WO2021140874A1 - B-stage coating film, laminate film and three-dimensional molded article, and methods respectively for production thereof - Google Patents
B-stage coating film, laminate film and three-dimensional molded article, and methods respectively for production thereof Download PDFInfo
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- 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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- 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
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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
- 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
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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
- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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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Abstract
The present invention is a method for producing a B-stage coating film, comprising the steps of: (1) forming a wet coating film on at least one surface of a film base material using a coating material containing (A) an active-energy-ray-curable resin and (B) a photopolymerization initiator; (2) pre-drying the wet coating film formed in step (1) to form a dry coating film; and (3) subjecting the dry coating film formed in step (2) to an autoclave treatment. The method may further include a step of overlaying a protection film on the surface of the dry coating film formed in step (2) and temporality bonding the protection film subsequent to step (2) or prior to step (3). The autoclave treatment in step (3) may be carried out under such a condition that the film is retained under a pressure of 0.15 to 1 MPa at a temperature of 23 to 100°C for 1 to 60 minutes. The method may further include a step of carrying out an aging treatment subsequent to step (3). The coating material may contain (C) microparticles (which may be an antibacterial agent or an antiviral agent).
Description
本発明は、Bステージ塗膜、及びBステージ塗膜の製造方法に関する。更に詳しくは、本発明は、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に関する。
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.
従来から、家電製品や情報電子機器の筐体等、及び自動車のインスツルメントパネル等の成形体には、表面硬度、及び耐擦傷性などの機能を付与するために、上記成形体の基体の表面の上に、アクリル系樹脂、メラミン系樹脂、イソシアネート系樹脂、及びウレタン系樹脂などの硬化性樹脂塗料を塗工し、硬化塗膜を形成することが、しばしば行われている。
Conventionally, in order to impart functions such as surface hardness and scratch resistance to molded bodies such as housings of home appliances and information electronic devices, and instrument panels of automobiles, the base material of the molded body has been used. 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.
上記硬化塗膜を形成する方法としては、先ず上記基体を成形し、得られた該基体の表面の上に、ディップコート、スプレーコート、スピンコート、及びエアナイフコートなどの方法を使用して、上記硬化性樹脂塗料を適用し、硬化する方法が広く採用されている。一方、上記方法には、特に上記基体が三次元形状/立体的形状(例えば、全体として湾曲する形状、表面に凹凸を有する形状など)を有している場合には、以下のような諸々の不都合、例えば、上記基体の表面の上に上記硬化性樹脂塗料を均一な厚みとなるように適用することが難しい;塗付後硬化前に上記硬化性樹脂塗料が流れ、硬化塗膜の厚みムラ/外観不良が生じ易い;及び、基体1個毎に塗料の適用を行うため生産性が不十分などの問題がある。
As a method for forming the cured coating film, first, 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. On the other hand, in the above method, particularly when 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. Inconvenience, for example, it is difficult to apply the curable resin paint on the surface of the substrate so as to have a uniform thickness; the curable resin paint flows after application and before curing, and the thickness of the cured coating film becomes uneven. / Poor appearance is likely to occur; and there are problems such as insufficient productivity because the paint is applied to each substrate.
そこで、熱可塑性樹脂フィルムの表面の上に、ロールコート、グラビアコート、リバースコート、及びダイコートなどのロール・トゥ・ロールの方法で生産性良く塗料を適用してBステージ塗膜を形成し、得られた積層フィルムを熱プレス成形などの方法により所定形状に賦形した後、上記Bステージ塗膜を完全硬化する方法;上記積層フィルムを射出成形の成形型内にインサートし、上記積層フィルムを加熱軟化させて所定形状に賦形し、所望の熱可塑性樹脂を上記成形型内に射出した後、上記Bステージ塗膜を完全硬化する方法などが提案されている(例えば、特許文献1、2参照)。しかし、これらの技術では、Bステージ塗膜を工業的に安定して製造すること、特に、ウェット塗膜をBステージ状態に硬化させることとウェット塗膜の硬化をBステージ状態に留めることとのバランスを工業的に安定して保つことが難しい。また塗膜がBステージのときの三次元成形性(三次元形状を付与したときの割れや白化などの不良現象の起こり難さ)が不十分である。更に塗膜を完全硬化した後の表面硬度や耐擦傷性も十分に満足できるものではない。
Therefore, 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 of completely curing the B-stage coating film after shaping the laminated film into a predetermined shape by a method such as hot press molding; the laminated film is inserted into a molding mold for injection molding, and the laminated film is heated. 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). ). However, in these techniques, it is possible to industrially stably produce a B-stage coating film, in particular, to cure the wet coating film to the B-stage state and to keep the curing of the wet coating film in the B-stage state. It is difficult to maintain a stable balance industrially. Further, when the coating film is in the B stage, the three-dimensional moldability (difficulty of defective phenomena such as cracking and whitening when the three-dimensional shape is given) is insufficient. Further, the surface hardness and scratch resistance after the coating film is completely cured are not sufficiently satisfactory.
本発明の課題は、新規なBステージ塗膜の製造方法を提供することにある。本発明の別の課題は、新規なBステージ塗膜を提供することにある。本発明の更なる課題は、三次元成形性(三次元形状を付与したときのヒビ、割れおよび外観不良(例えば白化)などの不良現象の起こり難さ)に優れたBステージ塗膜、及びその製造方法を提供することにある。本発明の更なる別の課題は、Bステージにおいては三次元成形性に優れ、完全硬化後(Cステージにおいて)は表面硬度、耐擦傷性、及び耐薬品性に優れる塗膜、該塗膜を有する積層フィルム、上記塗膜又は該積層フィルムを含む成形体、及びこれらの製造方法を提供することにある。
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.
本発明者は、鋭意研究した結果、特定の方法により、上記課題を達成できることを見出した。
As a result of diligent research, the present inventor has found that the above problems can be achieved by a specific method.
即ち、本発明の諸態様は以下の通りである。
[1].
Bステージ塗膜の製造方法であって、
(1)フィルム基材の少なくとも一方の面の上に、(A)活性エネルギー線硬化性樹脂及び(B)光重合開始剤を含む塗料を用いてウェット塗膜を形成する工程;
(2)上記工程(1)で形成された上記ウェット塗膜を予備乾燥し、乾燥塗膜を形成する工程;ならびに、
(3)上記工程(2)で形成された上記乾燥塗膜をオートクレーブ処理する工程
を含む上記製造方法。
[2].
更に、上記工程(2)の後、上記工程(3)の前に、上記工程(2)で形成された上記乾燥塗膜の面の上に、保護フィルムを重ね、仮貼りする工程を含む、上記[1]項に記載の方法。
[3].
上記工程(3)のオートクレーブ処理が、圧力0.15~1MPa、温度23~100℃で1~60分間の時間保持する条件で行われる、上記[1]項又は[2]項に記載の方法。
[4].
更に、上記工程(3)の後、エージング処理をする工程を含む、上記[1]~[3]項の何れか1項に記載の方法。
[5].
上記塗料が更に(C)微粒子を含む、上記[1]~[4]項の何れか1項に記載の方法。
[6].
上記成分(C)微粒子が、抗菌剤又は抗ウィルス剤として機能する微粒子を含む上記[5]項に記載の方法。
[7].
上記塗料が更に(D)撥水剤を含む、上記[1]~[6]項の何れか1項に記載の方法。
[8].
上記塗料が熱重合開始剤を含まない、上記[1]~[7]項の何れか1項に記載の方法。
[9].
上記(A)活性エネルギー線硬化性樹脂が(A1)ウレタン(メタ)アクリレートを含む、上記[1]~[8]項の何れか1項に記載の方法。
[10].
上記(A)活性エネルギー線硬化性樹脂が(A2)(a1)多官能(メタ)アクリレートと(a2)多官能チオールとの共重合体を含む、上記[1]~[9]項の何れか1項に記載の方法。
[11].
上記工程(3)で形成された上記フィルム基材上のオートクレーブ処理済み塗膜を、このフィルム基材以外の基材上に転写する工程を更に含む、上記[1]~[10]項の何れか1項に記載の方法。
[12].
