WO2021140875A1 - Ｂステージ塗膜形成用塗料、ｂステージ塗膜、及びｂステージ塗膜の製造方法 - Google Patents

Ｂステージ塗膜形成用塗料、ｂステージ塗膜、及びｂステージ塗膜の製造方法 Download PDF

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WO2021140875A1
WO2021140875A1 PCT/JP2020/047454 JP2020047454W WO2021140875A1 WO 2021140875 A1 WO2021140875 A1 WO 2021140875A1 JP 2020047454 W JP2020047454 W JP 2020047454W WO 2021140875 A1 WO2021140875 A1 WO 2021140875A1
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coating film
stage
meth
mass
component
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English (en)
French (fr)
Japanese (ja)
Inventor
昌孝 毛利
幹規 安藤
望 鷲尾
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Riken Technos Corp
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Riken Technos Corp
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Priority to JP2021569808A priority Critical patent/JP7687965B2/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

Definitions

  • the present invention relates to a coating material for forming a B-stage coating film, a B-stage coating film, and a method for producing a B-stage coating film. More specifically, the present invention relates to a coating material for forming a B-stage coating film, a B-stage coating film, a laminated film, a molded product (typically a three-dimensional molded product), and a method for producing a B-stage coating film.
  • a curable resin coating material such as an acrylic resin, a melamine resin, an isocyanate resin, and a urethane resin is often applied onto the surface to form a cured coating film.
  • the substrate is molded, and a method such as dip coating, spray coating, spin coating, or air knife coating is used on the surface of the obtained substrate to form the cured coating film.
  • a method of applying a curable resin paint and curing is widely adopted.
  • the substrate has a three-dimensional shape / three-dimensional shape (for example, a shape that is curved as a whole, a shape that has irregularities on the surface, etc.), the following various shapes are used.
  • a B-stage coating film is formed by applying a paint on the surface of the thermoplastic resin film with high productivity by a roll-to-roll method such as roll coating, gravure coating, reverse coating, and die coating.
  • a method has been proposed in which the B-stage coating film is completely cured after being softened and shaped into a predetermined shape, and a desired thermoplastic resin is injected into the molding mold (see, for example, Patent Documents 1 and 2). ).
  • An object of the present invention is to provide a novel paint for forming a B-stage coating film, a B-stage coating film using the same, and a method for producing the B-stage coating film.
  • a further object of the present invention is to form a B-stage coating film having excellent three-dimensional moldability (difficulty of defective phenomena such as cracks, cracks and poor appearance (for example, whitening) when a three-dimensional shape is given). It is an object of the present invention to provide a coating material which can be used, a B-stage coating film using the coating material, and a method for producing the B-stage coating film.
  • Another object of the present invention is to form a coating film having excellent three-dimensional moldability in the B stage and excellent surface hardness, scratch resistance, and chemical resistance after complete curing (in the C stage).
  • a paint capable of being formed a B-stage coating film using the coating film, a laminated film having the B-stage coating film, a molded product formed by using the B-stage coating film or the laminated film, and a method for producing these. It is in.
  • a coating material for forming a B-stage coating film wherein (A) 100 parts by mass of an active energy ray-curable resin; (B) 1 to 20 parts by mass of a photopolymerization initiator; and (C) 0.001 to 20 parts by mass of a thermosetting initiator.
  • the above-mentioned paint containing 1 part by mass.
  • the number of (meth) acryloyl groups contained in the above component (A1) urethane (meth) acrylate is 2 to 20 per 1000 polystyrene-equivalent number average molecular weight (Mn) obtained from the differential molecular weight distribution curve measured by gel permeation chromatography.
  • the B-stage coating film forming coating material according to any one of the above items [1] to [4], wherein the component (A) active energy ray-curable resin contains (A2) mercaptoalkyl glycol uryls. [6].
  • the component (A) active energy ray-curable resin contains 99 to 80% by mass of the component (A1) urethane (meth) acrylate and 1 to 20% by mass of the component (A2) mercaptoalkyl glycol uryls; here, the above component.
  • the sum of the blending amount of (A1) urethane (meth) acrylate and the blending amount of the above component (A2) mercaptoalkyl glycol uryls is 100% by mass, according to any one of the above items [1] to [5].
  • the B-stage coating film forming coating material according to item [7] above, wherein the component (D) fine particles contain fine particles that function as an antibacterial agent or an antiviral agent. [9].
  • (E) The B-stage coating film forming coating material according to any one of the above items [1] to [8], which contains 0.01 to 7 parts by mass of a water repellent. [10].
  • a method for producing a B-stage coating film wherein (1) the coating film for forming a B-stage coating film according to any one of items [1] to [9] is applied onto at least one surface of a film substrate. Step of forming a wet coating film by using; (2) The wet coating film formed in the above step (1) is treated at a temperature of 80 to 160 ° C. for 1 to 20 minutes to dry and the B stage.
  • the above-mentioned production method including a step of curing to a state; and (3) a step of cooling the temperature of the coating film treated in the above-mentioned step (2) to 60 ° C. or lower.
  • a B-stage coating film can be industrially and stably produced.
  • a B-stage coating film having excellent three-dimensional moldability can be industrially and stably produced.
  • the B-stage coating film of the present invention is excellent in three-dimensional moldability.
  • the preferred B-stage coating film of the present invention is excellent in three-dimensional moldability in the B stage, and is excellent in surface hardness, scratch resistance, and chemical resistance after complete curing (in the C stage). Therefore, the preferable B-stage coating film of the present invention and the molded product formed by using the laminated film of the present invention having the B-stage coating film are excellent in surface hardness, scratch resistance, chemical resistance, and surface appearance.
  • the B-stage coating film of the present invention and the laminated film of the present invention having this B-stage coating film are molded bodies having a three-dimensional shape / three-dimensional shape, for example, housings of home appliances and information electronic devices, and automobiles. It can be suitably used for imparting functions such as surface hardness, scratch resistance, and chemical resistance to the surface of a molded body such as an instrument panel.
  • FIG. 1 is a GPC curve of the component (A1-1) used in the examples.
  • FIG. 2 is a conceptual diagram illustrating vacuum forming.
  • FIG. 3 is a front view (a) and a plan view (b) of the molding die used in the embodiment.
  • the term "resin” is used as a term including a resin mixture containing two or more kinds of resins and a resin composition containing components other than the resin.
  • the term “film” is used interchangeably or interchangeably with “sheet”.
  • the terms “film” and “sheet” are used for those that can be industrially rolled up.
  • the term “board” is used for things that cannot be industrially rolled into rolls.
  • laminating a certain layer and another layer in order means directly laminating those layers and interposing one or more other layers such as an anchor coat between the layers. Includes both stacking.
  • the term "greater than or equal to” related to a numerical range is used to mean a certain numerical value or a certain numerical value or more. For example, 20% or more means 20% or more than 20%.
  • the term “less than or equal to” related to a numerical range is used to mean a certain numerical value or less than a certain numerical value. For example, 20% or less means 20% or less than 20%.
  • the symbol "-" related to the numerical range is used to mean a certain numerical value, more than a certain numerical value and less than another certain numerical value, or another certain numerical value.
  • 10-90% means 10%, more than 10% and less than 90%, or 90%.
  • the upper limit and the lower limit of the numerical range can be arbitrarily combined, and the embodiment in which the arbitrary combination can be read can be read. For example, “usually 10% or more, preferably 20% or more. On the other hand, usually 40% or less, preferably 30% or less.” Or “usually 10 to 40%, preferably 20.” From the description " ⁇ 30%", it can be read that the numerical range of the certain property is 10 to 40%, 20 to 30%, 10 to 30%, or 20 to 40% in one embodiment. To do.
  • thermosetting resins that is, "intermediate state of curing of thermosetting resins.
  • the resin in this state softens when heated. , It swells when it comes in contact with some kind of solvent, but it does not completely melt or dissolve.
  • the intermediate state of curing of the active energy ray-curable resin The resin in this state softens when heated and swells when it comes into contact with a certain solvent, but it must be completely melted and dissolved. It is used to mean "there is no.”
  • C stage applies mutatis mutandis to the meaning specified in JIS K6800-1985 for both thermosetting resins and active energy ray-curable resins, and is used for "curing reaction of curable resin”.
  • the final state The resin in this state is insoluble and insoluble.
  • the curable resin in the completely cured coating film is in this state. ”
  • the paint of the present invention contains (A) an active energy ray-curable resin; (B) a photopolymerization initiator; and (C) a thermopolymerization initiator.
  • the component (A) active energy ray-curable resin preferably contains (A1) urethane (meth) acrylate.
  • the component (A) active energy ray-curable resin preferably contains (A2) mercaptoalkyl glycol urils.
  • Active energy ray-curable resin (A) Active energy ray-curable resin
  • the above-mentioned component (A) active energy ray-curable resin functions to form a coating film by being polymerized and cured by active energy rays such as ultraviolet rays and electron beams.
  • component (A) active energy ray-curable resin examples include urethane (meth) acrylate (or polyurethane (meth) acrylate), polyester (meth) acrylate, polyacrylic (meth) acrylate, epoxy (meth) acrylate, and poly.
  • component (A) active energy ray-curable resin examples include urethane (meth) acrylate (or polyurethane (meth) acrylate), polyester (meth) acrylate, polyacrylic (meth) acrylate, epoxy (meth) acrylate, and poly.
  • examples thereof include (meth) acryloyl group-containing prepolymers or oligomers such as alkylene glycol poly (meth) acrylate and polyether (meth) acrylate.
