of the present invention is determined according to the use of the molded product, suitability for insert molding, handleability of the sheet, etc. For example, 100 ⁇ m to 800 ⁇ m is preferable, and 150 ⁇ m to 600 ⁇ m is more preferable.
  • the thickness ratio of the cured resin composition layer to the polycarbonate resin layer is preferably 1:10 to 10: 1.
  • the thickness of the cured resin composition layer in the decorative film of the present invention is preferably 20 ⁇ m or more and 80 ⁇ m or less, more preferably 25 ⁇ m or more and 50 ⁇ m or less, and 25 ⁇ m or more, from the viewpoint of scratch resistance and moldability. It is more preferably 40 ⁇ m or less.
  • the crack resistance of the decorative film will be described here.
  • a decorative film is used for decorating vehicle interior materials such as automobiles, various performances are required at a high level.
  • the inside of the car may be in a high temperature and high humidity environment (for example, temperature 85 ° C, humidity 85% RH), but a decorative film exposed to a high temperature and high humidity environment for a long time may easily crack the coating film. ..
  • the thickness of the cured resin composition layer is 25 ⁇ m or more and 50 ⁇ m or less, the cured resin composition layer is cracked after the wet heat test in a high temperature and high humidity environment (85 ° C., 85% RH). It can be suppressed.
  • the pencil hardness of the decorative film of the present invention in the cured resin composition layer is preferably H or higher. If the pencil hardness is H or more, sufficient scratch resistance can be ensured for decorative purposes.
  • the decorative film of the present invention preferably has a heating elongation of 150% or more at an atmospheric temperature of 160 ° C. If the heating elongation is 150% or more, it is possible to follow the deep drawing shape of the vehicle interior material or the like, and it is possible to secure sufficient moldability for decorative use.
  • FIG. 1 shows an example of a method for producing the decorative film of the present invention.
  • the composition is supplied in a fixed amount onto the polycarbonate-based resin film 11 which has been preliminarily formed by a known method.
  • the polycarbonate-based resin film 11 is continuously drawn out from the roll-shaped one at a constant speed according to the supply amount of the photocurable resin composition.
  • the cover film 13 is laminated on the liquid photocurable resin composition cast on the polycarbonate-based resin film 11 to a predetermined thickness to form a laminate, and then the cover film 13 side of the laminate.
  • the photocurable resin composition is cured by irradiating the ultraviolet light from the ultraviolet light source 14.
  • the obtained decorative film 16 is wound while continuously peeling and removing the cover film 13.
  • the cooling method there are known methods such as an air cooling method and a water cooling method.
  • the surface of the polycarbonate-based resin film 11 is surface-treated by a method such as corona discharge treatment in order to improve the adhesiveness between the curable resin composition layer and the printing layer, the pressure-sensitive adhesive layer, or the adhesive layer provided as needed. Can be applied.
  • liquid photocurable resin composition examples include a bar coater method, an applicator method, a curtain coater method, a roll coater method, a gravure coater method, a reverse coater method, a comma coater method, a lip coater method, and a die coater method. Method can be applied.
  • a solvent may be added if necessary for the purpose of adjusting the viscosity.
  • the solvent one type may be used alone, or two or more types may be mixed and used.
  • a known solvent can be used as long as the effect of the present invention can be obtained.
  • the solvent include toluene, xylene, ethyl acetate, butyl acetate, isopropanol, isobutanol, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone and the like.
  • the irradiation condition of ultraviolet rays for example, if it is about 75 ⁇ m thickness of the cured resin composition layer, 500mW / cm 2 ⁇ 3,000mW / irradiation intensity of cm 2, as the accumulated light quantity is 100mJ / cm 2 ⁇ 2 An example is 000 mJ / cm 2.
  • known light sources such as a high-pressure mercury lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a xenon lamp, and an LED lamp can be applied.
  • a method of decorating a molded product using the decorative film of the present invention a method of laminating a decorative film on the surface of a pre-molded molded product, or a method of decorating a decorative film set in a mold is targeted.
  • a method of injecting a resin for injection molding and integrating the molded product and the decorative film can be mentioned.
  • the polycarbonate resin layer side of the decorative film of the present invention is arranged on the surface of the molded product.
  • Example 1 The following mixture of components A to C was stirred until it was uniformly dissolved to prepare a photocurable resin composition for forming a cured resin composition layer.
  • Component A Bifunctional urethane acrylate oligomer: 100 parts by weight polyethylene glycol 200 (manufactured by Toho Chemical Industry Co., Ltd., trade name PEG200, solid content 100%) and isophorone diisocyanate (manufactured by Sumika Bayer Urethane Co., Ltd., trade name Death Module I, NCO group 37.5%) was added to the methyl methacrylate monomer, and the mixture was stirred and reacted at 30 ° C.
  • Bifunctional urethane acrylate oligomer 100 parts by weight polyethylene glycol 200 (manufactured by Toho Chemical Industry Co., Ltd., trade name PEG200, solid content 100%) and isophorone diisocyanate (manufactured by Sumika Bayer Urethane Co., Ltd., trade name Death
  • Component B Acryloyl morpholine (manufactured by KJ Chemicals Co., Ltd., trade name ACMO): 40 parts by weight
  • C component Polymerization initiator 2-hydroxy-2-methyl-1-phenylpropane (manufactured by BASF Japan, trade name Omnirad 1173): 5 Weight part
  • a photocurable resin composition is applied to a 180 ⁇ m-thick polycarbonate resin film (Panlite (registered trademark) PC-2151 manufactured by Teijin Limited), and the surface of the photocurable resin composition is corona-treated or easily adhered.
  • the thickness of the layer of the photocurable resin composition was adjusted from above the cover film by a film applicator so that the thickness after curing was 75 ⁇ m.
  • ultraviolet rays are irradiated from the cover film side at an integrated light amount of 1000 mJ / cm 2 to cure the photocurable resin composition, and then the cover film is peeled off to decorate with a thickness of 255 ⁇ m.
  • a film (cured resin composition layer 75 ⁇ m / polycarbonate resin layer 180 ⁇ m) was obtained.
  • the integrated light intensity was measured by Microcure MC-10A manufactured by Heleus Co., Ltd.
  • Example 2 A decorative film (cured resin composition layer 50 ⁇ m / polycarbonate resin layer 180 ⁇ m) was prepared under the same conditions as in Example 1 except that the thickness of the cured resin composition layer composed of the photocurable resin composition was 50 ⁇ m. ..
  • Example 3 A decorative film (cured resin composition layer 40 ⁇ m / polycarbonate resin layer 180 ⁇ m) was prepared under the same conditions as in Example 1 except that the thickness of the cured resin composition layer composed of the photocurable resin composition was 40 ⁇ m. ..
  • Example 4 A decorative film (cured resin composition layer 30 ⁇ m / polycarbonate resin layer 180 ⁇ m) was prepared under the same conditions as in Example 1 except that the thickness of the cured resin composition layer composed of the photocurable resin composition was 30 ⁇ m. ..
  • Example 5 A decorative film (cured resin composition layer 25 ⁇ m / polycarbonate resin layer 180 ⁇ m) was prepared under the same conditions as in Example 1 except that the thickness of the cured resin composition layer composed of the photocurable resin composition was 25 ⁇ m. ..
  • An ultraviolet curable hard coat agent is applied to a 300 ⁇ m-thick polycarbonate resin film (Panlite (registered trademark) PC-2151 manufactured by Teijin Co., Ltd.), and a bar coater is used so that the cured thickness is 5 ⁇ m. After casting and volatilizing the solvent, ultraviolet rays were irradiated with an integrated light amount of 400 mJ / cm 2 by an electrodeless ultraviolet lamp to cure the film, and a decorative film (hard coat layer 5 ⁇ m / polycarbonate resin layer 300 ⁇ m) having a thickness of 305 ⁇ m was applied. Made.
  • Comparative Example 2 The same evaluation as in Example was carried out using a polycarbonate resin film having a thickness of 300 ⁇ m (manufactured by Teijin Limited, Panlite (registered trademark) PC-2151) as Comparative Example 2.
  • Comparative Example 3 The same evaluation as in Example was carried out using a polycarbonate resin film having a thickness of 180 ⁇ m (manufactured by Teijin Limited, Panlite (registered trademark) PC-2151) as Comparative Example 3.
  • Comparative Example 4 A commercially available polycarbonate-based decorative film A (manufactured by Mitsubishi Gas Chemical Company, Inc., Iupiron (registered trademark) MRF08U, hard coat layer 3 ⁇ m / polymethylmethacrylate resin layer 50 ⁇ m / polycarbonate resin layer 260 ⁇ m) was used as Comparative Example 4 with Examples. The same evaluation was performed.
  • Comparative Example 5 Comparative example of a commercially available polycarbonate-based decorative film B (manufactured by MacDermid Performance Solutions Japan Co., Ltd., XtraForm (registered trademark) G250M, hard coat layer 8 ⁇ m / polycarbonate resin layer 260 ⁇ m, hard coat layer aftercure type) The same evaluation as in Example was carried out as 5.
  • Examples 1 to 5 and Comparative Examples 1 to 5 were evaluated for scratch resistance (pencil hardness), chemical resistance, moldability (heat elongation), crack resistance, and fingerprint visibility according to the method described later. The results are shown in Table 1.
  • a film cut to a size of 10 mm in width ⁇ 120 mm in length was used as a measurement sample.
  • the measurement sample was pulled at a speed of 500 mm / min at an ambient temperature of 160 ° C. and a distance between chucks of 50 mm.
  • a heating elongation of 150% or more represented by the following formula was evaluated as ⁇ , and a heating elongation of less than 150% was evaluated as x.
  • Heating elongation (%) Distance between chucks when an appearance abnormality occurs (mm) / 50 mm x 100 * Appearance abnormality: cracks or cracks in the cured resin composition layer or hard coat layer, whitening or breakage of the film, etc.