三次元成形体の製造方法であって、
(P)[1]~[11]項の何れか1項に記載の方法により、上記フィルム基材上に適用されたBステージ塗膜、または上記フィルム基材以外の基材上に転写されたBステージ塗膜を得る工程;
(Q)上記工程(P)で得た、上記フィルム基材上に適用された上記Bステージ塗膜、または上記フィルム基材以外の基材上に転写された上記Bステージ塗膜に三次元形状を付与する工程;及び、
(R)上記工程(Q)で三次元形状を付与された上記Bステージ塗膜を完全硬化させる工程を含む上記方法。 That is, various aspects of the present invention are as follows.
[1].
This is a method for manufacturing a B-stage coating film.
(1) A step of forming a wet coating film on at least one surface of a film substrate using a coating material containing (A) an active energy ray-curable resin and (B) a photopolymerization initiator;
(2) A step of pre-drying the wet coating film formed in the above step (1) to form a dry coating film;
(3) The above-mentioned production method including the step of autoclaving the above-mentioned dry coating film formed in the above-mentioned step (2).
[2].
Further, after the step (2) and before the step (3), 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. The method according to the above item [1].
[3].
The method according to item [1] or [2] above, wherein the autoclave treatment in step (3) is performed under the condition that the pressure is 0.15 to 1 MPa and the temperature is 23 to 100 ° C. for 1 to 60 minutes. ..
[4].
The method according to any one of the above items [1] to [3], further comprising a step of performing an aging treatment after the above step (3).
[5].
The method according to any one of the above items [1] to [4], wherein the coating material further contains (C) fine particles.
[6].
The method according to item [5] above, wherein the fine particles of the component (C) contain fine particles that function as an antibacterial agent or an antiviral agent.
[7].
The method according to any one of the above items [1] to [6], wherein the coating material further contains (D) a water repellent.
[8].
The method according to any one of the above items [1] to [7], wherein the coating material does not contain a thermal polymerization initiator.
[9].
The method according to any one of the above items [1] to [8], wherein the (A) active energy ray-curable resin contains (A1) urethane (meth) acrylate.
[10].
Any of the above items [1] to [9], wherein the (A) active energy ray-curable resin contains a copolymer of (A2) (a1) polyfunctional (meth) acrylate and (a2) polyfunctional thiol. The method according toitem 1.
[11].
Any of the above items [1] to [10], further comprising a step of transferring the autoclaved coating film on the film base material formed in the above step (3) onto a base material other than the film base material. Or the method described initem 1.
[12].
It is a method of manufacturing a three-dimensional molded product.
(P) By the method according to any one of [1] to [11], the film was transferred onto a B-stage coating film applied on the film substrate or a substrate other than the film substrate. 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).
[1].
Bステージ塗膜の製造方法であって、
(1)フィルム基材の少なくとも一方の面の上に、(A)活性エネルギー線硬化性樹脂及び(B)光重合開始剤を含む塗料を用いてウェット塗膜を形成する工程;
(2)上記工程(1)で形成された上記ウェット塗膜を予備乾燥し、乾燥塗膜を形成する工程;ならびに、
(3)上記工程(2)で形成された上記乾燥塗膜をオートクレーブ処理する工程
を含む上記製造方法。
[2].
更に、上記工程(2)の後、上記工程(3)の前に、上記工程(2)で形成された上記乾燥塗膜の面の上に、保護フィルムを重ね、仮貼りする工程を含む、上記[1]項に記載の方法。
[3].
上記工程(3)のオートクレーブ処理が、圧力0.15~1MPa、温度23~100℃で1~60分間の時間保持する条件で行われる、上記[1]項又は[2]項に記載の方法。
[4].
更に、上記工程(3)の後、エージング処理をする工程を含む、上記[1]~[3]項の何れか1項に記載の方法。
[5].
上記塗料が更に(C)微粒子を含む、上記[1]~[4]項の何れか1項に記載の方法。
[6].
上記成分(C)微粒子が、抗菌剤又は抗ウィルス剤として機能する微粒子を含む上記[5]項に記載の方法。
[7].
上記塗料が更に(D)撥水剤を含む、上記[1]~[6]項の何れか1項に記載の方法。
[8].
上記塗料が熱重合開始剤を含まない、上記[1]~[7]項の何れか1項に記載の方法。
[9].
上記(A)活性エネルギー線硬化性樹脂が(A1)ウレタン(メタ)アクリレートを含む、上記[1]~[8]項の何れか1項に記載の方法。
[10].
上記(A)活性エネルギー線硬化性樹脂が(A2)(a1)多官能(メタ)アクリレートと(a2)多官能チオールとの共重合体を含む、上記[1]~[9]項の何れか1項に記載の方法。
[11].
上記工程(3)で形成された上記フィルム基材上のオートクレーブ処理済み塗膜を、このフィルム基材以外の基材上に転写する工程を更に含む、上記[1]~[10]項の何れか1項に記載の方法。
[12].
三次元成形体の製造方法であって、
(P)[1]~[11]項の何れか1項に記載の方法により、上記フィルム基材上に適用されたBステージ塗膜、または上記フィルム基材以外の基材上に転写されたBステージ塗膜を得る工程;
(Q)上記工程(P)で得た、上記フィルム基材上に適用された上記Bステージ塗膜、または上記フィルム基材以外の基材上に転写された上記Bステージ塗膜に三次元形状を付与する工程;及び、
(R)上記工程(Q)で三次元形状を付与された上記Bステージ塗膜を完全硬化させる工程を含む上記方法。 That is, various aspects of the present invention are as follows.
[1].
This is a method for manufacturing a B-stage coating film.
(1) A step of forming a wet coating film on at least one surface of a film substrate using a coating material containing (A) an active energy ray-curable resin and (B) a photopolymerization initiator;
(2) A step of pre-drying the wet coating film formed in the above step (1) to form a dry coating film;
(3) The above-mentioned production method including the step of autoclaving the above-mentioned dry coating film formed in the above-mentioned step (2).
[2].
Further, after the step (2) and before the step (3), 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. The method according to the above item [1].
[3].
The method according to item [1] or [2] above, wherein the autoclave treatment in step (3) is performed under the condition that the pressure is 0.15 to 1 MPa and the temperature is 23 to 100 ° C. for 1 to 60 minutes. ..
[4].
The method according to any one of the above items [1] to [3], further comprising a step of performing an aging treatment after the above step (3).
[5].
The method according to any one of the above items [1] to [4], wherein the coating material further contains (C) fine particles.
[6].
The method according to item [5] above, wherein the fine particles of the component (C) contain fine particles that function as an antibacterial agent or an antiviral agent.
[7].
The method according to any one of the above items [1] to [6], wherein the coating material further contains (D) a water repellent.
[8].
The method according to any one of the above items [1] to [7], wherein the coating material does not contain a thermal polymerization initiator.
[9].
The method according to any one of the above items [1] to [8], wherein the (A) active energy ray-curable resin contains (A1) urethane (meth) acrylate.
[10].
Any of the above items [1] to [9], wherein the (A) active energy ray-curable resin contains a copolymer of (A2) (a1) polyfunctional (meth) acrylate and (a2) polyfunctional thiol. The method according to
[11].
Any of the above items [1] to [10], further comprising a step of transferring the autoclaved coating film on the film base material formed in the above step (3) onto a base material other than the film base material. Or the method described in
[12].
It is a method of manufacturing a three-dimensional molded product.
(P) By the method according to any one of [1] to [11], the film was transferred onto a B-stage coating film applied on the film substrate or a substrate other than the film substrate. 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).
本発明の製造方法により、Bステージ塗膜を工業的に安定して製造することができる。本発明の好ましい製造方法により、三次元成形性に優れたBステージ塗膜を工業的に安定して製造することができる。本発明のBステージ塗膜は三次元成形性に優れる。本発明の好ましいBステージ塗膜は、Bステージにおいては三次元成形性に優れ、完全硬化後(Cステージにおいて)は表面硬度、耐擦傷性、及び耐薬品性に優れる。そのため、本発明のBステージ塗膜やこのBステージ塗膜を有する本発明の積層フィルムを用いて成形される成形体は、表面硬度、耐擦傷性、及び耐薬品性に優れ、表面外観も良好である(ヒビ、割れおよび外観不良(例えば白化)などの不良現象がない)。そのため本発明のBステージ塗膜やこのBステージ塗膜を有する本発明の積層フィルムは、三次元形状/立体的形状を有する成形体、例えば、家電製品や情報電子機器の筐体等、及び自動車のインスツルメントパネル等の成形体の表面に表面硬度、耐擦傷性、及び耐薬品性などの機能を付与するために好適に用いることができる。
According to the production method of the present invention, the B stage coating film can be industrially stably produced. According to the preferred production method of the present invention, 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. (There are no defective phenomena such as cracks, cracks and poor appearance (for example, whitening)). Therefore, 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.
