WO2014162956A1 - Film de revêtement dur pour moulage - Google Patents

Film de revêtement dur pour moulage Download PDF

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Publication number
WO2014162956A1
WO2014162956A1 PCT/JP2014/058620 JP2014058620W WO2014162956A1 WO 2014162956 A1 WO2014162956 A1 WO 2014162956A1 JP 2014058620 W JP2014058620 W JP 2014058620W WO 2014162956 A1 WO2014162956 A1 WO 2014162956A1
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WO
WIPO (PCT)
Prior art keywords
film
hard coat
curable resin
ionizing radiation
radiation curable
Prior art date
Application number
PCT/JP2014/058620
Other languages
English (en)
Japanese (ja)
Inventor
長谷川　正英
俊和 江田
悟 糸部
康博 日高
Original Assignee
日本製紙株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本製紙株式会社 filed Critical 日本製紙株式会社
Priority to JP2015510032A priority Critical patent/JP6430368B2/ja
Publication of WO2014162956A1 publication Critical patent/WO2014162956A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
    • B29C37/0025—Applying surface layers, e.g. coatings, decorative layers, printed layers, to articles during shaping, e.g. in-mould printing
    • B29C37/0028—In-mould coating, e.g. by introducing the coating material into the mould after forming the article
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B29C51/02—Combined thermoforming and manufacture of the preform
    • 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
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2795/00—Printing on articles made from plastics or substances in a plastic state
    • B29C2795/002—Printing on articles made from plastics or substances in a plastic state before shaping
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B29C51/002—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B29C51/26—Component parts, details or accessories; Auxiliary operations
    • B29C51/264—Auxiliary operations prior to the thermoforming operation, e.g. cutting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
    • B29L2009/005—Layered products coated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
    • B29L2009/005—Layered products coated
    • B29L2009/006—Layered products coated painted
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/584—Scratch resistance
    • 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
    • B32B2307/718—Weight, e.g. weight per square meter

Definitions

  • the present invention relates to a molding hard coat film used for the production of a resin molded product by in-mold molding, insert molding, or vacuum molding.
  • Resin molded products are often used for mobile information terminal devices such as mobile phones, smartphones, notebook computers, home appliances, and interior / exterior parts of automobiles. As products become more commoditized, the need for differentiation in these products is increasing. Conventionally, as a method for decorating a resin molded product, a colored paint is applied to the surface of a three-dimensional resin molded product by injection molding or the like, or screen printing is performed. Furthermore, a method of applying a clear hard coat by spraying or dipping has been performed for the purpose of protecting the surface of the product.
  • a decorative film provided with a hard coat layer by printing or coating of a film has come to be used, and in-mold molding in which a highly designable decoration is provided on the surface of a resin molded product has become widespread.
  • the in-mold molding method is a technique in which a decorative film is adhered to the surface of a resin molding by simultaneously performing vacuum molding and injection in an injection mold.
  • Another method is a film insert molding method, in which the decorative film is heated (preliminary heating) to obtain a molded product of the decorative film with a mold and then preliminarily molded by injection molding as the next step.
  • the molded product and the resin molded product are bonded and integrated.
  • This method has the advantage that a general-purpose device can be used, but it needs to go through two steps.
  • a molding method using a decorative film there is a vacuum molding method in addition to the in-mold molding method.
  • the decorative film is heated (preliminary heating) and softened under vacuum, and then the vacuum is applied to the decorative film, and the decorative film is bonded to the surface of the resin molding while being stretched. Thereafter, the molded product is taken out by cooling and releasing the vacuum.
  • this vacuum forming method only a weak air pressure works rather than a mechanical strong force sandwiched between molds such as in-mold molding. Therefore, to make the decorative film follow the surface shape of the molded product, from the softening temperature of the film It is necessary to perform preheating at a sufficiently high temperature.
  • the preheating temperature is too low, when the decorative film is bonded to a resin molded product having a deep-drawn three-dimensional shape, the film is not stretched sufficiently. In the bent part, even if a decorative film is pasted, it does not become a sharp bend but becomes a shallow rounded shape, which impairs the original shape of the resin molded product. In addition, it is necessary to select an appropriate preheating temperature depending on the resin composition type used for the base film of the decorative film. Further, as an advantage, large-scale molding is easy.
  • the surface hardness is sufficient in addition to sufficient extensibility to follow three-dimensional molding (the hard coat layer does not crack when stretched). (Pencil hardness, scratch resistance) is also required.
  • the highly extensible resin used for the hard coat layer of the molding hard coat film is soft and does not express sufficient surface hardness, and the resin excellent in surface hardness is hard and does not express sufficient extensibility.
  • the surface hardness and extensibility are in a trade-off relationship.
  • an object of the present invention is to provide a hard coat film for molding having improved moldability (elongation rate), surface hardness, and scratch resistance characteristics.
  • the present invention provides an invention having the following configuration.
  • a coating composition containing a resin obtained by mixing an ionizing radiation curable resin (a) below and an ionizing radiation curable resin (b) is applied onto a base film and cured.
  • a second invention is a hard coat film for molding according to the first invention, wherein the coating composition further contains an ionizing radiation curable resin (c) below.
  • an ionizing radiation curable resin having a weight average molecular weight Mw of more than 10,000 and less than 150,000.
