WO2021140874A1 - Ｂステージ塗膜、積層フィルム、三次元成形体、及びこれらの製造方法 - Google Patents

Ｂステージ塗膜、積層フィルム、三次元成形体、及びこれらの製造方法 Download PDF

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Publication number
WO2021140874A1
WO2021140874A1 PCT/JP2020/047446 JP2020047446W WO2021140874A1 WO 2021140874 A1 WO2021140874 A1 WO 2021140874A1 JP 2020047446 W JP2020047446 W JP 2020047446W WO 2021140874 A1 WO2021140874 A1 WO 2021140874A1
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Prior art keywords
coating film
film
stage
meth
mass
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Ceased
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English (en)
French (fr)
Japanese (ja)
Inventor
望 鷲尾
幹規 安藤
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Riken Technos Corp
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Riken Technos Corp
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Priority to JP2021569807A priority Critical patent/JP7670624B2/ja
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Anticipated expiration legal-status Critical
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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
    • B05D3/12—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 mechanical means
    • 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
    • B05D7/02—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 to macromolecular substances, e.g. rubber
    • B05D7/04—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 to macromolecular substances, e.g. rubber to surfaces of films or sheets
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
    • B29C43/30—Making multilayered or multicoloured articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
    • B29C51/14—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor using multilayered preforms or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • 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
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal 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 B-stage coating film and a method for producing a B-stage coating film. More specifically, the present invention relates to a B-stage coating film, a laminated film, a three-dimensional molded product, and a method for producing these.
  • 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 on the surface of the thermoplastic resin film by applying a paint 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 method for producing a B-stage coating film. Another object of the present invention is to provide a novel B-stage coating film.
  • a further subject of the present invention is 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), and a B-stage coating film thereof.
  • the purpose is to provide a manufacturing method.
  • Another object of the present invention is to obtain 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). It is an object of the present invention to provide a laminated film having, the above-mentioned coating film or a molded product containing the laminated film, and a method for producing these.
  • a step of overlaying a protective film on the surface of the dry coating film formed in the step (2) and temporarily attaching the protective film is included.
  • Step to obtain B stage coating film (Q) The three-dimensional shape of the B-stage coating film applied on the film substrate or the B-stage coating film transferred onto a substrate other than the film substrate obtained in the step (P). The process of imparting; (R) The above method including the step of completely curing the B stage coating film imparted with a three-dimensional shape in the above step (Q).
  • the B stage coating film can be industrially stably produced.
  • a B-stage coating film having excellent three-dimensional moldability can be industrially 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 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, and chemical resistance, and have a good 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 conceptual diagram showing an example of an apparatus used for temporarily adhering a protective film on the surface of a dry coating film.
  • FIG. 2 is a GPC curve of the component (A1-1) used in the examples.
  • FIG. 3 is a GPC curve of the component (A2-1) used in the examples.
  • FIG. 4 is a conceptual diagram illustrating vacuum forming.
  • FIG. 5 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 production method of the present invention comprises (1) a coating film containing (A) an active energy ray-curable resin and (B) a photopolymerization initiator on at least one surface of a film substrate.
  • a step of forming a wet coating film using hereinafter, sometimes abbreviated as "B-stage coating film forming coating film”
  • the wet coating film formed in the above step (1) is pre-dried and dried. It includes a step of forming a coating film; and (3) a step of autoclaving the dry coating film formed in the above step (2).
  • the above step (1) is a step of forming a wet coating film on at least one surface of the film base material by using the above B stage coating film forming paint.
  • the step (1) is usually a step of forming a wet coating film on one surface of the film base material using the B-stage coating film forming paint.
  • 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 coating material described in "2. B-stage coating film” or the like described later can be preferably used.
  • the method of forming a wet coating film on the surface of the film substrate by using the B-stage coating film forming paint is not particularly limited, and a known web application method is used. be able to.
  • 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 step (2) is a step of pre-drying the wet coating film formed in the step (1) to form a dry coating film.
  • the pre-drying is, for example, for passing the web from the inlet to the outlet in a drying oven where the temperature is usually set to about 23 to 150 ° C., preferably to 50 to 130 ° C., more preferably 70 to 120 ° C. This can be done by passing at a line speed such that the time required is about 0.5 to 10 minutes, preferably 1 to 5 minutes.
  • the step (2) and before the step (3) it is preferable to superimpose a protective film on the surface of the dry coating film formed in the step (2) and temporarily attach the protective film. It is possible to suppress manufacturing troubles such as scratches on the coating film (dry coating film or B stage 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.
  • FIG. 1 is a conceptual diagram showing an example of an apparatus used for temporarily adhering the protective film on the surface of the dry coating film.
  • the laminate 1 obtained in the step (2) (the laminate having the dry coating film on one surface of the film substrate) is placed on the rotating rotating drum 3 as described above.
  • the surface opposite to the dry coating film is placed on the rotating drum 3 side, and the protective film 2 is placed on the surface of the dry coating film of the laminate 1 and crimped by the crimping roll 4.
  • the laminated body 5 in which the protective film 2 is laminated and temporarily attached on the surface of the dry coating film is released from the rotary drum 3 by the guide roll 6 and sent to the step (3).
  • the rotating drum 3 may be preheated to a desired temperature.
