WO2015046472A1 - Hard-coated film for molding - Google Patents

Hard-coated film for molding Download PDF

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Publication number
WO2015046472A1
WO2015046472A1 PCT/JP2014/075737 JP2014075737W WO2015046472A1 WO 2015046472 A1 WO2015046472 A1 WO 2015046472A1 JP 2014075737 W JP2014075737 W JP 2014075737W WO 2015046472 A1 WO2015046472 A1 WO 2015046472A1
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WO
WIPO (PCT)
Prior art keywords
film
hard coat
resin
curable resin
ionizing radiation
Prior art date
Application number
PCT/JP2014/075737
Other languages
French (fr)
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
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Application filed by 日本製紙株式会社 filed Critical 日本製紙株式会社
Priority to JP2015539400A priority Critical patent/JPWO2015046472A1/en
Publication of WO2015046472A1 publication Critical patent/WO2015046472A1/en

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Classifications

    • 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
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle 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
    • 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
    • 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
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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
    • B29C2791/00—Shaping characteristics in general
    • B29C2791/004—Shaping under special conditions
    • B29C2791/006—Using vacuum
    • 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
    • B29C51/10—Forming by pressure difference, e.g. vacuum
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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
    • 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
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C08J2483/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen

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.
  • new characteristics such as antifouling property and slipperiness of the surface are also required.
  • a first object of the present invention is to provide a molding hard coat film having improved moldability (elongation rate), surface hardness, and scratch resistance characteristics.
  • the second object of the present invention is to provide a molding hard coat film having improved moldability (elongation rate), surface hardness, antifouling property, slipperiness and scratch resistance.
  • an ionizing radiation curable resin having a weight average molecular weight Mw of 150,000 or more satisfying the following condition (a) on the substrate film, and an ionizing radiation having a weight average molecular weight Mw of 10,000 or less satisfying the following condition (b):
  • a molding hard comprising a hard coat layer formed by coating and curing a coating composition containing a resin obtained by mixing a curable resin and an ionizing radiation curable resin satisfying the following condition (c): It is a coat film.
  • a film is produced in which 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 is formed 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 second invention is a hard coat film for molding according to the first invention, wherein the coating composition further contains a fluorosiloxane resin.
  • a third invention is the hard coat film for molding according to the first or second invention, wherein the hard coat layer contains inorganic oxide fine particles having an average particle diameter of 5 to 50 nm.
  • a fourth invention is the molding hard coat film according to the third 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 decorative 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 seventh invention is characterized in that, in the sixth 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. This is a hard coat film for molding.
  • molding which improved the characteristics of moldability (elongation rate), surface hardness, and abrasion resistance can be provided.
  • lubricity, and abrasion resistance can be provided.
  • a hard coat layer formed by coating and curing a coating composition containing an ionizing radiation curable resin having a molecular weight Mw of 10,000 or less and an ionizing radiation curable resin satisfying the following condition (c) is provided. It is characterized by this.
  • a film is produced in which 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 is formed 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.
  • An ionizing radiation curable resin having a weight average molecular weight Mw of 150,000 or more that satisfies the above condition (a), an ionizing radiation curable resin having a weight average molecular weight Mw of 10,000 or less that satisfies the above condition (b), and the above condition (c) The ionizing radiation curable resin will be described in detail later.
  • a fluorosiloxane resin is further added to the hard coat layer.
  • 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 the ionizing radiation curable resin satisfying the condition (a), the ionizing radiation curable resin satisfying the condition (b), as described above, on the base film, And a hard coat layer formed by coating and curing a coating composition containing a resin in which three components of an ionizing radiation curable resin satisfying the condition (c) are mixed.
  • the ionizing radiation curable resin that satisfies the condition (a) has a weight average molecular weight Mw of 150,000 or more
  • the ionizing radiation curable resin that satisfies the condition (b) preferably has a weight average molecular weight Mw of 10,000 or less. Mw is 2,000 or less.
  • the ionizing radiation curable resin satisfying the condition (c) preferably has a weight average molecular weight Mw of 10,000 or less, more preferably Mw of 2,000 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 substance.
  • the ionizing radiation curable resin having the weight average molecular weight Mw of 150,000 or more is the following condition (a)
  • the ionizing radiation curable resin having the weight average molecular weight Mw of 10,000 or less is the following condition.
  • (b) it is important that the ionizing radiation curable resin having a weight average molecular weight Mw of 10,000 or less is an ionizing radiation curable resin satisfying the following condition (c).
  • Condition (b) The elongation measured by the same test method as in the above condition (a) is 1% or more, and the pencil hardness specified in JIS K5600 is H to 4H.
  • an ionizing radiation curable resin (component 1) having a weight average molecular weight Mw of 150,000 or more that satisfies the above condition (a), and an ionizing radiation curable resin having a weight average molecular weight Mw of 10,000 or less that satisfies the above condition (b)
  • the resin component of the hard coat layer ionizing radiation curable resin having a weight average molecular weight Mw of 150,000 or more satisfying the above condition (a), ionizing radiation having a weight average molecular weight Mw of 10,000 or less satisfying the above condition (b)
  • ionizing radiation curable resin having a weight average molecular weight Mw of 150,000 or more satisfying the above condition (a)
  • 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 fluorosiloxane resin means a compound obtained by hybridizing a fluorine resin and a siloxane resin, or a mixture obtained by mixing a fluorine resin and a siloxane resin.
  • the fluororesin is a compound containing a perfluoroalkyl group in which all or a part of hydrogen atoms in a hydrocarbon group are substituted with fluorine atoms, and is a perfluorooctanesulfonic acid perfluorooctanoic acid perfluoroalkylcarboxylic acid fluorine telomer.
  • Examples include alcohol.
  • the siloxane-based resin is a derivative having a basic structure of polydimethylsiloxane, such as polyether-modified polydimethylsiloxane, polymethylalkylsiloxane, and modified polysiloxane.
  • the compounding ratio of the fluorine resin and the siloxane resin in the compound obtained by hybridizing the fluorine resin and the siloxane resin or the mixture of the fluorine resin and the siloxane resin is as follows:
  • the resin is preferably 10:90 to 90:10 (% by weight).
  • the amount of fluorine-based siloxane resin added to the hard coat layer is preferably 0.1 to 3.0 parts by weight with respect to 100 parts by weight of the solid content of the hard coat layer coating composition.
  • the fluorosiloxane resin may be either a thermosetting type or an ionizing radiation curable type (UV curable type, EV curable type), but an ionizing ray curable type (particularly, UV curable type) resin is used. It is preferable to do so because the slipperiness and antifouling property are maintained even if the surface is rubbed.
  • 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.
  • the content is less than 0.1 parts by weight, it is difficult to obtain the effect of improving the scratch resistance.
  • 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 said decoration layer is comprised by the pattern layer and / or a concealment layer, a metal vapor deposition layer, etc., for example.
  • 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 characteristic 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 vinyl chloride-vinyl acetate copolymer resin and 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, such being undesirable.
  • 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 acrylic polymer UV curable resin “8BR-500 (trade name)” used in the following has a weight average molecular weight Mw 180,000, and the elongation is not cracked until the base substrate PET is broken, and the pencil hardness B It corresponds to an ionizing radiation curable resin having a weight average molecular weight Mw satisfying the above condition (a) of 150,000 or more.
  • the polyfunctional monomer UV curable resin “Biscoat V # 802 (trade name)” has a weight average molecular weight Mw of 1,100, an elongation of 4.0% and a pencil hardness of 2H, and satisfies the above condition (b). Corresponds to ionizing radiation curable resin with Mw of 10,000 or less.
  • the urethane acrylate UV curable resin “RC29-047 (trade name)” has a weight average molecular weight Mw of 1,650, an elongation of 45.0% and a pencil hardness of H, and satisfies the above condition (c). Corresponds to resin.
  • said weight average molecular weight Mw was measured by the gel permeation chromatography (GPC). Polystyrene was used as a standard sample for GPC measurement.
  • ⁇ Hard coat film production> For elongation test, apply the above paint on one side of 125 ⁇ m thick PET film “A4350 (trade name)” (manufactured by Toray) with a bar coater and dry with hot air at 80 ° C. for 1 minute. and cured at cm 2. The thickness of the obtained coating film was 1.5 ⁇ m.
  • the above coating was applied to one side of a 125 ⁇ m-thick PMMA film (manufactured by Sumitomo) for pencil hardness and scratch resistance testing using a bar coater, dried with hot air at 80 ° C. for 1 minute, and an ultraviolet light intensity of 450 mJ / and cured at cm 2. The thickness of the obtained coating film was 1.5 ⁇ m.
  • Example 1-2 ⁇ Preparation of paint> 50 parts of acrylic polymer UV curable resin “8BR-500 (trade name)” (solid content 37%, manufactured by Taisei Fine Chemical) and polyfunctional monomer UV curable resin “V # 802 (trade name)” (solid content) 100 parts, made by Osaka Organic Chemical Co., Ltd.) and 40 parts urethane acrylate UV curable resin “RC29-047 (trade name)” (solid content 75%, made by DIC). It was prepared according to -1. ⁇ Hard coat film production> Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was produced in the same manner as in Example 1-1.
  • Example 1-3 ⁇ Preparation of paint> 50 parts of acrylic polymer UV curable resin “8BR-500 (trade name)” (solid content 37%, manufactured by Taisei Fine Chemical) and polyfunctional monomer UV curable resin “V # 802 (trade name)” (solid content) 100 parts, made by Osaka Organic Co., Ltd.) and 15 parts urethane acrylate UV curable resin “RC29-047 (trade name)” (solid content 75%, made by DIC). It was prepared according to -1. ⁇ Hard coat film production> Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was produced in the same manner as in Example 1-1.
  • Example 1-1 ⁇ Preparation of paint> The main component was 100 parts of an acrylic polymer UV curable resin “8BR-500 (trade name)” (solid content 37%, manufactured by Taisei Fine Chemical), and other additives were prepared according to Example 1-1.
  • 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.
  • Comparative Examples 1-4 to 1-6 in which two of the three components of the ionizing radiation curable resin are used as the resin component of the hard coat layer moldability (elongation rate), surface hardness, and scratch resistance It is difficult to improve all the characteristics. That is, as in the present invention, only by using a specific ionizing radiation curable resin 3 component as the resin component of the hard coat layer, any of moldability (elongation rate), surface hardness (pencil hardness), and scratch resistance can be obtained. Therefore, a molding hard coat film with improved properties can be obtained.
  • ⁇ Hard coat film production> For elongation test, apply the above paint on one side of 125 ⁇ m thick PET film “A4350 (trade name)” (manufactured by Toray) with a bar coater and dry with hot air at 80 ° C. for 1 minute. and cured at cm 2. The thickness of the obtained coating film was 1.5 ⁇ m.
  • the above coating was applied to one side of a 125 ⁇ m-thick PMMA film (manufactured by Sumitomo) for pencil hardness and scratch resistance testing using a bar coater, dried with hot air at 80 ° C. for 1 minute, and an ultraviolet light intensity of 450 mJ / and cured at cm 2. The thickness of the obtained coating film was 1.5 ⁇ m.
  • Example 2-2 ⁇ Preparation of paint> 50 parts of acrylic polymer UV curable resin “8BR-500 (trade name)” (solid content 37%, manufactured by Taisei Fine Chemical) and polyfunctional monomer UV curable resin “V # 802 (trade name)” (solid content 100) 10 parts urethane acrylate UV curable resin “RC29-047 (trade name)” (solid content 75%, made by DIC) 40 parts, the other additives are Example 2-1 It was prepared according to ⁇ Hard coat film production> A hard coat film was produced in the same manner as in Example 2-1, using the coating material.
  • Example 2-3 ⁇ Preparation of paint> 50 parts of acrylic polymer UV curable resin “8BR-500 (trade name)” (solid content 37%, manufactured by Taisei Fine Chemical) and polyfunctional monomer UV curable resin “V # 802 (trade name)” (solid content 100) %, Manufactured by Osaka Organic Chemical Co., Ltd.), 15 parts, urethane acrylate UV curable resin “RC29-047 (trade name)” (solid content 75%, manufactured by DIC) 35 parts, and other additives are Example 2-1 It was prepared according to ⁇ Hard coat film production> A hard coat film was produced in the same manner as in Example 2-1, using the coating material.
  • Example 2-4 ⁇ Preparation of paint> 0.10 parts of fluorosiloxane resin “RS922 (trade name)” (manufactured by DIC) was added, and other additives and resins were prepared according to Example 2-2.
  • Example 2-5 ⁇ Preparation of paint> 0.50 part of a fluorosiloxane-based resin “RS922 (trade name)” (manufactured by DIC) was added, and other additives and resins were prepared according to Example 2-1.
  • Example 2-6 ⁇ Preparation of paint> 1.4 parts of fluorosiloxane resin “RS922 (trade name)” (manufactured by DIC) was added, and other additives and resins were prepared according to Example 2-2.
  • Example 2-7 ⁇ Preparation of paint> 0.4 parts of fluororesin “RS75 (trade name)” (manufactured by DIC) and 0.3 part of siloxane resin “RS576 (trade name)” (manufactured by DIC) were mixed and added. Other additives and resins were prepared according to Example 2-2.
  • Example 2-8 ⁇ Preparation of paint> Fluorine resin “RS75 (trade name)” (manufactured by DIC) 0.2 part and siloxane resin “RS576 (trade name)” (manufactured by DIC) 0.5 part were mixed and added. Other additives and resins were prepared according to Example 2-2. ⁇ Hard coat film production> A hard coat film was produced in the same manner as in Example 2-1, using the coating material.
  • Example 2-1 ⁇ Preparation of paint> The main component was 100 parts of an acrylic polymer UV curable resin “8BR-500 (trade name)” (solid content 37%, manufactured by Taisei Fine Chemical), and other additives were prepared according to Example 2-1.