  • ⁇ The edges of the cut are completely smooth and there are no cracks in any of the grids.
  • ⁇ There are small cracks in the coating film at the intersections of the cuts (the area of the cracks is 5% or less).
  • ⁇ The coating film has cracks along the edge of the cut and / or at the intersection (the area of the cracked portion exceeds 5% and 15% or less).
  • X The coating film has large cracks partially or entirely along the edge of the cut (the area of the cracked portion exceeds 15%).
  • a sample piece obtained by cutting a film into a size of 50 mm in width and 50 mm in length is cut out, and the sample piece is laminated with a black acrylic resin plate (thickness 2 mm) via an adhesive so that the polycarbonate resin layer side becomes an adhesive surface.
  • the surface of the cured resin composition layer or the hard coat layer was washed with ethanol.
  • the surface of the cured resin composition layer or the hard coat layer was pressed with the pad of a finger to attach a fingerprint, and the invisibleness (inconspicuousness) of the fingerprint at the portion to which the fingerprint was attached was visually evaluated according to the following evaluation criteria. ..
  • ⁇ When the fingerprint is attached from the cured resin composition layer or the hard coat layer side from various angles, it is difficult to see the fingerprint at any angle.
  • ⁇ Fingerprint from the cured resin composition layer or the hard coat layer side. Fingerprints are easy to see at any angle when the area where the plastic is attached is viewed from various angles.
  • the decorative films of Examples 1 to 5 showed excellent results in all properties of scratch resistance, chemical resistance, moldability, crack resistance and fingerprint visibility. Further, Examples 2 to 5 in which the thickness of the cured resin composition layer was 25 ⁇ m to 50 ⁇ m showed excellent results in crack resistance of the cured resin composition layer after being exposed to a high temperature and high humidity environment for a long time. ..
  • the decorative film of Comparative Example 1 showed no problem in moldability and crack resistance, but was inferior in scratch resistance, chemical resistance and fingerprint visibility.
  • the decorative films of Comparative Examples 2 and 3 showed inferior scratch resistance, chemical resistance, and fingerprint visibility.
  • the decorative film of Comparative Example 5 showed no problem in scratch resistance and crack resistance, but was inferior in chemical resistance, moldability, and fingerprint visibility.
  • the decorative film of Comparative Example 4 showed no problem in moldability and crack resistance, but was inferior in chemical resistance and fingerprint visibility. Further, the decorative film of Comparative Example 4 is inferior to other decorative films in terms of manufacturing cost because the hard coat layer is an aftercure type and a curing step of the hard coat layer is required after the decorative molding. is there.

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Abstract

[Problem] Conventionally, a hard coat layer was provided on decorative films formed from polycarbonate resin in order to achieve scratch resistance. However, the hard coat layer had to be thick to ensure sufficient surface hardness, and it was problematic that, due to the hardness, the moldability required of a decorative film during molding would become worse. Because of this, there was a need for development of a novel decorative film that solves these problems. [Solution] This decorative film is a laminate formed from a polycarbonate resin layer and a cured resin composition layer obtained by reacting (A) bifunctional urethane (meth)acrylate oligomers with a weight average molecular weight of 1000-10,000 and (B) reactive diluent monomers.

Description

加飾フィルム及び加飾成型品Decorative film and decorative molded product
　本発明は、成型品の加飾用途に適用される加飾フィルム及びそれにより加飾された加飾成型品に関する。 The present invention relates to a decorative film applied to a decorative use of a molded product and a decorative molded product decorated by the decorative film.
　従来、意匠性付与のために、スマートフォン等の携帯情報端末機器、ノート型パソコン、家電製品、自動車内外装部品などの成型品は、塗装や印刷により表面に加飾が施されている。また、表面保護のために、成型品は、スプレー塗装やディッピング塗装により表面にハードコート層が設けられている。しかし、このような従来の加飾方法は、意匠性の高い加飾を行うことが困難である。また、生産性にも難点がある。このため、これに代わる方法として、基材フィルム上に図柄やハードコート層を設けた加飾フィルムを用いて、樹脂成型品の表面を加飾する方法が普及してきている。 Conventionally, in order to impart design, molded products such as mobile information terminal devices such as smartphones, notebook computers, home appliances, and interior / exterior parts of automobiles have been decorated on the surface by painting or printing. Further, in order to protect the surface, the molded product is provided with a hard coat layer on the surface by spray coating or dipping coating. However, with such a conventional decoration method, it is difficult to perform decoration with a high degree of design. There is also a drawback in productivity. For this reason, as an alternative method, a method of decorating the surface of a resin molded product by using a decorative film in which a pattern or a hard coat layer is provided on a base film has become widespread.
　加飾フィルムを用いる方法としては、予め成型された成型品の表面に加飾フィルムを積層する方法や、金型内にセットした加飾フィルムに加飾対象の射出成型用樹脂を射出し、樹脂成型品と加飾フィルムとを一体化する方法等がある。後者の方法は、射出成型用樹脂の射出に先立ち、加飾フィルムを予備成型しておくこともできる。 As a method of using a decorative film, a method of laminating a decorative film on the surface of a pre-molded molded product, or a method of injecting an injection molding resin to be decorated into a decorative film set in a mold, and resin. There is a method of integrating the molded product and the decorative film. In the latter method, the decorative film can be premolded prior to injection of the injection molding resin.
　加飾フィルムとしては、成型性、射出樹脂が射出された際の耐熱性、射出樹脂との密着性などを担保する必要があることから、ポリカーボネート系樹脂を主成分とする熱可塑性樹脂が好適に用いられている。（特許文献１） As the decorative film, a thermoplastic resin containing a polycarbonate resin as a main component is preferable because it is necessary to ensure moldability, heat resistance when the injection resin is injected, and adhesion to the injection resin. It is used. (Patent Document 1)
　しかしながら、ポリカーボネート系樹脂を主成分とする加飾フィルムを用いて加飾した成型品は、表面硬度が十分でなく、耐擦傷性に劣るという問題がある。また、ポリカーボネート系樹脂は、薬品に対して影響を受けやすく、耐薬品性に劣るという問題がある。そこで、ポリカーボネート系樹脂を主成分とする加飾フィルムの表面にアクリル系樹脂組成物からなるハードコート層を形成し、耐擦傷性及び耐薬品性を改善することが行われている。（特許文献２） However, a molded product decorated with a decorative film containing a polycarbonate resin as a main component has a problem that the surface hardness is not sufficient and the scratch resistance is inferior. Further, the polycarbonate resin has a problem that it is easily affected by chemicals and is inferior in chemical resistance. Therefore, a hard coat layer made of an acrylic resin composition is formed on the surface of a decorative film containing a polycarbonate resin as a main component to improve scratch resistance and chemical resistance. (Patent Document 2)
　しかしながら、本発明者等の知見によると従来のアクリル系樹脂組成物からなるハードコート層は、耐擦傷性や耐薬品性が不十分である。例えば、上記のアクリル系樹脂組成物からなるハードコート層を加飾用途に耐えうる表面硬度とするためには２０μｍ程度の厚膜とする必要があるが、ハードコート層が厚くなると加飾フィルムの成型性が悪化し、ハードコート層の割れや剥離が発生するという問題が新たに発生する。 However, according to the knowledge of the present inventors, the hard coat layer made of the conventional acrylic resin composition has insufficient scratch resistance and chemical resistance. For example, in order to make the hard coat layer made of the above acrylic resin composition have a surface hardness that can withstand the decorative use, it is necessary to make a thick film of about 20 μm, but when the hard coat layer becomes thick, the decorative film becomes thicker. A new problem arises in which the moldability deteriorates and the hard coat layer cracks or peels off.
特開２０１５－１３１４６２公報JP 2015-131462 特開２０１８－６５９４７公報JP-A-2018-56947
　本発明はこのような問題に鑑みなされたものであり、その目的とするところは耐擦傷性、耐薬品性及び成型性のいずれにも優れ得る加飾フィルムを提供することである。 The present invention has been made in view of such a problem, and an object of the present invention is to provide a decorative film having excellent scratch resistance, chemical resistance and moldability.
　すなわち、本発明によると、
（１）重量平均分子量が１，０００～１０，０００の２官能ウレタン（メタ）アクリレート系オリゴマー（Ａ）と反応性希釈モノマー（Ｂ）との反応で得られる硬化樹脂組成物層及びポリカーボネート系樹脂層から構成される積層体であることを特徴とする加飾フィルムが提供される。 That is, according to the present invention
(1) A cured resin composition layer and a polycarbonate-based resin obtained by reacting a bifunctional urethane (meth) acrylate-based oligomer (A) having a weight average molecular weight of 1,000 to 10,000 with a reactive diluent monomer (B). Provided is a decorative film characterized by being a laminate composed of layers.
（２）２官能ウレタン（メタ）アクリレート系オリゴマー（Ａ）が（ポリ）アルキレングリコール（ａ１）と脂肪族環式ジイソシアネート（ａ２）とヒドロキシル（メタ）アクリレート（ａ３）との反応で得られるオリゴマーであることを特徴とする（１）記載の加飾フィルムが提供される。 (2) The bifunctional urethane (meth) acrylate-based oligomer (A) is an oligomer obtained by the reaction of (poly) alkylene glycol (a1), aliphatic cyclic diisocyanate (a2) and hydroxyl (meth) acrylate (a3). (1) The decorative film according to (1) is provided.
（３）硬化樹脂組成物層の厚さが２５μｍ以上５０μｍ以下であることを特徴とする（１）又は（２）記載の加飾フィルムが提供される。 (3) The decorative film according to (1) or (2), wherein the thickness of the cured resin composition layer is 25 μm or more and 50 μm or less is provided.
（３）反応性希釈モノマー（Ｂ）はＳＰ値が９～１２の（メタ）アクリレートを主成分として含むことを特徴とする（１）乃至（３）の何れかに記載の加飾フィルムが提供される。 (3) The decorative film according to any one of (1) to (3), wherein the reactive diluting monomer (B) contains (meth) acrylate having an SP value of 9 to 12 as a main component. Will be done.