  • the temperature of the rotating drum 3 may be usually room temperature (about 23 ° C.) to about 100 ° C., preferably room temperature (about 23 ° C.) to about 50 ° C.
  • a film having active energy ray transmittance (hereinafter, may be referred to as "active energy ray transparent protective film”) is preferable.
  • active energy ray transparent protective film a film having active energy ray transmittance
  • the thickness of the protective film is not particularly limited, but may be, for example, in the range of about 10 ⁇ m to about 600 ⁇ m, preferably in the range of 20 ⁇ m to 250 ⁇ m.
  • the active energy ray transmittance of the film is usually 70% or more, preferably 80% or more.
  • the active energy ray transmittance is a wavelength of 200 to 600 nanometers with respect to the integrated area of the transmission spectrum assuming that the transmittance of the active energy ray in the entire range of wavelengths of 200 to 600 nanometers is 100%. It is the ratio of the integrated area of the transmission spectrum of the active energy ray in.
  • the transmission spectrum is measured by incident light on a film at an incident angle of 0 ° using a spectrophotometer.
  • a spectrophotometer for example, a spectrophotometer "SolidSpec-3700" (trade name) manufactured by Shimadzu Corporation can be used.
  • Examples of the active energy ray-permeable protective film include a polyethylene terephthalate resin film, a polypropylene resin film, an aromatic polycarbonate resin film, and a fluororesin-containing resin film.
  • the surface of the protective film to be bonded to the dry coating film may be easily peeled, not easily peeled, or easily adhered. May be good.
  • the easy peeling treatment may be any known treatment method such as forming a peeling layer with a silicone resin or the like.
  • the easy-adhesion treatment may be any known treatment method such as corona discharge treatment, plasma treatment, and anchor coat formation.
  • a film having an embossed pattern on the bonding surface is typically used, and the shape thereof is changed to the above. Even when an embossed pattern is to be formed on the surface of the dry coating film by transferring to the dry coating film, it is possible to suppress manufacturing troubles when the protective film is peeled off or removed.
  • the B-stage coating film forming paint has a tack-free property only by drying the coating film. Even when it is expressed, the adhesion between the dry coating film and the protective film can be maintained at the minimum level required for web handling.
  • the "tack-free property" here means that the coating film is less likely to be scratched or have a poor appearance due to contact with a transfer roll or the like during web handling.
  • a protective film whose bonding surface with the dry coating film is easily adhered means that the B-stage coating film forming surface is easily peeled off as the film base material used in the step (1). It is useful as one of the embodiments when the above-mentioned one is used.
  • the B-stage coating film is usually used by being transferred from the film base material used in the step (1) to the protective film. In this case, it goes without saying that "temporary pasting" can be technically read as “pasting and adhering”.
  • the surface of the protective film to be bonded to the dry coating film may be highly smooth, satin-finished, or embossed.
  • the fully cured (C stage) coating film formed by using the B stage coating film of the present invention has high gloss.
  • the completely cured (C-stage) coating film formed by using the B-stage coating film of the present invention becomes matte (those having low gloss).
  • the completely cured (C stage) coating film formed by using the B stage coating film of the present invention has an embossed pattern.
  • the step (3) is a step of autoclaving the dry coating film formed in the step (2).
  • a three-dimensional molded product is produced using the laminate having the B-stage coating film of the present invention by the above step (3), for example, a step of imparting a three-dimensional shape to the B-stage coating film of the present invention, or In the step of completely curing (to C stage) the B-stage coating film of the present invention, it is possible to suppress manufacturing troubles such as foaming of the coating film.
  • the shape of the bonding surface of the protective film with the dry coating film can be transferred to the surface of the dry coating film by the step (3).
  • the protective film even if air is caught between the protective film and the dry coating film by the step (3), the air is eliminated and the appearance is poor. Can be prevented from occurring.
  • the above step (3) can be performed by the following procedure.
  • the dry coating film formed in the step (2) inside the autoclave apparatus a laminate having the dry coating film on at least one surface of the film substrate; A laminate having the dry coating film on at least one surface of the film substrate, and the protective film being laminated and temporarily attached on the surface; or a wound body of these laminates; The same applies hereinafter in this paragraph
  • the lid of the autoclave device is closed.
  • the inside of the autoclave device is heated to a predetermined temperature and pressure, and after reaching the temperature and pressure, the temperature and pressure are maintained for a predetermined time (hereinafter, may be referred to as “holding time”). To do.
  • the lid of the autoclave device can be opened and the dry coating film formed in the step (2) can be taken out.
  • the autoclave device is not particularly limited, but any known autoclave device can be used.
  • the temperature, pressure, and holding time of the autoclave treatment can be appropriately selected in consideration of the characteristics of the coating material used for forming the B-stage coating film of the present invention and the film substrate.
  • the temperature, pressure, and holding time of the autoclave treatment take into consideration the characteristics of the paint used for forming the B-stage coating film of the present invention, the film substrate, and the protective film in the embodiment using the protective film. Can be selected as appropriate.
  • the pressure of the autoclave treatment is usually higher than the normal pressure (0.1 MPa), preferably 0.15 to 1 MPa, more preferably 0.2 to 0.7 MPa, still more preferably 0.3 to 0.6 MPa. It may be there.