  • component (A) active energy ray-curable resin examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
  • active energy ray-curable resin examples include 1,2-ethanedithiol, ethylene glycol bis (3-mercaptopropionate), diethylene glycol bis (3-mercaptopropionate), and 1,4-.
  • (meth) acrylate means acrylate or methacrylate.
  • the blending amount of the above-mentioned component (A1) is 100 mass by mass of the total of the above-mentioned components (A).
  • the percentage is usually 10% by mass or more, preferably 40% by mass or more, more preferably 70% by mass or more, still more preferably 80 to 100% by mass, from the viewpoint of surely obtaining the effect of using the above component (A1). Good.
  • (A1) Urethane (meth) acrylate is a compound having a urethane structure (-NH-CO-O-) or a derivative thereof, and has one or more (meth) acryloyl groups. It is a compound having.
  • Examples of the compound having two or more isocyanate groups in one molecule include diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, and methylenebis (4-cyclohexyl isocyanate). Examples thereof include compounds having an isocyanate group.
  • Other examples of the compound having two or more isocyanate groups in one molecule include a trimethylolpropane adduct body of tolylene diisocyanate, a trimethylol propane adduct body of hexamethylene diisocyanate, and a trimethylol propane adduct body of isophorone diisocyanate.
  • Polyisocyanates such as an isocyanurate form of tolylene diisocyanate, an isocyanurate form of hexamethylene diisocyanate, an isocyanurate form of isophorone diisocyanate, and a biuret form of hexamethylene diisocyanate can be mentioned.
  • the compound having two or more isocyanate groups in the above one molecule one kind or a mixture of two or more kinds of these can be used.
  • polyol compound examples include polyether polyols, polyester polyols, polycarbonate polyols and the like.
  • polyether polyol examples include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; polyethylene oxide, and polyalkylene oxides such as polypropylene oxide; copolymers of ethylene oxide and propylene oxide; ethylene. Copolymers of oxide and tetrahydrofuran; Copolymers of divalent phenol compounds and polyoxyalkylene glycol; and alkylene oxides of divalent phenol and 2-4 carbon atoms (eg, ethylene oxide, propylene oxide, 1,2- Examples thereof include copolymers with one or more of (butylene oxide, 1,4-butylene oxide, etc.) and the like.
  • polyester polyol examples include poly (ethylene adipate), poly (butylene adipate), poly (neopentyl adipate), poly (hexamethylene adipate), poly (butylene azelaate), poly (butylene sebacate), and the like. Polycaprolactone and the like can be given.
  • polycarbonate polyol examples include poly (butanediol carbonate), poly (hexanediol carbonate), and poly (nonanediol carbonate).
  • polyol compound one kind or a mixture of two or more kinds of these can be used.
  • hydroxyl group-containing (meth) acrylate examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-.
  • Hydroxyalkyl (meth) acrylates such as hydroxyhexyl (meth) acrylates and 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylates; dipropylene glycol (meth) acrylates, polyethylene glycol mono (meth) acrylates, And glycol-based (meth) acrylates such as polypropylene glycol mono (meth) acrylates; glycerin-based (meth) acrylates such as glycerinji (meth) acrylates; fatty acid-modified-modified glycidyl-based (meth) acrylates such as glycidyl (meth) acrylates; Phosphor-atom-containing (meth) acrylates such as 2-hydroxyethylacryloyl phosphate; (meth) acrylic acid adducts of esters or ester derivatives such as 2- (meth) acryloyloxyethyl-2-hydroxypropylphthalate;
  • hydroxyl group-containing (meth) acrylate one or a mixture of two or more of these can be used.
  • GPC curve Polystyrene-equivalent number obtained from the differential molecular weight distribution curve (hereinafter, may be abbreviated as GPC curve) measured by gel permeation chromatography (hereinafter, may be abbreviated as GPC) of the above component (A1) urethane (meth) acrylate.
  • the average molecular weight (Mn) may be usually 1000 or more, preferably 1600 or more, and more preferably 2000 or more from the viewpoint of three-dimensional moldability.
  • the number average molecular weight (Mn) may be usually 50,000 or less, preferably 30,000 or less, from the viewpoint of coatability.
  • the polystyrene-equivalent mass average molecular weight (Mw) obtained from the GPC curve of the component (A1) urethane (meth) acrylate measured by GPC is usually 2000 or more, preferably 4000 or more, from the viewpoint of three-dimensional moldability. Good.
  • the mass average molecular weight (Mw) may be usually 100,000 or less, preferably 50,000 or less, from the viewpoint of coatability.
  • the polystyrene-equivalent Z average molecular weight (Mz) obtained from the GPC curve of the above component (A1) urethane (meth) acrylate measured by GPC is usually 2500 or more, preferably 2500 or more, from the viewpoint of three-dimensional moldability and web handling. It may be 4500 or more.
  • the Z average molecular weight (Mz) may be usually 200,000 or less, preferably 150,000 or less, from the viewpoint of coatability.
  • the number of (meth) acryloyl groups contained in the above component (A1) urethane (meth) acrylate is usually 2 or more per 1000 polystyrene-equivalent number average molecular weight (Mn) obtained from the GPC curve, from the viewpoint of web handleability. It may be preferably 3 or more. From the viewpoint of surface hardness, scratch resistance, and chemical resistance after complete curing (in the C stage), the number may be more preferably 6 or more. On the other hand, the number of (meth) acryloyl groups may be usually 20 or less, preferably 12 or less, and more preferably 10 or less from the viewpoint of three-dimensional moldability.
  • the web handling property here means that the coating film is less likely to cause scratches or poor appearance due to contact with the transfer roll or the like during web handling.
  • GPC measurement is performed by Toso Co., Ltd.'s high performance liquid chromatography system "HLC-8320" (trade name) (system including degasser, liquid feed pump, autosampler, column oven and RI (differential refractometer) detector).
  • HLC-8320 high performance liquid chromatography system
  • KF-806L trade name
  • KF-802 trade name
  • KF-801 trade name
  • the flow rate is 1.0 ml / min
  • the column temperature is 40 ° C.
  • the sample concentration is 1 mg / ml
  • the sample injection amount is 100 microliters.
  • the elution amount at each holding capacity can be obtained from the amount detected by the RI detector, assuming that the refractive index of the measurement sample does not depend on the molecular weight.
  • the calibration curve from the holding capacity to the polystyrene-equivalent molecular weight can be prepared using a commercially available standard polystyrene. At that time, it should be noted that standard polystyrene should be appropriately selected so that the measured value is interpolated in the calibration curve.
  • FIG. 1 shows the differential molecular weight distribution curve of the following component (A1-1) used in the examples.
  • One sharp peak is observed in a region having a relatively low molecular weight, and the polystyrene-equivalent molecular weight at the peak top position is 720.
  • a peak of the main component is observed on the high molecular weight side of this peak, and the polystyrene-equivalent molecular weight at the peak top position is 5800.
  • the total number average molecular weight (Mn) is 2500
  • the mass average molecular weight (Mw) is 9100
  • the Z average molecular weight (Mz) is 23000.
  • the number of (meth) acryloyl groups per molecule is 10
  • the number of (meth) acryloyl groups per 1000 of polystyrene-equivalent number average molecular weight (Mn) obtained from the GPC curve is 4.
  • (A2) Mercaptoalkyl Glycol Uryls As the component (A) active energy ray-curable resin, it is preferable to use a resin containing (A2) mercaptoalkyl glycol uryls.
  • the web handling property here means that the coating film is less likely to cause scratches or poor appearance due to contact with the transfer roll or the like during web handling.
  • the blending ratio of the component (A2) is 100% by mass of the total of the components (A). % May be usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 4% by mass or more, from the viewpoint of surely obtaining the effect of using the above component (A2). ..
  • the blending ratio of the above component (A2) is usually 20% by mass or less, preferably 15% by mass or less, more preferably 12% by mass or less, still more preferably 10% by mass, from the viewpoint of three-dimensional moldability in the B stage coating film. It may be less than or equal to%.
  • the number of mercaptoalkyl groups contained in the component (A2) mercaptoalkyl glycol uryls may be preferably 2 to 4, more preferably 4 from the viewpoint of surely obtaining the effect of using the above component (A2).
  • Examples of the component (A2) mercaptoalkyl glycol urils include mercaptoalkyl glycol urils having two mercaptoalkyl groups in one molecule such as 1,3-bis (3-mercaptopropyl) glycol uryl; 1, 3,4,6-Tetrakiss (2-mercaptoethyl) glycoluryl, 1,3,4,6-tetrakis (2-mercaptopropyl) glycoluryl, and 1,3,4,6-tetrakis (3-mercaptopropyl) Examples thereof include mercaptoalkyl glycol urils having four mercaptoalkyl groups in one molecule such as glycol uryl. As the component (A2) mercaptoalkyl glycol uryls, one or a mixture of two or more of these can be used.
  • component (A) active energy ray-curable resin containing the component (A1) urethane (meth) acrylate and the component (A2) mercaptoalkyl glycol uryls. It is possible to further improve both the three-dimensional moldability of the B-stage coating film; and the surface hardness, scratch resistance, and chemical resistance after complete curing (at the C stage) in a well-balanced manner.
  • the blending amount of the component (A1) and the above component (A1) are used. Assuming that the sum with the blending amount of the component (A2) is 100% by mass, the blending amount of the component (A1) is usually 99 to 80% by mass (the blending amount of the component (A2) is 1 to 20% by mass), preferably.
  • the component (A) active energy ray-curable resin containing the component (A1) urethane (meth) acrylate and the component (A2) mercaptoalkyl glycol uryls is used, the blending amount of the component (A1) and the above component (A1) are used.