  • a third invention is a hard coat film for molding according to the first or second invention, wherein the ionizing radiation curable resin (a) satisfies the following conditions.
  • a fourth invention is a hard coat film for molding according to any one of the first to third inventions, wherein the ionizing radiation curable resin (b) satisfies the following conditions.
  • a fifth invention is a hard coat film for molding according to any one of the second to fourth inventions, wherein the ionizing radiation curable resin of (c) satisfies the following conditions.
  • a film is prepared by forming a 1.5 ⁇ m coating film of an ionizing radiation curable resin cured with an ultraviolet light quantity of 50 to 1000 mJ / cm 2 on a polyethylene terephthalate film.
  • a test piece having a width of 15 mm and a length of 150 mm was produced from the produced film, and the test piece was pulled at a tensile speed of 50 mm / min in an environment of a temperature of 25 ° C. and a humidity of 50% RH.
  • the elongation rate until the coating film cracks is 20% or more, and the pencil hardness specified in JIS K5600 is HB to 2H.
  • a sixth invention is a hard coat film for molding according to any one of the first to fifth inventions, wherein the hard coat layer contains inorganic oxide fine particles having an average particle diameter of 5 to 50 nm.
  • a seventh invention is the molding hard coat film according to the sixth invention, wherein the inorganic oxide fine particles contain aluminum as a main component.
  • the content of the inorganic oxide fine particles is 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the solid content of the coating composition.
  • This is a hard coating film for molding.
  • a decoration layer is formed on the surface of the base film opposite to the surface on which the hard coat layer is provided via a primer layer.
  • the primer layer is a hard coat film for molding characterized in that it contains a vinyl chloride-vinyl acetate copolymer resin and a polymethyl methacrylate resin.
  • a tenth invention is characterized in that, in the ninth invention, the blending ratio (parts by weight) of the vinyl chloride-vinyl acetate copolymer resin and the polymethyl methacrylate resin is in the range of 80/20 to 25/75. Hard coat film for molding.
  • a hard coat film for molding having improved moldability (elongation rate), surface hardness, and scratch resistance characteristics.
  • the molding hard coat film of the present invention is applied on a base film with a coating composition containing a resin obtained by mixing the following ionizing radiation curable resin (a) and ionizing radiation curable resin (b): A hard coat layer formed by curing is provided.
  • the ionizing radiation curable resin (a) and the ionizing radiation curable resin (b) will be described in detail later.
  • the said base film is demonstrated.
  • a base film which can be used for this invention It is a material which can be thermoformed, Comprising: The stress at the time of an expansion
  • an acrylic film such as a polyethylene terephthalate (PET) film or a polymethyl methacrylate (PMMA) film, a polycarbonate (PC) film, or the like can be preferably used.
  • a general-purpose biaxially stretched PET film may be used, but in order to obtain better moldability, it is particularly preferable to use a biaxially stretchable easily molded PET film.
  • This biaxially stretchable and easy-to-mold PET film has a low heat softening temperature, can be stretched with a weak force, and is a relatively inexpensive material.
  • the acrylic film and the polycarbonate (PC) film are both unstretched films and can be suitably used for any molding method.
  • the thickness of the base film is not particularly limited, but a film having a thickness of about 25 ⁇ m to 150 ⁇ m is used, for example.
  • the resin contained in the hard coat layer can be used without particular limitation as long as it is a resin that forms a film, but in particular, imparts hardness (pencil hardness, scratch resistance) to the hard coat layer surface.
  • the degree of cross-linking can be adjusted by the exposure amount of ultraviolet rays and the like, and the ionizing radiation curable type can be adjusted in the stretchability and surface hardness (pencil hardness, scratch resistance) of the hard coat layer. It is preferable to use a resin.
  • the ionizing radiation curable resin used in the present invention is a transparent resin that is cured by irradiation with ultraviolet rays (hereinafter abbreviated as “UV”) or electron beams (hereinafter abbreviated as “EB”). It is not specifically limited, For example, it can select suitably from urethane acrylate resin, polyester acrylate resin, etc., for example.
  • Preferred examples of the ionizing radiation-type resin include those made of a polyfunctional acrylate curable with UV or EB having two or more (meth) acryloyl groups in the molecule.
  • UV or EB curable polyfunctional acrylate having two or more (meth) acryloyl groups in the molecule include neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Polyol polyacrylates such as trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A Diglycidyl ether diacrylate, neopentyl glycol diglycidyl ether diacrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, etc.
  • the urethane (meth) acrylate obtained by making (meth) acrylate react, polysiloxane poly (meth) acrylate, etc. can be mentioned.
  • the characteristic configuration is that, as described above, a resin obtained by mixing the ionizing radiation curable resin (a) and the ionizing radiation curable resin (b) on the base film. That is, a hard coat layer formed by coating and curing the coating composition contained is provided.
  • the ionizing radiation curable resin (a) is an ionizing radiation curable resin having a weight average molecular weight Mw of 150,000 or more
  • the ionizing radiation curable resin (b) is a weight average molecular weight Mw of 10,000 or less.
  • the weight average molecular weight Mw of the ionizing radiation curable resin is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard sample.
  • a resin component of the hard coat layer a mixture of an ionizing radiation curable resin having a weight average molecular weight Mw of 150,000 or more and an ionizing radiation curable resin having a weight average molecular weight Mw of 10,000 or less is used for molding. It is possible to improve all the characteristics of the hard coat film, such as moldability (elongation), surface hardness, and scratch resistance.