  • the temperature of the autoclave treatment may be usually room temperature (about 23 ° C.) to 100 ° C., preferably 30 to 80 ° C., and more preferably 40 to 60 ° C.
  • the holding time of the autoclave treatment may be usually 1 to 60 minutes, preferably 3 to 30 minutes, and more preferably 5 to 20 minutes.
  • the characteristics of the B-stage coating film of the present invention can be stabilized. Further, when producing a three-dimensional molded product using the laminated film having the B-stage coating film of the present invention, for example, a step of imparting a three-dimensional shape to the B-stage coating film of the present invention or a B-stage coating of the present invention. In the process of completely curing the film (to the C stage), the risk of manufacturing troubles such as foaming of the coating film can be further suppressed.
  • the conditions for the aging process are not particularly limited.
  • the temperature of the aging treatment may be usually about 23 to 150 ° C., preferably a temperature of 50 to 120 ° C., and more preferably 70 to 100 ° C.
  • the time of the aging treatment is usually about 10 minutes to 10 hours, preferably 30 minutes to 4 hours, and more preferably 1 to 3 hours.
  • the B-stage coating film of the present invention uses the above-mentioned paint for forming a B-stage coating film (a coating material containing the above-mentioned component (A) active energy ray-curable resin and the above-mentioned component (B) photopolymerization initiator). It is formed by any method.
  • the B-stage coating film of the present invention preferably uses the above-mentioned B-stage coating film forming coating material (a coating material containing the above-mentioned component (A) active energy ray-curable resin and the above-mentioned component (B) photopolymerization initiator). It is formed by the manufacturing method of the present invention.
  • the paint for forming a B-stage coating film (a paint containing the component (A) active energy ray-curable resin and the component (B) photopolymerization initiator) will be described.
  • 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 ratio of the above-mentioned component (A1) is 100% by mass of the total of the above-mentioned components (A).
  • The% may be usually 10% by mass or more, preferably 25% by mass or more, and more preferably 40% by mass or more, from the viewpoint of surely obtaining the effect of using the above component (A1).
  • the blending ratio of the above component (A1) is usually 99% by mass or less, preferably 95% by mass or less, more preferably 93% by mass or less, still more preferably 85% by mass or less, most preferably from the viewpoint of surface hardness. It may be 65% by mass or less.
  • the compounding ratio of the above component (A1) is the sum of the above components (A). As 100% by mass, it may be preferably 65 to 100% by mass, more preferably 75 to 100% by mass.
  • component (A) active energy ray-curable resin it is preferable to use a resin containing a copolymer of (A2) (a1) polyfunctional (meth) acrylate and (a2) polyfunctional thiol.
  • A2) (a1) polyfunctional (meth) acrylate and (a2) polyfunctional thiol a resin containing a copolymer of (A2) (a1) polyfunctional (meth) acrylate and (a2) polyfunctional thiol.
  • the surface hardness, scratch resistance, and chemical resistance after complete curing (at the C stage) can be improved.
  • the B-stage coating film of the present invention is formed only on one surface of the film base material, curling and warpage of the laminated body can be suppressed.
  • the component (A) active energy ray-curable resin containing a copolymer of the component (A2) (a1) polyfunctional (meth) acrylate and (a2) polyfunctional thiol is used
  • the component (A2) ) Is usually 1% by mass or more, preferably 5% by mass or more, more preferably 1% by mass or more, from the viewpoint of surely obtaining the effect of using the above component (A2), assuming that the total of the above components (A) is 100% by mass. It may be 7% by mass or more.
  • the compounding ratio of the above component (A2) is usually 90% by mass or less, preferably 75% by mass or less, and more preferably 60% by mass or less from the viewpoint of crack resistance after complete curing (in the C stage). You can.
  • the component (A) active energy ray-curable resin the copolymer of the component (A1) urethane (meth) acrylate and the components (A2) (a1) polyfunctional (meth) acrylate and (a2) polyfunctional thiol. It is more preferable to use one containing coalescence. Three-dimensional moldability in the B-stage coating film; and both surface hardness, scratch resistance, and chemical resistance after complete curing (in the C stage) can be further improved in a well-balanced manner.
  • the component (A) active energy ray-curable resin a copolymer of the component (A1) urethane (meth) acrylate and the component (A2) (a1) polyfunctional (meth) acrylate and (a2) polyfunctional thiol.
  • the compounding ratio (the mass of the above component (A1) / the mass of the above component (A2)) is the three-dimensional moldability in the B stage coating film.
  • this compounding ratio is preferably 99/1 to 65/35, more preferably 99/1 to 65/35. It may be 95/5 to 75/25, more preferably 93/7 to 75/25.
  • component (A) active energy ray-curable resin a copolymer of the component (A1) urethane (meth) acrylate and the component (A2) (a1) polyfunctional (meth) acrylate and (a2) polyfunctional thiol.
  • the sum of the blending amount of the component (A1) and the blending amount of the component (A2) is such that the total of the components (A) is 100% by mass, and the three-dimensional moldability in the B stage coating film is formed.
  • it is usually 80% by mass or more, preferably 90% by mass or more, and more preferably 95% by mass. As described above, it may be more preferably 98 to 100% by mass.
  • (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 differential molecular weight distribution curve
  • GPC gel permeation chromatography
  • Mn urethane (meth) acrylate of the above component (A1).