本明細書において「樹脂」の用語は、2種以上の樹脂を含む樹脂混合物や、樹脂以外の成分を含む樹脂組成物をも含む用語として使用する。本明細書において「フィルム」の用語は、「シート」と相互交換的に又は相互置換可能に使用する。本明細書において、「フィルム」及び「シート」の用語は、工業的にロール状に巻き取ることのできるものに使用する。「板」の用語は、工業的にロール状に巻き取ることのできないものに使用する。また本明細書において、ある層と他の層とを順に積層することは、それらの層を直接積層すること、及び、それらの層の間にアンカーコートなどの別の層を1層以上介在させて積層することの両方を含む。
In the present specification, 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. As used herein, the term "film" is used interchangeably or interchangeably with "sheet". As used herein, 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. Further, in the present specification, 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.
本明細書において数値範囲に係る「以上」の用語は、ある数値又はある数値超の意味で使用する。例えば、20%以上は、20%又は20%超を意味する。数値範囲に係る「以下」の用語は、ある数値又はある数値未満の意味で使用する。例えば、20%以下は、20%又は20%未満を意味する。また数値範囲に係る「~」の記号は、ある数値、ある数値超かつ他のある数値未満、又は他のある数値の意味で使用する。ここで、他のある数値は、ある数値よりも大きい数値とする。例えば、10~90%は、10%、10%超かつ90%未満、又は90%を意味する。更に、数値範囲の上限と下限とは、任意に組み合わせることができるものとし、任意に組み合わせた実施形態が読み取れるものとする。例えば、ある特性の数値範囲に係る「通常10%以上、好ましくは20%以上である。一方、通常40%以下、好ましくは30%以下である。」や「通常10~40%、好ましくは20~30%である。」という記載から、そのある特性の数値範囲は、一実施形態において10~40%、20~30%、10~30%、又は20~40%であることが読み取れるものとする。
In this specification, 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%. In addition, 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. Here, it is assumed that some other numerical value is larger than a certain numerical value. For example, 10-90% means 10%, more than 10% and less than 90%, or 90%. Further, 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.
実施例以外において、又は別段に指定されていない限り、本明細書及び特許請求の範囲において使用されるすべての数値は、「約」という用語により修飾されるものとして理解されるべきである。特許請求の範囲に対する均等論の適用を制限しようとすることなく、各数値は、有効数字に照らして、及び通常の丸め手法を適用することにより解釈されるべきである。
Unless otherwise specified, or unless otherwise specified, all numbers used herein and in the claims should be understood as being modified by the term "about". Without attempting to limit the application of the doctrine of equivalents to the claims, each number should be interpreted in the light of significant figures and by applying conventional rounding techniques.
本明細書において「Bステージ」の用語は、熱硬化性樹脂については、JIS K6800-1985に規定された意味、即ち「熱硬化性樹脂の硬化中間状態。この状態での樹脂は加熱すると軟化し、ある種の溶剤に触れると膨潤するが、完全に溶融・溶解することはない。」の意味で使用する。活性エネルギー線硬化性樹脂については、「活性エネルギー線硬化性樹脂の硬化中間状態。この状態での樹脂は加熱すると軟化し、ある種の溶剤に触れると膨潤するが、完全に溶融・溶解することはない。」の意味で使用する。
In the present specification, the term "B stage" has the meaning defined in JIS K6800-1985 for 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. " Regarding the active energy ray-curable resin, "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."
本明細書において「Cステージ」の用語は、熱硬化性樹脂、及び活性エネルギー線硬化性樹脂の何れについても、JIS K6800-1985に規定された意味を準用し、「硬化性樹脂の硬化反応の最終状態。この状態の樹脂は、不溶不融性である。完全に硬化した塗膜中の硬化性樹脂はこの状態にある。」の意味で使用する。
In the present specification, the term "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. ”
1.Bステージ塗膜の製造方法
本発明の製造方法は、(1)フィルム基材の少なくとも一方の面の上に、(A)活性エネルギー線硬化性樹脂及び(B)光重合開始剤を含む塗料(以下、「Bステージ塗膜形成用塗料」と略すことがある)を用いてウェット塗膜を形成する工程;(2)上記工程(1)で形成された上記ウェット塗膜を予備乾燥し、乾燥塗膜を形成する工程;及び(3)上記工程(2)で形成された上記乾燥塗膜をオートクレーブ処理する工程を含む。 1. 1. Method for Producing B-Stage Coating Film 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"); (2) 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).
本発明の製造方法は、(1)フィルム基材の少なくとも一方の面の上に、(A)活性エネルギー線硬化性樹脂及び(B)光重合開始剤を含む塗料(以下、「Bステージ塗膜形成用塗料」と略すことがある)を用いてウェット塗膜を形成する工程;(2)上記工程(1)で形成された上記ウェット塗膜を予備乾燥し、乾燥塗膜を形成する工程;及び(3)上記工程(2)で形成された上記乾燥塗膜をオートクレーブ処理する工程を含む。 1. 1. Method for Producing B-Stage Coating Film 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"); (2) 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).
上記工程(1)は、フィルム基材の少なくとも一方の面の上に、上記Bステージ塗膜形成用塗料を用いてウェット塗膜を形成する工程である。上記工程(1)は、通常は、上記フィルム基材の一方の面の上に、上記Bステージ塗膜形成用塗料を用いてウェット塗膜を形成する工程である。
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.
上記工程(1)において用いるフィルム基材は、特に制限されず、任意のフィルムをフィルム基材として用いることができる。上記工程(1)において用いるフィルム基材としては、後述する「3.Bステージ塗膜積層フィルム」などにおいて説明するフィルム基材を好ましく用いることができる。上記工程(1)において用いる上記Bステージ塗膜形成用塗料としては、後述する「2.Bステージ塗膜」などにおいて説明する塗料を好ましく用いることができる。
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. As 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. As the B-stage coating film forming coating material used in the above step (1), the coating material described in "2. B-stage coating film" or the like described later can be preferably used.
上記工程(1)において、上記フィルム基材の面の上に、上記Bステージ塗膜形成用塗料を用いてウェット塗膜を形成する方法は、特に制限されず、公知のウェブ適用方法を使用することができる。上記ウェブ適用方法としては、ロール・トゥ・ロールの方法で生産性良く塗料を適用する観点から、例えば、ロッドコート、ロールコート、グラビアコート、リバースコート、キスリバースコート、及びダイコートなどの方法が好ましい。
In the step (1), 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. As the 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. ..
上記工程(2)は、上記工程(1)で形成された上記ウェット塗膜を予備乾燥し、乾燥塗膜を形成する工程である。上記ウェット塗膜を予備乾燥し、上記乾燥塗膜とすることにより、上記工程(3)において、塗膜が発泡するなどの製造トラブルを抑制することができる。上記予備乾燥は、例えば、ウェブを通常は温度23~150℃程度、好ましくは温度50~130℃、より好ましくは70~120℃に設定された乾燥炉内を、入口から出口までパスするのに要する時間が0.5~10分程度、好ましくは1~5分となるようなライン速度でパスさせることにより行うことができる。
The step (2) is a step of pre-drying the wet coating film formed in the step (1) to form a dry coating film. By pre-drying the wet coating film to obtain the dried coating film, it is possible to suppress manufacturing troubles such as foaming of the coating film in the step (3). 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.
上記工程(2)の後、上記工程(3)の前に、上記工程(2)で形成された上記乾燥塗膜の面の上に、保護フィルムを重ね、仮貼りすることは好ましい。完全硬化(Cステージに)する前の塗膜(乾燥塗膜又はBステージ塗膜)に傷が入るなどの製造トラブルを抑制することができる。また三次元成形後、塗膜に活性エネルギー線を照射し、BステージからCステージにする工程において、酸素障害による硬化不良などの製造トラブルを抑制することができる。
After 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.