  • the resin component of the hard coat layer in addition to an ionizing radiation curable resin having a weight average molecular weight Mw of 150,000 or more and an ionizing radiation curable resin having a weight average molecular weight Mw of 10,000 or less, (c) As the ionizing radiation curable resin, it is more preferable to use a mixture of ionizing radiation curable resins having a weight average molecular weight Mw of more than 10,000 and less than 150,000.
  • an ionizing radiation curable resin satisfying the following conditions is preferable.
  • a film is prepared by forming a 1.5 ⁇ m coating film of an ionizing radiation curable resin cured with an ultraviolet light quantity of 50 to 1000 mJ / cm 2 on a polyethylene terephthalate film.
  • a test piece having a width of 15 mm and a length of 150 mm was produced from the produced film, and the test piece was pulled at a tensile speed of 50 mm / min in an environment of a temperature of 25 ° C. and a humidity of 50% RH.
  • the elongation rate until the coating film cracks is 50% or more, and the pencil hardness specified in JIS K5600 is B to H.
  • the ionizing radiation curable resins (b) having a weight average molecular weight Mw of 10,000 or less the elongation measured by the same test method as described above is 1% or more and the pencil hardness is H to 4H.
  • An ionizing radiation curable resin is preferable.
  • the ionizing radiation curable resins having a weight average molecular weight Mw of (c) of more than 10,000 and less than 150,000 the elongation measured by the same test method as described above is 20% or more, and the pencil hardness is HB.
  • An ionizing radiation curable resin having ⁇ 2H is preferred.
  • these resins are used in addition to the ionizing radiation curable resin (a) and the ionizing radiation curable resin (b), when the ionizing radiation curable resin (c) is used in combination, these resins are used.
  • the mixing ratio of (a) :( b) :( c) is preferably 20 to 55:40 to 60: 5 to 30 (parts by weight). When the mixing ratio is outside this range, the effect of using the ionizing radiation curable resin (c) in addition to the ionizing radiation curable resin (a) and the ionizing radiation curable resin (b) is obtained. It becomes difficult.
  • the resin contained in the hard coat layer includes thermoplastic resins such as polyethylene, polypropylene, polystyrene, polycarbonate, and polyester, phenol resins, urea resins, and unsaturated polyesters.
  • a thermosetting resin such as epoxy or silicon resin may be contained within a range that does not impair the effects of the present invention, that is, the extensibility, hardness, and scratch resistance of the hard coat layer.
  • the photopolymerization initiator for the ionizing radiation curable resin contained in the hard coat layer known ones such as acetophenones and benzophenones can be used.
  • the hard coat layer preferably contains inorganic oxide fine particles.
  • the average particle size of the inorganic oxide fine particles is preferably 5 to 50 nm, and more preferably 10 to 20 nm. If the average particle diameter is less than 5 nm, it is difficult to obtain sufficient surface hardness. On the other hand, when the average particle diameter exceeds 50 nm, the gloss and transparency of the hard coat layer are lowered, and the flexibility is also lowered.
  • examples of the inorganic oxide fine particles include alumina and silica.
  • alumina containing aluminum as a main component is particularly suitable because it has a high hardness and can obtain an effect with a smaller amount of addition than silica.
  • the content of the inorganic oxide fine particles is preferably 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the solid content of the hard coat layer coating composition. When the content is less than 0.1 parts by weight, it is difficult to obtain the effect of improving the scratch resistance. On the other hand, if the content exceeds 5.0 parts by weight, the haze increases, and the design of the molded body using the molding hard coat film may be impaired.
  • an antifoaming agent a leveling agent, a surface tension adjusting agent, an antifouling agent, an antioxidant, an antistatic agent, You may contain a ultraviolet absorber, a light stabilizer, etc. as needed.
  • the coating thickness of the hard coat layer is not particularly limited, but is preferably in the range of, for example, about 1 to 10 ⁇ m. If the coating thickness is less than 1 ⁇ m, it will be difficult to obtain the required hardness. Moreover, when the coating film thickness is thicker than 10 ⁇ m, it becomes difficult to obtain good extensibility.
  • the hard coat layer in addition to the ionizing radiation type resin described above, is coated on the base film with a paint in which inorganic oxide fine particles, a polymerization initiator, other additives, etc. are dissolved and dispersed in an appropriate solvent. It is formed by drying.
  • the solvent can be appropriately selected depending on the solubility of the resin contained therein, and may be any solvent that can uniformly dissolve or disperse at least a solid content (resin, polymerization initiator, other additives, etc.).
  • Examples of such a solvent include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons ( Cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated carbons (dichloromethane, dichloroethane, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, etc.), alcohols (methanol, ethanol, isopropanol, Butanol, cyclohexanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, sulfoxides, amides and the like.
  • the coating method of the hard coat layer is not particularly limited, but it is usually easy to adjust the coating thickness, such as gravure coating, micro gravure coating, fountain bar coating, slide die coating, slot die coating, etc. Coating is possible by the method.
  • the film thickness of the coated hard coat layer can be measured, for example, by actually measuring with a micrometer.