Abstract

　The present invention provides a hard-coated film for molding with improved molding properties, surface hardness, and scratch resistance.　This hard-coated film for molding is formed by providing a hard coating layer atop a substrate film, said layer being formed by applying and curing a coating composition containing a resin in which are mixed: an ionizing radiation curable resin which satisfies condition (a) and of which the weight average molecular weight (Mw) is at least 150,000; an ionizing radiation curable resin which satisfies condition (b) and of which the weight average molecular weight (Mw) is at most 10,000; and an ionizing radiation curable resin which satisfies condition (c). Condition (a): Elongation is at least 50%, and pencil hardness is B-H. Condition (b): Elongation is at least 1%, and pencil hardness is H-4H. Condition (c): Elongation is at least 20%, and pencil hardness is HB-2H.

Description

成型用ハードコートフィルムHard coat film for molding
　本発明は、インモールド成型やインサート成型、または真空成型法による樹脂成型品の製造に用いられる成型用ハードコートフィルムに関する。 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.
　携帯電話機等の携帯情報端末機器スマートフォン、ノート型パソコン、家電製品、自動車内外装部品などには樹脂成型品が多く用いられている。製品のコモディティ化が進む中、これらの製品においては、デザインによる差別化ニーズが高まっている。従来、樹脂成型品への加飾方法としては、射出成型等による３次元形状の樹脂成型品の表面に、着色塗料を塗装し、またはスクリーン印刷を施していた。さらに製品の表面保護を目的としてスプレーやディッピングによりクリアハードコートを施す手法が行われていた。 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.
しかし、このような従来方法は、高いデザイン性の加飾を行うことが困難であり、またスプレー塗装などでは使用する塗料等に含まれる揮発性溶剤などの化学物質による作業環境への影響の懸念がある。そこで代替方法として、フィルムの印刷や塗布によるハードコート層を設けた加飾フィルムが用いられるようになり、樹脂成型物の表面にデザイン性の高い加飾を設けるインモールド成型が普及してきた。
インモールド成型法は、射出成型用金型内で同時に真空成型と射出を行い、加飾フィルムを樹脂成型物表面へ接着する技術である。一工程で製品が得られる長所があり、工程の短縮・塗装の省略が可能となる。 However, such conventional methods are difficult to decorate with high design, and there is a concern about the impact on the work environment by chemical substances such as volatile solvents contained in the paint used in spray coating etc. There is. Therefore, as an alternative method, 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. There is an advantage that a product can be obtained in one process, and the process can be shortened and painting can be omitted.
また、別の方法としてフィルムインサート成型法があり、加飾フィルムを加熱（予備加熱）し、金型により加飾フィルムの成型物を得てから、次工程として射出成型により予備成型した加飾フィルム成型物と樹脂成型物とを接着し、一体化させる方法である。この方法は汎用装置が流用できる長所があるが、二つの工程を経る必要がある。 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. In this method, 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.
　また、加飾フィルムを利用した成型方法として、上記インモールド成型法の他に、真空成型法がある。この真空成型法は、真空下で、加飾フィルムを加熱（予備加熱）軟化させた後、加飾フィルムとの間を真空にし、伸ばしながら樹脂成型物の表面に貼り合わせる。その後、冷却および真空開放して成形品を取り出す。この真空成型法では、インモールド成型のような金型で挟み込む機械的な強い力でなく弱い空気圧しか働かないため、加飾フィルムを成型物の表面形状に追従させるには、フィルムの軟化温度より十分に高い温度で予備加熱を行う必要がある。予備加熱の温度が低すぎると、深絞りの３次元形状を持つ樹脂成型物へ加飾フィルムを貼り合わせる場合では、フィルムの伸ばされ方が不十分となり、例えば樹脂成型物が凹んだ９０度の曲げ部分では、加飾フィルムを貼合してもシャープな曲げとならず浅い丸みを帯びた形状となり、樹脂成型物の本来の形状を損なう。また、加飾フィルムの基材フィルムに用いられる樹脂組成種により適切な予備加熱温度を選択する必要がある。また、長所としては大型成型が容易である。 Further, as a molding method using a decorative film, there is a vacuum molding method in addition to the in-mold molding method. In this vacuum 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. In 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. If 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.
　以上のような加飾フィルムを利用した成型方法に用いられる加飾フィルムとして、従来より種々の構成が提案されている（特許文献１～特許文献３を参照）。 Various configurations have been conventionally proposed as a decorative film used in the molding method using the decorative film as described above (see Patent Documents 1 to 3).
特開２０１２－１９３２６５号公報JP 2012-193265 A 特開２０１２－８１６２８号公報JP 2012-81628 A 特開２０１２－５１２４７号公報JP 2012-512247 A
　成型用ハードコートフィルムが様々な分野に利用されるようになるに伴い、３次元成型に追従する十分な伸長性（伸ばされてもハードコート層にクラック等が入らないこと）の他、表面硬度（鉛筆硬度、耐擦傷性）も要求される。しかしながら、成型用ハードコートフィルムのハードコート層に使用される伸長性の高い樹脂は柔らかいため十分な表面硬度が発現せず、表面硬度に優れる樹脂は硬いため十分な伸長性は発現しないといったように、表面硬度と伸長性とがトレードオフの関係にある。また、表面の防汚性や易滑性といった新たな特性も求められている。 As hard coating films for molding are used in various fields, 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. However, 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. In addition, new characteristics such as antifouling property and slipperiness of the surface are also required.
　そこで、本発明は成型性（伸び率）と表面硬度、耐擦傷性の特性を向上させた成型用ハードコートフィルムを提供することを第１の目的とする。また、本発明は成型性（伸び率）と表面硬度、防汚性、易滑性、耐擦傷性の特性を向上させた成型用ハードコートフィルムを提供することを第２の目的とする。 Therefore, a first object of the present invention is to provide a molding hard coat film having improved moldability (elongation rate), surface hardness, and scratch resistance characteristics. The second object of the present invention is to provide a molding hard coat film having improved moldability (elongation rate), surface hardness, antifouling property, slipperiness and scratch resistance.
　本発明は、上記課題を解決するため、以下の構成を有する発明を提供するものである。
第１の発明は、基材フィルム上に、下記条件(a)を満たす重量平均分子量Mwが150,000以上の電離放射線硬化型樹脂、下記条件(b)を満たす重量平均分子量Mwが10,000以下の電離放射線硬化型樹脂、および下記条件(c)を満たす電離放射線硬化型樹脂を混合させた樹脂を含有する塗料組成物を塗工し硬化させてなるハードコート層を設けたことを特徴とする成型用ハードコートフィルムである。
　条件(a)：ポリエチレンテレフタレートフィルム上に、紫外線光量50～1000mJ/cm2で硬化させた電離放射線硬化型樹脂の1.5μｍの塗膜を形成させたフィルムを作製する。次に、当該作製したフィルムから、幅１５ｍｍ×長さ１５０ｍｍの試験片を作製し、温度２５℃、湿度５０％ＲＨの環境下で、当該試験片を引張速度５０ｍｍ／分にて引張った際に、前記塗膜にクラックが入るまでの伸び率が５０％以上で、かつ、JIS K5600に規定される鉛筆硬度がB～Hである。
　条件(b)：ポリエチレンテレフタレートフィルム上に、紫外線光量50～1000mJ/cm2で硬化させた電離放射線硬化型樹脂の1.5μｍの塗膜を形成させたフィルムを作製する。次に、当該作製したフィルムから、幅１５ｍｍ×長さ１５０ｍｍの試験片を作製し、温度２５℃、湿度５０％ＲＨの環境下で、当該試験片を引張速度５０ｍｍ／分にて引張った際に、前記塗膜にクラックが入るまでの伸び率が１％以上で、かつ、JIS K5600に規定される鉛筆硬度がH～4Hである。
　条件(c)：ポリエチレンテレフタレートフィルム上に、紫外線光量50～1000mJ/cm2で硬化させた電離放射線硬化型樹脂の1.5μｍの塗膜を形成させたフィルムを作製する。次に、当該作製したフィルムから、幅１５ｍｍ×長さ１５０ｍｍの試験片を作製し、温度２５℃、湿度５０％ＲＨの環境下で、当該試験片を引張速度５０ｍｍ／分にて引張った際に、前記塗膜にクラックが入るまでの伸び率が２０％以上で、かつ、JIS K5600に規定される鉛筆硬度がHB～2Hである。 In order to solve the above-described problems, the present invention provides an invention having the following configuration.
In the first invention, an ionizing radiation curable resin having a weight average molecular weight Mw of 150,000 or more satisfying the following condition (a) on the substrate film, and an ionizing radiation having a weight average molecular weight Mw of 10,000 or less satisfying the following condition (b): A molding hard comprising a hard coat layer formed by coating and curing a coating composition containing a resin obtained by mixing a curable resin and an ionizing radiation curable resin satisfying the following condition (c): It is a coat film.
Condition (a): A film in which a 1.5 μm coating film of an ionizing radiation curable resin cured with an ultraviolet light quantity of 50 to 1000 mJ / cm 2 is formed on a polyethylene terephthalate film is prepared. Next, 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.
Condition (b): A film in which a 1.5 μm coating film of an ionizing radiation curable resin cured with an ultraviolet light quantity of 50 to 1000 mJ / cm 2 is formed on a polyethylene terephthalate film is produced. Next, 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 until cracks occur in the coating film is 1% or more, and the pencil hardness specified in JIS K5600 is H to 4H.
Condition (c): A film is produced in which a 1.5 μm coating film of an ionizing radiation curable resin cured with an ultraviolet light quantity of 50 to 1000 mJ / cm 2 is formed on a polyethylene terephthalate film. Next, 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.
第２の発明は、第１の発明において、前記塗料組成物中にさらにフッ素シロキサン系樹脂を含有することを特徴とする成型用ハードコートフィルムである。
第３の発明は、第１又は第２の発明において、前記ハードコート層は、平均粒子径５～５０ｎｍの無機酸化物微粒子を含有することを特徴とする成型用ハードコートフィルムである。
　第４の発明は、第３の発明において、前記無機酸化物微粒子はアルミニウムを主成分とすることを特徴とする成型用ハードコートフィルムである。 A second invention is a hard coat film for molding according to the first invention, wherein the coating composition further contains a fluorosiloxane resin.
A third invention is the hard coat film for molding according to the first or second invention, wherein the hard coat layer contains inorganic oxide fine particles having an average particle diameter of 5 to 50 nm.
A fourth invention is the molding hard coat film according to the third invention, wherein the inorganic oxide fine particles contain aluminum as a main component.
　第５の発明は、第３又は第４の発明において、前記無機酸化物微粒子の含有量が、塗料組成物の固形分１００重量部に対して０．１～５．０重量部であることを特徴とする成型用ハードコートフィルムである。
第６の発明は、第１乃至第５のいずれかの発明において、前記基材フィルムの前記ハードコート層を設けた面とは反対側の面に、プライマー層を介して加飾層を形成し、前記プライマー層は、塩化ビニル－酢酸ビニル共重合樹脂及びポリメチルメタクリレート樹脂を含有することを特徴とする成型用ハードコートフィルムである。
第７の発明は、第６の発明において、前記塩化ビニル－酢酸ビニル共重合樹脂とポリメチルメタクリレート樹脂との配合比率（重量部）が８０／２０～２５／７５の範囲であることを特徴とする成型用ハードコートフィルムである。 According to a fifth invention, in the third or fourth invention, 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.
In a sixth aspect of the present invention based on any one of the first to fifth aspects, a decorative 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 seventh invention is characterized in that, in the sixth 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. This is a hard coat film for molding.
　本発明によれば、成型性（伸び率）と表面硬度、耐擦傷性の特性を向上させた成型用ハードコートフィルムを提供することができる。
　また、本発明によれば、成型性（伸び率）と表面硬度、防汚性、易滑性、耐擦傷性の特性を向上させた成型用ハードコートフィルムを提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the hard coat film for shaping | molding which improved the characteristics of moldability (elongation rate), surface hardness, and abrasion resistance can be provided.
Moreover, according to this invention, the hard coat film for shaping | molding which improved the characteristics of moldability (elongation rate), surface hardness, antifouling property, slipperiness | lubricity, and abrasion resistance can be provided.
　以下、本発明の実施の形態について詳細に説明する。
本発明の成型用ハードコートフィルムは、上記のとおり、基材フィルム上に、下記条件(a)を満たす重量平均分子量Mwが150,000以上の電離放射線硬化型樹脂、下記条件(b)を満たす重量平均分子量Mwが10,000以下の電離放射線硬化型樹脂、および下記条件(c)を満たす電離放射線硬化型樹脂を混合させた樹脂を含有する塗料組成物を塗工し硬化させてなるハードコート層を設けたことを特徴とするものである。
条件(a)：ポリエチレンテレフタレートフィルム上に、紫外線光量50～1000mJ/cm2で硬化させた電離放射線硬化型樹脂の1.5μｍの塗膜を形成させたフィルムを作製する。次に、当該作製したフィルムから、幅１５ｍｍ×長さ１５０ｍｍの試験片を作製し、温度２５℃、湿度５０％ＲＨの環境下で、当該試験片を引張速度５０ｍｍ／分にて引張った際に、前記塗膜にクラックが入るまでの伸び率が５０％以上で、かつ、JIS K5600に規定される鉛筆硬度がB～Hである。
条件(b)：ポリエチレンテレフタレートフィルム上に、紫外線光量50～1000mJ/cm2で硬化させた電離放射線硬化型樹脂の1.5μｍの塗膜を形成させたフィルムを作製する。次に、当該作製したフィルムから、幅１５ｍｍ×長さ１５０ｍｍの試験片を作製し、温度２５℃、湿度５０％ＲＨの環境下で、当該試験片を引張速度５０ｍｍ／分にて引張った際に、前記塗膜にクラックが入るまでの伸び率が１％以上で、かつ、JIS K5600に規定される鉛筆硬度がH～4Hである。
条件(c)：ポリエチレンテレフタレートフィルム上に、紫外線光量50～1000mJ/cm2で硬化させた電離放射線硬化型樹脂の1.5μｍの塗膜を形成させたフィルムを作製する。次に、当該作製したフィルムから、幅１５ｍｍ×長さ１５０ｍｍの試験片を作製し、温度２５℃、湿度５０％ＲＨの環境下で、当該試験片を引張速度５０ｍｍ／分にて引張った際に、前記塗膜にクラックが入るまでの伸び率が２０％以上で、かつ、JIS K5600に規定される鉛筆硬度がHB～2Hである。 Hereinafter, embodiments of the present invention will be described in detail.
The molding hard coat film of the present invention, as described above, on the base film, an ionizing radiation curable resin having a weight average molecular weight Mw of 150,000 or more that satisfies the following condition (a), and a weight average that satisfies the following condition (b): A hard coat layer formed by coating and curing a coating composition containing an ionizing radiation curable resin having a molecular weight Mw of 10,000 or less and an ionizing radiation curable resin satisfying the following condition (c) is provided. It is characterized by this.
Condition (a): A film in which a 1.5 μm coating film of an ionizing radiation curable resin cured with an ultraviolet light quantity of 50 to 1000 mJ / cm 2 is formed on a polyethylene terephthalate film is prepared. Next, 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.
Condition (b): A film in which a 1.5 μm coating film of an ionizing radiation curable resin cured with an ultraviolet light quantity of 50 to 1000 mJ / cm 2 is formed on a polyethylene terephthalate film is produced. Next, 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 until cracks occur in the coating film is 1% or more, and the pencil hardness specified in JIS K5600 is H to 4H.
Condition (c): A film is produced in which a 1.5 μm coating film of an ionizing radiation curable resin cured with an ultraviolet light quantity of 50 to 1000 mJ / cm 2 is formed on a polyethylene terephthalate film. Next, 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.
上記条件(a)を満たす重量平均分子量Mwが150,000以上の電離放射線硬化型樹脂、上記条件(b)を満たす重量平均分子量Mwが10,000以下の電離放射線硬化型樹脂、および上記条件(c)を満たす電離放射線硬化型樹脂については後で詳しく説明する。
また、本発明の成型用ハードコートフィルムにおいては、前記ハードコート層にさらにフッ素シロキサン系樹脂を添加することも好ましい実施態様である。 An ionizing radiation curable resin having a weight average molecular weight Mw of 150,000 or more that satisfies the above condition (a), an ionizing radiation curable resin having a weight average molecular weight Mw of 10,000 or less that satisfies the above condition (b), and the above condition (c) The ionizing radiation curable resin will be described in detail later.