上記乾燥塗膜の面の上に、上記保護フィルムを重ねて仮貼りする方法の例を、図1を用いて説明する。図1は、上記乾燥塗膜の面の上に、上記保護フィルムを重ねて仮貼りするために使用する装置の一例を示す概念図である。上記工程(2)で得られた積層体1(上記フィルム基材の一方の面の上に、上記乾燥塗膜を有する積層体)は、回転する回転ドラム3の上に、積層体1の上記乾燥塗膜とは反対側の面が回転ドラム3側となるように載せられ、更に保護フィルム2が積層体1の上記乾燥塗膜の面の上に載せられ、圧着ロール4により圧着される。上記乾燥塗膜の面の上に保護フィルム2を重ねて仮貼りされた積層体5は、ガイドロール6により回転ドラム3からリリースされ、工程(3)へと送られる。回転ドラム3は、所望の温度に予熱してもよい。回転ドラム3の温度は、通常、室温(約23℃)~約100℃、好ましくは室温(約23℃)~約50℃であってよい。
An example of a method of temporarily pasting the protective film on the surface of the dry coating film will be described with reference to FIG. 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.
上記保護フィルムとしては、活性エネルギー線透過性を有するもの(以下、「活性エネルギー線透過性保護フィルム」と称することがある)が好ましい。本発明のBステージ塗膜を完全硬化(Cステージに)する際に、保護フィルムを剥離しなくても活性エネルギー線の照射ができるため、製造トラブルを抑制することができる。また、保護フィルムの厚みは、特に限定されないが、例えば、約10μm~約600μmの範囲、好ましくは20μm~250μmの範囲であってよい。
As the protective film, a film having active energy ray transmittance (hereinafter, may be referred to as "active energy ray transparent protective film") is preferable. When the B-stage coating film of the present invention is completely cured (to the C stage), the active energy rays can be irradiated without peeling off the protective film, so that manufacturing troubles can be suppressed. The thickness of the protective film is not particularly limited, but may be, for example, in the range of about 10 μm to about 600 μm, preferably in the range of 20 μm to 250 μm.
ここで、「活性エネルギー線透過性を有する」とは、フィルムの活性エネルギー線透過率が通常70%以上、好ましくは80%以上であることを意味する。本明細書において、活性エネルギー線透過率は、波長200~600ナノメートルの全範囲における活性エネルギー線の透過率が100%であると仮定した場合の透過スペクトルの積分面積に対する波長200~600ナノメートルにおける活性エネルギー線の透過スペクトルの積分面積の割合である。上記透過スペクトルは分光光度計を用い、光を入射角0°でフィルムに入射させて測定する。上記分光光度計としては、例えば、島津製作所株式会社の分光光度計「SolidSpec-3700」(商品名)を用いることができる。
Here, "having active energy ray transmittance" means that the active energy ray transmittance of the film is usually 70% or more, preferably 80% or more. In the present specification, 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. As the spectrophotometer, for example, a spectrophotometer "SolidSpec-3700" (trade name) manufactured by Shimadzu Corporation can be used.
上記活性エネルギー線透過性保護フィルムとしては、例えば、ポリエチレンテレフタレート系樹脂フィルム、ポリプロピレン系樹脂フィルム、芳香族ポリカーボネート系樹脂フィルム、及び含弗素系樹脂フィルムなどを挙げることができる。
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.
上記保護フィルムの上記乾燥塗膜との貼合面は、易剥離処理されているものであってもよく、易剥離処理されていないものであってもよく、易接着処理されたものであってもよい。
上記易剥離処理は、例えば、シリコーン樹脂等による剥離層形成などの任意の公知の処理方法であってよい。
上記易接着処理は、例えば、コロナ放電処理、プラズマ処理、及びアンカーコート形成などの任意の公知の処理方法であってよい。 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.
上記易剥離処理は、例えば、シリコーン樹脂等による剥離層形成などの任意の公知の処理方法であってよい。
上記易接着処理は、例えば、コロナ放電処理、プラズマ処理、及びアンカーコート形成などの任意の公知の処理方法であってよい。 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.
上記保護フィルムとして、上記乾燥塗膜との貼合面が易剥離処理されているものを用いることにより、典型的には、該貼合面にエンボス模様を有するものを使用し、その形状を上記乾燥塗膜に転写することにより上記乾燥塗膜の表面にエンボス模様を形成しようとする場合であっても、上記保護フィルムを剥離、除去する際の製造トラブルを抑制することができる。
By using a protective film whose bonding surface with the dry coating film is easily peeled off, 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.
上記保護フィルムとして、上記乾燥塗膜との貼合面が易剥離処理されていないものを用いることにより、特に、上記Bステージ塗膜形成用塗料が、塗膜を乾燥するのみでタックフリー性を発現するものである場合であっても、上記乾燥塗膜と上記保護フィルムとの密着性を、ウェブハンドリングを行う際に最低限必要となるレベルには保持することができる。ここでの「タックフリー性」は、ウェブハンドリングの際に、塗膜が移送ロールなどに接触することによる、傷や外観不良の生じ難さを意味する。
By using a protective film whose bonding surface with the dry coating film is not easily peeled off, in particular, 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.
上記保護フィルムとして、上記乾燥塗膜との貼合面が易接着処理されているものを用いることは、上記工程(1)において用いるフィルム基材として、そのBステージ塗膜形成面が易剥離処理されたものを用いる場合の実施形態の1つとして有用である。この場合、通常、Bステージ塗膜は上記工程(1)において用いるフィルム基材から上記保護フィルムに転写されて用いられる。またこの場合、「仮貼りする」は、技術的に「貼合し、接着する」と読み替えられうることは言うまでもない。
Using 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. In this case, 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".
上記保護フィルムの上記乾燥塗膜との貼合面は、高度に平滑なものであってもよく、梨地のものであってもよく、エンボス模様を有するものであってもよい。高度に平滑な貼合面を有する保護フィルムを用いることにより、本発明のBステージ塗膜を用いて形成される完全硬化(Cステージ)塗膜は、高い光沢を有するものになる。梨地の貼合面を有する保護フィルムを用いることにより、本発明のBステージ塗膜を用いて形成される完全硬化(Cステージ)塗膜は、艶消し(低い光沢を有するもの)になる。エンボス模様を有する貼合面を有する保護フィルムを用いることにより、本発明のBステージ塗膜を用いて形成される完全硬化(Cステージ)塗膜は、エンボス模様を有するものになる。
The surface of the protective film to be bonded to the dry coating film may be highly smooth, satin-finished, or embossed. By using a protective film having a highly smooth bonded surface, the fully cured (C stage) coating film formed by using the B stage coating film of the present invention has high gloss. By using a protective film having a satin-coated surface, 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). By using a protective film having a bonded surface having an embossed pattern, the completely cured (C stage) coating film formed by using the B stage coating film of the present invention has an embossed pattern.
上記工程(3)は、上記工程(2)で形成された上記乾燥塗膜をオートクレーブ処理する工程である。上記工程(3)により、本発明のBステージ塗膜を有する積層体を用いて3次元成形体を製造する際に、例えば、本発明のBステージ塗膜に3次元形状を付与する工程や、本発明のBステージ塗膜を完全硬化(Cステージに)する工程などにおいて、塗膜が発泡するなどの製造トラブルを抑制することができる。また上記保護フィルムを用いる実施形態にあっては、上記工程(3)により、上記保護フィルムの上記乾燥塗膜との貼合面の形状を、上記乾燥塗膜の表面に転写することができる。更に上記保護フィルムを用いる実施形態にあっては、上記工程(3)により、上記保護フィルムと上記乾燥塗膜との間にエアを噛み込んでしまったとしても、このエアを排除し、外観不良が生じるのを防止することができる。
The step (3) is a step of autoclaving the dry coating film formed in the step (2). When 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. Further, in the embodiment using the protective 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). Further, in the embodiment using 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.
上記工程(3)は、以下の手順で行うことができる。典型的な一実施形態において、先ず、オートクレーブ装置の内部に上記工程(2)で形成された上記乾燥塗膜(上記フィルム基材の少なくとも一方の面の上に上記乾燥塗膜を有する積層体;上記フィルム基材の少なくとも一方の面の上に上記乾燥塗膜を有し、更にその面の上に上記保護フィルムが重ねられ仮貼りされている積層体;又は、これら積層体の巻回体;以下、本段落において同じ)を静置し、上記オートクレーブ装置の蓋を閉める。次に、上記オートクレーブ装置の内部を所定の温度及び圧力に昇温昇圧し、当該温度及び圧力に到達後、所定の時間(以下、「保持時間」ということがある)、当該温度及び圧力を保持する。続いて、圧力を常圧に下げ、好ましくは温度も室温付近にまで下げた後、上記オートクレーブ装置の蓋を開け、上記工程(2)で形成された上記乾燥塗膜を取り出すことができる。
The above step (3) can be performed by the following procedure. In a typical embodiment, first, 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), and the lid of the autoclave device is closed. Next, 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. Subsequently, after the pressure is lowered to normal pressure and the temperature is preferably lowered to around room temperature, the lid of the autoclave device can be opened and the dry coating film formed in the step (2) can be taken out.