  • the sum with the blending amount of the above component (A2) is the three-dimensional moldability in the B stage coating film, where the total of the above components (A) is 100% by mass; and the surface hardness and resistance after complete curing (in the C stage). From the viewpoint of balancing both scratch resistance and chemical resistance, it may be usually 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 98 to 100% by mass.
  • the above-mentioned component (B) Photopolymerization Initiator is a compound that generates active species such as radicals by irradiation with active energy rays.
  • the above component (B) photopolymerization initiator polymerizes and cures the above component (A) active energy ray-curable resin by generating active species such as radicals, and completely cures the coating film (to the C stage). To work.
  • component (B) photopolymerization initiator examples include benzophenone, methyl-o-benzoylbenzoate, 4-methylbenzophenone, 4,4'-bis (diethylamino) benzophenone, methyl o-benzoylbenzoate, and 4-phenylbenzophenone.
  • Alkylphenone compounds such as methylanthraquinone, 2-ethylanthraquinone, and 2-amylanthraquinone; thioxanthone compounds such as thioxanthone, 2,4-diisopropylthioxanthone, and 2,4-diisopropylthioxanthone; acylphosphine Examples thereof include oxide-based compounds; biimidazole compounds; titanosen-based compounds; oxime ester-based compounds; oximephenyl acetate-based compounds; hydroxyketone-based compounds; triazine-based compounds; and aminobenzoate-based compounds.
  • alkylphenone-based compound is defined as a compound having a structure derived from an acetophenone skeleton (benzene ring-CO-alkyl group) or an acetophenone skeleton.
  • the photopolymerization initiator of the component (B) a compound that generates radicals by irradiation with active energy rays is preferable from the viewpoint of ensuring complete curing (to the C stage) of the coating film after three-dimensional molding.
  • an alkylphenone-based compound such as an acetophenone-based compound is preferable, and a hydroxyacetophenone-based compound (hydroxyacetophenone-based compound) is preferable from the viewpoint of stably holding the coating film in the B-stage state until three-dimensional molding is performed.
  • a hydroxyalkylphenone compound such as an acetophenone compound having a hydroxyl group is more preferable. Further, from the viewpoint of suppressing volatilization of the photopolymerization initiator due to heat during three-dimensional molding, one having low volatility is preferable. Examples of the low volatile photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone and 2-hirodoxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl ⁇ -2. -Methyl-propane-1-one can be mentioned. As the component (B), one kind or a mixture of two or more kinds of these can be used.
  • the blending amount of the above component (B) photopolymerization initiator is from the viewpoint of curing the coating film to the B stage state, from the viewpoint of keeping the curing of the coating film in the B stage state, and keeping the coating film in the B stage state until three-dimensional molding is performed. It may be appropriately selected in consideration of the viewpoint of stable holding and the viewpoint of surely completely curing (to C stage) after three-dimensional molding.
  • the blending amount of the above component (B) photopolymerization initiator is certain from the viewpoint of curing the coating film to the B stage state with respect to 100 parts by mass of the above component (A) active energy ray-curable resin, and after three-dimensional molding.
  • the viewpoint of complete curing (to C stage) it may be usually 1 part by mass or more, preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and further preferably 4 parts by mass or more.
  • the blending amount of the above component (B) photopolymerization initiator is from the viewpoint of keeping the coating film cured in the B stage state and from the viewpoint of stably holding the coating film in the B stage state until three-dimensional molding is performed. It may be usually 20 parts by mass or less, preferably 15 parts by mass or less, more preferably 12 parts by mass or less, and further preferably 10 parts by mass or less.
  • the above-mentioned component (C) Thermal Polymerization Initiator is a compound that generates active species such as radicals by heating.
  • the component (C) functions to cure the coating film to the B stage state.
  • compounds that generate active species such as radicals by irradiation with active energy rays (or light irradiation) or by heating are classified as thermal polymerization initiators.
  • the time required to completely cure (to the C stage) the coating film from the uncured state is generally heat.
  • the photopolymerization initiator is considerably shorter than the polymerization initiator. Therefore, when a photopolymerization initiator is used, it is industrially difficult to keep the coating film cured in the B stage state.
  • a thermal polymerization initiator when used, it takes a long time to completely cure the coating film (to the C stage). Therefore, in the present invention, a thermal polymerization initiator is used to cure the coating film to the B stage state, and a photopolymerization initiator is used to completely cure the coating film (to the C stage). It solves the problem.
  • component (C) thermal polymerization initiator examples include 2,2'-azobisisobutyronitrile (2,2'-azobis (2-methylpropionitrile)) and 2,2'-azobis (2). , 4-Dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis ( Cyclohexane-1-carbonitrile), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-methylpropionic acid) dimethyl, 1,1'-azobis (methyl cyclohexanecarboxylic acid), 2,2'-azobis (n-butyl-2-methylpropionamide), 2,2'-azobis (2-methylpropionamidine) dihydrochloride, dimethyl 1,1-azobis (1-cyclohexanecarboxylate), and Azobisisobuty such as 2,2'-azobis [2- (2-imidi
  • the above component (C) thermal polymerization initiator a compound that generates radicals is preferable.
  • the above-mentioned component (C) thermal polymerization initiator is inactive near room temperature, and is completely consumed in the process of curing the coating film to the B stage state from the viewpoint of suppressing an unintended curing reaction, and three-dimensional molding is performed.
  • the azo compound is preferable from the viewpoint of stably holding the coating film in the B stage state.
  • Azo compounds having a molecular weight (molecular weight calculated from a chemical formula) of 250 or more, preferably 300 to 1000, are more preferable.
  • the thermal polymerization initiator of the component (C) one kind or a mixture of two or more kinds of these can be used.
  • the blending amount of the above component (C) thermal polymerization initiator is from the viewpoint of curing the coating film in the B stage state, from the viewpoint of keeping the curing of the coating film in the B stage state, and the B stage state of the coating film until three-dimensional molding is performed. It may be selected as appropriate in consideration of the viewpoint of stable maintenance.
  • the blending amount of the above component (C) thermosetting initiator is usually 0.001 part by mass from the viewpoint of curing the coating film in the B stage state with respect to 100 parts by mass of the above component (A) active energy ray-curable resin. As mentioned above, it may be preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, and further preferably 0.02 parts by mass or more.
  • the blending amount of the above component (C) thermal polymerization initiator is from the viewpoint of keeping the coating film cured in the B stage state and from the viewpoint of stably holding the coating film in the B stage state until three-dimensional molding is performed. It may be usually 1 part by mass or less, preferably 0.5 part by mass or less, more preferably 0.3 part by mass or less, still more preferably 0.2 part by mass or less, and most preferably 0.1 part by mass or less.
  • the coating material of the present invention may preferably further contain the above-mentioned component (D) fine particles.
  • the fine particles of the component (D) have a function of increasing the surface hardness of the molded product (the coating film is the C stage) obtained by using the B-stage coating film of the present invention.
  • Examples of the component (D) fine particles include inorganic fine particles and organic fine particles.
  • Examples of the inorganic fine particles include silica (silicon dioxide); metal oxide fine particles such as aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, antimony oxide, and cerium oxide.
  • Metal fluoride fine particles such as magnesium fluoride and sodium fluoride; metal sulfide fine particles; metal nitride fine particles; and metal fine particles and the like can be mentioned.
  • organic fine particles examples include resin fine particles such as silicone-based resin, styrene-based resin, acrylic-based resin, fluororesin, polycarbonate-based resin, ethylene-based resin, and cured resin of amino-based compound and formaldehyde. it can.
  • resin fine particles such as silicone-based resin, styrene-based resin, acrylic-based resin, fluororesin, polycarbonate-based resin, ethylene-based resin, and cured resin of amino-based compound and formaldehyde. it can.
  • fine particles of silica and aluminum oxide are preferable, and fine particles of silica are more preferable, from the viewpoint of obtaining higher surface hardness.
  • examples of commercially available silica fine particles include Snowtex (trade name) of Nissan Chemical Industries, Ltd. and Quattron (trade name) of Fuso Chemical Industries, Ltd.
  • the surface of the fine particles of the component (D), especially when inorganic fine particles are used as the component (D), the surface of the inorganic fine particles is a silane coupling agent such as vinylsilane and aminosilane; a titanate coupling agent; an aluminate.
  • the fine particles of the component (D) may contain fine particles (hereinafter, may be referred to as "functional fine particles") that function as an antibacterial agent or an antiviral agent in one of the embodiments.
  • functional fine particles By using the functional fine particles in a part or all of the component (D) fine particles (that is, in an amount of more than 0% by mass to 100% by mass or less of the component (D)), the coating film of the present invention has antibacterial properties. And antiviral properties can be imparted.
  • the ratio of the functional fine particles in the component (C) fine particles is usually 10% by mass or more to 100% by mass or less, preferably 30% by mass or more to 100% by mass or less, and more. It may be preferably from 50% by mass or more to 100% by mass or less.
  • the functional fine particles may be referred to as, for example, inorganic fine particles that function as antibacterial agents or antiviral agents such as copper compounds, silver compounds, tin compounds, molybdenum compounds, and zinc compounds (hereinafter, referred to as "functional inorganic fine particles”).
  • the copper compound include cuprous halide such as cuprous chloride (CuCl), cuprous bromide (CuBr), and cuprous iodide (CuI), and cuprous thiocyanate (CuSCN).
  • cupric compounds such as cupric carbonate (CuCO 3 ), cupric oxide (CuO), and cupric chloride (CuCl 2 ).
  • Examples of the silver compound include silver halide compounds such as first silver iodide (AgI).
  • Examples of the tin compound include tin halide compounds such as tin tetraiodide (SnI 4 ).