In the molding hard coat film of the present invention, it is also a preferred embodiment that a fluorosiloxane resin is further added to the hard coat layer.
 [基材フィルム]
　まず、上記基材フィルムについて説明する。
本発明に用いることのできる基材フィルムとしては、特に限定されないが、熱成型可能な材料であって、伸長時応力が低く、弱い力で伸ばすことが可能な材料であることが好ましい。本発明においては、たとえば、ポリエチレンテレフタレート（ＰＥＴ）フィルム、ポリメチルメタアクリレート（ＰＭＭＡ）フィルム等のアクリルフィルム、ポリカーボネート（ＰＣ）フィルムなどを好ましく使用することができる。上記ＰＥＴフィルムの場合、汎用の二軸延伸ＰＥＴフィルムを用いてもよいが、より良好な成型性を得るためには、二軸延伸易成型ＰＥＴフィルムを用いることが特に好ましい。この二軸延伸易成型ＰＥＴフィルムは、熱軟化温度が低く、弱い力で伸ばすことができ、しかも比較的安価な材料である。 [Base film]
First, the said base film is demonstrated.
Although it does not specifically limit as 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 | extension is low, and it is preferable that it is a material which can be extended with weak force. In the present invention, for example, 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. In the case of the PET film, 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.
　また、上記アクリルフィルム、ポリカーボネート（ＰＣ）フィルムは、いずれも無延伸フィルムで、いずれの成型法にも好適に利用することができる。
基材フィルムの厚さについても特に制限はないが、例えば２５μｍ～１５０μｍ程度の厚さのフィルムが使用される。 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 μm to 150 μm is used, for example.
[ハードコート層]
　次に、上記ハードコート層について説明する。
本発明において、上記ハードコート層に含まれる樹脂としては、被膜を形成する樹脂であれば特に制限なく用いることができるが、特にハードコート層表面に硬度（鉛筆硬度、耐擦傷性）を付与し、また紫外線等の露光量によって架橋度合を調節することが可能であり、ハードコート層の伸長性と表面硬度（鉛筆硬度、耐擦傷性）の調節が可能になるという点で、電離放射線硬化型樹脂を用いることが好ましい。 [Hard coat layer]
Next, the hard coat layer will be described.
In the present invention, 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. In addition, 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.
　本発明に用いられる電離放射線硬化型樹脂は、紫外線（以下「ＵＶ」と略記する。）や電子線（以下「ＥＢ」と略記する。）を照射することによって硬化する透明な樹脂であれば、特に限定されるものではなく、例えば、ウレタンアクリレート系樹脂、ポリエステルアクリレート系樹脂等の中から適宜選択することができる。電離放射線型樹脂として好ましいものは、分子内に２個以上の（メタ）アクリロイル基を有するＵＶまたはＥＢにて硬化可能な多官能アクリレートからなるものが挙げられる。分子内に２個以上の（メタ）アクリロイル基を有するＵＶまたはＥＢ硬化可能な多官能アクリレートの具体例としては、ネオペンチルグリコールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等のポリオールポリアクリレート、ビスフェノールＡジグリシジルエーテルのジアクリレート、ネオペンチルグリコールジグリシジルエーテルのジアクリレート、１，６－ヘキサンジオールジグリシジルエーテルのジ（メタ）アクリレートなどのエポキシ（メタ）アクリレート、多価アルコールと多価カルボン酸及び／またはその無水物とアクリル酸とをエステル化することによって得ることができるポリエステル（メタ）アクリレート、多価アルコール、多価イソシアネート及び水酸基含有（メタ）アクリレートを反応させることによって得られるウレタン（メタ）アクリレート、ポリシロキサンポリ（メタ）アクリレート等を挙げることができる。なお、多官能アクリレートは３種以上混合して用いてもよい。 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. Specific examples of 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. Polyester (meth) acrylate, polyhydric alcohol, polyhydric isocyanate, and hydroxyl group-containing compounds that can be obtained by esterifying xyl (meth) acrylate, polyhydric alcohol and polyhydric carboxylic acid and / or anhydride and acrylic acid The urethane (meth) acrylate obtained by making (meth) acrylate react, polysiloxane poly (meth) acrylate, etc. can be mentioned. In addition, you may mix and use 3 or more types of polyfunctional acrylate.
本発明のハードコートフィルムにおいて、特徴的な構成は、前述のとおり、基材フィルム上に、前記条件(a)を満たす電離放射線硬化型樹脂、前記条件(b)を満たす電離放射線硬化型樹脂、および前記条件(c)を満たす電離放射線硬化型樹脂の３成分を混合させた樹脂を含有する塗料組成物を塗工し硬化させてなるハードコート層を設けたことである。 In the hard coat film of the present invention, as described above, the characteristic configuration is that the ionizing radiation curable resin satisfying the condition (a), the ionizing radiation curable resin satisfying the condition (b), as described above, on the base film, And a hard coat layer formed by coating and curing a coating composition containing a resin in which three components of an ionizing radiation curable resin satisfying the condition (c) are mixed.
ここで、条件(a)を満たす電離放射線硬化型樹脂は、重量平均分子量Mwが150,000以上であり、条件(b)を満たす電離放射線硬化型樹脂は、重量平均分子量Mwが10,000以下であり、好ましくはMwが2,000以下である。また、条件(c)を満たす電離放射線硬化型樹脂は、好ましくは重量平均分子量Mwが10,000以下であり、より好ましくはMwが2,000以下である。
なお、本発明において、電離放射線硬化型樹脂の重量平均分子量Mwは、ポリスチレンを標準物質に用いてゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定した値である。 Here, the ionizing radiation curable resin that satisfies the condition (a) has a weight average molecular weight Mw of 150,000 or more, and the ionizing radiation curable resin that satisfies the condition (b) preferably has a weight average molecular weight Mw of 10,000 or less. Mw is 2,000 or less. The ionizing radiation curable resin satisfying the condition (c) preferably has a weight average molecular weight Mw of 10,000 or less, more preferably Mw of 2,000 or less.
In the present invention, 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 substance.
また、本発明においては、上記の重量平均分子量Mwが150,000以上の電離放射線硬化型樹脂が以下の条件(a)を、上記の重量平均分子量Mwが10,000以下の電離放射線硬化型樹脂が以下の条件(b)を、上記の好ましくは重量平均分子量Mwが10,000以下の電離放射線硬化型樹脂が以下の条件(c)をそれぞれ満たす電離放射線硬化型樹脂であることが重要である。 In the present invention, the ionizing radiation curable resin having the weight average molecular weight Mw of 150,000 or more is the following condition (a), and the ionizing radiation curable resin having the weight average molecular weight Mw of 10,000 or less is the following condition. In (b), it is important that the ionizing radiation curable resin having a weight average molecular weight Mw of 10,000 or less is an ionizing radiation curable resin satisfying the following condition (c).
条件(a)：ポリエチレンテレフタレートフィルム上に、紫外線光量50～1000mJ/cm2で硬化させた電離放射線硬化型樹脂の1.5μｍの塗膜を形成させたフィルムを作製する。次に、当該作製したフィルムから、幅１５ｍｍ×長さ１５０ｍｍの試験片を作製し、温度２５℃、湿度５０％ＲＨの環境下で、当該試験片を引張速度５０ｍｍ／分にて引張った際に、前記塗膜にクラックが入るまでの伸び率が５０％以上で、かつ、JIS K5600に規定される鉛筆硬度がB～Hである。
条件(b)：上記条件(a)と同様の試験法により測定した伸び率が１％以上で、かつ、JIS K5600に規定される鉛筆硬度がH～4Hである。
条件(c)：上記条件(a)と同様の試験法により測定した伸び率が２０％以上で、かつ、JIS K5600に規定される鉛筆硬度がHB～2Hである。 Condition (a): A film in which a 1.5 μm coating film of an ionizing radiation curable resin cured with an ultraviolet light quantity of 50 to 1000 mJ / cm 2 is formed on a polyethylene terephthalate film is prepared. Next, 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.
Condition (b): The elongation measured by the same test method as in the above condition (a) is 1% or more, and the pencil hardness specified in JIS K5600 is H to 4H.
Condition (c): The elongation measured by the same test method as in the above condition (a) is 20% or more, and the pencil hardness specified in JIS K5600 is HB to 2H.
　本発明において、上記条件(a)を満たす重量平均分子量Mwが150,000以上の電離放射線硬化型樹脂（成分１）、上記条件(b)を満たす重量平均分子量Mwが10,000以下の電離放射線硬化型樹脂（成分２）、および上記条件(c)を満たす電離放射線硬化型樹脂（成分３）の混合比率は、成分１：成分２：成分３＝２０～７０：５～３０：２０～７０（重量部）であることが好ましい。この混合比率外であると、成型性（伸び率）と表面硬度、耐擦傷性のいずれの特性も向上させることが難しくなる。 In the present invention, an ionizing radiation curable resin (component 1) having a weight average molecular weight Mw of 150,000 or more that satisfies the above condition (a), and an ionizing radiation curable resin having a weight average molecular weight Mw of 10,000 or less that satisfies the above condition (b) ( The mixing ratio of the component 2) and the ionizing radiation curable resin (component 3) satisfying the above condition (c) is as follows: Component 1: Component 2: Component 3 = 20 to 70: 5 to 30:20 to 70 (parts by weight) It is preferable that If the mixing ratio is outside this range, it is difficult to improve all of the properties of moldability (elongation), surface hardness, and scratch resistance.
このように、ハードコート層の樹脂成分として、上記条件(a)を満たす重量平均分子量Mwが150,000以上の電離放射線硬化型樹脂、上記条件(b)を満たす重量平均分子量Mwが10,000以下の電離放射線硬化型樹脂、および上記条件(c)を満たす電離放射線硬化型樹脂の３成分を混合して用いることにより、成型用ハードコートフィルムの成型性（伸び率）と表面硬度、耐擦傷性のいずれの特性も向上させることが可能となる。 Thus, as the resin component of the hard coat layer, ionizing radiation curable resin having a weight average molecular weight Mw of 150,000 or more satisfying the above condition (a), ionizing radiation having a weight average molecular weight Mw of 10,000 or less satisfying the above condition (b) By mixing and using three components of a curable resin and an ionizing radiation curable resin that satisfies the above condition (c), any of moldability (elongation rate), surface hardness, and scratch resistance of the molding hard coat film can be obtained. The characteristics can also be improved.
また、上記ハードコート層に含まれる樹脂としては、上述の電離放射線硬化型樹脂の他に、ポリエチレン、ポロプロピレン、ポリスチレン、ポリカーボネート、ポリエステル等の熱可塑性樹脂や、フェノール樹脂、ウレア樹脂、不飽和ポリエステル、エポキシ、ケイ素樹脂等の熱硬化性樹脂を本発明の効果、すなわちハードコート層の伸長性と硬度、耐擦傷性を損なわない範囲内で含有してもよい。 In addition to the ionizing radiation curable resin described above, 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. Further, 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.
また、上記ハードコート層に含まれる電離放射線硬化型樹脂の光重合開始剤としては、アセトフェノン類、ベンゾフェノン類などの公知のものが利用できる。 As 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.
　本発明においては、上記ハードコート層にフッ素シロキサン系樹脂を添加することで防汚性、易滑性（ハードコート層表面のタッチ感）、耐擦傷性を向上させることができる。
本発明において、フッ素シロキサン系樹脂とは、フッ素系樹脂とシロキサン系樹脂とをハイブリッドさせた化合物、あるいはフッ素系樹脂とシロキサン系樹脂とを混合した混合物を意味する。前記フッ素系樹脂は、炭化水素基中の水素原子のすべてあるいは一部をフッ素原子に置換したパーフルオロアルキル基を含有する化合物であり、パーフルオロオクタンスルホン酸パーフルオロオクタン酸ペルフルオロアルキルカルボン酸フッ素テロマーアルコールなどが挙げられる。また、前記シロキサン系樹脂としてはポリジメチルシロキサンを基本構造とする誘導体であり、ポリエーテル変性ポリジメチルシロキサン、ポリメチルアルキルシロキサン、変性ポリシロキサン等がある。
　本発明において、フッ素系樹脂とシロキサン系樹脂とをハイブリッドさせた化合物、あるいはフッ素系樹脂とシロキサン系樹脂とを混合した混合物におけるフッ素系樹脂とシロキサン系樹脂の配合比率は、フッ素系樹脂：シロキサン系樹脂＝10:90～90:10（重量％）であることが好ましい。 In the present invention, antifouling property, slipperiness (touch feeling on the surface of the hard coat layer) and scratch resistance can be improved by adding a fluorosiloxane resin to the hard coat layer.
In the present invention, the fluorosiloxane resin means a compound obtained by hybridizing a fluorine resin and a siloxane resin, or a mixture obtained by mixing a fluorine resin and a siloxane resin. The fluororesin is a compound containing a perfluoroalkyl group in which all or a part of hydrogen atoms in a hydrocarbon group are substituted with fluorine atoms, and is a perfluorooctanesulfonic acid perfluorooctanoic acid perfluoroalkylcarboxylic acid fluorine telomer. Examples include alcohol. The siloxane-based resin is a derivative having a basic structure of polydimethylsiloxane, such as polyether-modified polydimethylsiloxane, polymethylalkylsiloxane, and modified polysiloxane.
In the present invention, the compounding ratio of the fluorine resin and the siloxane resin in the compound obtained by hybridizing the fluorine resin and the siloxane resin or the mixture of the fluorine resin and the siloxane resin is as follows: The resin is preferably 10:90 to 90:10 (% by weight).
　本発明において、ハードコート層に添加するフッ素系シロキサン系樹脂の添加量は、ハードコート層用塗料組成物の固形分100重量部に対して0.1～3.0重量部であることが好ましい。
本発明おいて、フッ素シロキサン系樹脂は、熱硬化型あるいは電離放射線硬化型（ＵＶ硬化型、ＥＶ硬化型）のどちらでも構わないが、電離線硬化型（特に、ＵＶ硬化型）の樹脂を使用することは、表面を擦っても易滑性や防汚性が維持されるため好ましい。 In the present invention, the amount of fluorine-based siloxane resin added to the hard coat layer is preferably 0.1 to 3.0 parts by weight with respect to 100 parts by weight of the solid content of the hard coat layer coating composition.
In the present invention, the fluorosiloxane resin may be either a thermosetting type or an ionizing radiation curable type (UV curable type, EV curable type), but an ionizing ray curable type (particularly, UV curable type) resin is used. It is preferable to do so because the slipperiness and antifouling property are maintained even if the surface is rubbed.
本発明においては、表面硬度のより一層の向上の観点から、上記ハードコート層に無機酸化物微粒子を含有させることが好ましい。この場合、無機酸化物微粒子の平均粒子径は５～５０ｎｍであることが好ましく、さらに好ましくは平均粒子径１０～２０ｎｍである。平均粒子径が５ｎｍ未満であると十分な表面硬度を得ることが困難である。一方、平均粒子径が５０ｎｍを超えるとハードコート層の光沢、透明性が低下し、可撓性も低下する。 In the present invention, it is preferable to contain inorganic oxide fine particles in the hard coat layer from the viewpoint of further improving the surface hardness. In this case, 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.
　本発明において上記無機酸化物微粒子としては、例えばアルミナやシリカなどを挙げることができる。これらの中でも、アルミニウムを主成分とするアルミナは高硬度を有するため、シリカよりも少ない添加量で効果を得られることから特に好適である。 In the present invention, examples of the inorganic oxide fine particles include alumina and silica. Among these, 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.
　本発明において、無機酸化物微粒子の含有量は、ハードコート層用塗料組成物の固形分１００重量部に対して０．１～５．０重量部であることが好ましい。含有量が０．１重量部未満であると、耐擦傷性の向上効果が得られ難い。一方、含有量が５．０重量部を超えるとヘイズが上がってしまい、成型用ハードコートフィルムを用いた成型体の意匠性が損なわれることがある。 In the present invention, 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.
また、上記ハードコート層に添加するその他の添加剤として、本発明の効果を損わない範囲で、消泡剤、レベリング剤、表面張力調整剤、防汚剤、酸化防止剤、帯電防止剤、紫外線吸収財、光安定化剤などを必要に応じて含有してもよい。 Further, as other additives to be added to the hard coat layer, as long as the effect of the present invention is not 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.
　本発明において、上記ハードコート層の塗膜厚さは、特に制約されるわけではないが、例えば１～１０μｍ程度の範囲であることが好適である。塗膜厚さが１μｍよりも薄いと必要な硬度が得られ難くなる。また、塗膜厚さが１０μｍよりも厚いと良好な伸長性が得られ難くなる。 In the present invention, 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 μm. If the coating thickness is less than 1 μm, it will be difficult to obtain the required hardness. Moreover, when the coating film thickness is thicker than 10 μm, it becomes difficult to obtain good extensibility.