  • a decorative layer such as a printing layer, a coloring / adhesive film, or the like may be provided on the opposite side of the base film from the side on which the hard coat layer is provided. .
  • the decorative layer is composed of, for example, a picture layer and / or a concealing layer, a metal vapor deposition layer, and the like.
  • the pattern layer is a layer provided to express a pattern such as a pattern or characters
  • the concealing layer is a solid layer, and is a layer provided to conceal the coloring of the resin or the like.
  • a metal vapor deposition layer is the layer which vapor-deposited one part or the whole surface, and is provided for the purpose of expressing the layer provided for concealing coloring etc. of resin etc., or a resin layer in a metal tone. Is a layer.
  • the decorative layer (for example, the pattern layer and / or the concealment layer) can be formed by a known printing method such as gravure printing, offset printing, or screen printing.
  • the formation thickness of the decorative layer is not particularly limited, but is preferably 3 to 50 ⁇ m, and more preferably 10 to 30 ⁇ m from the viewpoint of design.
  • the said metal vapor deposition layer can be formed into a film by methods, such as sputtering.
  • binders for printing inks used to form decorative layers include polyester resins, vinyl chloride-vinyl acetate copolymer resins, polyurethane resins, acrylic two-component curable resins, cellulose resins, acrylic resins, etc. it can.
  • the printing ink is usually provided in a form dissolved or dispersed in a solvent.
  • Solvents include aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane, methylcyclohexane and ethylcyclohexane, ester solvents such as ethyl acetate and butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone and anone.
  • a ketone solvent, an alcohol solvent such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, butanol, or a mixture of the above solvents can be used.
  • a general-purpose solvent used for adjusting the solvent-based paint can be used.
  • the said decoration layer is formed by printing directly on a base film
  • the adhesion of a decoration layer (printing layer) and a base film becomes inadequate, and the problem of dropping off of a decoration layer generate
  • the primer layer which has adhesiveness with both a base film and a decoration layer between a base film and a decoration layer.
  • the decorative film provided with this primer layer is used as a film for molding, in addition to the adhesion between the base film and the decorative layer as a property of the primer layer, the elongation of the base film at the time of molding It is also necessary that the following physical properties (elongation) are good.
  • the primer layer preferably contains a vinyl chloride-vinyl acetate copolymer resin and a polymethyl methacrylate resin as main components.
  • the solvent resistance of the dried coating film of the primer layer 2 is lowered.
  • primer layer Since the coating film is eroded and the decorativeness and adhesion are likely to be lowered, and the heat resistance is lowered, operational problems may occur. Furthermore, problems such as crimping or blocking occur when the molding film is wound up.
  • the blending ratio of the vinyl chloride-vinyl acetate copolymer resin to the polymethyl methacrylate resin is less than 25 parts by weight, the adhesion to the base film or the decorative layer is lowered.
  • the ratio of vinyl chloride is low, there are concerns that operational problems due to a decrease in heat resistance, problems such as crimping and blocking during winding, and the like may occur.
  • the ratio of vinyl chloride is less than 65 parts by weight, there is a problem that the hardness and solvent resistance of the coating film are likely to be lowered.
  • the ratio is more than 90 parts by weight, the solubility in a solvent is lowered with a decrease in flexibility and an improvement in solvent resistance, which is not preferable.
  • the ratio between vinyl chloride and vinyl acetate can be calculated from the following formula I.
  • the glass transition temperature (Tg) of the vinyl chloride-vinyl acetate copolymer resin is preferably 65 ° C. or higher.
  • the polymethyl methacrylate resin is a homopolymer and usually has a glass transition temperature of 105 ° C.
  • the primer layer has a UV absorber such as benzotriazole or benzophenone for the purpose of imparting light resistance, various leveling agents (fluorine, siloxane, acrylic, etc.) for the purpose of improving coating properties, light It is also possible to blend stabilizers, antistatic treatment agents, antifoaming agents, antistatic agents, flame retardants, and the like.
  • aromatic solvents such as toluene and xylene
  • aliphatic solvents such as cyclohexane, methylcyclohexane and ethylcyclohexane
  • ester solvents such as ethyl acetate and butyl acetate
  • a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and anone
  • an alcohol solvent such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, and butanol, or a mixture of the above solvents
  • a general-purpose solvent used for adjusting the solvent-based paint can be used.
  • the primer layer can be formed by a known coating method such as gravure coating, micro gravure coating, fountain bar coating, slide die coating, slot die coating, or screen printing method. After that, it is usually dried at a temperature of about 50 to 100 ° C.
  • the coating thickness of the primer layer after drying is not particularly limited, but it is usually preferably in the range of 0.1 ⁇ m to 1.0 ⁇ m, more preferably in the range of 0.2 ⁇ m to 0.5 ⁇ m.
  • the coating thickness is less than 0.1 ⁇ m, when the decoration layer is formed on the primer layer, the adhesion layer is eroded by the solvent in the decoration layer paint and the adhesion layer is eroded. There is a problem that it tends to cause a decrease.
  • the coating thickness exceeds 1.0 ⁇ m, the effect of improving the adhesion with the base film and the decorative layer cannot be obtained, and on the contrary, the cost becomes high, and when the film for molding is stretched, Whitening tends to occur, which is not preferable.