  • Examples of the molybdenum compound include molybdenum oxide (MoO 3 ), molybdenum / silver composite oxide, molybdenum / zinc composite oxide, and molybdenum oxide compound such as molybdenum / copper composite oxide.
  • Examples of the zinc compound include zinc oxide compounds such as zinc oxide (ZnO).
  • Other functional fine particles include, for example, potassium aluminum sulfate, silver / sodium / hydrogen / zirconium phosphate, silver / magnesium / aluminum / phosphate glass (FCN registration number 433 of the US Food and Drug Administration), silver / magnesium.
  • Calcium / phosphoric acid / zeolite glass (FCN registration number 432 of the US Food and Drug Administration), silver / zinc / magnesium / aluminum / calcium / sodium / zeolite / zeolite glass (FCN registration number 476 of the US Food and Drug Administration), silver / Magnesium / sodium / phosphate glass (FCN registration number 434 of the US Food and Drug Administration), silver / magnesium / zinc / aluminum / calcium / sodium / boric acid / phosphoric acid glass (FCN registration number 1981 of the US Food and Drug Administration), silver zeolite (CAS number 0130328-18-6), silver-copper zeolite (CAS number 0130328-19-7), silver-zinc zeolite (CAS number 0130328-20-0), and functional inorganic fine particles such as copper-tin alloys can be mentioned. it can.
  • component (D) fine particles one or a mixture of two or more of these can be used.
  • component (C) fine particles one kind or a mixture of two or more kinds of organic fine particles and inorganic fine particles can be used.
  • component (C) fine particles one or a mixture of two or more of functional fine particles and other fine particles (organic fine particles and / or inorganic fine particles) can be used.
  • the average particle size of the component (D) fine particles is usually 300 nm or less, preferably 200 nm or less, more preferably 120 nm or less, from the viewpoint of maintaining the transparency of the coating film and surely obtaining the hardness improving effect. Good.
  • the fine particles that are usually available are at most about 1 nm.
  • the average particle size of the fine particles is 50% by mass in the particle size distribution curve measured by the laser diffraction / scattering method using a laser diffraction / scattering particle size analyzer. Is the particle size.
  • the laser diffraction / scattering type particle size analyzer for example, "MT3200II" (trade name) manufactured by Nikkiso Co., Ltd. can be used.
  • the blending amount of the above component (D) fine particles is not particularly limited because it is an optional component.
  • the blending amount of the above component (D) fine particles may be appropriately selected from the viewpoint of surface hardness and crack resistance after complete curing (C stage).
  • the blending amount of the component (D) is preferably 10 parts by mass or more from the viewpoint of the surface hardness after complete curing (C stage) with respect to 100 parts by mass of the active energy ray-curable resin of the component (A). , More preferably 80 parts by mass or more, further preferably 120 parts by mass or more, and most preferably 150 parts by mass or more.
  • the blending amount of the component (D) fine particles is preferably 500 parts by mass or less, more preferably 400 parts by mass or less, still more preferably 300 parts by mass, from the viewpoint of crack resistance after complete curing (C stage). It may be parts or less, most preferably 250 parts by mass or less.
  • the blending amount of the functional fine particles is such that the total amount of the component (D) is the above-mentioned from the viewpoint of surely expressing antibacterial property and antiviral property. Determine appropriately from the viewpoint of not exceeding the range.
  • the blending amount of the functional fine particles is usually 1 part by mass or more, preferably 4 parts by mass with respect to 100 parts by mass of the active energy ray-curable resin of the component (A), from the viewpoint of surely expressing antibacterial properties and antiviral properties. It may be 10 parts by mass or more, more preferably 7 parts by mass or more, and further preferably 10 parts by mass or more.
  • the blending amount of the functional fine particles is preferably 500 parts by mass or less, more preferably 400 parts by mass or less, still more preferably 300 parts by mass or less, from the viewpoint of crack resistance after complete curing (C stage). Most preferably, it may be 250 parts by mass or less. In another embodiment, the blending amount of the functional fine particles may be 10 parts by mass or more and 200 parts by mass or less, or 10 parts by mass or more and 100 parts by mass or less, or 10 parts by mass or more and 50 parts by mass or less, from the above viewpoint. It may be less than or equal to a part.
  • the coating material of the present invention may preferably further contain the above component (E) water repellent agent.
  • the molded product (coating film is C stage) obtained by using the B stage coating film of the present invention has scratch resistance, stain adhesion prevention property, and stain wiping. The sex can be improved.
  • component (E) water repellent examples include wax-based water repellents such as paraffin wax, polyethylene wax, and acrylic / ethylene copolymer wax; silicone oil, silicone resin, polydimethylsiloxane, alkylalkoxysilane, and the like. Silicone-based water repellents; examples include fluoropolyether-based water repellents, fluoropolyalkyl-based water repellents, and other fluorine-containing water repellents.
  • a fluorine-containing water repellent is preferable from the viewpoint of scratch resistance and water repellency.
  • the component (E) water repellent has scratch resistance, water repellency, and the component (E) is chemically bonded or strongly interacts with the component (A) active energy ray-curable resin to cause the component (E).
  • the (meth) acryloyl group-containing fluorine-based water repellent has one or more (meth) acryloyl groups in the molecule, and one or more, preferably three or more, more preferably five in the molecule.
  • a compound that has the above-mentioned fluorine-carbon bond typically, a structure in which one or more hydrogen atoms of an organic functional group such as a hydrocarbon group are replaced with a fluorine atom
  • exhibits a water-repellent function. is there.
  • Examples of the (meth) acryloyl group-containing fluorine-based water repellent include (meth) acryloyl group-containing fluoroether-based water repellent, (meth) acryloyl group-containing fluoroalkyl-based water repellent, and (meth) acryloyl group-containing flow.
  • a (meth) acryloyl group-containing fluoropolyether-based water repellent (a compound containing a (meth) acryloyl group and a fluoropolyether group in the molecule) is more preferable.
  • the water repellent for the component (E) the chemical bond or interaction between the component (E) and the active energy ray-curable resin is appropriately adjusted to maintain high transparency and good scratch resistance.
  • the amount of the above component (E) water repellent is not particularly limited because it is an optional component.
  • the blending amount of the above component (E) water repellent agent should be appropriately determined from the viewpoint of improving scratch resistance after complete curing (C stage), stain adhesion prevention property, and dirt wiping property. Just do it.
  • the blending amount of the component (E) water repellent is usually 0.01 mass by mass from the viewpoint of obtaining the effect of using the component (E) with respect to 100 parts by mass of the active energy ray-curable resin of the component (A). It may be 10 parts or more, preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and further preferably 0.2 parts by mass or more.
  • the blending amount of the component (E) water repellent is usually 7 parts by mass or less, preferably 4 parts by mass or less, more preferably 2 from the viewpoint of preventing troubles such as bleeding out of the component (E). It may be parts by mass or less, more preferably 1 part by mass or less.
  • the coating material of the present invention contains, if desired, a compound having two or more isocyanate groups in one molecule, an antioxidant, a surfactant, a leveling agent, an ergonomics-imparting agent, to the extent not contrary to the object of the present invention.
  • Anticontamination agents, printability improvers, antioxidants, weathering stabilizers, lightfastening stabilizers, UV absorbers, heat stabilizers, inorganic particles, inorganic colorants, organic particles, organic colorants, and dispersants eg, Amine-based dispersant such as a phosphoric acid ester salt of a high molecular weight copolymer having a polyamine structure
  • dispersants eg, Amine-based dispersant such as a phosphoric acid ester salt of a high molecular weight copolymer having a polyamine structure
  • the blending amount is not particularly limited, but is usually 0.001 part by mass or more from the viewpoint of obtaining the effect of using the additive with respect to 100 parts by mass of the above component (A). It may be usually 10 parts by mass or less from the viewpoint of not interfering with the desired effect according to the present invention.
  • the paint of the present invention may contain a solvent, if desired, in order to dilute it to a concentration that is easy to apply.
  • the solvent is particularly limited as long as it does not react with the components (A) to (C) and other optional components, or catalyze (promote) the self-reaction (including deterioration reaction) of these components. Not done.
  • the solvent include 1-methoxy-2-propanol, ethyl acetate, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, acetone and the like.
  • the solvent one kind or a mixture of two or more kinds of these can be used.
  • the paint of the present invention can be obtained by mixing and stirring these components.
  • the B-stage coating film of the present invention can be formed by any method using the coating film of the present invention.
  • the B-stage coating of the present invention can usually be formed on the surface of a film substrate.
  • the B-stage coating film of the present invention is preferably (1) A step of forming a wet coating film on at least one surface of a film substrate, usually on one surface of a film substrate, using the coating material of the present invention; (2) The wet coating film formed in the above step (1) is subjected to a time of 1 to 20 minutes, preferably 3 to 15 minutes at a temperature of 80 to 160 ° C., preferably 90 to 150 ° C., more preferably 100 to 140 ° C.
  • the above step (1) is a step of forming a wet coating film on at least one surface of the film base material using the paint of the present invention.
  • the step (1) is usually a step of forming a wet coating film on one surface of the film substrate using the coating material of the present invention.
  • the film base material used in the above step (1) is not particularly limited, and any film can be used as the film base material.
  • the film base material used in the above step (1) the film base material described in "3. B stage coating film laminated film” described later can be preferably used.
  • the paint of the present invention used in the above step (1) has been described in "1. Paint”.
  • the method of forming a wet coating film on the surface of the film base material using the paint of the present invention is not particularly limited, and a known web application method can be used.