（４）（１）乃至（４）何れかに記載の加飾フィルムが表面に貼合されている加飾成型品が提供される。 (4) Provided is a decorative molded product in which the decorative film according to any one of (1) to (4) is bonded to the surface.
　本発明の加飾フィルムは、電子機器や自動車等の車両内装用の成型品の加飾用途に適用可能で、耐擦傷性及び耐薬品性に優れ成型加工に適した加飾フィルムとして有用である。 The decorative film of the present invention can be applied to decorative applications of molded products for vehicle interiors such as electronic devices and automobiles, and is useful as a decorative film having excellent scratch resistance and chemical resistance and suitable for molding processing. ..
図１は、本発明の加飾フィルムを製造する方法の一例を示す概略図である。FIG. 1 is a schematic view showing an example of a method for producing the decorative film of the present invention.
　以下、本発明の加飾フィルムの実施形態について説明する。尚、本発明は以下の形態に限定されるものではなく、同様の効果を奏する範囲において種々の形態をとることができる。 Hereinafter, embodiments of the decorative film of the present invention will be described. The present invention is not limited to the following forms, and various forms can be taken as long as the same effect is exhibited.
　本発明の加飾フィルムのポリカーボネート系樹脂層を構成する樹脂成分は、ポリカーボネート系樹脂を主成分として含むものでれば特に制限するものではなく、必要に応じてスチレン系樹脂、スチレン・アクリロニトリル系樹脂、アクリル系樹脂等が含まれてもよい。ポリカーボネート系樹脂としては、構造中にカーボネート構造を有する樹脂であれば特に制限するものではないが、例えば、ビスフェノールＡ構造を有する芳香族ポリカーボネート樹脂を好適に使用することができる。 The resin component constituting the polycarbonate-based resin layer of the decorative film of the present invention is not particularly limited as long as it contains the polycarbonate-based resin as the main component, and is not particularly limited as long as it contains a styrene-based resin or a styrene / acrylonitrile-based resin, if necessary. , Acrylic resin and the like may be included. The polycarbonate-based resin is not particularly limited as long as it has a carbonate structure in its structure, but for example, an aromatic polycarbonate resin having a bisphenol A structure can be preferably used.
　スチレン系樹脂は、スチレン、α－メチルスチレン等のスチレン系化合物の単独重合体や共重合体、又はそれらの混合樹脂である。また、スチレン・アクリロニトリル系樹脂は、スチレンとアクリロニトリルの共重合体からなる樹脂である。さらに、アクリル系樹脂は、各種アクリル系単量体の単独重合体や共重合体、又はそれらの混合樹脂である。 The styrene resin is a homopolymer or copolymer of a styrene compound such as styrene or α-methylstyrene, or a mixed resin thereof. The styrene / acrylonitrile resin is a resin composed of a copolymer of styrene and acrylonitrile. Further, the acrylic resin is a homopolymer or copolymer of various acrylic monomers, or a mixed resin thereof.
　本発明において用いられる重量平均分子量が１，０００～１０，０００の２官能ウレタン（メタ）アクリレート系オリゴマー（Ａ）は、分子内に２個以上のラジカル重合性（メタ）アクリロイル基とウレタン結合を有する化合物である。なお、本明細書において、（メタ）アクリレートとはアクリレートとメタクリレートとの双方を包含する。また（ポリ）アルキレングリコールとは、アルキレングリコールとポリアルキレングリコールの双方を包含する。 The bifunctional urethane (meth) acrylate-based oligomer (A) having a weight average molecular weight of 1,000 to 10,000 used in the present invention has two or more radically polymerizable (meth) acryloyl groups and urethane bonds in the molecule. It is a compound that has. In addition, in this specification, (meth) acrylate includes both acrylate and methacrylate. Further, the (poly) alkylene glycol includes both alkylene glycol and polyalkylene glycol.
　本発明において用いられる２官能ウレタン（メタ）アクリレート系オリゴマー（Ａ）は、様々な種類のモノマーを組み合わせて反応させることで得られ、特に制限するものではないが、例えば、（ポリ）アルキレングリコール（ａ１）と脂肪族環式ジイソシアネート（ａ２）とヒドロキシル（メタ）アクリレート（ａ３）との反応で有られるウレタン（メタ）アクリレートであることが好ましい。２官能ウレタン（メタ）アクリレート系オリゴマー（Ａ）の重量平均分子量は、１，０００～１０，０００であり、２，５００～７，０００が好ましい。２官能ウレタン（メタ）アクリレート系オリゴマー（Ａ）の重量平均分子量が１，０００未満では硬化物の分子量が小さくなり凝集力が低くまた硬化収縮が大きくなり、１０，０００超では粘度が高くなり作業性に難がありまた架橋性が低下し耐熱性も低下して不適である。２官能ウレタン（メタ）アクリレート系オリゴマー（Ａ）の官能基数は、２官能が好ましく、３官能以上では架橋点が多くなり可撓性が低下するため成型性が低くなる。 The bifunctional urethane (meth) acrylate-based oligomer (A) used in the present invention can be obtained by reacting various types of monomers in combination, and is not particularly limited, but for example, (poly) alkylene glycol (poly) alkylene glycol ( A urethane (meth) acrylate obtained by reacting a1) with an aliphatic cyclic diisocyanate (a2) and a hydroxyl (meth) acrylate (a3) is preferable. The weight average molecular weight of the bifunctional urethane (meth) acrylate-based oligomer (A) is 1,000 to 10,000, preferably 2,500 to 7,000. When the weight average molecular weight of the bifunctional urethane (meth) acrylate-based oligomer (A) is less than 1,000, the molecular weight of the cured product becomes small, the cohesive force becomes low, the curing shrinkage becomes large, and when it exceeds 10,000, the viscosity becomes high. It is unsuitable because it has difficulty in properties, crosslinkability is lowered, and heat resistance is also lowered. The number of functional groups of the bifunctional urethane (meth) acrylate-based oligomer (A) is preferably bifunctional, and if it is trifunctional or higher, the number of cross-linked points increases and the flexibility decreases, resulting in low moldability.
　（ポリ）アルキレングリコール（ａ１）としては、例えば（ポリ）エチレングリコール、（ポリ）プロピレングリコール、（ポリ）テトラメチレンエーテルグリコール、ヘキサエチレングリコール、１，３－（ポリ）ブチレングリコール、１，４－（ポリ）ブチレングリコールなどがあり、これらを単独で用いてもよいし２種以上を併用してもよい。これらの中でも、エーテル結合点が多く可撓性が高い（ポリ）エチレングリコールが好ましい。 Examples of the (poly) alkylene glycol (a1) include (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene ether glycol, hexaethylene glycol, 1,3- (poly) butylene glycol, and 1,4-. There are (poly) butylene glycol and the like, and these may be used alone or in combination of two or more. Among these, (poly) ethylene glycol having many ether bond points and high flexibility is preferable.
　脂肪族環式ジイソシアネート（ａ２）としては、例えばイソホロンジイソシアネート、ジシクロヘキシルメタン－４，４’－ジイソシアネート、水添キシリレンジイソシアネート、メチルシクロヘキシレンジイソシアネート、６－ノルボルナンジイソシアネートなどがあり、これらを単独で用いてもよいし２種以上を併用してもよい。これらの中でも、剛性を向上できるイソホロンジイソシアネートが好ましい。 Examples of the aliphatic cyclic diisocyanate (a2) include isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, hydrogenated xylylene diisocyanate, methylcyclohexylene diisocyanate, and 6-norbornane diisocyanate, which are used alone. You may use two or more kinds together. Among these, isophorone diisocyanate, which can improve the rigidity, is preferable.
　ヒドロキシル（メタ）アクリレート（ａ３）としては、例えば２－ヒドロキシエチル（メタ）アクリレート、２‐ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、６－ヒドロキシヘキシル（メタ）アクリレート、８－ヒドロキシオクチル（メタ）アクリレート、１，４－シクロヘキサンジメタノールモノアクリレート、４－ヒドロキシシクロヘキシル（メタ）アクリレートなどがあり、これらを単独で用いてもよいし２種以上を併用してもよい。これらの中でも、合成した樹脂の結晶化抑制やゲル化抑制の点で２‐ヒドロキシプロピルアクリレートおよび２ヒドロキシエチルアクリレートが好ましい。 Examples of the hydroxyl (meth) acrylate (a3) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-. There are hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 1,4-cyclohexanedimethanol monoacrylate, 4-hydroxycyclohexyl (meth) acrylate, etc., which may be used alone or in combination of two or more. May be used together. Among these, 2-hydroxypropyl acrylate and 2-hydroxyethyl acrylate are preferable in terms of suppressing crystallization and gelation of the synthesized resin.
　２官能ウレタン（メタ）アクリレート系オリゴマー（A）の製造方法としては、（ポリ）アルキレングリコール（ａ１）を脂肪族環式ジイソシアネート（ａ２）が過剰な条件下で反応させた、末端がイソシアネートのウレタンプレポリマーに、ヒドロキシル（メタ）アクリレート（ａ３）を反応させるプレポリマー法に加え、（ａ１）（ａ２）（ａ３）を同時に添加して反応させるワンショット方法などがある。ワンショット法と比較してプレポリマー法は、反応がコントロールしやすく副生成物も少ないため好ましい。 As a method for producing the bifunctional urethane (meth) acrylate-based oligomer (A), (poly) alkylene glycol (a1) is reacted with an aliphatic cyclic diisocyanate (a2) under excessive conditions, and the terminal is an isocyanate urethane. In addition to the prepolymer method in which hydroxyl (meth) acrylate (a3) is reacted with the prepolymer, there is a one-shot method in which (a1), (a2) and (a3) are simultaneously added and reacted. Compared with the one-shot method, the prepolymer method is preferable because the reaction is easy to control and there are few by-products.