上記オートクレーブ装置としては、特に限定されないが、任意の公知のオートクレーブ装置を使用することができる。オートクレーブ処理の温度、圧力、及び保持時間は、本発明のBステージ塗膜の形成に用いる塗料、及び上記フィルム基材の特性を勘案して適宜選択することができる。オートクレーブ処理の温度、圧力、及び保持時間は、上記保護フィルムを用いる実施形態にあっては、本発明のBステージ塗膜の形成に用いる塗料、上記フィルム基材、及び上記保護フィルムの特性を勘案して適宜選択することができる。オートクレーブ処理の圧力は、通常、常圧(0.1MPa)よりも高い圧力、好ましくは0.15~1MPa、より好ましくは0.2~0.7MPa、更に好ましくは0.3~0.6MPaであってよい。オートクレーブ処理の温度は、通常、室温(約23℃)~100℃、好ましくは30~80℃、より好ましくは40~60℃であってよい。オートクレーブ処理の保持時間は、通常1~60分間、好ましくは3~30分間、より好ましくは5~20分間であってよい。
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.
上記工程(3)の後、エージング処理を行うことは好ましい。本発明のBステージ塗膜の特性を安定化することができる。また本発明のBステージ塗膜を有する積層フィルムを用いて3次元成形体を製造する際に、例えば、本発明のBステージ塗膜に3次元形状を付与する工程や、本発明のBステージ塗膜を完全硬化(Cステージに)する工程などにおいて、塗膜が発泡するなどの製造トラブルが起こるリスクを更に抑制することができる。上記エージング処理の条件は、特に制限されない。上記エージング処理の温度は、通常23~150℃程度、好ましくは温度50~120℃、より好ましくは70~100℃であってよい。上記エージング処理の時間は、通常10分間~10時間程度、好ましくは30分間~4時間、より好ましくは1~3時間であってよい。
It is preferable to perform the aging treatment after the above step (3). 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.
理論に拘束される意図はないが、上記工程(2)における予備乾燥時の熱;上記保護フィルムを用いる実施形態にあっては、上記保護フィルムを重ねて仮貼りする際の熱;上記工程(3)におけるオートクレーブ処理時の熱と圧力;及び(行われる場合)エージング処理時の熱により、塗膜は少しずつ熱による硬化が進行し、Bステージ状態になると考察される。
Although not intended to be bound by theory, the heat during pre-drying in the above step (2); in the embodiment using the above-mentioned protective film, the heat when the above-mentioned protective films are laminated and temporarily attached; the above-mentioned step ( It is considered that the heat and pressure during the autoclave treatment in 3); and the heat during the aging treatment (if performed) gradually cause the coating film to gradually cure due to heat, resulting in a B stage state.
2.Bステージ塗膜
本発明のBステージ塗膜は、上記Bステージ塗膜形成用塗料(上記成分(A)活性エネルギー線硬化性樹脂と上記成分(B)光重合開始剤を含む塗料)を用い、任意の方法により形成される。本発明のBステージ塗膜は、好ましくは、上記Bステージ塗膜形成用塗料(上記成分(A)活性エネルギー線硬化性樹脂と上記成分(B)光重合開始剤を含む塗料)を用い、本発明の製造方法により形成される。以下、上記Bステージ塗膜形成用塗料(上記成分(A)活性エネルギー線硬化性樹脂と上記成分(B)光重合開始剤を含む塗料)について説明する。 2. B-stage coating film 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. Hereinafter, 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.
本発明のBステージ塗膜は、上記Bステージ塗膜形成用塗料(上記成分(A)活性エネルギー線硬化性樹脂と上記成分(B)光重合開始剤を含む塗料)を用い、任意の方法により形成される。本発明のBステージ塗膜は、好ましくは、上記Bステージ塗膜形成用塗料(上記成分(A)活性エネルギー線硬化性樹脂と上記成分(B)光重合開始剤を含む塗料)を用い、本発明の製造方法により形成される。以下、上記Bステージ塗膜形成用塗料(上記成分(A)活性エネルギー線硬化性樹脂と上記成分(B)光重合開始剤を含む塗料)について説明する。 2. B-stage coating film 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. Hereinafter, 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.
(A)活性エネルギー線硬化性樹脂
上記成分(A)活性エネルギー線硬化性樹脂は、紫外線や電子線等の活性エネルギー線により重合・硬化して、塗膜を形成する働きをする。 (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.
上記成分(A)活性エネルギー線硬化性樹脂は、紫外線や電子線等の活性エネルギー線により重合・硬化して、塗膜を形成する働きをする。 (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.
上記成分(A)活性エネルギー線硬化性樹脂としては、例えば、ウレタン(メタ)アクリレート(またはポリウレタン(メタ)アクリレート)、ポリエステル(メタ)アクリレート、ポリアクリル(メタ)アクリレート、エポキシ(メタ)アクリレート、ポリアルキレングリコールポリ(メタ)アクリレート、及び、ポリエーテル(メタ)アクリレート等の(メタ)アクリロイル基含有プレポリマー又はオリゴマーをあげることができる。
Examples of the component (A) active energy ray-curable resin 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.
上記成分(A)活性エネルギー線硬化性樹脂としては、例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n-ブチル(メタ)アクリレート、ヘキシル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、ラウリル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、ジシクロペンテニロキシエチル(メタ)アクリレート、フェニル(メタ)アクリレート、フェニルセロソルブ(メタ)アクリレート、2-メトキシエチル(メタ)アクリレート、ヒドロキシエチル(メタ)アクリレート、ヒドロキシプロピル(メタ)アクリレート、2-アクリロイルオキシエチルハイドロゲンフタレート、ジメチルアミノエチル(メタ)アクリレート、トリフルオロエチル(メタ)アクリレート、及び、トリメチルシロキシエチルメタクリレート等の(メタ)アクリロイル基含有単官能反応性モノマー;N-ビニルピロリドン、スチレン等の単官能反応性モノマー;ジエチレングリコールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、2,2’-ビス(4-(メタ)アクリロイルオキシポリエチレンオキシフェニル)プロパン、及び、2,2’-ビス(4-(メタ)アクリロイルオキシポリプロピレンオキシフェニル)プロパン等の(メタ)アクリロイル基含有2官能反応性モノマー;トリメチロールプロパントリ(メタ)アクリレート、及びトリメチロールエタントリ(メタ)アクリレート等の(メタ)アクリロイル基含有3官能反応性モノマー;ペンタエリスリトールテトラ(メタ)アクリレート等の(メタ)アクリロイル基含有4官能反応性モノマー;ジペンタエリスリトールヘキサアクリレート等の(メタ)アクリロイル基含有6官能反応性モノマー;トリペンタエリスリトールオクタアクリレート等の(メタ)アクリロイル基含有8官能反応性モノマー;及び、これらの1種以上を構成モノマーとするプレポリマー又はオリゴマーなどをあげることができる。
Examples of the component (A) active energy ray-curable resin include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Lauryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenyl (meth) acrylate, phenylcellosolve (meth) acrylate, 2-methoxyethyl (meth) ) Acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-acryloyloxyethyl hydrogenphthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, trimethylsiloxyethyl methacrylate and the like ( Meta) Acryloyl group-containing monofunctional reactive monomer; Monofunctional reactive monomer such as N-vinylpyrrolidone, styrene; diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, 2,2'-bis (4- (meth) acryloyloxypolyethyleneoxyphenyl) propane, and 2,2'-bis (4- (meth) acryloyloxypolypropylene oxyphenyl) ) (Meta) acryloyl group-containing bifunctional reactive monomer such as propane; (meth) acryloyl group-containing trifunctional reactive monomer such as trimethylolpropanetri (meth) acrylate and trimethylol ethanetri (meth) acrylate; pentaerythritol (Meta) acryloyl group-containing tetrafunctional reactive monomer such as tetra (meth) acrylate; (meth) acryloyl group-containing hexafunctional reactive monomer such as dipentaerythritol hexaacrylate; (meth) acryloyl group such as tripentaerythritol octaacrylate Examples thereof include 8-functional reactive monomers contained; and prepolymers or oligomers containing one or more of these as constituent monomers.