　上記ハードコート層は、上述の電離放射線型樹脂の他に、無機酸化物微粒子、重合開始剤、その他の添加剤等を適当な溶媒に溶解、分散した塗料を上記基材フィルム上に塗工、乾燥して形成される。溶媒としては、含有される前記樹脂の溶解性に応じて適宜選択でき、少なくとも固形分（樹脂、重合開始剤、その他添加剤など）を均一に溶解あるいは分散できる溶媒であればよい。そのような溶媒としては、例えば、ケトン類（アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等）、エーテル類（ジオキサン、テトラヒドロフラン等）、脂肪族炭化水素類（ヘキサン等）、脂環式炭化水素類（シクロヘキサン等）、芳香族炭化水素類（トルエン、キシレン等）、ハロゲン化炭素類（ジクロロメタン、ジクロロエタン等）、エステル類（酢酸メチル、酢酸エチル、酢酸ブチル等）、アルコール類（メタノール、エタノール、イソプロパノール、ブタノール、シクロヘキサノール等）、セロソルブ類（メチルセロソルブ、エチルセロソルブ等）、セロソルブアセテート類、スルホキシド類、アミド類などが例示できる。また、溶媒は単独で使用しても２種類以上を混合して使用してもよい。 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. Moreover, a solvent may be used individually or may be used in mixture of 2 or more types.
　ハードコート層の塗工方法については特に限定されないが、通常、グラビア塗工、マイクログラビア塗工、ファウンテンバー塗工、スライドダイ塗工、スロットダイ塗工など、塗膜厚さの調整が容易な方式で塗工が可能である。なお、塗工したハードコート層の膜厚は、例えばマイクロメーターで実測することにより測定可能である。 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.
　また、本発明の成型用ハードコートフィルムにおいては、上記基材フィルムのハードコート層を設けた側とは反対面に例えば印刷層などの加飾層や、着色・接着フィルムなどを設けてもよい。 In the molding hard coat film of the present invention, 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. .
上記加飾層は、例えば絵柄層及び／又は隠蔽層、金属蒸着層等により構成される。ここで、絵柄層は、模様や文字等とパターン状の絵柄を表現するために設けられる層であり、隠蔽層は全面ベタ層であり樹脂等の着色等を隠蔽するために設けられる層である。また、金属蒸着層は、一部或いは全面を金属調に蒸着した層であり、樹脂等の着色等を隠蔽するために設けられる層、或いは樹脂層を金属調に表現することを目的に設けられる層である。 The said decoration layer is comprised by the pattern layer and / or a concealment layer, a metal vapor deposition layer, etc., for example. Here, the pattern layer is a layer provided to express a pattern such as a pattern or characters, and the concealing layer is a solid layer, and is a layer provided to conceal the coloring of the resin or the like. . Moreover, 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.
加飾層（例えば絵柄層及び／又は隠蔽層）は、グラビア印刷、オフセット印刷、スクリーン印刷等の公知の印刷法により形成することができる。加飾層の形成厚みは、特に制約は無いが、意匠性の観点からは例えば３～５０μｍが好ましく、更に好ましくは１０～３０μｍである。また、上記金属蒸着層は、スパッタリングなどの方法で成膜することができる。 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 μm, and more preferably 10 to 30 μm from the viewpoint of design. Moreover, the said metal vapor deposition layer can be formed into a film by methods, such as sputtering.
加飾層の形成に使用される印刷インキのバインダーとしては、ポリエステル系樹脂、塩化ビニル－酢酸ビニル共重合樹脂、ポリウレタン系樹脂、アクリル２液硬化型樹脂、セルロース系樹脂、アクリル系樹脂等を例示できる。印刷インキは、通常、溶剤に溶解又は分散した態様で提供される。溶剤としては、トルエン、キシレンなどの芳香族系溶剤、シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン等の脂肪族系溶剤、酢酸エチル、酢酸ブチル等のエステル系溶剤、アセトン、メチルエチルケトン、メチルイソブチルケトン、アノン等のケトン系溶剤、メタノール、エタノール、イソプロピルアルコール、ｎ－プロピルアルコール、ブタノール等のアルコール系溶剤、或いは前記の溶剤の混合物を使用できる。通常、溶剤系塗料を調整の際に使用する汎用溶剤を用いることができる。 Examples of 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. Usually, a general-purpose solvent used for adjusting the solvent-based paint can be used.
なお、基材フィルム上に直接印刷して上記加飾層を形成した場合、加飾層（印刷層）と基材フィルムとの密着性が不十分となりやすく加飾層の脱落といった問題が発生するおそれがある。このため、基材フィルムと加飾層の間に基材フィルムと加飾層の両者との密着性を有するプライマー層を設けることが好ましい。また、このプライマー層を設けた加飾フィルムを成型用フィルムとして使用する場合、プライマー層の特性として基材フィルムと加飾層の両者との密着性の他、成型時の基材フィルムの伸びに追従する物性（伸び）が良好であることも必要とされる。 In addition, when 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 | occur | produces. There is a fear. For this reason, it is preferable to provide the primer layer which has adhesiveness with both a base film and a decoration layer between a base film and a decoration layer. In addition, when 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 characteristic 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.
本発明において、上記プライマー層は、塩化ビニル－酢酸ビニル共重合樹脂及びポリメチルメタクリレート樹脂を主成分として含有する構成とすることが好ましい。また、この場合、その配合比率（重量部）を、塩化ビニル－酢酸ビニル共重合樹脂／ポリメチルメタクリレート樹脂＝８０／２０～２５／７５の範囲とすることが好ましい。 In the present invention, the primer layer preferably contains vinyl chloride-vinyl acetate copolymer resin and polymethyl methacrylate resin as main components. In this case, the blending ratio (parts by weight) is preferably in the range of vinyl chloride-vinyl acetate copolymer resin / polymethyl methacrylate resin = 80/20 to 25/75.
上記ポリメチルメタクリレート樹脂に対する上記塩化ビニル－酢酸ビニル共重合樹脂の配合比率が８０重量部超では、プライマー層２の乾燥塗膜の耐溶剤性が低下するため、加飾層を形成する塗料（インキなど）に含まれる溶剤（例えばインキ溶剤の代表的な組成：ＮＰＲ（ｎ－プロピルアルコール）／トルエン／酢酸エチル／ＭＥＫ（メチルエチルケトン）＝３０／３０／２０／２０（重量部）など）でプライマー層塗膜が侵食され、加飾性、密着性の低下を生じ易いこと、また耐熱性が低下するため、操業上の問題が生じる場合がある。さらに、成型用フィルムを巻き取った際に圧着あるいはブロッキングなどの問題を発生する。一方、上記ポリメチルメタクリレート樹脂に対する上記塩化ビニル－酢酸ビニル共重合樹脂の配合比率が２５重量部未満では、基材フィルムあるいは加飾層との密着性が低下する。 When the blending ratio of the vinyl chloride-vinyl acetate copolymer resin to the polymethyl methacrylate resin is more than 80 parts by weight, the solvent resistance of the dried coating film of the primer layer 2 is lowered. Etc.) (for example, typical composition of ink solvent: NPR (n-propyl alcohol) / toluene / ethyl acetate / MEK (methyl ethyl ketone) = 30/30/20/20 (parts by weight)) 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. On the other hand, when 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.
上記塩化ビニル－酢酸ビニル共重合樹脂における塩化ビニルと酢酸ビニルとの比率は特に限定されるものではないが、塩化ビニル／酢酸ビニル＝６５／３５～９０／１０（重量部）であることが好ましく、より好ましくは７０／３０～９０／１０（重量部）である。塩化ビニルの比率が低いと、耐熱性の低下による操業上の問題、巻き取った際の圧着、ブロッキングなどの問題が発生する懸念がある。たとえば、塩化ビニルの比率が６５重量部未満では塗膜の硬度低下や耐溶剤性が低下し易くなる問題点がある。一方、上記比率が９０重量部超では柔軟性の低下や耐溶剤性の向上に伴い溶剤への溶解性が低下するため好ましくない。 The ratio of vinyl chloride and vinyl acetate in the vinyl chloride-vinyl acetate copolymer resin is not particularly limited, but is preferably vinyl chloride / vinyl acetate = 65/35 to 90/10 (parts by weight). More preferably, it is 70/30 to 90/10 (parts by weight). When 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. For example, when 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. On the other hand, if 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, such being undesirable.
なお、塩化ビニルと酢酸ビニルとの比率は下記の式Ｉから算出することができる。
［式Ｉ］
　塩化ビニル－酢酸ビニル共重合樹脂のガラス転移温度（Ｔｇ）＝ポリ塩化ビニルのガラス転移温度（８７℃）×塩化ビニルの比率（ａ）＋ポリ酢酸ビニルのガラス転移温度（２９℃）×酢酸ビニルの比率（ｂ＝１－ａ） The ratio between vinyl chloride and vinyl acetate can be calculated from the following formula I.
[Formula I]
Glass transition temperature (Tg) of vinyl chloride-vinyl acetate copolymer resin = glass transition temperature of polyvinyl chloride (87 ° C.) × vinyl chloride ratio (a) + glass transition temperature of polyvinyl acetate (29 ° C.) × vinyl acetate Ratio (b = 1-a)
本発明において、上記塩化ビニル－酢酸ビニル共重合樹脂のガラス転移温度（Ｔｇ）が６５℃以上であることが好ましい。ガラス転移温度が６５℃未満では、耐熱性の低下による操業上の問題、フィルムを巻き取った際の圧着、ブロッキングなどの問題が発生する懸念がある。なお、上記ポリメチルメタクリレート樹脂は、ホモポリマーであり、通常、ガラス転移温度は１０５℃である。 In the present invention, the glass transition temperature (Tg) of the vinyl chloride-vinyl acetate copolymer resin is preferably 65 ° C. or higher. When the glass transition temperature is less than 65 ° C., there are concerns that operational problems due to a decrease in heat resistance, and problems such as pressure bonding and blocking when the film is wound up may occur. The polymethyl methacrylate resin is a homopolymer and usually has a glass transition temperature of 105 ° C.
上記プライマー層には、耐光性の付与を目的にベンゾトリアゾール系或いはベンゾフェノン系等の紫外線吸収剤、塗工性の改善を目的とした各種レベリング剤（フッ素系、シロキサン系、アクリル系等）、光安定剤、静防処理剤、消泡剤、帯電防止剤、難燃剤等を配合することも可能である。また、プライマー層用塗料の溶剤として使用する場合には、トルエン、キシレンなどの芳香族系溶剤、シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン等の脂肪族系溶剤、酢酸エチル、酢酸ブチル等のエステル系溶剤、アセトン、メチルエチルケトン、メチルイソブチルケトン、アノン等のケトン系溶剤、メタノール、エタノール、イソプロピルアルコール、ｎ－プロピルアルコール、ブタノール等のアルコール系溶剤、或いは前記の溶剤の混合物を使用することができる。通常、溶剤系塗料を調整の際に使用する汎用溶剤を用いることができる。 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. In addition, when used as a solvent for primer layer paints, 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 can be used. Usually, a general-purpose solvent used for adjusting the solvent-based paint can be used.
上記プライマー層の形成（成膜）方法としては、グラビア塗工、マイクログラビア塗工、ファウンテンバー塗工、スライドダイ塗工、スロットダイ塗工、スクリーン印刷法等の公知の塗工方式で塗設した後、通常５０～１００℃程度の温度で乾燥する。 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.
上記プライマー層の乾燥後の塗工厚みに関しては、特に限定されないが、通常、０．１μｍから１．０μｍの範囲であることが好ましく、さらに好ましくは０．２μｍから０．５μｍの範囲である。塗工厚みが０．１μｍ未満では、基材フィルムとの密着性の低下や、プライマー層上に加飾層を形成する際、加飾層塗料中の溶剤でプライマー層表層が浸食され密着性の低下を生じ易い問題点がある。一方、塗工厚みが１．０μｍ超では、基材フィルム、加飾層とのより一層の密着性の向上効果は得られず、かえってコスト高となること、また成型用フィルムを延伸の際、白化が生じ易くなるため好ましくない。 The coating thickness of the primer layer after drying is not particularly limited, but it is usually preferably in the range of 0.1 μm to 1.0 μm, more preferably in the range of 0.2 μm to 0.5 μm. When the coating thickness is less than 0.1 μm, 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. On the other hand, if the coating thickness exceeds 1.0 μm, 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.
上記プライマー層には、さらに無機あるいは有機微粒子を配合することは成型用フィルムを巻き取った際の圧着、ブロッキングなどの防止の点から好ましい。その場合、配合量（重量部）は、プライマー層を形成する熱可塑性樹脂／無機或いは有機微粒子＝９９．８／０．２～９５．０／５．０であることが好ましい。上記微粒子の配合量が５．０重量部を超えると透明性の低下や成型用ハードコートフィルムの延伸時に白化が発生し易くなるため好ましくない。一方、上記微粒子の配合量が０．２重量部未満であると十分な効果が発現しない懸念がある。 It is preferable to add inorganic or organic fine particles to the primer layer from the viewpoint of preventing pressure bonding and blocking when the molding film is wound. In this case, the blending amount (parts by weight) is preferably thermoplastic resin / inorganic or organic fine particles forming the primer layer = 99.8 / 0.2 to 95.0 / 5.0. When 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.
無機微粒子としては、アルミナ、酸化亜鉛、シリカ等の微粒子を例示することができ、有機微粒子としては、ポリメチルメタクリレート、メラミン・ホルムアルデヒド縮合物等の微粒子を例示することができる。粒子径としては、例えば０．０８５μｍ～０．５０μｍの微粒子の使用が好ましい。粒子径が０．０８５μｍ未満では、プライマー層面とハードコート層面とを重ねて巻き取った際にブロッキングの発生はないが圧着し易いため好ましくない。一方、粒子径が０．５０μｍ超では、それ以上の圧着或いはブロッキングの防止効果は得られず、かえってコスト高となること、外部ヘイズが高くなり透明性の低下を生じ易くなるため好ましくない。 Examples of the inorganic fine particles include fine particles such as alumina, zinc oxide, and silica, and examples of the organic fine particles include fine particles such as polymethyl methacrylate and melamine / formaldehyde condensate. As the particle diameter, for example, it is preferable to use fine particles of 0.085 μm to 0.50 μm. When the particle diameter is less than 0.085 μm, 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. On the other hand, if the particle diameter is more than 0.50 μm, 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.
　以上説明したように、塩化ビニル－酢酸ビニル共重合樹脂及びポリメチルメタクリレート樹脂を、好ましくは、該塩化ビニル－酢酸ビニル共重合樹脂とポリメチルメタクリレート樹脂との配合比率（重量部）が８０／２０～２５／７５の範囲で含有するプライマー層を設けることにより、該プライマー層は基材フィルムと加飾層の両者との密着性に優れ、該プライマー層を介しての基材フィルムと加飾層との密着性を向上させることができる。また、上記構成によるプライマー層は、成型時の基材フィルムの伸びに追従する物性（伸び）が良好である。 As described above, it is preferable that 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. By providing a primer layer containing in the range of 25/75, 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. Moreover, 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 | molding.
　以下、実施例にて本発明を例証するが、本発明を限定することを意図するものではない。
なお、特に断らない限り、以下に記載する「部」及び「％」は、それぞれ「重量部」及び「重量％」を表す。
　なお、以下で使用するアクリルポリマー系紫外線硬化型樹脂「8BR-500（商品名）」は、重量平均分子量Mw180,000、伸び率はベース基材PETが破断するまでクラックが入らず、鉛筆硬度Ｂであり、前記の条件(a)を満たす重量平均分子量Mwが150,000以上の電離放射線硬化型樹脂に相当する。
　また、多官能モノマー紫外線硬化型樹脂「ビスコートV#802（商品名）」は、重量平均分子量Mw1,100、伸び率4.0％、鉛筆硬度２Ｈであり、前記の条件(b)を満たす重量平均分子量Mwが10,000以下の電離放射線硬化型樹脂に相当する。
　また、ウレタンアクリレート系紫外線硬化型樹脂「RC29‐047（商品名）」は、重量平均分子量Mw1,650、伸び率45.0％、鉛筆硬度Ｈであり、前記の条件(c)を満たす電離放射線硬化型樹脂に相当する。
なお、上記の重量平均分子量Mwは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定した。ＧＰＣ測定の標準サンプルにはポリスチレンを使用した。 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 acrylic polymer UV curable resin “8BR-500 (trade name)” used in the following has a weight average molecular weight Mw 180,000, and the elongation is not cracked until the base substrate PET is broken, and the pencil hardness B It corresponds to an ionizing radiation curable resin having a weight average molecular weight Mw satisfying the above condition (a) of 150,000 or more.
The polyfunctional monomer UV curable resin “Biscoat V # 802 (trade name)” has a weight average molecular weight Mw of 1,100, an elongation of 4.0% and a pencil hardness of 2H, and satisfies the above condition (b). Corresponds to ionizing radiation curable resin with Mw of 10,000 or less.
The urethane acrylate UV curable resin “RC29-047 (trade name)” has a weight average molecular weight Mw of 1,650, an elongation of 45.0% and a pencil hardness of H, and satisfies the above condition (c). Corresponds to resin.
In addition, said weight average molecular weight Mw was measured by the gel permeation chromatography (GPC). Polystyrene was used as a standard sample for GPC measurement.
[実施例１－１]
＜塗料調製＞
アクリルポリマー系紫外線硬化型樹脂「8BR-500（商品名）」（固形分37％、大成ファインケミカル製）50部と、多官能モノマー系紫外線硬化型樹脂「V#802（商品名）」（固形分100％、大阪有機製）5部と、ウレタンアクリレート系紫外線硬化型樹脂「RC29-047(商品名)」（固形分75％、ＤＩＣ社製）45部を主剤とし、イルガキュア１８４（光重合開始剤、ＢＡＳＦ製）5部と、ヒンダードアミン系化合物「TINUVIN 770DF（商品名）」（ＢＡＳＦ製）0.5部と、ヒドロキシフェニルトリアジン系化合物「TINUVIN479（商品名）」（ＢＡＳＦ製）0.5部と、アルミニウムを主成分とした微粒子「ALMIBK H06（商品名）」（平均粒径13nm、CIKナノテック製）の対固形分3%を酢酸ブチル/n-プロピルアルコール＝50/50（重量％）で紫外線硬化型樹脂の塗料中の固形分濃度が16％となるまで希釈し十分攪拌してハードコート層塗料を調製した。