　２官能ウレタン（メタ）アクリレート系オリゴマー（Ａ）と反応性希釈モノマー（Ｂ）との全固形分に対する２官能ウレタン（メタ）アクリレート系オリゴマー（Ａ）の配合量は３５～７５重量％が好ましく、４０～７０重量％が更に好ましい。３５重量％以上とする事で充分な凝集力と皮膜強度を確保でき、また７５重量％以下とする事で組成物の粘度を適度にコントロールでき良好な作業性を確保できる。 The blending amount of the bifunctional urethane (meth) acrylate-based oligomer (A) with respect to the total solid content of the bifunctional urethane (meth) acrylate-based oligomer (A) and the reactive diluted monomer (B) is preferably 35 to 75% by weight. It is more preferably 40 to 70% by weight. When it is 35% by weight or more, sufficient cohesive force and film strength can be secured, and when it is 75% by weight or less, the viscosity of the composition can be appropriately controlled and good workability can be ensured.
　本発明において用いられる反応性希釈モノマー（Ｂ）は、２官能ウレタン（メタ）アクリレート系オリゴマー（Ａ）を希釈すると共に硬化反応性を向上させ樹脂皮膜を構成する主要材料である。反応性希釈モノマー（Ｂ）としては、例えば、アルキル系（メタ）アクリレート、芳香族系（メタ）アクリレート、これらの（メタ）アクリレートに水酸基やアミノ基等の極性基を含有した（メタ）アクリレートが挙げられる。アルキル系（メタ）アクリレートとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、エチルへキシル（メタ）アクリレート、イソノニル（メタ）アクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、イソボルニルアクリレート等が挙げられる。 The reactive diluting monomer (B) used in the present invention is a main material that dilutes the bifunctional urethane (meth) acrylate-based oligomer (A) and improves the curing reactivity to form a resin film. Examples of the reactive diluting monomer (B) include alkyl-based (meth) acrylates, aromatic (meth) acrylates, and (meth) acrylates containing polar groups such as hydroxyl groups and amino groups in these (meth) acrylates. Can be mentioned. Alkyl-based (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, and octyl (meth) acrylate. , Ethylhexyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, isobornyl acrylate and the like.
　芳香族系（メタ）アクリレートとしては、フェノキシエチルアクリレート、２-ヒドロキシ－３－フェノキシプロピルアクリレート、メチルフェノキシエチルアクリレート、フェノキシジエチレングリコールアクリレート、フェノキシポリエチレングリコールアクリレート等がある。水酸基を含有した（メタ）アクリレートとしては、２－ヒドロキシエチル（メタ）アクリレート、２‐ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート等が挙げられる。アミノ基を含有した（メタ）アクリレートとしては、アクリルアミド、Ｎ，Ｎ‐ジメチルアクリルアミド、Ｎ，Ｎ‐ジエチルアクリルアミド、Ｎ－イソプロピルアクリルアミド、アクリロイルモルホリン等が挙げられる。これらのモノマーは単独で用いてもよいし２種以上を併用してもよい。 Examples of aromatic (meth) acrylates include phenoxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, methylphenoxyethyl acrylate, phenoxydiethylene glycol acrylate, and phenoxypolyethylene glycol acrylate. Examples of the (meth) acrylate containing a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like. .. Examples of the (meth) acrylate containing an amino group include acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, acryloyl morpholine and the like. These monomers may be used alone or in combination of two or more.
　本発明に用いられる反応性希釈モノマー（Ｂ）の粘度は、配合物の粘度を調整しやすくするため１０，０００ｍＰａ・ｓ以下である事が望ましい。また、反応性希釈モノマー（Ｂ）は、硬化収縮を抑え伸び率を高くするため単官能であることが好ましい。 The viscosity of the reactive diluent monomer (B) used in the present invention is preferably 10,000 mPa · s or less so that the viscosity of the formulation can be easily adjusted. Further, the reactive diluting monomer (B) is preferably monofunctional in order to suppress curing shrinkage and increase the elongation rate.
　本発明に用いられる反応性希釈モノマー（Ｂ）は、２官能ウレタン（メタ）アクリレート系オリゴマー（Ａ）との相溶性から極性の高い（メタ）アクリレート（１）が好ましく、Ｃ数の少ない（メタ）アクリレート（１－１）や極性基を有する（メタ）アクリレート（１－２）が挙げられる。極性の高い（メタ）アクリレートは、ＳＰ値（溶解度パラメーター）が９～１２であり、例えば、Ｃ数が少ないアクリレート（１－１）としてメチルメタクリレートが好ましく、極性基であるアミノ基を有する（メタ）アクリレート（１－２）としてＮ，Ｎ‐ジエチルアクリルアミド、アクリロイルモルホリンなどが好ましい。反応性希釈モノマー（Ｂ）としてＳＰ値が９～１２の極性の高い（メタ）アクリレート（１）を含む場合、反応性希釈モノマー（Ｂ）の主成分であることが好ましい。 The reactive diluting monomer (B) used in the present invention is preferably a highly polar (meth) acrylate (1) because of its compatibility with the bifunctional urethane (meth) acrylate-based oligomer (A), and has a small C number (meth). ) Acrylate (1-1) and (meth) acrylate having a polar group (1-2) can be mentioned. The highly polar (meth) acrylate has an SP value (solubility parameter) of 9 to 12, and for example, methyl methacrylate is preferable as the acrylate (1-1) having a small C number, and it has an amino group as a polar group (meth). ) As the acrylate (1-2), N, N-diethylacrylamide, acryloylmorpholin and the like are preferable. When the reactive diluent monomer (B) contains a highly polar (meth) acrylate (1) having an SP value of 9 to 12, it is preferably the main component of the reactive diluent monomer (B).
　なお、ここで加飾フィルムの指紋視認性について説明する。加飾フィルムを電子機器や自動車等の車両内装材の加飾用途として使用する場合、加飾フィルムの表面に人が触れることが通常であり、加飾フィルムの表面に指の腹等が接触すると加飾フィルムの表面に指紋が付き、その指紋の付着跡がくっきり残ってしまう。特に、近年の車両の内装材等においては、落ち着いた雰囲気が好まれるため、車両内を黒やグレー等のモノトーンの色調が多く使用される。モノトーンで加飾された内装材の表面に指紋の付着跡がくっきり残っていると、清潔感が損なわれることから、指紋の付着跡が見えにくい（目立ちにくい）ということは、内装材の美観を維持するうえで非常に重要である。そして、本発明においては、硬化樹脂組成物層を形成する反応性希釈モノマー（Ｂ）として、ＳＰ値が９～１２の極性の高い（メタ）アクリレートを配合することにより、指紋の付着跡が見えにくくなるという効果を奏する。 The fingerprint visibility of the decorative film will be described here. When a decorative film is used for decorating vehicle interior materials such as electronic devices and automobiles, it is normal for a person to touch the surface of the decorative film, and when the surface of the decorative film is touched by a finger pad or the like. Fingerprints are attached to the surface of the decorative film, and the traces of the fingerprints are clearly left. In particular, in recent vehicle interior materials and the like, a calm atmosphere is preferred, so monotone color tones such as black and gray are often used inside the vehicle. If fingerprints are clearly left on the surface of the interior material decorated in monotone, the cleanliness will be impaired. Therefore, it is difficult to see the fingerprints (not noticeable), which makes the interior material aesthetically pleasing. Very important to maintain. Then, in the present invention, by blending a highly polar (meth) acrylate having an SP value of 9 to 12 as the reactive diluting monomer (B) forming the cured resin composition layer, fingerprint adhesion marks can be seen. It has the effect of making it difficult.
　２官能ウレタン（メタ）アクリレート系オリゴマー（Ａ）と反応性希釈モノマー（Ｂ）との全固形分に対する反応性希釈モノマー（Ｂ）の配合量は２５～６５重量％が好ましく、３０～６０重量％が更に好ましい。２５重量％以上とすることで速硬化性を得られ、６５重量％以下とすることで硬化収縮率を小さくコントロールする事ができる。 The blending amount of the reactive diluted monomer (B) with respect to the total solid content of the bifunctional urethane (meth) acrylate-based oligomer (A) and the reactive diluted monomer (B) is preferably 25 to 65% by weight, preferably 30 to 60% by weight. Is more preferable. When it is 25% by weight or more, quick curing property can be obtained, and when it is 65% by weight or less, the curing shrinkage rate can be controlled to be small.
　本発明の加飾フィルムの硬化樹脂組成物層は、本発明の効果が得られる範囲において、本発明の２官能ウレタン（メタ）アクリレート系オリゴマー（Ａ）及び反応性希釈モノマー（Ｂ）以外の他の成分をさらに含有していてもよい。このような他の成分としては、例えば、活性エネルギー線硬化性オリゴマー、重合開始剤、添加剤、及び溶剤が挙げられる。 The cured resin composition layer of the decorative film of the present invention is other than the bifunctional urethane (meth) acrylate-based oligomer (A) and the reactive diluent monomer (B) of the present invention as long as the effects of the present invention can be obtained. It may further contain the component of. Examples of such other components include active energy ray-curable oligomers, polymerization initiators, additives, and solvents.
　重合開始剤は、主に、紫外線、電子線等の活性エネルギー線照射で進行する重合反応の開始効率を向上させる等の目的で用いられる。重合開始剤としては、光によりラジカルを発生する性質を有する化合物である光ラジカル重合開始剤が一般的であり、本発明の効果が得られる範囲で公知の光ラジカル重合開始剤を使用可能である。重合開始剤は、１種を単独で用いてもよく、２種以上を混合して用いてもよい。 The polymerization initiator is mainly used for the purpose of improving the initiation efficiency of the polymerization reaction that proceeds by irradiation with active energy rays such as ultraviolet rays and electron beams. As the polymerization initiator, a photoradical polymerization initiator which is a compound having a property of generating radicals by light is generally used, and a known photoradical polymerization initiator can be used as long as the effect of the present invention can be obtained. .. As the polymerization initiator, one type may be used alone, or two or more types may be mixed and used.