  • the blending amount of the fine particles exceeds 5.0 parts by weight, it is not preferable because the transparency is lowered and whitening is likely to occur when the molding hard coat film is stretched. On the other hand, there is a concern that a sufficient effect is not exhibited when the amount of the fine particles is less than 0.2 parts by weight.
  • the inorganic fine particles include fine particles such as alumina, zinc oxide, and silica
  • examples of the organic fine particles include fine particles such as polymethyl methacrylate and melamine / formaldehyde condensate.
  • the particle diameter for example, it is preferable to use fine particles of 0.085 ⁇ m to 0.50 ⁇ m. When the particle diameter is less than 0.085 ⁇ m, blocking does not occur when the primer layer surface and the hard coat layer surface are rolled up, but this is not preferable because it is easy to press-bond.
  • the particle diameter is more than 0.50 ⁇ m, it is not preferable because the effect of preventing further pressure bonding or blocking cannot be obtained, and on the contrary, the cost is increased and the external haze is increased and the transparency is easily lowered.
  • the vinyl chloride-vinyl acetate copolymer resin and the polymethyl methacrylate resin have a blending ratio (parts by weight) of the vinyl chloride-vinyl acetate copolymer resin and the polymethyl methacrylate resin of 80/20.
  • the primer layer is excellent in adhesion between the base film and the decorative layer, and the base film and the decorative layer through the primer layer Adhesiveness can be improved.
  • the primer layer by the said structure has the favorable physical property (elongation) which follows the elongation of the base film at the time of shaping
  • the following examples illustrate the invention, but are not intended to limit the invention. Unless otherwise specified, “parts” and “%” described below represent “parts by weight” and “% by weight”, respectively.
  • the urethane acrylate UV curable resin “8BR-500 (trade name)” used below has a weight average molecular weight of Mw 180,000, and the elongation is not cracked until the base substrate PET breaks, and the pencil hardness is HB. Yes, it corresponds to the ionizing radiation curable resin (a).
  • the urethane acrylate UV curable resin “UN904 (trade name)” has a weight average molecular weight Mw of 4,100, an elongation of 4.0% and a pencil hardness of 2H, and corresponds to the ionizing radiation curable resin (b) described above.
  • the acrylic polymer UV curable resin “8KX-012C (trade name)” has a weight average molecular weight Mw of 29,000, an elongation of 40%, and a pencil hardness of H, which corresponds to the ionizing radiation curable resin (c) described above. To do.
  • said weight average molecular weight Mw was measured by the gel permeation chromatography (GPC). Polystyrene was used as a standard sample for GPC measurement.
  • the paint was applied to one side of a 125 ⁇ m thick biaxially stretchable PET film “Lumirror U463 (trade name)” (manufactured by Toray) with a bar coater and dried with hot air at 80 ° C. for 1 minute. Then, it was hardened with an ultraviolet light quantity of 450 mJ / m 2 . The thickness of the obtained coating film was 5 ⁇ m.
  • the paint was applied to one side of a 75 ⁇ m thick PMMA film (manufactured by Sumitomo) for pencil hardness and scratch resistance tests, dried with hot air at 80 ° C. for 1 minute, and then irradiated with ultraviolet light of 450 mJ / Cured at m 2 . The thickness of the obtained coating film was 1.5 ⁇ m.
  • Example 2 ⁇ Preparation of paint> Urethane acrylate UV curable resin “8BR-500 (trade name)” (solid content 37%, Taisei Fine Chemical) 70 parts and urethane acrylate UV curable resin “UN904 (trade name)” (solid content 100%, Negami 30 parts by weight (manufactured by Kogyo Co., Ltd.) was used as the main agent, and other additives were prepared according to Example 1.
  • Example 3 ⁇ Preparation of paint> Urethane acrylate UV curable resin "8BR-500 (trade name)" (solid content 37%, Taisei Fine Chemical) 65 parts and urethane acrylate UV curable resin "UN904 (trade name)” (solid content 100%, Negami (Manufactured) 35 parts as a main ingredient, other additives were prepared according to Example 1.
  • urethane acrylate UV curable resin "UN904 (trade name)” solid content 100%, Negami (Manufactured) 35 parts as a main ingredient, other additives were prepared according to Example 1.
  • Example 4 ⁇ Preparation of paint> Urethane acrylate UV curable resin “8BR-500 (trade name)” (solid content 37%, manufactured by Taisei Fine Chemical) 60 parts and urethane acrylate UV curable resin “UN904 (trade name)” (solid content 100%, Negami 40 parts by weight) (manufactured by Kogyo Co., Ltd.) were used as the main ingredients, and other additives were prepared according to Example 1.
  • Example 5 ⁇ Preparation of paint> Acrylic polymer UV curable resin “8KX-012C (trade name)” (solid content 39%, manufactured by Taisei Fine Chemical) 45 parts and urethane acrylate UV curable resin “8BR-500 (trade name)” (solid content 37% , Manufactured by Taisei Fine Chemical Co., Ltd.) and 5 parts urethane acrylate UV curable resin “UN904 (trade name)” (100% solids, manufactured by Negami Kogyo Co., Ltd.). Other additives were prepared according to Example 1. did. ⁇ Hard coat film production> Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was prepared in the same manner as in Example 1.