  • a known web application method for example, a rod coat, a roll coat, a gravure coat, a reverse coat, a kiss reverse coat, and a die coat are preferable from the viewpoint of applying the paint with high productivity by the roll-to-roll method. ..
  • the wet coating film formed in the step (1) is subjected to a time of 1 to 20 minutes at a temperature of 80 to 160 ° C., preferably 90 to 150 ° C., more preferably 100 to 140 ° C. It is a step of drying and curing to a B stage state by treating for preferably 3 to 15 minutes, more preferably 4 to 10 minutes.
  • the treatment time of the above step (2) is considerably shorter than the time required for completely curing (to the C stage) the coating film using the thermal polymerization initiator. Further, the cooling in the above step (3) stops the progress of the curing reaction due to heat. Further, in the preferred coating material of the present invention, the amount of the thermal polymerization initiator contained therein is considerably small, and the progress of the curing reaction should be considerably slow. Therefore, it is considered that the coating film remains in the B stage state.
  • the process of the above step (2) can be performed by any method.
  • the process of the above step (2) is for passing the web from the inlet to the outlet, for example, in a drying oven set to a temperature of 80 to 160 ° C, preferably 90 to 150 ° C, more preferably 100 to 140 ° C. This can be done by passing at a line speed such that the time required is 1 to 20 minutes, preferably 3 to 15 minutes, and more preferably 4 to 10 minutes.
  • the temperature of the coating film treated in the step (2) is usually cooled to 60 ° C. or lower, preferably 50 ° C. or lower, more preferably 40 ° C. or lower, and the progress of the curing reaction by heat is stopped. It is a process to make it.
  • the step (3) is preferably performed immediately after the step (2) for the purpose of stopping the progress of the curing reaction due to heat.
  • the process of the above step (3) can be performed by any method.
  • the process of the above step (3) can be performed, for example, by handling the web.
  • the calorific value of the coating film treated in the above step (2) is usually not so large. Therefore, it can be expected that the web will be cooled sufficiently quickly and the temperature will be 60 ° C. or lower by handling the web while holding it in a transfer roll whose temperature is not controlled.
  • the process of the above step (3) can preferably be performed by handling the web while holding it in a chill roll.
  • the temperature of the chill roll is usually set to 60 ° C. or lower, preferably 50 ° C. or lower, more preferably room temperature (about 23 ° C.) to 40 ° C.
  • the number of the chill rolls is not limited to one, and may be two or more.
  • the processing of the above step (3) is performed by using the web coming out of the drying oven as it is. , It can be carried out by handling while being held in a transfer roll whose temperature is not controlled, preferably a chill roll set to a predetermined temperature.
  • step (3) it is preferable to superimpose a protective film on the surface of the formed B stage coating film and temporarily attach it. It is possible to suppress manufacturing troubles such as scratches on the coating film before it is completely cured (to the C stage). Further, in the step of irradiating the coating film with active energy rays after three-dimensional molding to change from the B stage to the C stage, it is possible to suppress manufacturing troubles such as curing failure due to oxygen damage.
  • the thickness of the B stage coating film of the present invention is not particularly limited.
  • the thickness of the B-stage coating film of the present invention is usually 0.5 ⁇ m or more, preferably 1 ⁇ m or more, more preferably 1 ⁇ m or more, from the viewpoint of surface hardness, scratch resistance, and chemical resistance after complete curing (C stage). It may be 5 ⁇ m or more, more preferably 10 ⁇ m or more.
  • the thickness of the B-stage coating film may be usually 100 ⁇ m or less, preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, and further preferably 20 ⁇ m or less from the viewpoint of three-dimensional moldability.
  • the tensile elongation of the B-stage coating film of the present invention may be usually 10% or more, preferably 15% or more, more preferably 20% or more, still more preferably 25% or more. Higher tensile elongation is preferred.
  • the tensile elongation is based on JIS K7127: 1999, and the test piece type 2 (width 15 mm, total length) collected so that the width direction and the tension direction of the B-stage coating film or the laminated film having the B-stage coating film coincide with each other. It is a value measured using a test piece (150 mm) under the conditions of a distance between marked lines of 50 mm, an initial distance of 100 mm between chucks, and a test speed of 10 mm / min.
  • the pencil hardness of the surface of the B-stage coating film of the present invention after being completely cured (made into C stage) is usually H or more (1H or more), preferably 3H or more, more preferably 4H or more, still more preferably 5H or more, and most. It may be preferably 6H or more. Higher pencil hardness is preferred.
  • the pencil hardness is a value measured according to JIS K5600-5-4: 1999 under the conditions of a test length of 25 mm and a load of 750 g.
  • the B-stage coating film laminated film of the present invention includes the B-stage coating film of the present invention.
  • the B-stage coating film laminated film of the present invention has the B-stage coating film of the present invention on at least one surface of the film substrate.
  • the B-stage coating film laminated film of the present invention usually has the B-stage coating film of the present invention on one side of a film substrate, and the B-stage coating film forms a surface.
  • the B-stage coating film laminated film of the present invention is produced by forming the B-stage coating film of the present invention on at least one surface of the film substrate by an arbitrary method using the coating film of the present invention. be able to.
  • the B-stage coating film laminated film of the present invention preferably uses the coating film of the present invention, and uses the method described in the section "2. Method for producing B-stage coating film and B-stage coating film" to obtain the above-mentioned film substrate. It can be produced by forming the B-stage coating film of the present invention on at least one surface.
  • the film base material is a film that serves as a base material for forming the B-stage coating film of the present invention on at least one surface thereof.
  • the film base material is not particularly limited, and any film can be used as the film base material.
  • the film include polyester resins such as aromatic polyesters and aliphatic polyesters; acrylic resins; polycarbonate resins; poly (meth) acrylicimide resins; polyethylene, polypropylene, and poly 4-methylpentene-1.
  • Polyethylene-based resins such as cellophane, triacetyl cellulose, diacetyl cellulose, and acetyl cellulose butyrate; polystyrene, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), styrene-ethylene-butadiene-styrene copolymer , Sterium / ethylene / propylene / styrene copolymers, and styrene resins such as styrene / ethylene / ethylene / propylene / styrene copolymers; polyvinyl chloride resins; polyvinylidene chloride resins; Related resins; Other examples include resin films such as polyvinyl alcohol, ethylene vinyl alcohol, polyether ether ketone, nylon, polyamide, polyimide, polyurethane, polyetherimide, polysulphon, and polyethersulphon.
  • ABS resin acrylon
  • These films include non-stretched films, uniaxially stretched films, and biaxially stretched films. Further, it includes a laminated film in which two or more layers of one or more of these are laminated. Further, these films may be transparent, opaque, concealing, colored, or have a unique color. ..
  • the film base material is used as one of the constituent materials of the molded product
  • the film base material is used as one of the constituent materials of the molded product of the present invention (described later in the section of "4. Molded product")
  • the coating film-forming surface of the film substrate is easily adhered by corona discharge treatment, plasma treatment, anchor coat formation, or the like. It may be processed.
  • the thickness of the film base material is appropriately determined in consideration of the use of the molded product.
  • the thickness of the film base material may be usually 20 ⁇ m or more, preferably 50 ⁇ m or more from the viewpoint of handleability.
  • the thickness of the film base material may be usually 100 ⁇ m or more, preferably 150 ⁇ m or more, from the viewpoint of the strength of the molded product.
  • the thickness of the film base material may be usually 2000 ⁇ m or less, preferably 800 ⁇ m or less, and more preferably 600 ⁇ m or less from the viewpoint of weight reduction of the molded product.
  • the film base material When the film base material is used as one of the constituent materials of the molded product of the present invention, it is preferable to use a film base material having high transparency and no color.
  • the B-stage coating film laminated film of the present invention can be suitably used as a vehicle member such as an article requiring high transparency and colorlessness, for example, an instrument panel of a vehicle.
  • a film include a cellulose ester resin such as triacetyl cellulose; a polyester resin such as polyethylene terephthalate; a cyclic hydrocarbon resin such as an ethylene norbornene copolymer; polymethyl methacrylate, poly ethyl methacrylate, and the like.
  • acrylic resins such as vinylcyclohexane and methyl (meth) acrylate copolymers; aromatic polycarbonate resins; polyolefin resins such as polypropylene and poly4-methylpentene-1; polyamide resins; polyarylate resins; Examples thereof include polymer-type urethane acrylate-based resins; and transparent resin films such as polyimide-based resins.
  • These films include non-stretched films, uniaxially stretched films, and biaxially stretched films. Further, these films include a laminated film in which one or more of these are laminated in two or more layers.
  • the total light transmittance of the B-stage coating film laminated film of the present invention completely cures the B-stage coating film ( After (C stage), it may be usually 80% or more, preferably 85% or more, more preferably 88% or more, still more preferably 90% or more.
  • the total light transmittance is a value measured according to JIS K7361-1: 1997.
  • a turbidity meter "NDH2000" (trade name) manufactured by Nippon Denshoku Kogyo Co., Ltd. can be used.
  • the haze of the B-stage coating film laminated film of the present invention is used.
  • the B-stage coating film may be usually 3% or less, preferably 2% or less, and more preferably 1% or less.
  • a low haze is preferable from the viewpoint of obtaining a clean and transparent feeling.
  • the haze of the B-stage coating film laminated film of the present invention is the same.
  • the B-stage coating film is completely cured (C-stage), it is usually 3 to 30%, preferably 5 to 25%, and more preferably 7 to 20%, depending on the desired level of antiglare. It's okay.
  • the yellowness index of the B-stage coating film laminated film of the present invention is usually 5 or less, preferably 3 or less. It may be preferably 2 to -2, more preferably 1 to -1.