  • the polystyrene-equivalent number average molecular weight (Mn) is determined from the viewpoint of three-dimensional moldability, and in the embodiment in which the protective film is used, the adhesion between the dry coating film and the protective film is determined when web handling is performed. From the viewpoint of maintaining the minimum required level, it may be usually 500 or more, preferably 1000 or more. On the other hand, the number average molecular weight (Mn) may be usually 30,000 or less, preferably 20,000 or less, from the viewpoint of coatability.
  • the polystyrene-equivalent mass average molecular weight (Mw) obtained from the GPC curve of the urethane (meth) acrylate of the component (A1) measured by GPC is determined from the viewpoint of three-dimensional moldability and in the embodiment using the protective film. From the viewpoint of maintaining the adhesion between the dry coating film and the protective film to the minimum level required for web handling, it may be usually 1000 or more, preferably 2000 or more. On the other hand, the mass average molecular weight (Mw) may be usually 100,000 or less, preferably 50,000 or less, from the viewpoint of coatability.
  • the number of (meth) acryloyl groups contained in the urethane (meth) acrylate of the above component (A1) is per 1000 of polystyrene-equivalent number average molecular weight (Mn) determined from the GPC curve, from the viewpoint of web handleability, and after complete curing ( From the viewpoint of surface hardness, scratch resistance, and chemical resistance (in the C stage), the number may be usually 2 or more, preferably 3 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 handleability here means that the coating film is less likely to be scratched or have a poor appearance due to contact with the transfer roll or the like during web handling.
  • the polystyrene-equivalent Z average molecular weight (Mz) determined from the GPC curve of the urethane (meth) acrylate of the component (A1) measured by GPC is determined from the viewpoint of three-dimensional moldability and in the embodiment using the protective film. From the viewpoint of maintaining the adhesion between the dry coating film and the protective film to the minimum level required for web handling, it may be usually 1500 or more, preferably 2500 or more. On the other hand, the Z average molecular weight (Mz) may be usually 150,000 or less, preferably 100,000 or less, from the viewpoint of coatability.
  • 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. 2 shows the differential molecular weight distribution curve of the following component (A1-1) used in the examples.
  • Two sharp peaks are observed in the region of relatively low molecular weight, and the polystyrene-equivalent molecular weights at the peak top positions are 280 and 610 in order from the low molecular weight side.
  • a peak of the main component is observed on the high molecular weight side of these two peaks, and the polystyrene-equivalent molecular weight at the peak top position is 2400.
  • the total number average molecular weight (Mn) is 1000
  • the mass average molecular weight (Mw) is 2900
  • the Z average molecular weight (Mz) is 4700.
  • the number of (meth) acryloyl groups per molecule is 2, the number of (meth) acryloyl groups per 1000 of polystyrene-equivalent number average molecular weight (Mn) obtained from the GPC curve is 2.
  • (A2) (a1) Copolymer of polyfunctional (meth) acrylate and (a2) polyfunctional thiol
  • the above component (A2) is a copolymer of (a1) polyfunctional (meth) acrylate and (a2) polyfunctional thiol. It is a copolymer. Since both the component (a1) and the component (a2) are polyfunctional monomers, the component (A2) is usually a copolymer having a highly branched structure, that is, a so-called dendrimer structure.
  • the component (a1) polyfunctional (meth) acrylate is a (meth) acrylate having two or more (meth) acryloyl groups in one molecule.
  • the number of (meth) acryloyl groups in one molecule of the component (a1) is preferably 3 or more, more preferably 3 or more, from the viewpoint of making the structure of the component (A2) copolymer have a so-called dendrimer structure. It may be 4 or more, more preferably 5 or more.
  • the number may be usually 20 or less, preferably 12 or less.
  • component (a1) polyfunctional (meth) acrylate examples include diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and polyethylene glycol di (meth).
  • (Meta) acryloyl groups such as acrylate, 2,2'-bis (4- (meth) acryloyloxypolyethyleneoxyphenyl) propane, and 2,2'-bis (4- (meth) acryloyloxypolypropylene oxyphenyl) propane.
  • bifunctional reactive monomer Containing bifunctional reactive monomer; (meth) acryloyl group-containing trifunctional reactive monomer such as trimethylolpropantri (meth) acrylate, trimethylol ethanetri (meth) acrylate, and ethoxylated trimethylolprophantri (meth) acrylate; Ditrimethylolpropantetra (meth) acrylate and (meth) acryloyl group-containing tetrafunctional reactive monomer such as pentaerythritol tetramethacrylate; (meth) acryloyl group-containing hexafunctional reactive monomer such as dipentaerythritol hexaacrylate; tripentaerythritol (Meta) acryloyl group-containing octafunctional reactive monomers such as octaacrylate; and polymers (oligomers and prepolymers) containing one or more of these as constituent monomers, and two or more (meth
  • the component (a1) examples include polyurethane (meth) acrylate, polyester (meth) acrylate, polyacrylic (meth) acrylate, polyepoxy (meth) acrylate, polyalkylene glycol poly (meth) acrylate, and poly.
  • Prepolymers or oligomers such as ether (meth) acrylates, which have two or more (meth) acryloyl groups in one molecule, can be mentioned.
  • the component (a1) one kind or a mixture of two or more kinds of these can be used.