上記成分(A)活性エネルギー線硬化性樹脂としては、例えば、1,2-エタンジチオール、エチレングリコールビス(3-メルカプトプロピオネート)、ジエチレングリコールビス(3-メルカプトプロピオネート)、1,4-ビス(3-メルカプトブチリルオキシ)ブタン、及びテトラエチレングリコールビス(3-メルカプトプロピオネート)等の1分子中に2個のチオール基を有する化合物;1,3,5-トリス(3-メルカプトブチリルオキシエチル)-1,3,5-トリアジン-2,4,6(1H,3H,5H)-トリオン、トリメチロールプロパントリス(3-メルカプトブチレート)、トリメチロールエタントリス(3-メルカプトブチレート)、及びトリス[(3-メルカプトプロピオニルオキシ)エチル]イソシアヌレート等の1分子中に3個のチオール基を有する化合物;ペンタエリスリトールテトラキス(3-メルカプトプロピオネート)、及びペンタエリスリトールテトラキス(3-メルカプトブチレート)等の1分子中に4個のチオール基を有する化合物;及び、ジペンタエリスリトールヘキサキス(3-メルカプトプロピオネート)等の1分子中に6個のチオール基を有する化合物などをあげることができる。
Examples of the above-mentioned component (A) active energy ray-curable resin include 1,2-ethanedithiol, ethylene glycol bis (3-mercaptopropionate), diethylene glycol bis (3-mercaptopropionate), and 1,4-. Compounds having two thiol groups in one molecule, such as bis (3-mercaptobutyryloxy) butane and tetraethylene glycol bis (3-mercaptopropionate); 1,3,5-tris (3-mercapto) Butyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropanthris (3-mercaptobutyrate), trimethylol ethanetris (3-mercaptobuty) Rate), and tris [(3-mercaptopropionyloxy) ethyl] isocyanurate and other compounds having three thiol groups in one molecule; pentaerythritol tetrakis (3-mercaptopropionate), and pentaerythritol tetrakis (3). -Compounds having 4 thiol groups in one molecule such as mercaptobutyrate); and compounds having 6 thiol groups in one molecule such as dipentaerythritol hexakis (3-mercaptopropionate), etc. Can be given.
上記成分(A)活性エネルギー線硬化性樹脂としては、これらの1種又は2種以上の混合物あるいはこれらのうちの特定の2種以上から形成された共重合体を用いることができる。なお本明細書において、(メタ)アクリレートとは、アクリレート又はメタクリレートの意味である。
As the active energy ray-curable resin of the component (A), a copolymer formed from one or a mixture of two or more of these or a specific two or more of these can be used. In addition, in this specification, (meth) acrylate means acrylate or methacrylate.
上記成分(A)活性エネルギー線硬化性樹脂として、(A1)ウレタン(メタ)アクリレートを含むものを用いることは好ましい。これにより、Bステージ塗膜における三次元成形性;ならびに、完全硬化後(Cステージにおいて)の表面硬度、耐擦傷性及び耐薬品性の両方をバランス良く向上させることができる。
It is preferable to use a resin containing (A1) urethane (meth) acrylate as the component (A) active energy ray-curable resin. As a result, both the three-dimensional moldability of the B-stage coating film; and the surface hardness, scratch resistance, and chemical resistance after complete curing (at the C stage) can be improved in a well-balanced manner.
上記成分(A)活性エネルギー線硬化性樹脂として、上記成分(A1)ウレタン(メタ)アクリレートを含むものを用いる場合、上記成分(A1)の配合比は、上記成分(A)の総和を100質量%として、上記成分(A1)の使用効果を確実に得る観点から、通常10質量%以上、好ましくは25質量%以上、より好ましくは40質量%以上であってよい。一方、上記成分(A1)の配合比は、表面硬度の観点から、通常99質量%以下、好ましくは95質量%以下、より好ましくは93質量%以下、更に好ましくは85質量%以下、最も好ましくは65質量%以下であってよい。下記実施例の試験(iv)及び試験(v)の環境試験に従い測定される耐環境性が特に重視される場合には、上記成分(A1)の配合比は、上記成分(A)の総和を100質量%として、好ましくは65~100質量%、より好ましくは75~100質量%であってよい。
When a resin containing the above-mentioned component (A1) urethane (meth) acrylate is used as the above-mentioned component (A) active energy ray-curable resin, 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). On the other hand, 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. When the environmental resistance measured according to the test (iv) and the environmental test (v) of the following examples is particularly important, 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.
上記成分(A)活性エネルギー線硬化性樹脂として、(A2)(a1)多官能(メタ)アクリレートと(a2)多官能チオールとの共重合体を含むものを用いることは好ましい。これにより、完全硬化後(Cステージにおいて)の表面硬度、耐擦傷性、及び耐薬品性を向上させることができる。また上記フィルム基材の一方の面の上にのみ本発明のBステージ塗膜を形成する実施形態にあっては、積層体のカール、反りを抑制することができる。
As the 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. Thereby, the surface hardness, scratch resistance, and chemical resistance after complete curing (at the C stage) can be improved. Further, in the embodiment in which 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.
上記成分(A)活性エネルギー線硬化性樹脂として、上記成分(A2)(a1)多官能(メタ)アクリレートと(a2)多官能チオールとの共重合体を含むものを用いる場合、上記成分(A2)の配合比は、上記成分(A)の総和を100質量%として、上記成分(A2)の使用効果を確実に得る観点から、通常1質量%以上、好ましくは5質量%以上、より好ましくは7質量%以上であってよい。一方、上記成分(A2)の配合比は、完全硬化後(Cステージにおいて)の耐クラック性の観点から、通常90質量%以下、好ましくは75質量%以下、より好ましくは60質量%以下であってよい。
When 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. On the other hand, 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.
上記成分(A)活性エネルギー線硬化性樹脂として、上記成分(A1)ウレタン(メタ)アクリレート、及び上記成分(A2)(a1)多官能(メタ)アクリレートと(a2)多官能チオールとの共重合体を含むものを用いることはより好ましい。Bステージ塗膜における三次元成形性;ならびに、完全硬化後(Cステージにおいて)の表面硬度、耐擦傷性、及び耐薬品性の両方を更にバランス良く向上させることができる。
As 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.
上記成分(A)活性エネルギー線硬化性樹脂として、上記成分(A1)ウレタン(メタ)アクリレート及び上記成分(A2)(a1)多官能(メタ)アクリレートと(a2)多官能チオールとの共重合体を含むものを用いる場合、上記成分(A1)と上記成分(A2)との配合比(上記成分(A1)の質量/上記成分(A2)の質量)は、Bステージ塗膜における三次元成形性;ならびに、完全硬化後(Cステージにおいて)の表面硬度、耐擦傷性、及び耐薬品性の両方のバランスの観点から、通常99/1~10/90、好ましくは95/5~25/75、より好ましくは93/7~40/60であってよい。下記実施例の試験(iv)及び試験(v)の環境試験に従い測定される耐環境性が特に重視される場合には、この配合比は、好ましくは99/1~65/35、より好ましくは95/5~75/25、更に好ましくは93/7~75/25であってよい。
As 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. When a compound containing the above component (A1) and the above component (A2) is used, 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. Also, from the viewpoint of the balance of both surface hardness, scratch resistance, and chemical resistance after complete curing (in the C stage), it is usually 99/1 to 10/90, preferably 95/5 to 25/75, More preferably, it may be 93/7 to 40/60. When the environmental resistance measured according to the test (iv) and the environmental test (v) of the following examples is particularly important, 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.