  • the yellowness index is a value measured according to JIS K7105: 1981.
  • a chromaticity meter for example, a chromaticity meter "SolidSpec-3700" (trade name) manufactured by Shimadzu Corporation can be used.
  • the transparent resin film is preferably a transparent resin film made of an acrylic resin.
  • the acrylic resin for example, a constituent unit derived from a (meth) acrylic acid ester (co) polymer or a (meth) acrylic acid ester is mainly (usually 50 mol% or more, preferably 65 mol% or more, more preferably 65 mol% or more). Can be mentioned as copolymers containing 70 mol% or more, and modified products thereof.
  • the (meth) acrylic means acrylic or methacryl.
  • the (co) polymer means a polymer or a copolymer.
  • Examples of the (meth) acrylate (co) polymer include methyl poly (meth) acrylate, ethyl poly (meth) acrylate, propyl poly (meth) acrylate, and butyl poly (meth) acrylate. Examples thereof include a methyl (meth) acrylate / butyl acrylate copolymer and an ethyl (meth) acrylate / butyl (meth) acrylate copolymer.
  • Examples of the copolymer mainly containing the structural unit derived from the (meth) acrylate ester include ethylene / methyl (meth) acrylate copolymer, styrene / methyl (meth) acrylate copolymer, and vinylcyclohexane. Examples thereof include (meth) methyl acrylate copolymer, maleic anhydride / (meth) methyl acrylate copolymer, and N-substituted maleimide / (meth) methyl acrylate copolymer.
  • modified product examples include a polymer in which a lactone ring structure is introduced by an intramolecular cyclization reaction; a polymer in which a glutaric anhydride is introduced by an intramolecular cyclization reaction; and an imidizing agent (for example, methyl).
  • an imidizing agent for example, methyl
  • the transparent resin film of the acrylic resin examples include a film of one or a mixture of two or more of these. Further, these films include a laminated film in which one or more of these are laminated in two or more layers.
  • the transparent resin film examples include a copolymer of a (meth) acrylic acid ester such as an N-substituted maleimide / methyl (meth) acrylate copolymer and a polymerizable monomer having an imide structure; and an imide of an acrylic resin.
  • a transparent film of a polymer having an imide structure introduced by reacting with an agent hereinafter, these may be collectively referred to as "poly (meth) acrylicimide-based resin", the above-mentioned poly (meth) acrylicimide-based resin.
  • a transparent multilayer film containing one or more layers formed by using a resin is more preferable.
  • the molded product formed by using the B-stage coating film laminated film of the present invention has a surface hardness. It can be excellent in scratch resistance, transparency, surface smoothness, appearance, rigidity, heat resistance, and heat dimensional stability.
  • the poly (meth) acrylicimide-based resin can also be defined as a thermoplastic resin having both an acrylic structure and an imide structure. Since the poly (meth) acrylicimide-based resin has an acrylic structure, it has the characteristics of high transparency, high surface hardness, and high rigidity of the acrylic resin. Further, since the poly (meth) acrylicimide-based resin has an imide structure, it has a feature of being excellent in heat resistance and dimensional stability of polyimide. Further, the poly (meth) acrylicimide-based resin has an improved drawback that it is usually colored from light yellow to reddish brown of polyimide.
  • the glass transition temperature of the poly (meth) acrylicimide-based resin is usually 110 ° C. or higher, preferably 115 ° C. or higher, more preferably 120 ° C. or higher, still more preferably 130 ° C. or higher, still more preferably. It may be 140 ° C. or higher.
  • the glass transition temperature of the poly (meth) acrylicimide-based resin is usually 170 ° C. or lower, preferably 165 ° C. or lower, more preferably 160 ° C. or lower, still more preferably 155 ° C. or lower, from the viewpoint of three-dimensional moldability. It may be there.
  • the glass transition temperature is maintained at 250 ° C. for 3 minutes, cooled to 20 ° C. at 10 ° C./min, held at 20 ° C. for 3 minutes, and raised to 250 ° C. at 10 ° C./min according to JIS K7121-1987. It is the midpoint glass transition temperature calculated from the curve of the last heating process measured by the program.
  • the differential scanning calorimetry for example, Diamond DSC of PerkinElmer Japan Co., Ltd. can be used.
  • the yellowness index of the poly (meth) acrylicimide-based resin may be usually 5 or less, preferably 3 or less, more preferably 2 to -2, and further preferably 1 to -1.
  • a poly (meth) acrylicimide-based resin having a yellowness index of 5 or less a B-stage coating film laminated film having a color suitable for a vehicle member such as a vehicle instrument panel, and a molded product using the same color can be obtained. Obtainable.
  • the yellowness index is a value measured according to JIS K7105: 1981.
  • chromaticity meter for example, a chromaticity meter "SolidSpec-3700" (trade name) manufactured by Shimadzu Corporation can be used.
  • the melt mass flow rate of the poly (meth) acrylicimide-based resin is preferably 0 from the viewpoint of extrusion load during film formation and stability of the molten film. It may be 1 to 20 g / 10 minutes, more preferably 0.5 to 10 g / 10 minutes.
  • the poly (meth) acrylicimide-based resin may be a thermoplastic resin other than the poly (meth) acrylicimide-based resin, if desired, to the extent that it does not contradict the object of the present invention; pigments, inorganic fillers, organic fillers, resin fillers; Additives such as lubricants, antioxidants, weathering stabilizers, heat stabilizers, mold release agents, antistatic agents, and surfactants can be further included.
  • the blending amount of these optional components is usually 10 parts by mass or less, or about 0.01 to 10 parts by mass, when the poly (meth) acrylicimide-based resin is 100 parts by mass.
  • the transparent resin film is preferably a transparent multilayer film in which an acrylic resin layer ( ⁇ ); an aromatic polycarbonate resin layer ( ⁇ ) is directly laminated in this order.
  • the transparent resin film is more preferably a transparent multilayer film in which a first acrylic resin layer ( ⁇ 1); an aromatic polycarbonate resin layer ( ⁇ ); and a second acrylic resin layer ( ⁇ 2) are directly laminated in this order. It may be.
  • Acrylic resins have excellent surface hardness but tend to have insufficient machinability, whereas aromatic polycarbonate resins have excellent machinability but tend to have insufficient surface hardness. .. Therefore, by using the transparent multilayer film having the above layer structure, the weak points of both are compensated for, and after the B stage coating film is completely cured (C stage), the B stage coating is excellent in both surface hardness and machinability. A film laminated film can be easily obtained.
  • the transparent multilayer film in which the first acrylic resin layer ( ⁇ 1); the aromatic polycarbonate resin layer ( ⁇ ); the second acrylic resin layer ( ⁇ 2) are directly laminated in this order is B on the ⁇ 1 layer side. It will be described as assuming that a stage coating film is formed.
  • the layer thickness of the ⁇ 1 layer is not particularly limited, but from the viewpoint of the surface hardness after the B stage coating film is completely cured (C stage), it is usually 20 ⁇ m or more, preferably 40 ⁇ m or more, more preferably 50 ⁇ m or more, still more preferably. It may be 80 ⁇ m or more.
  • the layer thickness of the ⁇ 2 layer is not particularly limited, but from the viewpoint of curl resistance, it is preferable that the layer thickness is the same as that of the ⁇ 1 layer.
  • “same layer thickness” should not be interpreted as the same layer thickness in a physicochemically strict sense. It should be interpreted as the same layer thickness within the range of fluctuations in process and quality control that are usually performed in industry. This is because the curl resistance of the multilayer film can be kept good if the layer thickness is the same within the range of the fluctuation width of the process / quality control that is usually performed industrially.
  • the process and quality are usually controlled with a width of about -5 to +5 ⁇ m. Therefore, for example, a layer thickness of 65 ⁇ m and 75 ⁇ m are interpreted as the same. Should be.
  • the layer thickness of the ⁇ layer is not particularly limited, but from the viewpoint of machinability, it may be usually 20 ⁇ m or more, preferably 70 ⁇ m or more.
  • the acrylic resin used for the ⁇ 1 layer and the ⁇ 2 layer is described above.
  • the acrylic resin used for the ⁇ 1 layer and the acrylic resin used for the ⁇ 2 layer may have different resin characteristics, for example, different acrylic resins such as type, melt mass flow rate, and glass transition temperature. .. From the viewpoint of curl resistance of the hard coat laminated film of the present invention, it is preferable to use one having the same resin characteristics. For example, using the same lot of the same grade is one of the preferred embodiments.
  • aromatic polycarbonate-based resin used for the ⁇ layer examples include aromatic dihydroxy compounds such as bisphenol A, dimethylbisphenol A, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and phosgen. Polymers obtained by the interfacial polymerization method with; aromatic dihydroxy compounds such as bisphenol A, dimethylbisphenol A, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and carbonic acid such as diphenyl carbonate.
  • aromatic dihydroxy compounds such as bisphenol A, dimethylbisphenol A, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane
  • carbonic acid such as diphenyl carbonate.
  • One or a mixture of two or more aromatic polycarbonate-based resins such as a polymer obtained by an ester exchange reaction with a diester can be used.
  • core-shell rubber As a preferable optional component that can be contained in the aromatic polycarbonate-based resin, core-shell rubber can be mentioned.
  • the core shell rubber is 0 to 30 parts by mass (100 to 70 parts by mass of the aromatic polycarbonate resin), preferably 0 to 10 parts by mass (aromatic).
  • core-shell rubber examples include methacrylic acid ester / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / ethylene / propylene rubber graft copolymer, and acrylonitrile / styrene / acrylic.