  • the above component (a2) polyfunctional thiol is a compound having two or more thiol groups in one molecule.
  • the number of thiol groups in one molecule of the component (a2) is preferably 3 or more, more preferably 4 or more, from the viewpoint of making the structure of the component (A2) copolymer have a so-called dendrimer structure. May be.
  • the number may be usually 20 or less, preferably 12 or less.
  • the thiol group contained in the component (a2) may be preferably a secondary thiol group from the viewpoint of the balance between reactivity and handleability.
  • the above component (a2) polyfunctional thiol has one or more (meth) acryloyl groups, vinyl groups, epoxy groups, isocyanate groups and other polymerizable functional groups other than thiol groups in one molecule. There may be.
  • a compound having two or more thiol groups in one molecule and having two or more (meth) acryloyl groups is classified into the above component (a2).
  • Examples of the component (a2) polyfunctional thiol include 1,2-ethanedithiol, ethylene glycol bis (3-mercaptopropionate), diethylene glycol bis (3-mercaptopropionate), and 1,4-bis (3).
  • the above-mentioned component (A2) copolymer is a monomer copolymerizable with the above-mentioned component (a1) polyfunctional (meth) acrylate and the above-mentioned component (a2) polyfunctional thiol as long as it does not contradict the object of the present invention. It may include a structural unit derived from.
  • the copolymerizable monomer is usually a compound having a carbon-carbon double bond, and typically a compound having an ethylenic double bond.
  • the content of the structural unit derived from the component (a1) polyfunctional (meth) acrylate in the component (A2) copolymer (hereinafter, may be abbreviated as "(a1) content”) is polymerizable.
  • the total of the structural units derived from the monomers is usually 50 mol% or more, preferably 50 mol% or more. May be 60 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more.
  • the structure of the above component (A2) copolymer having a so-called dendrimer structure and from the viewpoint of crack resistance and handleability after the coating film is completely cured (at the C stage), it is usually 99 mol%.
  • it may be preferably 97 mol% or less, more preferably 95 mol% or less, still more preferably 93 mol% or less.
  • the content of the structural unit derived from the component (a2) polyfunctional thiol in the component (A2) copolymer (hereinafter, may be abbreviated as "(a2) content”) is derived from the polymerizable monomer.
  • (a2) content is derived from the polymerizable monomer.
  • the structure of the above component (A2) copolymer having a so-called dendrimer structure is usually 50 mol% or less, preferably 40 mol% or less, more preferably 30 mol%.
  • it may be more preferably 20 mol% or less.
  • the sum of the above (a1) polyfunctional (meth) acrylate content and the above (a2) polyfunctional thiol content is usually 80 mol% or more, where the total of the structural units derived from the polymerizable monomer is 100 mol%. It may be preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 99 mol% or more, and 100 mol% or less.
  • the "polymerizable monomer” means the above-mentioned component (a1), the above-mentioned component (a2), and a monomer copolymerizable with these components.
  • the copolymerizable monomer is usually a compound having a carbon-carbon double bond, and typically a compound having an ethylenic double bond.
  • the sulfur content in the component (A2) copolymer is usually 0.1 to 12% by mass, preferably 0.5 to 10 from the viewpoint of keeping the (a2) polyfunctional thiol content in the above-mentioned preferable range. It may be% by mass, more preferably 1 to 7% by mass, still more preferably 1.5 to 5% by mass.
  • the sulfur content is determined by ashing (wet decomposition) the sample using a mixed acid of nitric acid and hydrochloric acid (volume ratio 8: 2) using a microwave device, and then adding an aqueous hydrochloric acid solution and filtering. Then, the measurement sample obtained by rectifying the filtrate with purified water is a value measured by an atomic absorption spectrometry method. At this time, yttrium is used as an internal standard.
  • sulfur should be prevented because it binds to iron and the like and easily precipitates.
  • the sulfur content can be measured in the same manner as in the methods described in paragraphs 0035 to 0039 of JP-A-2018-187924.
  • the polystyrene-equivalent mass average molecular weight (Mw) obtained from the GPC curve of the above component (A2) copolymer measured by GPC is a balance between scratch resistance and crack resistance after the coating film is completely cured (at the C stage). From the viewpoint of the above, it may be preferably 5,000 or more, more preferably 8,000 or more, and further preferably 10,000 or more. On the other hand, the mass average molecular weight (Mw) is preferably 200,000 or less, more preferably 100,000 or less, still more preferably 50,000 or less, from the viewpoint of coatability of the coating material containing the above component (A2) copolymer. It may be there.
  • the polystyrene-equivalent Z average molecular weight (Mz) obtained from the GPC curve of the component (A2) copolymer is determined from the viewpoint of the balance between scratch resistance and crack resistance after the coating film is completely cured (at the C stage). It may be preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 30,000 or more. On the other hand, the Z average molecular weight (Mz) is preferably 200,000 or less, more preferably 150,000 or less, still more preferably 120,000 or less, from the viewpoint of coatability of the paint containing the above component (A2) copolymer. It may be there.
  • the polystyrene-equivalent number average molecular weight (Mn) obtained from the GPC curve of the component (A2) copolymer is determined from the viewpoint of the balance between scratch resistance and crack resistance after the coating film is completely cured (at the C stage). It may be preferably 300 or more, more preferably 500 or more. On the other hand, the number average molecular weight (Mn) is preferably 100,000 or less, more preferably 50,000 or less, still more preferably 20,000 or less, from the viewpoint of coatability of the coating material containing the above component (A2) copolymer. It may be there.