＜ハードコートフィルム作製＞
伸び試験用として厚さ125μｍのＰＥＴフィルム「Ａ4350（商品名）」（東レ製）の一方の面に上記塗料をバーコーターで塗工し、80℃で１分間熱風乾燥した後、紫外線光量450ｍＪ/ｃｍ２で硬化させた。得られた塗膜の厚さは1.5μｍであった。
次いで、鉛筆硬度、耐擦傷性試験用として厚さ125μｍのＰＭＭＡフィルム（住友製）の一方の面に上記塗料をバーコーターで塗工し、80℃で１分間熱風乾燥した後、紫外線光量450ｍＪ/cｍ２で硬化させた。得られた塗膜の厚さは1.5μｍであった。 [Example 1-1]
<Preparation of paint>
50 parts of acrylic polymer UV curable resin “8BR-500 (trade name)” (solid content 37%, manufactured by Taisei Fine Chemical) and polyfunctional monomer UV curable resin “V # 802 (trade name)” (solid content) Irgacure 184 (photopolymerization initiator) with 5 parts of urethane acrylate UV curable resin “RC29-047 (trade name)” (solid content 75%, manufactured by DIC) 45 parts Mainly aluminum, 5 parts, hindered amine compound “TINUVIN 770DF (trade name)” (BASF) 0.5 part, hydroxyphenyl triazine compound “TINUVIN479 (trade name)” (BASF) 0.5 part, and aluminum 3% solid content of the fine particle “ALMIBK H06 (trade name)” (average particle size 13 nm, manufactured by CIK Nanotech) as a component of butyl acetate / n-propyl alcohol = 50/50 (wt%) of UV curable resin Solid content concentration in paint is 16% To prepare a hard coat layer paint in diluted sufficiently stirring.
<Hard coat film production>
For elongation test, apply the above paint on one side of 125μm thick PET film “A4350 (trade name)” (manufactured by Toray) with a bar coater and dry with hot air at 80 ° C. for 1 minute. and cured at cm 2. The thickness of the obtained coating film was 1.5 μm.
Next, the above coating was applied to one side of a 125 μm-thick PMMA film (manufactured by Sumitomo) for pencil hardness and scratch resistance testing using a bar coater, dried with hot air at 80 ° C. for 1 minute, and an ultraviolet light intensity of 450 mJ / and cured at cm 2. The thickness of the obtained coating film was 1.5 μm.
 [実施例１－２] 
＜塗料調製＞
アクリルポリマー系紫外線硬化型樹脂「8BR-500（商品名）」（固形分37％、大成ファインケミカル製）50部と、多官能モノマー系紫外線硬化型樹脂「V#802（商品名）」（固形分100％、大阪有機製）10部と、ウレタンアクリレート系紫外線硬化型樹脂「RC29-047(商品名)」（固形分75％、ＤＩＣ製）40部を主剤とし、他の添加剤は実施例１－１に準じて調製した。
＜ハードコートフィルム作製＞
上記塗料を用いて実施例１－１と同様にして伸び試験用と鉛筆硬度、耐擦傷性用ハードコートフィルムを作製した。 [Example 1-2]
<Preparation of paint>
50 parts of acrylic polymer UV curable resin “8BR-500 (trade name)” (solid content 37%, manufactured by Taisei Fine Chemical) and polyfunctional monomer UV curable resin “V # 802 (trade name)” (solid content) 100 parts, made by Osaka Organic Chemical Co., Ltd.) and 40 parts urethane acrylate UV curable resin “RC29-047 (trade name)” (solid content 75%, made by DIC). It was prepared according to -1.
<Hard coat film production>
Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was produced in the same manner as in Example 1-1.
 [実施例１－３] 
＜塗料調製＞
アクリルポリマー系紫外線硬化型樹脂「8BR-500（商品名）」（固形分37％、大成ファインケミカル製）50部と、多官能モノマー系紫外線硬化型樹脂「V#802（商品名）」（固形分100％、大阪有機製）15部と、ウレタンアクリレート系紫外線硬化型樹脂「RC29-047(商品名)」（固形分75％、ＤＩＣ製）35部を主剤とし、他の添加剤は実施例１－１に準じて調製した。
＜ハードコートフィルム作製＞
上記塗料を用いて実施例１－１と同様にして伸び試験用と鉛筆硬度、耐擦傷性用ハードコートフィルムを作製した。 [Example 1-3]
<Preparation of paint>
50 parts of acrylic polymer UV curable resin “8BR-500 (trade name)” (solid content 37%, manufactured by Taisei Fine Chemical) and polyfunctional monomer UV curable resin “V # 802 (trade name)” (solid content) 100 parts, made by Osaka Organic Co., Ltd.) and 15 parts urethane acrylate UV curable resin “RC29-047 (trade name)” (solid content 75%, made by DIC). It was prepared according to -1.
<Hard coat film production>
Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was produced in the same manner as in Example 1-1.
 [比較例１－１] 
＜塗料調製＞
アクリルポリマー系紫外線硬化型樹脂「8BR-500（商品名）」（固形分37％、大成ファインケミカル製）100部を主剤とし、他の添加剤は実施例１－１に準じて調製した。
＜ハードコートフィルム作製＞
上記塗料を用いて実施例１－１と同様にして伸び試験用と鉛筆硬度、耐擦傷性用ハードコートフィルムを作製した。 [Comparative Example 1-1]
<Preparation of paint>
The main component was 100 parts of an acrylic polymer UV curable resin “8BR-500 (trade name)” (solid content 37%, manufactured by Taisei Fine Chemical), and other additives were prepared according to Example 1-1.
<Hard coat film production>
Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was produced in the same manner as in Example 1-1.
 [比較例１－２] 
＜塗料調製＞
多官能モノマー系紫外線硬化型樹脂「V#802（商品名）」（固形分100％、大阪有機製）100部を主剤とし、他の添加剤は実施例１－１に準じて調製した。
＜ハードコートフィルム作製＞
上記塗料を用いて実施例１－１と同様にして伸び試験用と鉛筆硬度、耐擦傷性用ハードコートフィルムを作製した。 [Comparative Example 1-2]
<Preparation of paint>
The main component was 100 parts of a polyfunctional monomer-based UV curable resin “V # 802 (trade name)” (100% solid content, manufactured by Osaka Organic Chemicals), and other additives were prepared according to Example 1-1.
<Hard coat film production>
Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was produced in the same manner as in Example 1-1.
 [比較例１－３] 
＜塗料調製＞
ウレタンアクリレート系紫外線硬化型樹脂「RC29-047(商品名)」（固形分75％、ＤＩＣ製）100部を主剤とし、他の添加剤は実施例１－１に準じて調製した。
＜ハードコートフィルム作製＞
上記塗料を用いて実施例１－１と同様にして伸び試験用と鉛筆硬度、耐擦傷性用ハードコートフィルムを作製した。 [Comparative Example 1-3]
<Preparation of paint>
The main component was 100 parts of a urethane acrylate UV curable resin “RC29-047 (trade name)” (solid content: 75%, manufactured by DIC), and other additives were prepared according to Example 1-1.
<Hard coat film production>
Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was produced in the same manner as in Example 1-1.
 [比較例１－４] 
＜塗料調製＞
アクリルポリマー系紫外線硬化型樹脂「8BR-500（商品名）」（固形分37％、大成ファインケミカル製）70部と、多官能モノマー系紫外線硬化型樹脂「V#802（商品名）」（固形分100％、大阪有機製）30部を主剤とし、他の添加剤は実施例１－１に準じて調製した。
＜ハードコートフィルム作製＞
上記塗料を用いて実施例１－１と同様にして伸び試験用と鉛筆硬度、耐擦傷性用ハードコートフィルムを作製した。 [Comparative Example 1-4]
<Preparation of paint>
70 parts of acrylic polymer UV curable resin “8BR-500 (trade name)” (solid content 37%, manufactured by Taisei Fine Chemical) and polyfunctional monomer UV curable resin “V # 802 (trade name)” (solid content) 100 parts, manufactured by Osaka Organic Chemical Co., Ltd.) was used as a main ingredient, and other additives were prepared according to Example 1-1.
<Hard coat film production>
Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was produced in the same manner as in Example 1-1.
[比較例１－５] 
＜塗料調製＞
アクリルポリマー系紫外線硬化型樹脂「8BR-500（商品名）」（固形分37％、大成ファインケミカル製）65部と、多官能モノマー系紫外線硬化型樹脂「V#802（商品名）」（固形分100％、大阪有機製）35部を主剤とし、他の添加剤は実施例１－１に準じて調製した。
＜ハードコートフィルム作製＞
上記塗料を用いて実施例１－１と同様にして伸び試験用と鉛筆硬度、耐擦傷性用ハードコートフィルムを作製した。 [Comparative Example 1-5]
<Preparation of paint>
65 parts of acrylic polymer UV curable resin “8BR-500 (trade name)” (solid content 37%, manufactured by Taisei Fine Chemical) and polyfunctional monomer UV curable resin “V # 802 (trade name)” (solid content) 100 parts, manufactured by Osaka Organic Chemical Co., Ltd.) was 35 parts, and the other additives were prepared according to Example 1-1.
<Hard coat film production>
Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was produced in the same manner as in Example 1-1.
[比較例１－６] 
＜塗料調製＞
アクリルポリマー系紫外線硬化型樹脂「8BR-500（商品名）」（固形分37％、大成ファインケミカル製）60部と、多官能モノマー系紫外線硬化型樹脂「V#802（商品名）」（固形分100％、大阪有機製）40部を主剤とし、他の添加剤は実施例１－１に準じて調製した。
＜ハードコートフィルム作製＞
上記塗料を用いて実施例１－１と同様にして伸び試験用と鉛筆硬度、耐擦傷性用ハードコートフィルムを作製した。 [Comparative Example 1-6]
<Preparation of paint>
Acrylic polymer UV curable resin "8BR-500 (trade name)" (solid content 37%, manufactured by Taisei Fine Chemical) 60 parts, and polyfunctional monomer UV curable resin "V # 802 (trade name)" (solid content (100%, made by Osaka Organic Chemical Co., Ltd.) 40 parts were used as the main agent, and the other additives were prepared according to Example 1-1.
<Hard coat film production>
Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was produced in the same manner as in Example 1-1.
以上のようにして作製された実施例及び比較例のハードコートフィルムを次の項目について評価し、その結果を纏めて表１に示した。
（１）鉛筆硬度
　ＪＩＳ　Ｋ５６００に示される試験法により鉛筆硬度を測定した。
（２）成型性（伸び率）
　前述の伸び試験用のハードコートフィルムを使用し、サンプルサイズ幅１５ｍｍ×長さ１５０ｍｍの試験片を作製する。引張速度５０ｍｍ／分、チャック間距離１００ｍｍで引張り、表面のハードコート層にクラックが入るまでの引張伸度を測定した。
（３）耐擦傷性
　堅牢度試験機（テスター産業製）により、ハードコート層の磨耗及び摩擦に対する堅牢性試験を行った。ＰＭＭＡフィルム上に塗工されたハードコート層とスチールウール#0000を荷重１０２g/cm2×１０往復にて互いに摩擦し、試験前と後のヘイズ値の差を測定した（以下「ΔHaze」と略記する。）。なお、上記ヘイズ値は、村上色彩技術研究所製ヘイズメーター「ＨＭ１５０」を用いて測定した。
　ΔHaze＝（耐擦傷性試験後のヘイズ値）－（耐擦傷性試験前のヘイズ値）
　上記ΔHazeが低い方がハードコート表層の傷が少ないことを示す。 The hard coat films of Examples and Comparative Examples produced as described above were evaluated for the following items, and the results are summarized in Table 1.
(1) Pencil hardness Pencil hardness was measured by the test method shown in JIS K5600.
(2) 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.
(3) Scratch resistance A fastness test against abrasion and friction of the hard coat layer was performed by a fastness tester (manufactured by Tester Sangyo). The hard coat layer coated on the PMMA film and steel wool # 0000 were rubbed against each other with a load of 102 g / cm 2 × 10, and the difference between the haze values before and after the test was measured (hereinafter abbreviated as “ΔHaze”). To do.) The haze value was measured using a haze meter “HM150” manufactured by Murakami Color Research Laboratory.
ΔHaze = (Haze value after scratch resistance test) − (Haze value before scratch resistance test)
A lower ΔHaze indicates less scratches on the hard coat surface.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
上記表１の結果から明らかなように、ハードコート層の樹脂成分として特定の電離放射線硬化型樹脂３成分を使用した本発明の実施例によれば、成型性（伸び率）と表面硬度（鉛筆硬度）、耐擦傷性のいずれの特性も良好な成型用ハードコートフィルムが得られる。
　これに対し、ハードコート層の樹脂成分として前記電離放射線硬化型樹脂のいずれかを単独で使用した比較例１－１～１－３では、成型性（伸び率）と表面硬度、耐擦傷性のうちの少なくともいずれかの特性が不良であり、これらの特性をすべて向上させることが困難である。さらに、ハードコート層の樹脂成分として前記電離放射線硬化型樹脂３成分のうちの２成分を使用した比較例１－４～１－６においても、成型性（伸び率）と表面硬度、耐擦傷性の特性をすべて向上させることが困難である。
　つまり、本発明のように、ハードコート層の樹脂成分として特定の電離放射線硬化型樹脂３成分を使用することによってはじめて、成型性（伸び率）と表面硬度（鉛筆硬度）、耐擦傷性のいずれの特性も向上させた成型用ハードコートフィルムが得られるわけである。 As is apparent from the results in Table 1 above, according to the embodiment of the present invention using the specific ionizing radiation curable resin 3 component as the resin component of the hard coat layer, moldability (elongation rate) and surface hardness (pencil) Hardness film for molding and a hard coat film for molding having good scratch resistance can be obtained.
In contrast, in Comparative Examples 1-1 to 1-3 in which any one of the ionizing radiation curable resins is used alone as the resin component of the hard coat layer, the moldability (elongation rate), surface hardness, and scratch resistance are improved. At least one of these characteristics is defective, and it is difficult to improve all of these characteristics. Further, in Comparative Examples 1-4 to 1-6 in which two of the three components of the ionizing radiation curable resin are used as the resin component of the hard coat layer, moldability (elongation rate), surface hardness, and scratch resistance It is difficult to improve all the characteristics.
That is, as in the present invention, only by using a specific ionizing radiation curable resin 3 component as the resin component of the hard coat layer, any of moldability (elongation rate), surface hardness (pencil hardness), and scratch resistance can be obtained. Therefore, a molding hard coat film with improved properties can be obtained.
［実施例２－１］
＜塗料調製＞
　アクリルポリマー系紫外線硬化性樹脂「8BR-500（商品名）」（固形分37％、大成ファインケミカル製）50部と多官能モノマー系紫外線硬化性樹脂「V#802（商品名）」（固形分100％、大阪有機製）5部、ウレタンアクリレート系紫外線硬化性樹脂「RC29-047(商品名)」（固形分75％、ＤＩＣ製）45部を主剤とし、イルガキュア１８４（光重合開始剤、ＢＡＳＦ製）5部と、ヒンダードアミン系化合物「TINUVIN770DF（商品名）」（ＢＡＳＦ製）0.5部と、ヒドロキシフェニルトリアジン系化合物「TINUVIN479（商品名）」（ＢＡＳＦ製）0.5部と、フッ素シロキサン系樹脂「RS922（商品名）」（ＤＩＣ製）0.7部とアルミニウムを主成分とした微粒子「ALMIBKH06（商品名）」（平均粒径13nm、CIKナノテック製）の対固形分3%を酢酸ブチル/n-プロピルアルコール＝50/50（重量％）で紫外線硬化性樹脂の塗料中の固形分濃度が16％となるまで希釈し十分攪拌してハードコート層塗料を調製した。
＜ハードコートフィルム作製＞
　伸び試験用として厚さ125μｍのＰＥＴフィルム「Ａ4350（商品名）」（東レ製）の一方の面に上記塗料をバーコーターで塗工し、80℃で１分間熱風乾燥した後、紫外線光量450ｍＪ/cm２で硬化させた。得られた塗膜の厚さは1.5μｍであった。次いで、鉛筆硬度、耐擦傷性試験用として厚さ125μｍのＰＭＭＡフィルム（住友製）の一方の面に上記塗料をバーコーターで塗工し、80℃で１分間熱風乾燥した後、紫外線光量450ｍＪ/cm２で硬化させた。得られた塗膜の厚さは1.5μｍであった。 [Example 2-1]
<Preparation of paint>
50 parts of acrylic polymer UV curable resin “8BR-500 (trade name)” (solid content 37%, manufactured by Taisei Fine Chemical) and polyfunctional monomer UV curable resin “V # 802 (trade name)” (solid content 100) %, Osaka Organic) 5 parts, urethane acrylate UV curable resin “RC29-047 (trade name)” (solid content 75%, made by DIC) 45 parts, Irgacure 184 (photopolymerization initiator, made by BASF) ) 5 parts, 0.5 part of hindered amine compound “TINUVIN770DF (trade name)” (manufactured by BASF), 0.5 part of hydroxyphenyl triazine compound “TINUVIN479 (trade name)” (manufactured by BASF), and fluorosiloxane resin “RS922” (Trade name) ”(manufactured by DIC) 0.7 parts and aluminum fine particles“ ALMIBKH06 (trade name) ”(average particle size 13 nm, manufactured by CIK NANOTECH) 3% solid content in butyl acetate / n-propyl alcohol = 50/50 (wt%) The hard coat layer paint was prepared by diluting until the solid content concentration in the paint of the UV curable resin was 16% and stirring sufficiently.