  • Example 6 ⁇ Preparation of paint> Acrylic polymer UV curable resin “8KX-012C (trade name)” (solid content 39%, manufactured by Taisei Fine Chemical) 40 parts and urethane acrylate UV curable resin “8BR-500 (trade name)” (solid content 37% , Manufactured by Taisei Fine Chemical Co., Ltd.) and 10 parts urethane acrylate UV curable resin “UN904 (trade name)” (100% solids, manufactured by Negami Kogyo Co., Ltd.). Other additives were prepared according to Example 1. did. ⁇ Hard coat film production> Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was prepared in the same manner as in Example 1.
  • Example 7 ⁇ Preparation of paint> Acrylic polymer UV curable resin "8KX-012C (trade name)" (solid content 39%, manufactured by Taisei Fine Chemical) 35 parts and urethane acrylate UV curable resin "8BR-500 (trade name)” (solid content 37% , Manufactured by Taisei Fine Chemical Co., Ltd.) and 15 parts of urethane acrylate UV curable resin “UN904 (trade name)” (100% solids, manufactured by Negami Kogyo Co., Ltd.). Other additives were prepared according to Example 1. did. ⁇ Hard coat film production> Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was prepared in the same manner as in Example 1.
  • Example 8 ⁇ Preparation of paint> 30 parts of acrylic polymer UV curable resin “8KX-012C (trade name)” (solid content 39%, manufactured by Taisei Fine Chemical) and urethane acrylate UV curable resin “8BR-500 (trade name)” (solid content 37% , Manufactured by Taisei Fine Chemical Co., Ltd.) and 20 parts of urethane acrylate UV curable resin “UN904 (trade name)” (solid content: 100%, manufactured by Negami Kogyo Co., Ltd.). Other additives were prepared according to Example 1. did. ⁇ Hard coat film production> Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was prepared in the same manner as in Example 1.
  • Example 9 ⁇ Preparation of paint> Acrylic polymer UV curable resin “8KX-012C (trade name)” (solid content 39%, manufactured by Taisei Fine Chemical) 40 parts and urethane acrylate UV curable resin “8BR-500 (trade name)” (solid content 37% , Manufactured by Taisei Fine Chemical Co., Ltd.) and 10 parts urethane acrylate UV curable resin “UN904 (trade name)” (100% solids, manufactured by Negami Kogyo Co., Ltd.) (Trade name) ”(average particle size 40 nm, manufactured by Big Chemie) was added to 3% solids. Other additives were prepared according to Example 1. ⁇ Hard coat film production> Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was prepared in the same manner as in Example 1.
  • Example 10 ⁇ Preparation of paint> Acrylic polymer UV curable resin “8KX-012C (trade name)” (solid content 39%, manufactured by Taisei Fine Chemical) 40 parts and urethane acrylate UV curable resin “8BR-500 (trade name)” (solid content 37% , Manufactured by Taisei Fine Chemical) and 10 parts urethane acrylate UV curable resin “UN904 (trade name)” (100% solids, manufactured by Negami Kogyo Co., Ltd.). ) ”(Average particle size 13 nm, manufactured by CIK Nanotec) was added to 0.05% solids. Other additives were prepared according to Example 1. ⁇ Hard coat film production> Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was prepared in the same manner as in Example 1.
  • Example 11 ⁇ Preparation of paint> Acrylic polymer UV curable resin “8KX-012C (trade name)” (solid content 39%, manufactured by Taisei Fine Chemical) 40 parts and urethane acrylate UV curable resin “8BR-500 (trade name)” (solid content 37% , Manufactured by Taisei Fine Chemical) and 10 parts urethane acrylate UV curable resin “UN904 (trade name)” (100% solids, manufactured by Negami Kogyo Co., Ltd.). ) ”(Average particle size 13 nm, manufactured by CIK Nanotech) was added to 1.0% solids. Other additives were prepared according to Example 1. ⁇ Hard coat film production> Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was prepared in the same manner as in Example 1.
  • Example 12 ⁇ Preparation of paint> Acrylic polymer UV curable resin “8KX-012C (trade name)” (solid content 39%, manufactured by Taisei Fine Chemical) 40 parts and urethane acrylate UV curable resin “8BR-500 (trade name)” (solid content 37% , Manufactured by Taisei Fine Chemical) and 10 parts urethane acrylate UV curable resin “UN904 (trade name)” (100% solids, manufactured by Negami Kogyo Co., Ltd.). ) "(Average particle size 13 nm, manufactured by CIK Nanotech) was added to 2.0% solids. Other additives were prepared according to Example 1. ⁇ Hard coat film production> Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was prepared in the same manner as in Example 1.
  • Example 13 ⁇ Preparation of paint> Acrylic polymer UV curable resin “8KX-012C (trade name)” (solid content 39%, manufactured by Taisei Fine Chemical) 40 parts and urethane acrylate UV curable resin “8BR-500 (trade name)” (solid content 37% , Manufactured by Taisei Fine Chemical) and 10 parts urethane acrylate UV curable resin “UN904 (trade name)” (100% solids, manufactured by Negami Kogyo Co., Ltd.). ) ”(Average particle size 13 nm, manufactured by CIK Nanotech) was added to 5.0% solids. Other additives were prepared according to Example 1. ⁇ Hard coat film production> Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was prepared in the same manner as in Example 1.