  • the GPC measurement of the component (A2) copolymer can be carried out in the same manner as the method described above in the description of the component (A1).
  • FIG. 3 shows the differential molecular weight distribution curve of the following component (A2-1) used in the examples.
  • Three clear peaks are observed in the relatively low molecular weight region, and the polystyrene-equivalent molecular weights at the peak top positions are 340, 570, and 970 in order from the low molecular weight side. Further, a plurality of overlapping and broad peaks are observed on the high molecular weight side of these three peaks, and the polystyrene-equivalent molecular weight of the component on the highest molecular weight side is recognized to be about 200,000.
  • the total number average molecular weight (Mn) is 940, the mass average molecular weight (Mw) is 12,000, and the Z average molecular weight (Mz) is 73,000.
  • 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-hydroxycyclohexyl-phenylketone 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 paint for forming a B-stage coating film preferably further contains the above-mentioned component (C) fine particles.
  • the fine particles of the component (C) 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 (C) 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 (C), especially when inorganic fine particles are used as the component (C), 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 (C) 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 as a part or all of the component (C) fine particles (that is, in an amount of more than 0% by mass to 100% by mass or less of the component (C)), 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 (C) 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 (C) 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 (C) fine particles is not particularly limited because it is an optional component.
  • the blending amount of the above component (C) 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 (C) 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 (C) 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 (C) 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 paint for forming a B-stage coating film may preferably further contain the above-mentioned component (D) 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 (D) 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 repellent performance.
  • the component (D) water repellent has scratch resistance, water repellency, and the component (D) is chemically bonded or strongly interacts with the component (A) active energy ray-curable resin to cause the component (D).
  • 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 (D) the chemical bond or interaction between the component (D) and the active energy ray-curable resin is appropriately adjusted to maintain high transparency and good scratch resistance.
  • component (D) water repellent one or a mixture of two or more of these can be used.
  • the blending amount of the above component (D) water repellent is not particularly limited because it is an optional component.
  • the blending amount of the above component (D) 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 (D) water repellent is usually 0.01 mass by mass from the viewpoint of obtaining the effect of using the component (D) 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 (D) 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 (D). It may be parts by mass or less, more preferably 1 part by mass or less.
  • the coating material for forming a B-stage coating film (a coating material containing the above-mentioned component (A) active energy ray-curable resin and the above-mentioned component (B) photopolymerization initiator) may be used as desired to the extent not contrary to the object of the present invention.
  • Compounds having two or more isocyanate groups in one molecule antistatic agents, surfactants, leveling agents, thixogenic agents, anticontamination agents, printability improvers, antioxidants, weathering stabilizers, light resistance
  • Amine-based dispersions such as stabilizers, UV absorbers, heat stabilizers, inorganic particles, inorganic colorants, organic particles, organic colorants, and dispersants (for example, phosphate ester salts of high molecular weight copolymers having a polyamine structure). Agents) and other additives can be included in one or more.
  • the blending amount when these additives are used is not particularly limited, but is usually 0 from the viewpoint of obtaining the effect of using the additives with respect to 100 parts by mass of the above component (A) active energy ray-curable resin. It may be 001 parts by mass or more, and usually 10 parts by mass or less from the viewpoint of not interfering with the desired effect according to the present invention.
  • the paint for forming a B-stage coating film preferably does not contain a thermal polymerization initiator. Since the B-stage coating film forming paint does not contain the thermal polymerization initiator, the formed coating film is kept in the B-stage state, and the coating film is stably kept in the B-stage state until three-dimensional molding is performed. It will be easier to hold.
  • "not included” means that the above-mentioned thermal polymerization initiator is not intentionally blended. When the thermal polymerization initiator is intentionally blended, usually 0.01 part by mass or more is blended with respect to 100 parts by mass of the active energy ray-curable resin of the component (A).
  • the thermal polymerization initiator is a compound that generates active species such as radicals by heating.
  • 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 thermal polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile (2,2'-azobis (2-methylpropionitrile)); and organic peroxides such as benzoyl peroxide; And benzenesulfonic acid ester such as p-toluenesulfonic acid cyclohexyl can be exemplified.
  • the paint for forming a B-stage coating film may contain a solvent, if desired, in order to dilute it to a concentration that is easy to apply.
  • a solvent does not react with the component (A), the component (B), and other optional components, or catalyze (promote) the self-reaction (including deterioration reaction) of these components.
  • 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 above B-stage coating film forming paint can be obtained by mixing and stirring these components.
  • 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 20% or more, more preferably 25% or more, still more preferably 30% 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 uses the above-mentioned B-stage coating film forming coating material (a coating material containing the above-mentioned component (A) active energy ray-curable resin and the above-mentioned component (B) photopolymerization initiator), and is arbitrary. By the method, it can be produced by forming 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 preferably uses the above-mentioned B-stage coating film forming coating material, and the present invention is applied on at least one surface of the above-mentioned film substrate by the method for producing a B-stage coating film of the present invention. It can be manufactured by forming the B-stage coating film of.
  • the method for producing a B-stage coating film of the present invention has been described in the section "1.