<Hard coat film production>
For elongation test, apply the above paint on one side of 125μm thick PET film “A4350 (trade name)” (manufactured by Toray) with a bar coater and dry with hot air at 80 ° C. for 1 minute. and cured at cm 2. The thickness of the obtained coating film was 1.5 μm. Next, the above coating was applied to one side of a 125 μm-thick PMMA film (manufactured by Sumitomo) for pencil hardness and scratch resistance testing using a bar coater, dried with hot air at 80 ° C. for 1 minute, and an ultraviolet light intensity of 450 mJ / and cured at cm 2. The thickness of the obtained coating film was 1.5 μm.
[実施例２－２] 
＜塗料調製＞
　アクリルポリマー系紫外線硬化性樹脂「8BR-500（商品名）」（固形分37％、大成ファインケミカル製）50部と多官能モノマー系紫外線硬化性樹脂「V#802（商品名）」（固形分100％、大阪有機製）10部、ウレタンアクリレート系紫外線硬化性樹脂「RC29-047(商品名)」（固形分75％、ＤＩＣ製）40部を主剤とし、他の添加剤は実施例２－１に準じて調製した。
＜ハードコートフィルム作製＞
上記塗料を用いて実施例２－１と同様にしてハードコートフィルムを作製した。 [Example 2-2]
<Preparation of paint>
50 parts of acrylic polymer UV curable resin “8BR-500 (trade name)” (solid content 37%, manufactured by Taisei Fine Chemical) and polyfunctional monomer UV curable resin “V # 802 (trade name)” (solid content 100) 10 parts urethane acrylate UV curable resin “RC29-047 (trade name)” (solid content 75%, made by DIC) 40 parts, the other additives are Example 2-1 It was prepared according to
<Hard coat film production>
A hard coat film was produced in the same manner as in Example 2-1, using the coating material.
[実施例２－３]
＜塗料調製＞
アクリルポリマー系紫外線硬化性樹脂「8BR-500（商品名）」（固形分37％、大成ファインケミカル製）50部と多官能モノマー系紫外線硬化性樹脂「V#802（商品名）」（固形分100％、大阪有機製）15部、ウレタンアクリレート系紫外線硬化性樹脂「RC29-047(商品名)」（固形分75％、ＤＩＣ製）35部を主剤とし、他の添加剤は実施例２－１に準じて調製した。
＜ハードコートフィルム作製＞
上記塗料を用いて実施例２－１と同様にしてハードコートフィルムを作製した。 [Example 2-3]
<Preparation of paint>
50 parts of acrylic polymer UV curable resin “8BR-500 (trade name)” (solid content 37%, manufactured by Taisei Fine Chemical) and polyfunctional monomer UV curable resin “V # 802 (trade name)” (solid content 100) %, Manufactured by Osaka Organic Chemical Co., Ltd.), 15 parts, urethane acrylate UV curable resin “RC29-047 (trade name)” (solid content 75%, manufactured by DIC) 35 parts, and other additives are Example 2-1 It was prepared according to
<Hard coat film production>
A hard coat film was produced in the same manner as in Example 2-1, using the coating material.
[実施例２－４] 
＜塗料調製＞
　フッ素シロキサン系樹脂「RS922（商品名）」（ＤＩＣ製）0.10部添加し、他の添加剤及び樹脂は実施例２－２に準じて調製した。
＜ハードコートフィルム作製＞
　上記塗料を用いて実施例２－１と同様にしてハードコートフィルムを作製した。 [Example 2-4]
<Preparation of paint>
0.10 parts of fluorosiloxane resin “RS922 (trade name)” (manufactured by DIC) was added, and other additives and resins were prepared according to Example 2-2.
<Hard coat film production>
A hard coat film was produced in the same manner as in Example 2-1, using the coating material.
[実施例２－５] 
＜塗料調製＞
　フッ素シロキサン系樹脂「RS922（商品名）」（ＤＩＣ製）0.50部添加し、他の添加剤及び樹脂は実施例２－１に準じて調製した。
＜ハードコートフィルム作製＞
　上記塗料を用いて実施例２－１と同様にしてハードコートフィルムを作製した。 [Example 2-5]
<Preparation of paint>
0.50 part of a fluorosiloxane-based resin “RS922 (trade name)” (manufactured by DIC) was added, and other additives and resins were prepared according to Example 2-1.
<Hard coat film production>
A hard coat film was produced in the same manner as in Example 2-1, using the coating material.
[実施例２－６] 
＜塗料調製＞
　フッ素シロキサン系樹脂「RS922（商品名）」（ＤＩＣ製）1.4部添加し、他の添加剤及び樹脂は実施例２－２に準じて調製した。
＜ハードコートフィルム作製＞
　上記塗料を用いて実施例２－１と同様にしてハードコートフィルムを作製した。 [Example 2-6]
<Preparation of paint>
1.4 parts of fluorosiloxane resin “RS922 (trade name)” (manufactured by DIC) was added, and other additives and resins were prepared according to Example 2-2.
<Hard coat film production>
A hard coat film was produced in the same manner as in Example 2-1, using the coating material.
[実施例２－７] 
＜塗料調製＞
　フッ素系樹脂「RS75（商品名）」（ＤＩＣ製）0.4部、シロキサン系樹脂「RS576（商品名）」（ＤＩＣ製）0.3部を混合、添加した。他の添加剤及び樹脂は実施例２－２に準じて調製した。
＜ハードコートフィルム作製＞
　上記塗料を用いて実施例２－１と同様にしてハードコートフィルムを作製した。 [Example 2-7]
<Preparation of paint>
0.4 parts of fluororesin “RS75 (trade name)” (manufactured by DIC) and 0.3 part of siloxane resin “RS576 (trade name)” (manufactured by DIC) were mixed and added. Other additives and resins were prepared according to Example 2-2.
<Hard coat film production>
A hard coat film was produced in the same manner as in Example 2-1, using the coating material.
[実施例２－８] 
＜塗料調製＞
　フッ素系樹脂「RS75（商品名）」（ＤＩＣ製）0.2部、シロキサン系樹脂「RS576（商品名）」（ＤＩＣ製）0.5部を混合、添加した。他の添加剤及び樹脂は実施例２－２に準じて調製した。
＜ハードコートフィルム作製＞
　上記塗料を用いて実施例２－１と同様にしてハードコートフィルムを作製した。 [Example 2-8]
<Preparation of paint>
Fluorine resin “RS75 (trade name)” (manufactured by DIC) 0.2 part and siloxane resin “RS576 (trade name)” (manufactured by DIC) 0.5 part were mixed and added. Other additives and resins were prepared according to Example 2-2.
<Hard coat film production>
A hard coat film was produced in the same manner as in Example 2-1, using the coating material.
[比較例２－１] 
＜塗料調製＞
　アクリルポリマー系紫外線硬化性樹脂「8BR-500（商品名）」（固形分37％、大成ファインケミカル製）100部を主剤とし、他の添加剤は実施例２－１に準じて調製した。
＜ハードコートフィルム作製＞
上記塗料を用いて実施例２－１と同様にして伸び試験用と鉛筆硬度、耐擦傷性用ハードコートフィルムを作製した。 [Comparative Example 2-1]
<Preparation of paint>
The main component was 100 parts of an acrylic polymer UV curable resin “8BR-500 (trade name)” (solid content 37%, manufactured by Taisei Fine Chemical), and other additives were prepared according to Example 2-1.
<Hard coat film production>
Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was produced in the same manner as in Example 2-1.
[比較例２－２] 
＜塗料調製＞
　多官能モノマー系紫外線硬化性樹脂「V#802（商品名）」（固形分100％、大阪有機製）100部を主剤とし、他の添加剤は実施例２－１に準じて調製した。
＜ハードコートフィルム作製＞
　上記塗料を用いて実施例２－１と同様にして用ハードコートフィルムを作製した。 [Comparative Example 2-2]
<Preparation of paint>
The main component was 100 parts of a polyfunctional monomer-based ultraviolet curable resin “V # 802 (trade name)” (100% solid content, manufactured by Osaka Organic Chemicals), and other additives were prepared according to Example 2-1.
<Hard coat film production>
A hard coat film was prepared in the same manner as in Example 2-1, using the coating material.
[比較例２－３] 
＜塗料調製＞
　ウレタンアクリレート系紫外線硬化性樹脂「RC29-047(商品名)」（固形分75％、ＤＩＣ製）100部を主剤とし、他の添加剤は実施例２－１に準じて調製した。
＜ハードコートフィルム作製＞
　上記塗料を用いて実施例２－１と同様にしてハードコートフィルムを作製した。 [Comparative Example 2-3]
<Preparation of paint>
The main component was 100 parts of a urethane acrylate UV curable resin “RC29-047 (trade name)” (solid content: 75%, manufactured by DIC), and other additives were prepared according to Example 2-1.
<Hard coat film production>
A hard coat film was produced in the same manner as in Example 2-1, using the coating material.
[比較例２－４] 
＜塗料調製＞
　アクリルポリマー系紫外線硬化性樹脂「8BR-500（商品名）」（固形分37％、大成ファインケミカル製）50部と多官能モノマー系紫外線硬化性樹脂「V#802（商品名）」（固形分100％、大阪有機製）10部、ウレタンアクリレート系紫外線硬化性樹脂「RC29-047(商品名)」（固形分75％、ＤＩＣ製）40部を主剤とし、他の添加剤はアルミニウムを主成分とした微粒子「ALMIBKH06（商品名）」を除き、実施例２－１に準じて調製した。
＜ハードコートフィルム作製＞
　上記塗料を用いて実施例２－１と同様にしてハードコートフィルムを作製した。 [Comparative Example 2-4]
<Preparation of paint>
50 parts of acrylic polymer UV curable resin “8BR-500 (trade name)” (solid content 37%, manufactured by Taisei Fine Chemical) and polyfunctional monomer UV curable resin “V # 802 (trade name)” (solid content 100) %, Osaka Organic) 10 parts, urethane acrylate UV curable resin "RC29-047 (trade name)" (solid content 75%, made by DIC) 40 parts, the other additives are mainly aluminum Except for the microparticles “ALMIBKH06 (trade name)”, it was prepared according to Example 2-1.
<Hard coat film production>
A hard coat film was produced in the same manner as in Example 2-1, using the coating material.
[比較例２－５] 
＜塗料調製＞
　フッ素シロキサン系樹脂「RS922（商品名）」（ＤＩＣ製）を添加せずに実施例２－２に準じて調製した。
＜ハードコートフィルム作製＞
　上記塗料を用いて実施例２－１と同様にしてハードコートフィルムを作製した。 [Comparative Example 2-5]
<Preparation of paint>
It was prepared according to Example 2-2 without adding the fluorosiloxane resin “RS922 (trade name)” (manufactured by DIC).
<Hard coat film production>
A hard coat film was produced in the same manner as in Example 2-1, using the coating material.
［比較例２－６］
＜塗料調製＞
　フッ素シロキサン系樹脂「RS922（商品名）」（ＤＩＣ製）0.05部添加し、他の添加剤及び樹脂は実施例２－２に準じて調製した。
＜ハードコートフィルム作製＞
　上記塗料を用いて実施例２－１と同様にしてハードコートフィルムを作製した。 [Comparative Example 2-6]
<Preparation of paint>
0.05 part of fluorosiloxane resin “RS922 (trade name)” (manufactured by DIC) was added, and other additives and resins were prepared according to Example 2-2.
<Hard coat film production>
A hard coat film was produced in the same manner as in Example 2-1, using the coating material.
[比較例２－７] 
＜塗料調製＞
　フッ素系樹脂「RS75（商品名）」（ＤＩＣ製）0.7部を添加した。他の添加剤及び樹脂は実施例２－２に準じて調製した。
＜ハードコートフィルム作製＞
　上記塗料を用いて実施例２－１と同様にしてハードコートフィルムを作製した。 [Comparative Example 2-7]
<Preparation of paint>
0.7 parts of fluororesin “RS75 (trade name)” (manufactured by DIC) was added. Other additives and resins were prepared according to Example 2-2.
<Hard coat film production>
A hard coat film was produced in the same manner as in Example 2-1, using the coating material.
[比較例２－８] 
＜塗料調製＞
シロキサン系樹脂「RS576（商品名）」（ＤＩＣ製）0.7部を添加した。他の添加剤及び樹脂は実施例２－２に準じて調製した。
＜ハードコートフィルム作製＞
　上記塗料を用いて実施例２－１と同様にしてハードコートフィルムを作製した。 [Comparative Example 2-8]
<Preparation of paint>
0.7 parts of siloxane-based resin “RS576 (trade name)” (manufactured by DIC) was added. Other additives and resins were prepared according to Example 2-2.
<Hard coat film production>
A hard coat film was produced in the same manner as in Example 2-1, using the coating material.
　以上のようにして作製された実施例及び比較例のハードコートフィルムを次の項目について評価し、その結果を纏めて表２に示した。
（１）鉛筆硬度
　前記と同じ方法。
（２）成型性（伸び率）
　前記と同じ方法。
（３）耐擦傷性
　前記と同じ方法。 The hard coat films of Examples and Comparative Examples produced as described above were evaluated for the following items, and the results are summarized in Table 2.
(1) Pencil hardness Same method as above.
(2) Formability (elongation rate)
Same method as above.
(3) Scratch resistance Same method as above.
（４）防汚性
　ＪＩＳ Ｋ5500に準じて、成型用ハードコートフィルムのハードコート層に対する水の接触角を測定した。なお、接触角が大きいほど水系の汚れに対して有効である。
　また、成型用ハードコートフィルムのハードコート層面のマジックインキ（寺西化学工業製）に対するハジキ性を油系の汚れに対する評価とした。なお、ハジキ性は、成型用ハードコートフィルムのハードコート層面に、マジックインキ（寺西化学工業製）を用いて、筆記し、次の基準で目視評価を行った。
　　はじく ◎ ＞ ○ （実用上問題ないレベル）＞ △＞× はじかない
（５）易滑性
　表面測定器（HEIDON製、試験片寸法は27mm×65mm、500gの荷重）により、動摩擦係数μを測定した。
（６）ROD TEST
　引掻き式硬度計（ERICHSEN318、荷重：3N）で測定した後のヘコミ具合を次の基準で目視評価した。
　　ヘコミ無し ◎ ＞ ○（実用上問題ないレベル） ＞ △ ＞ × ヘコミあり (4) Antifouling property According to JIS K5500, the contact angle of water with respect to the hard coat layer of the molding hard coat film was measured. Note that the larger the contact angle, the more effective against water-based dirt.
Moreover, the repellency with respect to the magic ink (made by Teranishi Chemical Industry) of the hard coat layer surface of the hard coat film for molding was evaluated as an oil stain. The repelling property was written on the hard coat layer surface of the molding hard coat film using magic ink (manufactured by Teranishi Chemical Industry) and visually evaluated according to the following criteria.
Flip ◎> ○ (Practically no problem level)>△> × Does not repel (5) Easiness of sliding Measure the coefficient of dynamic friction μ with a surface measuring instrument (made by HEIDON, test piece dimensions are 27 mm × 65 mm, 500 g load) .
(6) ROD TEST
The degree of dent after measurement with a scratch hardness tester (ERICHSEN318, load: 3N) was visually evaluated according to the following criteria.
No dent ◎> ○ (Practical level) △ △> × With dent
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
上記表２の結果から明らかなように、ハードコート層の樹脂成分として特定の電離放射線硬化型樹脂の３成分にフッ素シロキサン系樹脂を混合させた樹脂を使用した本発明の実施例によれば、成型性（伸び率）と表面硬度（鉛筆硬度）、防汚性、易滑性、耐擦傷性のいずれの特性も良好な成型用ハードコートフィルムが得られる。
　これに対し、ハードコート層の樹脂成分として前記電離放射線硬化型樹脂のいずれかを単独で使用した比較例では、成型性（伸び率）と表面硬度、防汚性、易滑性、耐擦傷性のうちの少なくともいずれかの特性が不良であり、これらの特性をすべて向上させることが困難である。
  As is apparent from the results of Table 2 above, according to the examples of the present invention using a resin obtained by mixing a fluorosiloxane resin with three components of a specific ionizing radiation curable resin as the resin component of the hard coat layer, A molding hard coat film having excellent moldability (elongation rate), surface hardness (pencil hardness), antifouling property, slipperiness and scratch resistance can be obtained.
On the other hand, in the comparative example using any of the ionizing radiation curable resins alone as the resin component of the hard coat layer, moldability (elongation rate), surface hardness, antifouling property, slipperiness, scratch resistance At least one of these characteristics is defective, and it is difficult to improve all of these characteristics.