　光ラジカル重合開始剤としては、例えば、ベンゾフェノン、２，４，６－トリメチルベンゾフェノン、４，４－ビス（ジエチルアミノ）ベンゾフェノン、４－フェニルベンゾフェノン、メチルオルトベンゾイルベンゾエート、チオキサントン、ジエチルチオキサントン、イソプロピルチオキサントン、クロロチオキサントン、２－エチルアントラキノン、ｔ－ブチルアントラキノン、ジエトキシアセトフェノン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、ベンジルジメチルケタール、１－ヒドロキシシクロヘキシルフェニルケトン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、メチルベンゾイルホルメート、２－メチル－１－〔４－（メチルチオ）フェニル〕－２－モルホリノプロパン－１－オン、２，６－ジメチルベンゾイルジフェニルホスフィンオキシド、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキシド、ビス（２，６－ジメトキシベンゾイル）－２，４，４－トリメチルペンチルホスフィンオキシド、ビス（２，４，６－トリメチルベンゾイル）フェニルホスフィンオキシド、及び２－ヒドロキシ－１－〔４－［４－（２－ヒドロキシ－２－メチル－プロピオニル）－ベンジル］－フェニル〕－２－メチル－プロパン－１－オン等が挙げられる。 Examples of the photoradical polymerization initiator include benzophenone, 2,4,6-trimethylbenzophenone, 4,4-bis (diethylamino) benzophenone, 4-phenylbenzophenone, methyl orthobenzoylbenzoate, thioxanthone, diethylthioxanthone, isopropylthioxanthone, and chloro. Thioxanthone, 2-ethylanthraquinone, t-butyl anthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, benzoin methyl ether, benzoin ethyl Ether, benzoin isopropyl ether, benzoin isobutyl ether, methylbenzoylformate, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2 , 4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and 2- Examples thereof include hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl] -2-methyl-propane-1-one.
　本発明の加飾フィルムの硬化樹脂組成物層におけるこれらの重合開始剤の含有量は、２官能ウレタン（メタ）アクリレート系オリゴマー（Ａ）及び反応性希釈モノマー（Ｂ）の合計１００重量部に対して、１０重量部以下であることが好ましく、５重量部以下であることがより好ましい。重合開始剤の含有量が１０重量部以下であると、開始剤分解物による機械的強度の低下が起こり難いため好ましい。 The content of these polymerization initiators in the cured resin composition layer of the decorative film of the present invention is 100 parts by weight in total of the bifunctional urethane (meth) acrylate-based oligomer (A) and the reactive diluted monomer (B). It is preferably 10 parts by weight or less, and more preferably 5 parts by weight or less. When the content of the polymerization initiator is 10 parts by weight or less, the mechanical strength is unlikely to be lowered by the decomposition product of the initiator, which is preferable.
　本発明の加飾フィルムの硬化樹脂組成物層には、本発明の効果が得られる範囲において、光ラジカル重合開始剤に加えて光増感剤を配合しても良い。光増感剤は、重合開始剤と同じ目的で用いることができる。光増感剤は、１種を単独で用いてもよく、２種以上を混合して用いてもよい。光増感剤としては、本発明の効果が得られる範囲で公知の光増感剤を使用することができる。光増感剤としては、例えば、エタノールアミン、ジエタノールアミン、トリエタノールアミン、Ｎ－メチルジエタノールアミン、４－ジメチルアミノ安息香酸メチル、４－ジメチルアミノ安息香酸エチル、４－ジメチルアミノ安息香酸アミル、及び４－ジメチルアミノアセトフェノン等が挙げられる。 A photosensitizer may be added to the cured resin composition layer of the decorative film of the present invention in addition to the photoradical polymerization initiator as long as the effects of the present invention can be obtained. The photosensitizer can be used for the same purpose as the polymerization initiator. One type of photosensitizer may be used alone, or two or more types may be mixed and used. As the photosensitizer, known photosensitizers can be used as long as the effects of the present invention can be obtained. Examples of the photosensitizer include ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, and 4-. Examples thereof include dimethylaminoacetophenone.
　本発明の加飾フィルムの硬化樹脂組成物層における光増感剤の含有量は、２官能ウレタン（メタ）アクリレート系オリゴマー（Ａ）及び反応性希釈モノマー（Ｂ）の合計１００重量部に対して、１０重量部以下であることが好ましく、５重量部以下であることがより好ましい。光増感剤の含有量が１０重量部以下であると、架橋密度低下による機械的強度の低下が起こり難いため好ましい。 The content of the photosensitizer in the cured resin composition layer of the decorative film of the present invention is 100 parts by weight in total of the bifunctional urethane (meth) acrylate-based oligomer (A) and the reactive diluted monomer (B). It is preferably 10 parts by weight or less, and more preferably 5 parts by weight or less. When the content of the photosensitizer is 10 parts by weight or less, the mechanical strength is unlikely to decrease due to the decrease in the crosslink density, which is preferable.
　本発明の加飾フィルムの硬化樹脂組成物層に配合する添加剤としては、酸化防止剤、紫外線吸収剤、（近）赤外吸収剤、蛍光増白剤、難燃剤、充填剤、有機微粒子、無機微粒子、分散剤、シランカップリング剤、レベリング剤、消泡剤、界面活性剤、防指紋剤、帯電防止剤、抗菌剤、抗ウイルス剤、重合禁止剤、顔料や染料や色素などの着色剤、可塑剤などが挙げられる。 Additives to be blended in the cured resin composition layer of the decorative film of the present invention include antioxidants, ultraviolet absorbers, (near) infrared absorbers, fluorescent whitening agents, flame retardants, fillers, organic fine particles, and the like. Inorganic fine particles, dispersants, silane coupling agents, leveling agents, defoaming agents, surfactants, anti-fingerprint agents, antistatic agents, antibacterial agents, anti-virus agents, polymerization inhibitors, pigments, dyes, pigments and other colorants , Plasticizers and the like.
　本発明の加飾フィルムは、本発明の効果を損しない範囲で、硬化樹脂組成物層及びポリカーボネート系樹脂層以外の層が設けられてもよい。また、加飾フィルムの表面には、図柄や文字などの印刷層、粘着層、または接着層などを必要に応じて設けることができる。一般的には、印刷層、粘着層、または接着層は、ポリカーボネート系樹脂層の成型体と貼り合わされる側の表面に設けられる。 The decorative film of the present invention may be provided with a layer other than the cured resin composition layer and the polycarbonate-based resin layer as long as the effects of the present invention are not impaired. Further, on the surface of the decorative film, a printing layer such as a pattern or characters, an adhesive layer, an adhesive layer, or the like can be provided as needed. Generally, the printing layer, the adhesive layer, or the adhesive layer is provided on the surface of the polycarbonate resin layer on the side to be bonded to the molded body.
　本発明の加飾フィルムの厚さは、成型品の用途、インサート成型への適性、シートの取り扱い性等に応じて決定され、例えば、１００μｍ～８００μｍが好ましく、１５０μｍ～６００μｍがより好ましい。また、硬化樹脂組成物層とポリカーボネート樹脂層の厚さ比は、１：１０～１０：１が好ましい。 The thickness of the decorative film of the present invention is determined according to the use of the molded product, suitability for insert molding, handleability of the sheet, etc. For example, 100 μm to 800 μm is preferable, and 150 μm to 600 μm is more preferable. The thickness ratio of the cured resin composition layer to the polycarbonate resin layer is preferably 1:10 to 10: 1.
　本発明の加飾フィルムにおける硬化樹脂組成物層の厚さは、耐擦傷性及び成型性の観点から、２０μｍ以上８０μｍ以下であることが好ましく、２５μｍ以上５０μｍ以下であることがより好ましく、２５μｍ以上４０μｍ以下であることがさらに好ましい。 The thickness of the cured resin composition layer in the decorative film of the present invention is preferably 20 μm or more and 80 μm or less, more preferably 25 μm or more and 50 μm or less, and 25 μm or more, from the viewpoint of scratch resistance and moldability. It is more preferably 40 μm or less.
　なお、ここで加飾フィルムの耐クラック性について説明する。加飾フィルムを自動車等の車両内装材の加飾用途として使用する際、様々な性能が高い水準で求められる。夏場は車内が高温高湿環境（例えば温度８５℃、湿度８５％RH）となることがあるが、高温高湿環境に長時間曝された加飾フィルムは、塗膜が割れやすくなることがある。そして、本発明においては、硬化樹脂組成物層の厚さが２５μｍ以上５０μｍ以下であれば、高温高湿環境下（８５℃、８５％ＲＨ）における湿熱試験後の硬化樹脂組成物層の割れを抑制することができる。 The crack resistance of the decorative film will be described here. When a decorative film is used for decorating vehicle interior materials such as automobiles, various performances are required at a high level. In the summer, the inside of the car may be in a high temperature and high humidity environment (for example, temperature 85 ° C, humidity 85% RH), but a decorative film exposed to a high temperature and high humidity environment for a long time may easily crack the coating film. .. In the present invention, if the thickness of the cured resin composition layer is 25 μm or more and 50 μm or less, the cured resin composition layer is cracked after the wet heat test in a high temperature and high humidity environment (85 ° C., 85% RH). It can be suppressed.
　本発明の加飾フィルムの硬化樹脂組成物層における鉛筆硬度は、Ｈ以上であることが好ましい。鉛筆硬度がＨ以上であれば加飾用途として十分な耐擦傷性を確保できる。 The pencil hardness of the decorative film of the present invention in the cured resin composition layer is preferably H or higher. If the pencil hardness is H or more, sufficient scratch resistance can be ensured for decorative purposes.