  • Method for producing a B-stage coating film The paint for forming a B-stage coating film (a paint containing the above-mentioned component (A) active energy ray-curable resin and the above-mentioned component (B) photopolymerization initiator) has been described in the section of "2.
  • B-stage coating film a paint containing the above-mentioned component (A) active energy ray-curable resin and the above-mentioned component (B) photopolymerization initiator
  • 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. Good.
  • 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.
  • 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 transparent multilayer film, 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).
  • 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 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. 4 is a conceptual diagram showing an example of a vacuum forming apparatus.
  • the B-stage coating film laminated film 7 is heated and softened by using a heating device 8 such as an infrared heater.
  • the B-stage coating film laminated film 7 is removed from the heating device 8, and the surface of the B-stage coating film laminated film 7 opposite to the surface on the B-stage coating film side is quickly set to the mold 9 side. Cover the mold 9 so as to cover it (FIG. 4 (b)).
  • the molding die 9 may be preheated.
  • the space 10 between the B-stage coating film laminated film 7 and the molding die 9 is depressurized, the B-stage coating film laminated film 7 is brought into close contact with the molding die 9, and the shape of the molding die 9 is changed to the B-stage coating film. Transfer to the laminated film 7 to obtain a molded product 11 (the coating film is the B stage) (FIG. 4 (c)).
  • the mold 9 may be cooled before the molded product 11 is separated from the mold 9.
  • 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 11 using an arbitrary active energy ray irradiation device.
  • the pressure in the space 10 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 7 and the molding die 9 without leaving air.
  • the adhesion increases as the pressure in the space 10 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 7, it is practically used.
  • the lower limit of the pressure in the space 10 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 9, and the B-stage coating film laminated film 7 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. 5A 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. 5B 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 C stage 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.
  • the laminated film had a protective film
  • the B-stage coating film was completely cured by ultraviolet irradiation, and then the protective film was peeled off and used for visual observation.
  • A No cracks, cracks, or poor appearance were observed even when the loupe was used.
  • B No cracks or cracks were observed even when the loupe was used. However, when I looked through the light up close, there was a slight cloudiness.
  • C When the loupe was used, slight cracks and cracks were observed in the surrounding curved part.
  • 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.
  • 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. For those having a protective film, the protective film was peeled off before being subjected to the test.
  • 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 Polyfunctional urethane (meth) acrylate "EBECRYL284" (trade name) manufactured by Daicel Ornex Co., Ltd. Solid content 100% by mass, number of functional groups 2, number average molecular weight 1000, mass average molecular weight 2900, Z average molecular weight 4700.
  • A1-2 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 (a1) Copolymer of polyfunctional (meth) acrylate and (a2) polyfunctional thiol (A2-1) "SIRIUS-501" (trade name) of Osaka Organic Chemical Industry Co., Ltd.
  • Solid content 50% by mass, sulfur content 2.2% by mass, mass average molecular weight 12,000, number average molecular weight 940, Z average molecular weight 73,000.
  • 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) IGM Resins' acetophenone-based photopolymerization initiator (1-hydroxycyclohexyl-phenylketone) "Omnirad 184" (trade name).
  • C Fine Particles
  • C-1 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.
  • C-2) NBC Mesh Tech Co., Ltd.'s anti-virus 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 is 120 nm, and the solid content is 11% by mass.
  • D Water repellent
  • D-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.
  • D-2) Acryloyl group-containing fluoroalkyl water repellent (2- (perfluorobutyl) ethyl acrylate) "CHEMINOXFAAC-4" (trade name) of Unimatec Co., Ltd. Solid content 100% by mass.
  • E Other Ingredients (E-1) Amine-based dispersant "DISPERBY K-145" (trade name) of Big Chemie Japan Co., Ltd. A phosphate ester salt of a high molecular weight copolymer having a polyamine structure. Amine value 71 mgKOH / g. Solid content 100% by mass.
  • (H) B-stage coating film forming coating material (H-1) 50 parts by mass of the above component (A1-1), 100 parts by mass of the above component (A2-1) (50 parts by mass in terms of solid content), the above component (B-) 1) 5 parts by mass, 555 parts by mass of the above component (C-1) (233 parts by mass in terms of solid content), 1.25 parts by mass of the above component (D-1) (0.25 parts by mass in terms of solid content), and methyl.
  • 233 parts by mass of isobutyl ketone (described as "MIBK” in the table) was mixed and stirred to obtain a coating material for forming a B-stage coating film.
  • MIBK isobutyl ketone
  • 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.
  • Q Protective film
  • Q-1 Teijin Limited's aromatic polycarbonate-based resin film "Panlite Film PC-2151” (trade name), thickness 125 ⁇ m.
  • Q-2) A winder having a mechanism for niping a molten film extruded from the single-layer T-die with a single-layer T-die and a first chill roll (mirror surface metal roll) and a nip roll (silicon rubber roll).
  • the set temperature of the T-die is 250 ° C
  • the set temperature of the first chill roll is 50 ° C
  • a resin film having a thickness of 75 ⁇ m was obtained under the condition of a take-up speed of 10.8 m / min.
  • the surface (high gloss surface) on the first chill roll side of the resin film was used as the bonding surface with the coating film.
  • 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.
  • the wettability index was 64 mN / m on both sides.