  • Example 14 ⁇ Preparation of paint> Acrylic polymer UV curable resin “8KX-012C (trade name)” (solid content 39%, manufactured by Taisei Fine Chemical) 40 parts and urethane acrylate UV curable resin “8BR-500 (trade name)” (solid content 37% , Manufactured by Taisei Fine Chemical) and 10 parts urethane acrylate UV curable resin “UN904 (trade name)” (100% solids, manufactured by Negami Kogyo Co., Ltd.). ) ”(Average particle size 13 nm, manufactured by CIK Nanotech) was added to 10% solids. Other additives were prepared according to Example 1. ⁇ Hard coat film production> Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was prepared in the same manner as in Example 1.
  • Example 15 ⁇ Preparation of paint> Acrylic polymer UV curable resin “8KX-012C (trade name)” (solid content 39%, manufactured by Taisei Fine Chemical) 40 parts and urethane acrylate UV curable resin “8BR-500 (trade name)” (solid content 37% , Manufactured by Taisei Fine Chemical) and 10 parts urethane acrylate UV curable resin “UN904 (trade name)” (100% solids, manufactured by Negami Kogyo Co., Ltd.). ) ”(Average particle size 13 nm, manufactured by CIK Nanotech) was added at 15% of solids. Other additives were prepared according to Example 1. ⁇ Hard coat film production> Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was prepared in the same manner as in Example 1.
  • Example 16 ⁇ Preparation of paint> It was prepared by excluding fine particles mainly composed of aluminum from the coating material of Example 6. ⁇ Hard coat film production> Using the coating material, a hard coat film for elongation test and scratch resistance was produced in the same manner as in Example 1.
  • Pencil hardness Pencil hardness was measured by the test method shown in JIS K5600.
  • Formability (elongation rate) A test piece having a sample size width of 15 mm and a length of 150 mm is prepared using the above-described hard coat film for elongation test. The sample was pulled at a pulling rate of 50 mm / min and a distance between chucks of 100 mm, and the tensile elongation until cracking occurred in the hard coat layer on the surface was measured.
  • Example 2 and Example 6 As is apparent from the results in Table 1 above, according to the examples of the present invention, a molding hard coat film having good moldability (elongation rate), surface hardness, and scratch resistance is obtained. Furthermore, when Example 2 and Example 6, Example 4 and Example 7 are compared, the resin 2 component (Examples 2 and 4) and the resin 3 component (Examples 6 and 7) have the same haze value. However, the resin 3 component shows higher elongation. Therefore, the resin 3 component is superior to the resin 2 component.
  • Example A On the surface opposite to the surface provided with the hard coat layer of the molding hard coat film (base film is the PMMA film) prepared in Example 1, the following primer layer paint was applied with a bar coater at 90 ° C. Drying with hot air for 1 minute formed a primer layer having a coating thickness of 0.3 ⁇ m (Evaluation Sample 1). Next, a 200 ⁇ m screen mesh was used on the primer layer of the evaluation sample 1, and a decorative layer coating (two-component reaction curable screen ink “SS16-000 (trade name)” (urethane, manufactured by Toyo Ink Manufacturing Co., Ltd.) ) was solid-printed and dried with hot air at 60 ° C.
  • SS16-000 trade name
  • Example B For molding in the same manner as in Example A, except that the blending ratio (parts by weight) of the vinyl chloride-vinyl acetate copolymer resin “Solvine C” used in the primer layer coating material and the polymethyl methacrylate resin was changed to 80/20. A hard coat film was produced.
  • Example C For molding in the same manner as in Example A, except that the blending ratio (parts by weight) of the vinyl chloride-vinyl acetate copolymer resin “Solvine C” used for the primer layer coating material and the polymethyl methacrylate resin was changed to 25/75. A hard coat film was produced.
  • MEK-ST-ZL trade name
  • Example E A molding hard coat film was produced in the same manner as in Example A except that the primer layer was not provided (that is, a decorative layer was formed directly on the surface of the base film).
  • the evaluation criteria are as follows. In addition, (circle) and (circle) evaluation product determined that solvent resistance was a pass.
  • Adhesiveness Evaluation sample 1 for the base film and primer layer and adhesiveness in the hard coat film for molding obtained in each of the above examples, and evaluation sample 2 for adhesiveness between the primer layer and the decorative layer Evaluation was made by the following method.
  • 100 cross-cuts of 1 mm 2 were prepared under constant temperature and humidity conditions (23 ° C., 53% RH) using a cross-cut peel test jig, and Sekisui Chemical Co., Ltd. adhesive tape No. 252 was affixed on it, pressed uniformly with a spatula, peeled in the direction of 90 degrees, and the remaining number of each layer was evaluated in four stages.
  • the evaluation criteria are as follows, and ⁇ and ⁇ evaluation products were judged to have passed.
  • the item “PR layer” in Table 2 is an evaluation result of adhesion between the primer layer and the base film
  • “decoration layer” is an evaluation result of adhesion between the primer layer and the decoration layer.
  • the adhesiveness between the hard coat layer and the base film (the item “HC layer” in Table 2) When evaluated by the same method, it passed in any of the examples.