　本発明の加飾フィルムは、雰囲気温度１６０℃における加熱伸びが１５０％以上であることが好ましい。加熱伸びが１５０％以上であれば車両内装材等における深絞り形状に追従することができ、加飾用途として十分な成型性を確保できる。 The decorative film of the present invention preferably has a heating elongation of 150% or more at an atmospheric temperature of 160 ° C. If the heating elongation is 150% or more, it is possible to follow the deep drawing shape of the vehicle interior material or the like, and it is possible to secure sufficient moldability for decorative use.
　本発明の加飾フィルムを製造する方法は公知の方法を採用することができる。図１に本発明の加飾フィルムを製造する方法の一例を示した。ダイコーター１２により、硬化樹脂組成物層を形成するための２官能ウレタン（メタ）アクリレート系オリゴマー（Ａ）と反応性希釈モノマー（Ｂ）と光ラジカル重合開始剤とを含む液状の光硬化性樹脂組成物が、公知の方法により予め製膜されたポリカーボネート系樹脂フィルム１１上に一定量ずつ供給される。ポリカーボネート系樹脂フィルム１１は、ロール状に巻き取られたものから、光硬化性樹脂組成物の供給量に合わせた一定速度で連続的に引き出される。その後、ポリカーボネート系樹脂フィルム１１上に所定の厚さで流延された液状の光硬化性樹脂組成物の上に、カバーフィルム１３を積層して積層体とした後、積層体のカバーフィルム１３側に紫外線光源１４から紫外線を照射することで光硬化性樹脂組成物を硬化させる。得られた加飾フィルム１６はカバーフィルム１３を連続的に剥離除去しながら巻き取られる。紫外線の照射箇所には、冷却装置１５を有していることが好ましい。冷却装置１５により積層体を冷却し、紫外線照射によって光硬化性樹脂組成物を硬化させる温度を制御することにより、ポリカーボネート系樹脂フィルム１１及び加飾フィルム１６の熱変形を抑制することができる。冷却方式としては、空冷方式、水冷方式等の公知の方法がある。ポリカーボネート系樹脂フィルム１１は、硬化性樹脂組成物層及び必要に応じて設けられる印刷層、粘着剤層、または接着剤層との接着性を上げるために表面をコロナ放電処理等の手法により表面処理を施すことができる。 A known method can be adopted as the method for producing the decorative film of the present invention. FIG. 1 shows an example of a method for producing the decorative film of the present invention. A liquid photocurable resin containing a bifunctional urethane (meth) acrylate-based oligomer (A), a reactive diluting monomer (B), and a photoradical polymerization initiator for forming a cured resin composition layer by the die coater 12. The composition is supplied in a fixed amount onto the polycarbonate-based resin film 11 which has been preliminarily formed by a known method. The polycarbonate-based resin film 11 is continuously drawn out from the roll-shaped one at a constant speed according to the supply amount of the photocurable resin composition. Then, the cover film 13 is laminated on the liquid photocurable resin composition cast on the polycarbonate-based resin film 11 to a predetermined thickness to form a laminate, and then the cover film 13 side of the laminate. The photocurable resin composition is cured by irradiating the ultraviolet light from the ultraviolet light source 14. The obtained decorative film 16 is wound while continuously peeling and removing the cover film 13. It is preferable to have a cooling device 15 at the ultraviolet irradiation site. By cooling the laminate with the cooling device 15 and controlling the temperature at which the photocurable resin composition is cured by ultraviolet irradiation, thermal deformation of the polycarbonate resin film 11 and the decorative film 16 can be suppressed. As the cooling method, there are known methods such as an air cooling method and a water cooling method. The surface of the polycarbonate-based resin film 11 is surface-treated by a method such as corona discharge treatment in order to improve the adhesiveness between the curable resin composition layer and the printing layer, the pressure-sensitive adhesive layer, or the adhesive layer provided as needed. Can be applied.
　液状の光硬化性樹脂組成物を塗布する方法はバーコーター法、アプリケーター法、カーテンコーター法、ロールコーター法、グラビアコーター法、リバースコーター法、コンマコーター法、リップコーター法、ダイコーター法など、公知の方法が適用できる。　 Known methods for applying the liquid photocurable resin composition include a bar coater method, an applicator method, a curtain coater method, a roll coater method, a gravure coater method, a reverse coater method, a comma coater method, a lip coater method, and a die coater method. Method can be applied.
　液状の光硬化性樹脂組成物を塗布する際には、粘度を調製することを目的として、必要に応じて溶剤を配合しても良い。溶剤は、１種を単独で用いてもよく、２種以上を混合して用いてもよい。溶剤としては、本発明の効果が得られる範囲において公知の溶剤を使用することができる。溶剤としては、トルエン、キシレン、酢酸エチル、酢酸ブチル、イソプロパノール、イソブタノール、シクロヘキサノン、メチルエチルケトン、及びメチルイソブチルケトン等が挙げられる。 When applying the liquid photocurable resin composition, a solvent may be added if necessary for the purpose of adjusting the viscosity. As the solvent, one type may be used alone, or two or more types may be mixed and used. As the solvent, a known solvent can be used as long as the effect of the present invention can be obtained. Examples of the solvent include toluene, xylene, ethyl acetate, butyl acetate, isopropanol, isobutanol, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone and the like.
　紫外線の照射条件としては、例えば、硬化樹脂組成物層の厚さが７５μｍ程度であれば、５００ｍＷ／ｃｍ２～３，０００ｍＷ／ｃｍ２の照射強度で、積算光量としては１００ｍＪ／ｃｍ２～２，０００ｍＪ／ｃｍ２が例示できる。光源としては高圧水銀ランプ、中圧水銀ランプ、低圧水銀ランプ、メタルハライドランプ、キセノンランプ、ＬＥＤランプ等の公知の光源が適用可能である。 The irradiation condition of ultraviolet rays, for example, if it is about 75μm thickness of the cured resin composition layer, 500mW / cm 2 ~ 3,000mW / irradiation intensity of cm 2, as the accumulated light quantity is 100mJ / cm 2 ~ 2 An example is 000 mJ / cm 2. As the light source, known light sources such as a high-pressure mercury lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a xenon lamp, and an LED lamp can be applied.
　本発明の加飾フィルムを用いて成型品を加飾する方法としては、予め成型された成型品の表面に加飾フィルムを積層する方法や、金型内にセットした加飾フィルムに加飾対象の射出成型用樹脂を射出し、成型品と加飾フィルムとを一体化する方法等が挙げられる。本発明の加飾フィルムを用いて成型品を加飾する場合、本発明の加飾フィルムのポリカーボネート樹脂層側が成型品表面に配される。 As a method of decorating a molded product using the decorative film of the present invention, a method of laminating a decorative film on the surface of a pre-molded molded product, or a method of decorating a decorative film set in a mold is targeted. A method of injecting a resin for injection molding and integrating the molded product and the decorative film can be mentioned. When a molded product is decorated with the decorative film of the present invention, the polycarbonate resin layer side of the decorative film of the present invention is arranged on the surface of the molded product.
　以下、実施例により本発明を具体的に説明するが、本発明はこれによって限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.
（実施例１）
　以下のA乃至C成分の混合物を均一に溶解するまで撹拌したものを、硬化樹脂組成物層を形成するための光硬化性樹脂組成物とした。
　Ａ成分：２官能ウレタンアクリレートオリゴマー ：１００重量部
ポリエチレングリコール２００（東邦化学工業株式会社製、商品名ＰＥＧ２００、固形分１００％）とイソホロンジイソシアネート（住化バイエルウレタン株式会社製、商品名デスモジュールI、ＮＣＯ基３７．５％）とをメチルメタクリレートモノマーに加え、３０℃で３０分攪拌・反応させ、赤外吸収分析でイソシアネート基のピークが２分の１になった時点で反応を終了させた。次に、２ヒドロキシプロピルアクリレート（共栄社化学株式会社製、商品名ライトエステルＨＯＰ－Ａ、固形分１００％）を添加し、１０℃で３０分攪拌・反応させた後、６０℃で３０分攪拌・反応させ、赤外吸収分析でイソシアネート基の消滅したことを確認し、メチルメタクリレートの比率が４０％になるように調整して、Ｍｗ．６４００の２官能ウレタンアクリレートオリゴマーを得た。
　Ｂ成分：アクリロイルモルホリン（ＫＪケミカルズ株式会社製、商品名ＡＣＭＯ）：４０重量部
　Ｃ成分：重合開始剤２－ヒドロキシ－２－メチル－１－フェニルプロパン（ＢＡＳＦジャパン社製、商品名Ｏｍｎｉｒａｄ１１７３）：５重量部 (Example 1)
The following mixture of components A to C was stirred until it was uniformly dissolved to prepare a photocurable resin composition for forming a cured resin composition layer.
Component A: Bifunctional urethane acrylate oligomer: 100 parts by weight polyethylene glycol 200 (manufactured by Toho Chemical Industry Co., Ltd., trade name PEG200, solid content 100%) and isophorone diisocyanate (manufactured by Sumika Bayer Urethane Co., Ltd., trade name Death Module I, NCO group 37.5%) was added to the methyl methacrylate monomer, and the mixture was stirred and reacted at 30 ° C. for 30 minutes, and the reaction was terminated when the peak of the isocyanate group was halved by infrared absorption analysis. Next, 2 hydroxypropyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: light ester HOP-A, solid content 100%) was added, stirred and reacted at 10 ° C. for 30 minutes, and then stirred at 60 ° C. for 30 minutes. After reacting, it was confirmed by infrared absorption analysis that the isocyanate group had disappeared, and the ratio of methyl methacrylate was adjusted to 40%. 6400 bifunctional urethane acrylate oligomers were obtained.