  • the drying furnace set to the furnace temperature of 90 ° C. is passed at a line speed at which the time required to pass from the inlet to the outlet is 2 minutes, and the wet coating film is pre-dried and dried. It was made into a coating film.
  • the laminated body 1 having the dry coating film on the surface on the ⁇ 1 layer side of the above (P-1) is placed on the laminated body 1. It was placed on the rotating drum 3 so that the surface opposite to the dry coating film was on the rotating drum 3 side.
  • the protective film 2 of (Q-1) is placed on the dry coating film surface of the laminated body 1 on the surface (high gloss) of the protective film 2 of (Q-1) on the first chill roll side. The surface) is overlapped so as to be on the dry coating surface side, crimped by the crimping roll 4, then released from the rotating drum 3 by the guide roll 6 and placed on the dry coating surface of the laminated body 1.
  • a laminated body 5 in which the protective film 2 of the above (Q-1) was laminated and temporarily attached was obtained.
  • the temperature of the rotating drum 3 was set to room temperature (23 ° C.).
  • the above (P-1) the above dry coating film, and the above (Q-1) are placed in the autoclave.
  • an autoclave treatment was performed under the conditions of a temperature of 50 ° C., a pressure of 0.5 MPa, and a holding time of 10 minutes.
  • an aging treatment is carried out at a temperature of 80 ° C.
  • Examples 2-10 A laminated film having a B-stage coating film was obtained in the same manner as in Example 1 except that the coating material shown in Table 1 or 2 was 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 Table 1 or 2.
  • Example 11 Except that the above (H-11) was used instead of the above (H-1) as the paint for forming the B stage coating film, and the above (Q-2) was used instead of the above (Q-1) as the protective film. Obtained a laminated film having a B-stage coating film in the same manner as in Example 1. The above tests (i) to (xii) were performed. The results are shown in Table 2.
  • Example 12 A laminated film having a B-stage coating film was obtained in the same manner as in Example 1 except that the wet coating film was applied so that the thickness after complete curing (C stage) was 13 ⁇ m. The above tests (i) to (xii) were performed. The results are shown in Table 3.
  • Example 13 A laminated film having a B-stage coating film was obtained in the same manner as in Example 1 except that the pre-drying conditions were changed to the conditions shown in Table 1. The above tests (i) to (xii) were performed. The results are shown in Table 3.
  • Examples 14-17 A laminated film having a B-stage coating film was obtained in the same manner as in Example 1 except that the autoclave treatment conditions were changed to the conditions shown in Table 1. The above tests (i) to (xii) were performed. The results are shown in Table 3.
  • Example 18 A laminated film having a B-stage coating film was obtained in the same manner as in Example 1 except that the autoclave treatment was omitted.
  • the above test (i) was carried out, a large number of poor appearances due to foaming of the coating film were observed in the obtained molded product. Therefore, the tests (ii) to (xii) were omitted.
  • the B stage coating film could be industrially stably produced.
  • a B-stage coating film having excellent three-dimensional moldability could be industrially stably produced.
  • the preferable B-stage coating film of the present invention has excellent three-dimensional moldability in the B stage, and after complete curing (in the C stage), heat resistance, surface hardness, transparency, chemical resistance, coating film adhesion, and wet heat test. It was excellent in adhesion to the subsequent coating film and scratch resistance.
  • 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.
  • B stage coating film Formed using a paint containing (A) an active energy ray-curable resin and (B) a photopolymerization initiator; The tensile elongation of the B stage coating film is 10% or more; The above B stage coating film. [2].
  • the B-stage coating film according to any one of Items [1] to [3], wherein the coating material does not contain a thermal polymerization initiator. [5].
  • the B stage coating film according to the section.

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PCT/JP2020/047446 2020-01-08 2020-12-18 Ｂステージ塗膜、積層フィルム、三次元成形体、及びこれらの製造方法 Ceased WO2021140874A1 (ja)

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JP7210799B1 (ja) 2022-07-07 2023-01-23 大日本塗料株式会社 活性エネルギー線硬化性組成物および塗装体
CN119674165A (zh) * 2024-12-09 2025-03-21 湖北亿纬动力有限公司 Uv涂装电芯的预处理方法及电芯

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US20140087616A1 (en) * 2012-09-18 2014-03-27 Christopher Michael ADAMS Flexible Composite Systems
JP2016221922A (ja) * 2015-06-03 2016-12-28 Dic株式会社 加工用フィルム、加工フィルム及びそれらの製造方法
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JPS50157437A (https=) * 1974-04-30 1975-12-19
JPS52152941A (en) * 1976-06-15 1977-12-19 Matsushita Electric Works Ltd Method for forming inorganic cured coating layer
US20060024482A1 (en) * 2002-12-04 2006-02-02 Stachurski Zbigniew H Reinforced polymer composition
JP2012521476A (ja) * 2009-03-24 2012-09-13 チェイル インダストリーズ インコーポレイテッド ハードコーティング組成物、これを用いた多層シート及びその製造方法
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JP7210799B1 (ja) 2022-07-07 2023-01-23 大日本塗料株式会社 活性エネルギー線硬化性組成物および塗装体
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CN119674165A (zh) * 2024-12-09 2025-03-21 湖北亿纬动力有限公司 Uv涂装电芯的预处理方法及电芯

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