上記成分(A)活性エネルギー線硬化性樹脂として、上記成分(A1)ウレタン(メタ)アクリレート及び上記成分(A2)(a1)多官能(メタ)アクリレートと(a2)多官能チオールとの共重合体を含むものを用いる場合、上記成分(A1)の配合量と上記成分(A2)配合量との和は、上記成分(A)の総和を100質量%として、Bステージ塗膜における三次元成形性;ならびに、完全硬化後(Cステージにおいて)の表面硬度、耐擦傷性、及び耐薬品性の両方のバランスの観点から、通常80質量%以上、好ましくは90質量%以上、より好ましくは95質量%以上、更に好ましくは98~100質量%であってよい。
As 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. When a compound containing the above component (A1) is used, 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. In addition, from the viewpoint of the balance of surface hardness, scratch resistance, and chemical resistance after complete curing (in the C stage), 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)ウレタン(メタ)アクリレート
上記成分(A1)ウレタン(メタ)アクリレートは、ウレタン構造(-NH-CO-O-)を有する化合物、又はその誘導体であって1個以上の(メタ)アクリロイル基を有する化合物である。上記成分(A1)のウレタン(メタ)アクリレートは、特に限定されないが、典型的には、1分子中に2個以上のイソシアネート基(-N=C=O)を有する化合物、ポリオール化合物、及び水酸基含有(メタ)アクリレートを用いて製造されるもの、即ちこれらの化合物に由来する構成単位を含むものであってよい。 (A1) Urethane (meth) acrylate The above-mentioned component (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. The urethane (meth) acrylate of the above component (A1) is not particularly limited, but is typically a compound having two or more isocyanate groups (-N = C = O) in one molecule, a polyol compound, and a hydroxyl group. Those produced using the contained (meth) acrylate, that is, those containing a structural unit derived from these compounds may be used.
上記成分(A1)ウレタン(メタ)アクリレートは、ウレタン構造(-NH-CO-O-)を有する化合物、又はその誘導体であって1個以上の(メタ)アクリロイル基を有する化合物である。上記成分(A1)のウレタン(メタ)アクリレートは、特に限定されないが、典型的には、1分子中に2個以上のイソシアネート基(-N=C=O)を有する化合物、ポリオール化合物、及び水酸基含有(メタ)アクリレートを用いて製造されるもの、即ちこれらの化合物に由来する構成単位を含むものであってよい。 (A1) Urethane (meth) acrylate The above-mentioned component (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. The urethane (meth) acrylate of the above component (A1) is not particularly limited, but is typically a compound having two or more isocyanate groups (-N = C = O) in one molecule, a polyol compound, and a hydroxyl group. Those produced using the contained (meth) acrylate, that is, those containing a structural unit derived from these compounds may be used.
上記1分子中に2個以上のイソシアネート基を有する化合物としては、例えば、ジフェニルメタンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、トリレンジイソシアネート、及びメチレンビス(4-シクロヘキシルイソシアネート)などの1分子中に2個のイソシアネート基を有する化合物をあげることができる。上記1分子中に2個以上のイソシアネート基を有する化合物の他の例としては、トリレンジイソシアネートのトリメチロールプロパンアダクト体、ヘキサメチレンジイソシアネートのトリメチロールプロパンアダクト体、イソホロンジイソシアネートのトリメチロールプロパンアダクト体、トリレンジイソシアネートのイソシアヌレート体、ヘキサメチレンジイソシアネートのイソシアヌレート体、イソホロンジイソシアネートのイソシアヌレート体、及びヘキサメチレンジイソシアネートのビウレット体などのポリイソシアネートをあげることができる。
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.
上記1分子中に2個以上のイソシアネート基を有する化合物としては、これらの1種又は2種以上の混合物を用いることができる。
As 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.
上記ポリオール化合物としては、ポリエーテルポリオール、ポリエステルポリオール、及びポリカーボネートポリオールなどをあげることができる。
Examples of the polyol compound include polyether polyols, polyester polyols, polycarbonate polyols and the like.
上記ポリエーテルポリオールとしては、例えば、ポリエチレングリコール、ポリプロピレングリコール、及びポリテトラメチレングリコール等のポリアルキレングリコール;ポリエチレンオキサイド、及びポリプロピレンオキサイドなどのポリアルキレンオキサイド;エチレンオキサイドとプロピレンオキサイドとの共重合体;エチレンオキサイドとテトラヒドロフランとの共重合体;2価フェノール化合物とポリオキシアルキレングリコールとの共重合体;及び2価フェノールと炭素数2~4のアルキレンオキサイド(例えば、エチレンオキサイド、プロピレンオキサイド、1,2-ブチレンオキサイド、及び1,4-ブチレンオキサイドなど)の1種以上との共重合体などをあげることができる。
Examples of the polyether polyol 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.
上記ポリエステルポリオールとしては、例えば、ポリ(エチレンアジペート)、ポリ(ブチレンアジペート)、ポリ(ネオペンチルアジペート)、ポリ(ヘキサメチレンアジペート)、ポリ(ブチレンアゼラエート)、ポリ(ブチレンセバケート)、及びポリカプロラクトンなどをあげることができる。
Examples of the polyester polyol 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.
上記ポリカーボネートポリオールとしては、例えば、ポリ(ブタンジオールカーボネート)、ポリ(ヘキサンジオールカーボネート)、及びポリ(ノナンジオールカーボネート)などをあげることができる。
Examples of the polycarbonate polyol include poly (butanediol carbonate), poly (hexanediol carbonate), and poly (nonanediol carbonate).
上記ポリオール化合物としては、これらの1種又は2種以上の混合物を用いることができる。
As the above-mentioned polyol compound, one kind or a mixture of two or more kinds of these can be used.
上記水酸基含有(メタ)アクリレートとしては、例えば、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート、6-ヒドロキシヘキシル(メタ)アクリレート、及び2-ヒドロキシ-3-(メタ)アクリロイロキシプロピル(メタ)アクリレートなどのヒドロキシアルキル(メタ)アクリレート;ジプロピレングリコール(メタ)アクリレート、ポリエチレングリコールモノ(メタ)アクリレート、及びポリプロピレングリコールモノ(メタ)アクリレートなどのグリコール系(メタ)アクリレート;グリセリンジ(メタ)アクリレートなどのグリセリン系(メタ)アクリレート;脂肪酸変性-グリシジル(メタ)アクリレートなどの変性グリシジル系(メタ)アクリレート;2-ヒドロキシエチルアクリロイルホスフェートなどの燐原子含有(メタ)アクリレート;2-(メタ)アクリロイロキシエチル-2-ヒドロキシプロピルフタレートなどのエステル又はエステル誘導体の(メタ)アクリル酸付加物;ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、エチレンオキサイド変性ペンタエリスリトールトリ(メタ)アクリレート、及びエチレンオキサイド変性ジペンタエリスリトールペンタ(メタ)アクリレートなどのペンタエリスリトール系(メタ)アクリレート;及び、カプロラクトン変性2-ヒドロキシエチル(メタ)アクリレート、カプロラクトン変性ペンタエリスリトールトリ(メタ)アクリレート、及びカプロラクトン変性ジペンタエリスリトールペンタ(メタ)アクリレートなどのカプロラクトン変性(メタ)アクリレートをあげることができる。
Examples of the hydroxyl group-containing (meth) acrylate 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; pentaerythritol tris ( Pentaerythritol-based (meth) acrylates such as meta) acrylates, dipentaerythritol penta (meth) acrylates, ethylene oxide-modified pentaerythritol tri (meth) acrylates, and ethylene oxide-modified dipentaerythritol penta (meth) acrylates; and caprolactone-modified Examples thereof include caprolactone-modified (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, and caprolactone-modified dipentaerythritol penta (meth) acrylate.
上記水酸基含有(メタ)アクリレートとしては、これらの1種又は2種以上の混合物を用いることができる。
As the hydroxyl group-containing (meth) acrylate, one or a mixture of two or more of these can be used.
上記成分(A1)のウレタン(メタ)アクリレートのゲル浸透クロマトグラフィー(以下、「GPC」と略すことがある)により測定した微分分子量分布曲線(以下、「GPC曲線」と略すことがある)から求めたポリスチレン換算の数平均分子量(Mn)は、三次元成形性の観点、及び上記保護フィルムを使用する実施形態において、上記乾燥塗膜と上記保護フィルムとの密着性を、ウェブハンドリングを行う際に最低限必要となるレベルには保持する観点から、通常500以上、好ましくは1000以上であってよい。一方、この数平均分子量(Mn)は、塗工性の観点から、通常3万以下、好ましくは2万以下であってよい。
Obtained from the differential molecular weight distribution curve (hereinafter, may be abbreviated as "GPC curve") measured by gel permeation chromatography (hereinafter, may be abbreviated as "GPC") of 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.