  • Acid ester graft copolymer methacrylic acid ester / acrylic acid ester rubber graft copolymer, methacrylic acid ester / styrene / acrylic acid ester rubber graft copolymer, and methacrylic acid ester / acrylonitrile / acrylic acid ester rubber graft copolymer.
  • You can give core-shell rubber such as.
  • As the core-shell rubber one kind or a mixture of two or more kinds of these can be used.
  • the above aromatic polycarbonate resin may be optionally a thermoplastic resin other than the aromatic polycarbonate resin or the core shell rubber; a pigment, an inorganic filler, an organic filler, a resin filler; a lubricant, as long as it does not contradict the object of the present invention.
  • Additives such as antioxidants, weathering stabilizers, heat stabilizers, mold release agents, antistatic agents, and surfactants can be further included.
  • the blending amount of these optional components is usually 10 parts by mass or less, or about 0.01 to 10 parts by mass, when the total of the aromatic polycarbonate resin and the core-shell rubber is 100 parts by mass.
  • the manufacturing method of the transparent resin film is not particularly limited.
  • the transparent resin film is directly laminated in this order with the first poly (meth) acrylicimide-based resin layer ( ⁇ 1); the aromatic polycarbonate-based resin layer ( ⁇ ); and the second poly (meth) acrylicimide-based resin layer ( ⁇ 2).
  • the method described in JP-A-2015-0833370 can be mentioned.
  • corona discharge treatment, plasma treatment, anchor coat formation, etc. are performed in advance on one or both sides of the transparent resin film in order to increase the adhesive strength with the B-stage coating film. You may apply the easy-adhesion treatment of.
  • the total light transmittance of the transparent resin film may be usually 85% or more, preferably 88% or more, and more preferably 90% or more. The higher the total light transmittance, the more preferable.
  • a transparent resin film having a total light transmittance of 85% or more articles that require high transparency, for example, a B-stage coating film laminated film suitable as a vehicle member such as a vehicle instrument panel, and a B-stage coating film laminated film thereof.
  • a molded product using the above can be obtained.
  • the total light transmittance is a value measured according to JIS K7361-1: 1997.
  • As the turbidity meter for example, a turbidity meter "NDH2000" (trade name) manufactured by Nippon Denshoku Kogyo Co., Ltd. can be used.
  • the yellowness index of the transparent resin film may be usually 5 or less, preferably 3 or less, more preferably 2 to -2, and even more preferably 1 to -1.
  • a transparent resin film having a yellowness index of 5 or less an article that requires high colorlessness, for example, a B-stage coating film laminated film suitable for a vehicle member such as an instrument panel of a vehicle, and a B-stage coating film laminated film thereof are used. It is possible to obtain a molded product that has been used.
  • the yellowness index is a value measured according to JIS K7105: 1981.
  • chromaticity meter for example, a chromaticity meter "SolidSpec-3700" (trade name) manufactured by Shimadzu Corporation can be used.
  • the retardation of the transparent resin film may be usually 75 nm or less, preferably 50 nm or less, more preferably 40 nm or less, still more preferably 30 nm or less, still more preferably 20 nm or less, and most preferably 15 nm or less.
  • a transparent resin film having a retardation of 75 nm or less an article that requires a clear transparency, for example, a B-stage coating film laminated film suitable for a vehicle member such as an instrument panel of a vehicle, and a B-stage coating film laminated film, which is suitable for use.
  • a molded product can be obtained.
  • the retardation is a value measured by the parallel Nicol rotation method.
  • the phase difference measuring device "KOBRA-WR" (trade name) by the parallel Nicol rotation method of Oji Measuring Instruments Co., Ltd. can be used.
  • the B-stage coating film of the present invention formed on the surface of the film substrate can be used on another substrate (for example, film, sheet, plate).
  • the coating film-forming surface of the film substrate is easily peeled off. It may be there.
  • the easy peeling treatment may be any known treatment method such as forming a peeling layer with a silicone resin or the like.
  • the thickness of the film base material is not particularly limited.
  • the thickness of the film base material is usually preferably 20 ⁇ m or more from the viewpoint of handleability. May be 30 ⁇ m or more.
  • the thickness of the film base material may be usually 100 ⁇ m or less, preferably 75 ⁇ m or less, from the viewpoint of economy.
  • the film base material is, for example, a biaxial resin of a polyester resin such as polyethylene terephthalate. Stretched films, biaxially stretched films made of polypropylene-based resins, and the like are preferable.
  • the molded article of the present invention has a coating film (C stage) obtained by completely curing the B stage coating film of the present invention.
  • a coating film (C stage) obtained by completely curing the B stage coating film of the present invention usually constitutes a part or all of the surface of the molded product.
  • the molded product of the present invention can be produced by imparting a desired shape to the B-stage coating film (and the base material) of the present invention and then completely curing the B-stage coating film (to the C stage).
  • Examples of such a molded product include a film, a sheet, and a plate (a molded product in which a flat shape is maintained) having a coating film (C stage) obtained by completely curing the B-stage coating film of the present invention; the present invention.
  • C stage coating film obtained by completely curing the B-stage coating film of the present invention
  • the B stage coating film is completely cured (to the C stage).
  • the obtained molded product; and the film or sheet having the B-stage coating film of the present invention are inserted into the mold as a skin material, and an arbitrary thermoplastic resin is injected as a core material, and then the B-stage coating film is completely formed.
  • Examples thereof include a composite molded product obtained by curing (on the C stage).
  • the coating film is B-stage
  • a three-dimensional molding method such as vacuum forming and vacuum pressure air forming is applied to give a three-dimensional shape, and then the B-stage coating film is applied.
  • An example in the case of vacuum forming will be described with respect to the method of completely curing (to the C stage) to produce the molded product of the present invention.
  • FIG. 2 is a conceptual diagram showing an example of a vacuum forming apparatus.
  • the B-stage coating film laminated film 1 is heated by using a heating device 2 such as an infrared heater to soften it.
  • the B-stage coating film laminated film 1 is removed from the heating device 2, and the surface of the B-stage coating film laminated film 1 opposite to the surface on the B-stage coating film side is quickly set to the molding die 3 side. Cover the mold 3 so as to cover it (FIG. 2 (b)).
  • the molding die 3 may be preheated.
  • the space 4 between the B-stage coating film laminated film 1 and the molding die 3 is depressurized, the B-stage coating film laminated film 1 is brought into close contact with the molding die 3, and the shape of the molding die 3 is changed to the B-stage coating film.
  • Transfer to the laminated film 1 to obtain a molded product 5 (the coating film is the B stage) (FIG. 4 (c)).
  • the mold 3 may be cooled before the molded product 5 is separated from the mold 3.
  • the molded product of the present invention can be produced by completely curing (to the C stage) the B-stage coating film of the molded product 5 using an arbitrary active energy ray irradiation device.
  • the pressure in the space 4 may be preferably 10 KPa or less, more preferably 1 KPa or less, from the viewpoint of sufficiently adhering the air between the B-stage coating film laminated film 1 and the molding die 3 without leaving air.
  • the adhesion increases as the pressure in the space 4 decreases, but considering that reducing the pressure is costly at an accelerating rate and considering the mechanical strength of the B-stage coating film laminated film 1, it is practically used.
  • the lower limit of the pressure in the space 4 may be about 10-5 KPa.
  • the irradiation amount of the active energy rays is appropriately selected and determined from the viewpoint of making the irradiation amount necessary and sufficient for completely curing the B stage coating film (to the C stage).
  • the dose of the active energy rays usually 10 ⁇ 10000mJ / cm 2, preferably about 200 ⁇ 2000mJ / cm 2, may be more preferably 300 ⁇ 700mJ / cm 2.
  • the molded product of the present invention may have a coating film (C stage) obtained by completely curing the B stage coating film of the present invention and an arbitrary substrate.
  • C stage coating film obtained by completely curing the B stage coating film of the present invention and an arbitrary substrate.
  • the above-mentioned substrate is used instead of the molding die 3, the B-stage coating film laminated film 1 is adhered to and integrated with the above-mentioned substrate, and then the B-stage coating film is completely cured (to the C stage). ) Can be manufactured.
  • the substrate examples include substrates made of wood-based materials such as wood, plywood, laminated wood, particle board, and hard board; polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin), polycarbonate, polyester, polyvinyl chloride. , And a substrate made of a resin-based material such as polyolefin; a substrate made of a metal-based material such as iron and aluminum; and a substrate made of a mineral-based material such as gypsum and calcium silicate.
  • wood-based materials such as wood, plywood, laminated wood, particle board, and hard board
  • ABS resin acrylonitrile-butadiene-styrene copolymer
  • ABS resin acrylonitrile-butadiene-styrene copolymer
  • polycarbonate polyester
  • polyester polyvinyl chloride
  • a substrate made of a resin-based material such as polyolefin
  • the molded product of the present invention has preferable properties as described above, it can be suitably used as an article (including a member of the article).
  • the above-mentioned articles include image display devices such as liquid crystal displays, plasma displays, and electroluminescence displays, and members such as display face plates, transparent conductive substrates, and housings; televisions, personal computers, and tablet-type information devices. , Smartphones, and members such as their housings and display face plates; and further, refrigerators, washing machines, cupboards, clothes racks, and the panels that compose them; building windows and doors; vehicles, vehicle windows, windshields, etc. , Roof windows, instrument panels, etc .; head-up displays, electronic signs, and protective plates thereof; show windows; solar cells, and members such as their housings and front plates.
  • FIG. 3A is a front view of the molding die, where the height (h) is 10 mm and the radius of curvature (R) of the surrounding curved portion is 16.25 mm.