Component B: Acryloyl morpholine (manufactured by KJ Chemicals Co., Ltd., trade name ACMO): 40 parts by weight C component: Polymerization initiator 2-hydroxy-2-methyl-1-phenylpropane (manufactured by BASF Japan, trade name Omnirad 1173): 5 Weight part
　厚さ１８０μｍのポリカーボネート樹脂フィルム（帝人（株）製、パンライト（登録商標）ＰＣ－２１５１）に、光硬化性樹脂組成物を塗布し、光硬化性樹脂組成物表面に、コロナ処理や易接着処理等の表面処理がされていない厚さ５０μｍのＰＥＴフィルムをカバーフィルムとして積層し積層体とした。次いで、カバーフィルムの上から、フィルムアプリケーターにより、硬化後の厚さが７５μｍになるように光硬化性樹脂組成物の層の厚さを調整した。更に、無電極紫外線ランプを用いて、カバーフィルム側から、紫外線を積算光量１０００ｍJ／ｃｍ２照射し、光硬化性樹脂組成物を硬化させたのち、カバーフィルムを剥離させ、厚さ２５５μｍの加飾フィルム（硬化樹脂組成物層７５μｍ／ポリカーボネート樹脂層１８０μｍ）を得た。なお、積算光量は、へレウス株式会社製マイクロキュアＭＣ－１０Ａにより測定した。 A photocurable resin composition is applied to a 180 μm-thick polycarbonate resin film (Panlite (registered trademark) PC-2151 manufactured by Teijin Limited), and the surface of the photocurable resin composition is corona-treated or easily adhered. A PET film having a thickness of 50 μm, which had not been surface-treated such as treatment, was laminated as a cover film to form a laminated body. Next, the thickness of the layer of the photocurable resin composition was adjusted from above the cover film by a film applicator so that the thickness after curing was 75 μm. Further, using an electrodeless ultraviolet lamp, ultraviolet rays are irradiated from the cover film side at an integrated light amount of 1000 mJ / cm 2 to cure the photocurable resin composition, and then the cover film is peeled off to decorate with a thickness of 255 μm. A film (cured resin composition layer 75 μm / polycarbonate resin layer 180 μm) was obtained. The integrated light intensity was measured by Microcure MC-10A manufactured by Heleus Co., Ltd.
（実施例２）
　光硬化性樹脂組成物からなる硬化樹脂組成物層の厚さを５０μｍとしたこと以外は実施例１と同様の条件で加飾フィルム（硬化樹脂組成物層５０μｍ／ポリカーボネート樹脂層１８０μｍ）を作製した。 (Example 2)
A decorative film (cured resin composition layer 50 μm / polycarbonate resin layer 180 μm) was prepared under the same conditions as in Example 1 except that the thickness of the cured resin composition layer composed of the photocurable resin composition was 50 μm. ..
（実施例３）
光硬化性樹脂組成物からなる硬化樹脂組成物層の厚さを４０μｍとしたこと以外は実施例１と同様の条件で加飾フィルム（硬化樹脂組成物層４０μｍ／ポリカーボネート樹脂層１８０μｍ）を作製した。 (Example 3)
A decorative film (cured resin composition layer 40 μm / polycarbonate resin layer 180 μm) was prepared under the same conditions as in Example 1 except that the thickness of the cured resin composition layer composed of the photocurable resin composition was 40 μm. ..
（実施例４）
光硬化性樹脂組成物からなる硬化樹脂組成物層の厚さを３０μｍとしたこと以外は実施例１と同様の条件で加飾フィルム（硬化樹脂組成物層３０μｍ／ポリカーボネート樹脂層１８０μｍ）を作製した。 (Example 4)
A decorative film (cured resin composition layer 30 μm / polycarbonate resin layer 180 μm) was prepared under the same conditions as in Example 1 except that the thickness of the cured resin composition layer composed of the photocurable resin composition was 30 μm. ..
（実施例５）
光硬化性樹脂組成物からなる硬化樹脂組成物層の厚さを２５μｍとしたこと以外は実施例１と同様の条件で加飾フィルム（硬化樹脂組成物層２５μｍ／ポリカーボネート樹脂層１８０μｍ）を作製した。 (Example 5)
A decorative film (cured resin composition layer 25 μm / polycarbonate resin layer 180 μm) was prepared under the same conditions as in Example 1 except that the thickness of the cured resin composition layer composed of the photocurable resin composition was 25 μm. ..
（比較例１）
　厚さ３００μｍのポリカーボネート樹脂フィルム（帝人（株）製、パンライト（登録商標）ＰＣ－２１５１）に、紫外線硬化型ハードコート剤を、硬化後の厚さが５μｍになるように、バーコーターを使用して流延し、溶剤を揮散させたのち、無電極紫外線ランプにより紫外線を積算光量４００ｍJ／ｃｍ２照射し硬化させ、厚さ３０５μｍの加飾フィルム（ハードコート層５μｍ／ポリカーボネート樹脂層３００μｍ）を作製した。 (Comparative Example 1)
An ultraviolet curable hard coat agent is applied to a 300 μm-thick polycarbonate resin film (Panlite (registered trademark) PC-2151 manufactured by Teijin Co., Ltd.), and a bar coater is used so that the cured thickness is 5 μm. After casting and volatilizing the solvent, ultraviolet rays were irradiated with an integrated light amount of 400 mJ / cm 2 by an electrodeless ultraviolet lamp to cure the film, and a decorative film (hard coat layer 5 μm / polycarbonate resin layer 300 μm) having a thickness of 305 μm was applied. Made.
（比較例２）
　厚さ３００μｍのポリカーボネート樹脂フィルム（帝人（株）製、パンライト（登録商標）ＰＣ－２１５１）を比較例２として実施例と同じ評価を実施した。 (Comparative Example 2)
The same evaluation as in Example was carried out using a polycarbonate resin film having a thickness of 300 μm (manufactured by Teijin Limited, Panlite (registered trademark) PC-2151) as Comparative Example 2.
（比較例３）
　厚さ１８０μｍのポリカーボネート樹脂フィルム（帝人（株）製、パンライト（登録商標）ＰＣ－２１５１）を比較例３として実施例と同じ評価を実施した。 (Comparative Example 3)
The same evaluation as in Example was carried out using a polycarbonate resin film having a thickness of 180 μm (manufactured by Teijin Limited, Panlite (registered trademark) PC-2151) as Comparative Example 3.
（比較例４）
　市販品のポリカーボネート系加飾フィルムＡ（三菱ガス化学（株）製、ユーピロン（登録商標）MRF08U、ハードコート層３μｍ／ポリメチルメタクリレート樹脂層５０μｍ／ポリカーボネート樹脂層２６０μｍ）を比較例４として実施例と同じ評価を実施した。 (Comparative Example 4)
A commercially available polycarbonate-based decorative film A (manufactured by Mitsubishi Gas Chemical Company, Inc., Iupiron (registered trademark) MRF08U, hard coat layer 3 μm / polymethylmethacrylate resin layer 50 μm / polycarbonate resin layer 260 μm) was used as Comparative Example 4 with Examples. The same evaluation was performed.
（比較例５）
　市販品のポリカーボネート系加飾フィルムＢ（マクダーミッド・パフォーマンス・ソリューションズ・ジャパン（株）製、XtraForm（登録商標）G250M、ハードコート層８μｍ／ポリカーボネート樹脂層２６０μｍ、ハードコート層はアフターキュアタイプ）を比較例５として実施例と同じ評価を実施した。 (Comparative Example 5)
Comparative example of a commercially available polycarbonate-based decorative film B (manufactured by MacDermid Performance Solutions Japan Co., Ltd., XtraForm (registered trademark) G250M, hard coat layer 8 μm / polycarbonate resin layer 260 μm, hard coat layer aftercure type) The same evaluation as in Example was carried out as 5.
　実施例１乃至５、比較例１乃至５のフィルムについて、後述する方法に従い、耐擦傷性（鉛筆硬度）、耐薬品性、成型性（加熱伸び）、耐クラック性及び指紋視認性を評価した。結果を表１に示す。 The films of Examples 1 to 5 and Comparative Examples 1 to 5 were evaluated for scratch resistance (pencil hardness), chemical resistance, moldability (heat elongation), crack resistance, and fingerprint visibility according to the method described later. The results are shown in Table 1.
（耐擦傷性（鉛筆硬度））
　耐擦傷性の評価として、ＪＩＳ―Ｋ５６００－５－４を参考に、荷重は５００ｇとし、鉛筆硬度を測定した。 (Scratch resistance (pencil hardness))
As an evaluation of scratch resistance, the pencil hardness was measured with a load of 500 g with reference to JIS-K5600-5-4.
（耐薬品性）
　フィルムの表面に、ハンドクリーム（ニュートロジーナ社製ＳＰＦ４５）を、厚塗り（２mm厚さ）と薄塗り（厚塗りされた状態から平筆を用いて一回掃き取った状態）の２パターンで塗布し、８０℃雰囲気下で４時間放置後に、ハンドクリームを拭き取ったあとの表面状態を観察した。判定は以下の基準に従って行った。
・拭取
○：すべて拭き取れるもの
△：一部拭き取れるもの
×：全く拭き取れないもの
・痕跡
○：跡がないもの
△：跡が微小なもの
×：明確な跡があるもの (chemical resistance)
Hand cream (SPF45 manufactured by Neutrogena) is applied to the surface of the film in two patterns: thick coating (2mm thickness) and thin coating (a state in which the thick coating is swept once with a flat brush). After leaving the film in an atmosphere of 80 ° C. for 4 hours, the surface condition after wiping off the hand cream was observed. The judgment was made according to the following criteria.