Claims (7)

  1. 　基材フィルム上に、下記条件(a)を満たす重量平均分子量Mwが150,000以上の電離放射線硬化型樹脂、下記条件(b)を満たす重量平均分子量Mwが10,000以下の電離放射線硬化型樹脂、および下記条件(c)を満たす電離放射線硬化型樹脂を混合させた樹脂を含有する塗料組成物を塗工し硬化させてなるハードコート層を設けたことを特徴とする成型用ハードコートフィルム。
    　条件(a)：ポリエチレンテレフタレートフィルム上に、紫外線光量50～1000mJ/cm2で硬化させた電離放射線硬化型樹脂の1.5μｍの塗膜を形成させたフィルムを作製する。次に、当該作製したフィルムから、幅１５ｍｍ×長さ１５０ｍｍの試験片を作製し、温度２５℃、湿度５０％ＲＨの環境下で、当該試験片を引張速度５０ｍｍ／分にて引張った際に、前記塗膜にクラックが入るまでの伸び率が５０％以上で、かつ、JIS K5600に規定される鉛筆硬度がB～Hである。
    　条件(b)：ポリエチレンテレフタレートフィルム上に、紫外線光量50～1000mJ/cm2で硬化させた電離放射線硬化型樹脂の1.5μｍの塗膜を形成させたフィルムを作製する。次に、当該作製したフィルムから、幅１５ｍｍ×長さ１５０ｍｍの試験片を作製し、温度２５℃、湿度５０％ＲＨの環境下で、当該試験片を引張速度５０ｍｍ／分にて引張った際に、前記塗膜にクラックが入るまでの伸び率が１％以上で、かつ、JIS K5600に規定される鉛筆硬度がH～4Hである。
    　条件(c)：ポリエチレンテレフタレートフィルム上に、紫外線光量50～1000mJ/cm2で硬化させた電離放射線硬化型樹脂の1.5μｍの塗膜を形成させたフィルムを作製する。次に、当該作製したフィルムから、幅１５ｍｍ×長さ１５０ｍｍの試験片を作製し、温度２５℃、湿度５０％ＲＨの環境下で、当該試験片を引張速度５０ｍｍ／分にて引張った際に、前記塗膜にクラックが入るまでの伸び率が２０％以上で、かつ、JIS K5600に規定される鉛筆硬度がHB～2Hである。     On the base film, an ionizing radiation curable resin having a weight average molecular weight Mw of 150,000 or more satisfying the following condition (a), an ionizing radiation curable resin having a weight average molecular weight Mw of 10,000 or less satisfying the following condition (b), and the following: A molding hard coat film provided with a hard coat layer formed by coating and curing a coating composition containing a resin mixed with an ionizing radiation curable resin that satisfies the condition (c).
    Condition (a): A film in which a 1.5 μm coating film of an ionizing radiation curable resin cured with an ultraviolet light quantity of 50 to 1000 mJ / cm 2 is formed on a polyethylene terephthalate film is prepared. Next, 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.
    Condition (b): A film in which a 1.5 μm coating film of an ionizing radiation curable resin cured with an ultraviolet light quantity of 50 to 1000 mJ / cm 2 is formed on a polyethylene terephthalate film is produced. Next, 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 until cracks occur in the coating film is 1% or more, and the pencil hardness specified in JIS K5600 is H to 4H.
    Condition (c): A film is produced in which a 1.5 μm coating film of an ionizing radiation curable resin cured with an ultraviolet light quantity of 50 to 1000 mJ / cm 2 is formed on a polyethylene terephthalate film. Next, 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.
  2. 　前記塗料組成物中にさらにフッ素シロキサン系樹脂を含有することを特徴とする請求項１に記載の成型用ハードコートフィルム。 The hard coat film for molding according to claim 1, further comprising a fluorosiloxane resin in the coating composition.
  3. 　前記ハードコート層は、平均粒子径５～５０ｎｍの無機酸化物微粒子を含有することを特徴とする請求項１又は２に記載の成型用ハードコートフィルム。 3. The hard coat film for molding according to claim 1, wherein the hard coat layer contains inorganic oxide fine particles having an average particle diameter of 5 to 50 nm.
  4. 　前記無機酸化物微粒子はアルミニウムを主成分とすることを特徴とする請求項３に記載の成型用ハードコートフィルム。 The hard coat film for molding according to claim 3, wherein the inorganic oxide fine particles are mainly composed of aluminum.
  5. 　前記無機酸化物微粒子の含有量が、塗料組成物の固形分１００重量部に対して０．１～５．０重量部であることを特徴とする請求項３又は４に記載の成型用ハードコートフィルム。 5. The molding hard coat according to claim 3, wherein 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. the film.
  6. 　前記基材フィルムの前記ハードコート層を設けた面とは反対側の面に、プライマー層を介して加飾層を形成し、前記プライマー層は、塩化ビニル－酢酸ビニル共重合樹脂及びポリメチルメタクリレート樹脂を含有することを特徴とする請求項１乃至５のいずれかに記載の成型用ハードコートフィルム。 A decorative layer is formed via a primer layer on the surface of the base film opposite to the surface on which the hard coat layer is provided, and the primer layer comprises a vinyl chloride-vinyl acetate copolymer resin and polymethyl methacrylate. The hard coat film for molding according to any one of claims 1 to 5, comprising a resin.
  7. 　前記塩化ビニル－酢酸ビニル共重合樹脂とポリメチルメタクリレート樹脂との配合比率（重量部）が８０／２０～２５／７５の範囲であることを特徴とする請求項６に記載の成型用ハードコートフィルム。
     