  • FIG. 3B is a plan view of the molding die, wherein the outer diameter ( ⁇ ) is 90 mm.
  • the space between the laminated film and the molding die is set to a pressure of 1.0 ⁇ 10 -3 KPa.
  • the pressure was reduced, and the shape of the molding die was transferred to the laminated film to obtain a molded product (the coating film was B stage).
  • the B-stage coating film of the molded product is irradiated with a high-pressure mercury lamp type ultraviolet irradiation device under the condition of an integrated light amount of 600 mJ / cm 2 , and completely cured (to the C stage) to completely cure the molded product (coating film). Obtained C stage).
  • the appearance of the molded product was visually observed by a person with corrected visual acuity of 1.0 with the naked eye or using a loupe (10 times), and evaluated according to the following criteria.
  • D Cracks and cracks were also observed with the naked eye.
  • the test piece was visually observed, and the elongation at the moment when the coating film of the test piece was cracked was defined as the tensile elongation of the laminated film.
  • the value of the tensile elongation in the test (iii) is considered to correspond to the tensile elongation of the B-stage coating film possessed by the laminated film.
  • test (iv) tack-free test 1 and the test (v) tack-free test 2 have web handleability (during web handling, scratches caused by the coating film coming into contact with a transfer roll or the like). It is considered to be an index of (difficulty of occurrence of poor appearance).
  • the B-stage coating film of the laminated film having the B-stage coating film is irradiated with a high-pressure mercury lamp type ultraviolet irradiation device under the condition of an integrated light intensity of 600 mJ / cm 2 , and completely cured ( The one (on the C stage) was used as a sample.
  • Pencil hardness According to JIS K5600-5-4: 1999, under the conditions of a test length of 25 mm and a load of 750 g, using a pencil "Uni" (trade name) of Mitsubishi Pencil Co., Ltd., on the coated surface of the above sample. Pencil hardness was measured. Whether or not a scar was generated was determined by visually observing the surface of the sample under a fluorescent lamp at a position 50 cm away from the fluorescent lamp.
  • the test piece was visually observed by a person with corrected visual acuity of 1.0 with the naked eye or using a loupe (10 times), and evaluated according to the following criteria.
  • Category 3 The coating film was partially or wholly peeled along the edges of the cut, and / or various parts of the eye were partially or wholly peeled. The area affected by the cross-cut portion clearly exceeded 15% but never exceeded 35%.
  • Category 4 The coating film was partially or wholly peeled along the edge of the cut, and / or several eyes were partially or wholly peeled. The area affected by the cross-cut portion clearly exceeded 35% but never exceeded 65%.
  • Category 5 The case where the degree of peeling exceeds Category 4 is defined as this category.
  • A Active energy ray-curable resin
  • A1-1) Urethane (meth) acrylate
  • A1-2 Diluted solution of polyfunctional urethane (meth) acrylate of Negami Kogyo Co., Ltd. "Art Resin UN-953" (trade name).
  • Solid content 40% by mass, number of functional groups 20, number average molecular weight 2000, mass average molecular weight 26000, Z average molecular weight 110,000.
  • A1-3 Diluted solution of polyfunctional urethane (meth) acrylate of Negami Kogyo Co., Ltd. "Art Resin UN-954" (trade name), solid content 60% by mass, number of functional groups 6, number average molecular weight 2000, mass average molecular weight 4800, Z average molecular weight 9600.
  • A1-4 Polyfunctional urethane (meth) acrylate "EBECRYL4101” (trade name) of Daicel Ornex Co., Ltd. Solid content 100% by mass, number of functional groups 3, number average molecular weight 1100, mass average molecular weight 2800, Z average molecular weight 4900.
  • A2 Mercaptoalkyl Glycol Uryls
  • A2-1 Shikoku Chemicals Corporation's 1,3,4,6-tetrakis (2-mercaptoethyl) glycol uryl "TS-G” (trade name).
  • A2-2 Shikoku Kasei Kogyo Co., Ltd. 1,3,4,6-tetrakis (3-mercaptopropyl) glycoluril "C3TS-G” (trade name).
  • B Photopolymerization Initiator
  • B-1 Acetophenone-based Photopolymerization Initiator from IGM Resins (2-Hyrodoxy-1- ⁇ 4- [4- (2-Hydroxy-2-methyl-propionyl) -benzyl] phenyl ⁇ -2-Methyl-Propane-1-one) "Omnirad 127" (trade name).
  • B-2) An acetophenone-based photopolymerization initiator (1-hydroxycyclohexylphenyl ketone) "Omnirad 184" (trade name) manufactured by IGM Resins.
  • C Thermal polymerization initiator (C-1) Wako Pure Chemical Industries, Ltd. azo compound-based thermal polymerization initiator "VE-073" (trade name), dimethyl 1,1-azobis (1-cyclohexanecarboxylate) ..
  • D Fine Particles
  • D-1 A propylene glycol monomethyl ether dispersion of silica fine particles manufactured by Nissan Chemical Industries, Ltd. "PGM-AC-2140Y” (trade name). Solid content 42% by mass, average particle size 15 nm.
  • D-2) NBC Mesh Tech Co., Ltd.'s antivirus agent (ethanol suspension of cuprous iodide fine particles), average particle size of cuprous iodide fine particles (particle size distribution measured by laser diffraction / scattering method) In the curve, the particle size (particle size) in which the accumulation from the smaller particle is 50% by mass) is 120 nm, and the solid content is 11% by mass.
  • E Water repellent
  • E-1 A diluted solution of an acryloyl group-containing fluoropolyether-based water repellent from Shin-Etsu Chemical Co., Ltd. (trade name). Solid content 20% by mass.
  • E-2) Acryloyl group-containing fluoroalkyl water repellent (2- (perfluorobutyl) ethyl acrylate) "CHEMINOXFAAC-4" (trade name) of Unimatec Co., Ltd. Solid content 100% by mass.
  • (H) B-stage coating film forming coating material (H-1) 127 parts by mass (76 parts by mass in terms of solid content) of the above component (A1-1), 15 parts by mass of the above component (A1-4), the above component (A2-) 1) 9 parts by mass, 9 parts by mass of the component (B-1), 0.03 parts by mass of the component (C-1), 502 parts by mass of the component (D-1) (211 parts by mass in terms of solid content), the above. 1.14 parts by mass of component (E-1) (0.23 parts by mass in terms of solid content) and 220 parts by mass of methylisobutylketone (described as "MIBK" in the table) are mixed and stirred to form a B-stage coating film. Obtained paint for mass. In the table, all the values in terms of solid content are shown except for the solvent.
  • P Transparent resin film
  • P-1 Type 2 3-layer multi-manifold co-extruded T-die, first mirror surface roll (roll on the side that holds the molten film and sends it to the next transfer roll) and second mirror surface
  • Ebonic's poly (meth) acrylicimide is used as both outer layers ( ⁇ 1 layer and ⁇ 2 layer) of a two-kind three-layer multilayer resin film.
  • PLEXIMID TT50 trade name
  • the aromatic polycarbonate "Calibre 301-4" trade name of Sumika Stylon Polycarbonate Co., Ltd.
  • the ⁇ 1 layer is supplied and charged between the rotating first mirror surface roll and the second mirror surface roll so that the ⁇ 1 layer is on the first mirror surface roll side, and pressed to obtain a total thickness of 170 ⁇ m, a layer thickness of the ⁇ 1 layer of 50 ⁇ m, and a ⁇ layer.
  • a transparent resin film having a layer thickness of 70 ⁇ m and an ⁇ 2 layer thickness of 50 ⁇ m was obtained.
  • the setting conditions were a set temperature of the T die of 300 ° C., a set temperature of the first mirror surface roll of 130 ° C., a set temperature of the second mirror surface roll of 120 ° C., and a take-up speed of 9.5 m / min.
  • Example 1 Corona discharge treatment was performed on both sides of the above (P-1). The wettability index was 64 mN / m on both sides. (2) Next, after the above (H-1) is completely cured (made into a C stage) by using a die-type coating device on the surface of the above (P-1) on the ⁇ 1 layer side. It was applied so as to have a thickness of 18 ⁇ m to form a wet coating film. (3) Next, the drying furnace set to the furnace temperature of 130 ° C. is passed at a line speed at which the time required to pass from the inlet to the outlet (described as "required time” in the table) is 6 minutes. The wet coating film was dried and cured to a B stage state.
  • Examples 2-8, 10 A laminated film having a B-stage coating film was obtained in the same manner as in Example 1 except that the coating materials shown in Tables 1 and 2 were used instead of the above (H-1) as the coating material for forming the B-stage coating film. .. The above tests (i) to (xii) were performed. The results are shown in Tables 1 and 2.
  • Example 9 When the above (H-9) was used instead of the above (H-1) as the B-stage coating film forming paint, the web coming out of the drying oven was handled while being held by a chill roll set at a temperature of 25 ° C. In this process, a trouble occurred in which the coating film adhered to the apparatus, and the B-stage coating film laminated film could not be obtained.
  • the B-stage coating film can be industrially stably produced by using the B-stage coating film forming paint of the present invention.
  • the preferable B-stage coating film of the present invention is excellent in three-dimensional moldability and web handling property in the B stage, and surface hardness, transparency, chemical resistance, coating film adhesion, and moist heat after complete curing (in the C stage). It was excellent in coating film adhesion and scratch resistance after the test. Therefore, the B-stage coating film of the present invention is applied to the surface of a molded body having a three-dimensional shape / three-dimensional shape, for example, a housing of a home appliance or an information electronic device, and a molded body such as an instrument panel of an automobile. It can be suitably used to impart functions such as surface hardness, scratch resistance, and chemical resistance.

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