  • the primer layer is excellent in adhesion between the base film and the decorative layer, and in addition to moldability (elongation), hardware (pencil hardness), and winding ability. Further, a molding hard coat film excellent in solvent resistance, heat resistance and transparency can be obtained. Moreover, in Example E which formed the decorating layer directly on the base film surface, without providing the said primer layer, solvent resistance and adhesiveness with a decorating layer fall significantly. Also, problems such as crimping or blocking are likely to occur when the molding film is wound up.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Abstract

La présente invention concerne un film de revêtement dur pour moulage, dont l'aptitude au moulage, la dureté de surface et la résistance aux rayures sont améliorées. Ce film de revêtement dur pour moulage est doté d'une couche de revêtement dur obtenue en appliquant, sur un film de matériau de base, une composition de revêtement et en durcissant la composition de revêtement. La composition de revêtement contient une résine obtenue en mélangeant (a) une résine durcissable par rayons ionisants ayant une masse moléculaire moyenne en poids Mw de 150 000 ou plus et (b) une résine durcissable par rayons ionisants ayant une masse moléculaire moyenne en poids Mw de 10 000 ou moins.
PCT/JP2014/058620 2013-03-30 2014-03-26 Film de revêtement dur pour moulage WO2014162956A1 (fr)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015046472A1 (fr) * 2013-09-28 2015-04-02 日本製紙株式会社 Film à revêtement dur pour moulage
WO2016076302A1 (fr) * 2014-11-10 2016-05-19 住友化学株式会社 Composition de résine photodurcissable et procédé de production de stratifié
WO2016190427A1 (fr) * 2015-05-28 2016-12-01 大日本印刷株式会社 Feuille de transfert
JP2017178999A (ja) * 2016-03-28 2017-10-05 日本製紙株式会社 ハードコート塗料組成物及び成型用ハードコートフィルム
JP2018051919A (ja) * 2016-09-28 2018-04-05 大日本印刷株式会社 転写用ハードコートフィルム及びハードコート積層体
JP2020125400A (ja) * 2019-02-04 2020-08-20 リンテック株式会社 粘着フィルム
JP7160231B1 (ja) * 2021-01-18 2022-10-25 東洋紡株式会社 加飾成形体およびその製造方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008260202A (ja) * 2007-04-12 2008-10-30 Sumitomo Bakelite Co Ltd 射出成形用ハードコートフィルム及び該フィルムを利用した射出成形体の製造方法
JP2009241458A (ja) * 2008-03-31 2009-10-22 Kimoto & Co Ltd ハードコートフィルム及び樹脂成型品
JP2011131406A (ja) * 2009-12-22 2011-07-07 Toyobo Co Ltd 成型用ハードコートフィルム
JP2012056236A (ja) * 2010-09-10 2012-03-22 Dainippon Printing Co Ltd 三次元成形加飾シート及びそれを用いた加飾成形品
JP2012056237A (ja) * 2010-09-10 2012-03-22 Dainippon Printing Co Ltd 三次元成形加飾シート及びそれを用いた加飾成形品
JP2012091497A (ja) * 2010-09-29 2012-05-17 Dainippon Printing Co Ltd 加飾シート及び加飾成形品

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008260202A (ja) * 2007-04-12 2008-10-30 Sumitomo Bakelite Co Ltd 射出成形用ハードコートフィルム及び該フィルムを利用した射出成形体の製造方法
JP2009241458A (ja) * 2008-03-31 2009-10-22 Kimoto & Co Ltd ハードコートフィルム及び樹脂成型品
JP2011131406A (ja) * 2009-12-22 2011-07-07 Toyobo Co Ltd 成型用ハードコートフィルム
JP2012056236A (ja) * 2010-09-10 2012-03-22 Dainippon Printing Co Ltd 三次元成形加飾シート及びそれを用いた加飾成形品
JP2012056237A (ja) * 2010-09-10 2012-03-22 Dainippon Printing Co Ltd 三次元成形加飾シート及びそれを用いた加飾成形品
JP2012091497A (ja) * 2010-09-29 2012-05-17 Dainippon Printing Co Ltd 加飾シート及び加飾成形品

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015046472A1 (fr) * 2013-09-28 2015-04-02 日本製紙株式会社 Film à revêtement dur pour moulage
WO2016076302A1 (fr) * 2014-11-10 2016-05-19 住友化学株式会社 Composition de résine photodurcissable et procédé de production de stratifié
WO2016190427A1 (fr) * 2015-05-28 2016-12-01 大日本印刷株式会社 Feuille de transfert
JP2016221967A (ja) * 2015-05-28 2016-12-28 大日本印刷株式会社 転写箔
CN107531011A (zh) * 2015-05-28 2018-01-02 大日本印刷株式会社 转印箔
US10576711B2 (en) 2015-05-28 2020-03-03 Dai Nippon Printing Co., Ltd. Transfer film
CN107531011B (zh) * 2015-05-28 2023-12-29 大日本印刷株式会社 转印箔
JP2017178999A (ja) * 2016-03-28 2017-10-05 日本製紙株式会社 ハードコート塗料組成物及び成型用ハードコートフィルム
JP2018051919A (ja) * 2016-09-28 2018-04-05 大日本印刷株式会社 転写用ハードコートフィルム及びハードコート積層体
JP2020125400A (ja) * 2019-02-04 2020-08-20 リンテック株式会社 粘着フィルム
JP7202914B2 (ja) 2019-02-04 2023-01-12 リンテック株式会社 粘着フィルム
JP7160231B1 (ja) * 2021-01-18 2022-10-25 東洋紡株式会社 加飾成形体およびその製造方法

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