          7. The hard coat film for molding according to claim 6, wherein 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. .

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WO2018181503A1 (en) * 2017-03-31 2018-10-04 大日本印刷株式会社 Decorative sheet and decorated resin molded article
JP2018171755A (en) * 2017-03-31 2018-11-08 大日本印刷株式会社 Decorative sheet and decorative resin molded product
JP2018171756A (en) * 2017-03-31 2018-11-08 大日本印刷株式会社 Decorative sheet and decorative resin molded product
CN109071732A (en) * 2016-05-13 2018-12-21 阿科玛股份有限公司 Composition based on fluoropolymer, polymer that can be miscible with fluoropolymer and free-radical curable component
JP2019077807A (en) * 2017-10-25 2019-05-23 株式会社クラレ Active energy ray-curable resin composition and laminate and molded body containing the same
JP2021073107A (en) * 2021-01-06 2021-05-13 大日本印刷株式会社 Decorative sheet and decorative resin molded product

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JP2008260202A (en) * 2007-04-12 2008-10-30 Sumitomo Bakelite Co Ltd Hard coat film for injection molding and manufacturing method for injection-molding
JP2011131406A (en) * 2009-12-22 2011-07-07 Toyobo Co Ltd Hard coat film for molding
JP2013006346A (en) * 2011-06-24 2013-01-10 Hitachi Chemical Co Ltd Decorative sheet with topcoat, method of manufacturing decorative sheet with topcoat, and method of manufacturing insert molded article
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Cited By (8)

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CN109071732A (en) * 2016-05-13 2018-12-21 阿科玛股份有限公司 Composition based on fluoropolymer, polymer that can be miscible with fluoropolymer and free-radical curable component
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CN109071732B (en) * 2016-05-13 2021-12-24 阿科玛股份有限公司 Composition based on a fluoropolymer, a polymer miscible with fluoropolymer and a radically curable component
WO2018181503A1 (en) * 2017-03-31 2018-10-04 大日本印刷株式会社 Decorative sheet and decorated resin molded article
JP2018171755A (en) * 2017-03-31 2018-11-08 大日本印刷株式会社 Decorative sheet and decorative resin molded product
JP2018171756A (en) * 2017-03-31 2018-11-08 大日本印刷株式会社 Decorative sheet and decorative resin molded product
JP2019077807A (en) * 2017-10-25 2019-05-23 株式会社クラレ Active energy ray-curable resin composition and laminate and molded body containing the same
JP2021073107A (en) * 2021-01-06 2021-05-13 大日本印刷株式会社 Decorative sheet and decorative resin molded product

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