・ Wiping ○: All can be wiped off △: Partially wiped off ×: Can not be wiped off at all ・ Trace ○: No trace △: Small trace ×: Clear trace
（成型性（加熱伸び））
　フィルムを幅１０ｍｍ×長さ１２０ｍｍの寸法にカットしたものを測定試料とした。（株）島津製作所製の引張試験機ＡＧＳ－Ｘ を用い、雰囲気温度１６０℃、チャック間距離５０ｍｍで、前記測定試料を速度５００ｍｍ／ｍｉｎで引っ張った。以下の式で表される加熱伸びが１５０％以上を○、それ未満を×とした。
加熱伸び（％）＝　外観異常発生時のチャック間距離（ｍｍ）／５０ｍｍ×１００
※外観異常：硬化樹脂組成物層或いはハードコート層のクラックや割れ、フィルムの白化や破断等 (Moldability (heat elongation))
A film cut to a size of 10 mm in width × 120 mm in length was used as a measurement sample. Using a tensile tester AGS-X manufactured by Shimadzu Corporation, the measurement sample was pulled at a speed of 500 mm / min at an ambient temperature of 160 ° C. and a distance between chucks of 50 mm. A heating elongation of 150% or more represented by the following formula was evaluated as ◯, and a heating elongation of less than 150% was evaluated as x.
Heating elongation (%) = Distance between chucks when an appearance abnormality occurs (mm) / 50 mm x 100
* Appearance abnormality: cracks or cracks in the cured resin composition layer or hard coat layer, whitening or breakage of the film, etc.
（耐クラック性）
　フィルムを幅５０ｍｍ×長さ５０ｍｍの寸法にカットしたサンプル片を切り出し、該サンプルを温度８５℃、湿度８５％ＲＨの恒温恒湿機に入れ５００時間静置した後、サンプル片を取り出し、室温で２４時間養生した。次いで、ＪＩＳ Ｋ５６００－５－６を参考にクロスカット法にて直角の格子パターン（２５マス）をサンプル片の硬化樹脂組成物層或いはハードコート層に形成した。そして、サンプル片の硬化樹脂組成物層或いはハードコート層に切り込まれた格子パターンを下記評価基準にて目視評価した。
　◎：カットの縁が完全になめらかで、どの格子にも割れがない
　〇：カットの交差点において塗膜の小さな割れがある（割れの箇所の面積５％以下）
　△：塗膜がカットの縁に沿って、及び／又は交差点において割れがある（割れの箇所の面積５％を超え１５％以下）
　×：塗膜がカットの縁に沿って、部分的又は全面的に大きな割れがある（割れの箇所の面積１５％を超える） (Crack resistance)
A sample piece obtained by cutting a film into a size of 50 mm in width and 50 mm in length is cut out, the sample is placed in a constant temperature and humidity chamber at a temperature of 85 ° C. and a humidity of 85% RH, allowed to stand for 500 hours, and then the sample piece is taken out and at room temperature. It was cured for 24 hours. Next, a right-angled lattice pattern (25 squares) was formed on the cured resin composition layer or the hard coat layer of the sample piece by a cross-cut method with reference to JIS K5600-5-6. Then, the lattice pattern cut into the cured resin composition layer or the hard coat layer of the sample piece was visually evaluated according to the following evaluation criteria.
◎: The edges of the cut are completely smooth and there are no cracks in any of the grids. 〇: There are small cracks in the coating film at the intersections of the cuts (the area of the cracks is 5% or less).
Δ: The coating film has cracks along the edge of the cut and / or at the intersection (the area of the cracked portion exceeds 5% and 15% or less).
X: The coating film has large cracks partially or entirely along the edge of the cut (the area of the cracked portion exceeds 15%).
（指紋視認性）
　フィルムを幅５０ｍｍ×長さ５０ｍｍの寸法にカットしたサンプル片を切り出し、ポリカーボネート樹脂層側が接着面となるよう粘着剤を介して該サンプル片を黒色のアクリル樹脂板（厚さ２ｍｍ）と積層した後、硬化樹脂組成物層或いはハードコート層の表面をエタノールで洗浄した。次いで、硬化樹脂組成物層或いはハードコート層の表面を指の腹で押さえて指紋を付着させ、指紋が付着した箇所の指紋の見えにくさ（目立ちにくさ）を下記評価基準にて目視評価した。
　〇：硬化樹脂組成物層或いはハードコート層側から指紋が付着した箇所をさまざまな角度から目視した際、いずれの角度においても指紋が見えにくい
　×：硬化樹脂組成物層或いはハードコート層側から指紋が付着した箇所をさまざまな角度から目視した際、いずれの角度においても指紋が見えやすい (Fingerprint visibility)
A sample piece obtained by cutting a film into a size of 50 mm in width and 50 mm in length is cut out, and the sample piece is laminated with a black acrylic resin plate (thickness 2 mm) via an adhesive so that the polycarbonate resin layer side becomes an adhesive surface. , The surface of the cured resin composition layer or the hard coat layer was washed with ethanol. Next, the surface of the cured resin composition layer or the hard coat layer was pressed with the pad of a finger to attach a fingerprint, and the invisibleness (inconspicuousness) of the fingerprint at the portion to which the fingerprint was attached was visually evaluated according to the following evaluation criteria. ..
〇: When the fingerprint is attached from the cured resin composition layer or the hard coat layer side from various angles, it is difficult to see the fingerprint at any angle. ×: Fingerprint from the cured resin composition layer or the hard coat layer side. Fingerprints are easy to see at any angle when the area where the plastic is attached is viewed from various angles.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示す通り、実施例１乃至５の加飾フィルムは、耐擦傷性、耐薬品性、成型性、耐クラック性及び指紋視認性のすべての特性について優れる結果を示した。また、硬化樹脂組成物層の厚さが２５μｍ～５０μｍである実施例２乃至５は、高温高湿環境に長時間曝された後の硬化樹脂組成物層の耐クラック性に優れる結果を示した。
一方、比較例１の加飾フィルムは、成型性及び耐クラック性は問題ないものの、耐擦傷性、耐薬品性及び指紋視認性に劣る結果を示した。比較例２及び３の加飾フィルムは、耐擦傷性、耐薬品性及び指紋視認性に劣る結果を示した。比較例５の加飾フィルムは、耐擦傷性及び耐クラック性は問題ないものの、耐薬品性、成型性、指紋視認性に劣る結果を示した。比較例４の加飾フィルムは、成型性及び耐クラック性は問題ないものの、耐薬品性指紋視認性に劣る結果を示した。また、比較例４の加飾フィルムは、ハードコート層がアフターキュアタイプであり、加飾成型後にハードコート層の硬化工程が必要なため、製造コストにおいて他の加飾フィルムに比べて劣るものである。 As shown in Table 1, the decorative films of Examples 1 to 5 showed excellent results in all properties of scratch resistance, chemical resistance, moldability, crack resistance and fingerprint visibility. Further, Examples 2 to 5 in which the thickness of the cured resin composition layer was 25 μm to 50 μm showed excellent results in crack resistance of the cured resin composition layer after being exposed to a high temperature and high humidity environment for a long time. ..
On the other hand, the decorative film of Comparative Example 1 showed no problem in moldability and crack resistance, but was inferior in scratch resistance, chemical resistance and fingerprint visibility. The decorative films of Comparative Examples 2 and 3 showed inferior scratch resistance, chemical resistance, and fingerprint visibility. The decorative film of Comparative Example 5 showed no problem in scratch resistance and crack resistance, but was inferior in chemical resistance, moldability, and fingerprint visibility. The decorative film of Comparative Example 4 showed no problem in moldability and crack resistance, but was inferior in chemical resistance and fingerprint visibility. Further, the decorative film of Comparative Example 4 is inferior to other decorative films in terms of manufacturing cost because the hard coat layer is an aftercure type and a curing step of the hard coat layer is required after the decorative molding. is there.
１１：ポリカーボネート系樹脂フィルム
１２：ダイコーター
１３：カバーフィルム
１４：紫外線光源
１５：冷却装置
１６：加飾フィルム
 

  11: Polycarbonate resin film 12: Die coater 13: Cover film 14: Ultraviolet light source 15: Cooling device 16: Decorative film

Claims (5)

  1. 　重量平均分子量が１，０００～１０，０００の２官能ウレタン（メタ）アクリレート系オリゴマー（Ａ）と反応性希釈モノマー（Ｂ）との反応で得られる硬化樹脂組成物層及びポリカーボネート系樹脂層から構成される積層体であることを特徴とする加飾フィルム。 Consists of a cured resin composition layer and a polycarbonate resin layer obtained by reacting a bifunctional urethane (meth) acrylate-based oligomer (A) having a weight average molecular weight of 1,000 to 10,000 with a reactive diluent monomer (B). A decorative film characterized by being a laminated body.
  2. 　前記２官能ウレタン（メタ）アクリレート系オリゴマー（Ａ）が（ポリ）アルキレングリコール（ａ１）と脂肪族環式ジイソシアネート（ａ２）とヒドロキシル（メタ）アクリレート（ａ３）との反応で得られるオリゴマーであることを特徴とする請求項１に記載の加飾フィルム。 The bifunctional urethane (meth) acrylate-based oligomer (A) is an oligomer obtained by the reaction of (poly) alkylene glycol (a1), aliphatic cyclic diisocyanate (a2) and hydroxyl (meth) acrylate (a3). The decorative film according to claim 1, wherein the decorative film is characterized by.
  3. 　前記硬化樹脂組成物層の厚さが２５μｍ以上５０μｍ以下であることを特徴とする請求項１または２に記載の加飾フィルム。 The decorative film according to claim 1 or 2, wherein the thickness of the cured resin composition layer is 25 μm or more and 50 μm or less.
  4. 　前記反応性希釈モノマー（Ｂ）はＳＰ値が９～１２の（メタ）アクリレートを主成分として含むことを特徴とする請求項１乃至３の何れかに記載の加飾フィルム。 The decorative film according to any one of claims 1 to 3, wherein the reactive diluted monomer (B) contains (meth) acrylate having an SP value of 9 to 12 as a main component.
  5. 　請求項１乃至４の何れかに記載の加飾フィルムが表面に貼合されている加飾成型品。
     

          A decorative molded product in which the decorative film according to any one of claims 1 to 4 is bonded to the surface.
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