上記成分(A1)のウレタン(メタ)アクリレートのGPCにより測定したGPC曲線から求めたポリスチレン換算の質量平均分子量(Mw)は、三次元成形性の観点、及び上記保護フィルムを使用する実施形態において、上記乾燥塗膜と上記保護フィルムとの密着性を、ウェブハンドリングを行う際に最低限必要となるレベルには保持する観点から、通常1000以上、好ましくは2000以上であってよい。一方、この質量平均分子量(Mw)は、塗工性の観点から、通常10万以下、好ましくは5万以下であってよい。
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.
上記成分(A1)のウレタン(メタ)アクリレートが有する(メタ)アクリロイル基の数は、GPC曲線から求めたポリスチレン換算の数平均分子量(Mn)1000当たり、ウェブハンドリング性の観点、及び完全硬化後(Cステージにおいて)の表面硬度、耐擦傷性、及び耐薬品性の観点から、通常2個以上、好ましくは3個以上であってよい。一方、この(メタ)アクリロイル基の数は、三次元成形性の観点から、通常20個以下、好ましくは12個以下、より好ましくは10個以下であってよい。ここでのウェブハンドリング性は、上述と同様に、ウェブハンドリングの際に、塗膜が移送ロールなどに接触することによる、傷や外観不良の生じ難さを意味する。
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. As described above, 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.
上記成分(A1)のウレタン(メタ)アクリレートのGPCにより測定したGPC曲線から求めたポリスチレン換算のZ平均分子量(Mz)は、三次元成形性の観点、及び上記保護フィルムを使用する実施形態において、上記乾燥塗膜と上記保護フィルムとの密着性を、ウェブハンドリングを行う際に最低限必要となるレベルには保持する観点から、通常1500以上、好ましくは2500以上であってよい。一方、このZ平均分子量(Mz)は、塗工性の観点から、通常15万以下、好ましくは10万以下であってよい。
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の測定は、システムとして東ソー株式会社の高速液体クロマトグラフィーシステム「HLC-8320」(商品名)(デガッサー、送液ポンプ、オートサンプラー、カラムオーブン及びRI(示差屈折率)検出器を含むシステム)を使用し;GPCカラムとしShodex社のGPCカラム「KF-806L」(商品名)を2本、「KF-802」(商品名)及び「KF-801」(商品名)を各1本の合計4本を、上流側からKF-806L、KF-806L、KF-802、及びKF-801の順に連結して使用し;和光純薬工業株式会社の高速液体クロマトグラフ用テトラヒドロフラン(安定剤不含)を移動相として;流速1.0ミリリットル/分、カラム温度40℃、試料濃度1ミリグラム/ミリリットル、及び試料注入量100マイクロリットルの条件で行うことができる。各保持容量における溶出量は、測定試料の屈折率の分子量依存性が無いと見なしてRI検出器の検出量から求めることができる。また保持容量からポリスチレン換算分子量への較正曲線は、市販の標準ポリスチレンを使用して作成することができる。その際に測定値が検量線において内挿されるように標準ポリスチレンを適宜選択すべきことに留意する。解析プログラムは、東ソー株式会社の「TOSOH HLC-8320GPC EcoSEC」(商品名)を使用することができる。なおGPCの理論及び測定の実際については、共立出版株式会社の「サイズ排除クロマトグラフィー 高分子の高速液体クロマトグラフィー」(著者:森定雄、初版第1刷1991年12月10日)、株式会社オーム社の「合成高分子クロマトグラフィー」(編者:大谷肇、寶崎達也(「崎」はつくりの上部が「立」)、初版第1刷2013年7月25日)などの参考書を参照することができる。
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). As a GPC column, two GPC columns "KF-806L" (trade name) from Shodex, and one each of "KF-802" (trade name) and "KF-801" (trade name) are used. Four of them were connected and used in the order of KF-806L, KF-806L, KF-802, and KF-801 from the upstream side; tetrahydrofuran for high performance liquid chromatograph of Wako Pure Chemical Industries, Ltd. (without stabilizer). As a mobile phase; the flow rate is 1.0 ml / min, the column temperature is 40 ° C., the sample concentration is 1 mg / ml, and 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. Moreover, 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. As the analysis program, "TOSOH HLC-8320GPC EcoSEC" (trade name) of Tosoh Corporation can be used. Regarding the theory of GPC and the actual measurement, Kyoritsu Publishing Co., Ltd.'s "Size Exclusion Chromatography: High Performance Liquid Chromatography of Polymers" (Author: Sadao Mori, First Edition, 1st Edition, December 10, 1991), Ohm Co., Ltd. Refer to reference books such as "Synthetic Polymer Chromatography" (editor: Hajime Otani, Tatsuya Torasaki ("zaki" is "standing" at the top of the structure), first edition, first printing, July 25, 2013). be able to.
図2に実施例で用いた下記成分(A1-1)の微分分子量分布曲線を示す。相対的に低分子量の領域に2本のシャープなピークが認められ、そのピークトップ位置のポリスチレン換算分子量は、低分子量側から順に280、及び610である。これらの2本のピークよりも高分子量側に主要成分のピークが認められ、そのピークトップ位置のポリスチレン換算分子量は2400である。そして、全体の数平均分子量(Mn)は1000、質量平均分子量(Mw)は2900、Z平均分子量(Mz)は4700である。また1分子当たりの(メタ)アクリロイル基の数は2個であるから、GPC曲線から求めたポリスチレン換算の数平均分子量(Mn)1000当たりの(メタ)アクリロイル基の数は2個である。
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, and the Z average molecular weight (Mz) is 4700. Further, since 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)多官能(メタ)アクリレートと(a2)多官能チオールとの共重合体
上記成分(A2)は、(a1)多官能(メタ)アクリレートと(a2)多官能チオールとの共重合体である。上記成分(a1)と上記成分(a2)は何れも多官能モノマーであるため、上記成分(A2)は、通常、高度に枝分かれした構造、所謂デンドリマー構造を有する共重合体である。 (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.
上記成分(A2)は、(a1)多官能(メタ)アクリレートと(a2)多官能チオールとの共重合体である。上記成分(a1)と上記成分(a2)は何れも多官能モノマーであるため、上記成分(A2)は、通常、高度に枝分かれした構造、所謂デンドリマー構造を有する共重合体である。 (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.
上記成分(a1)多官能(メタ)アクリレートは、1分子中に2個以上の(メタ)アクリロイル基を有する(メタ)アクリレートである。上記成分(a1)の1分子中の(メタ)アクリロイル基の数は、上記成分(A2)共重合体の構造を所謂デンドリマー構造を有するものにする観点から、好ましくは3個以上、より好ましくは4個以上、更に好ましくは5個以上であってよい。一方、塗膜を完全硬化後(Cステージにおいて)の耐クラック性の観点から、通常20個以下、好ましくは12個以下であってよい。
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. On the other hand, from the viewpoint of crack resistance after the coating film is completely cured (in the C stage), the number may be usually 20 or less, preferably 12 or less.
上記成分(a1)多官能(メタ)アクリレートとしては、例えば、ジエチレングリコールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、2,2’-ビス(4-(メタ)アクリロイルオキシポリエチレンオキシフェニル)プロパン、及び、2,2’-ビス(4-(メタ)アクリロイルオキシポリプロピレンオキシフェニル)プロパン等の(メタ)アクリロイル基含有2官能反応性モノマー;トリメチロールプロパントリ(メタ)アクリレート、トリメチロールエタントリ(メタ)アクリレート、及びエトキシ化トリメチロールプロパントリ(メタ)アクリレート等の(メタ)アクリロイル基含有3官能反応性モノマー;ジトリメチロールプロパンテトラ(メタ)アクリレート、及びペンタエリスリトールテトラメタクリレート等の(メタ)アクリロイル基含有4官能反応性モノマー;ジペンタエリスリトールヘキサアクリレート等の(メタ)アクリロイル基含有6官能反応性モノマー;トリペンタエリスリトールオクタアクリレート等の(メタ)アクリロイル基含有8官能反応性モノマー;及びこれらの1種以上を構成モノマーとする重合体(オリゴマーやプレポリマー)であって、1分子中に2個以上の(メタ)アクリロイル基を有するものをあげることができる。また、上記成分(a1)としては、例えば、ポリウレタン(メタ)アクリレート、ポリエステル(メタ)アクリレート、ポリアクリル(メタ)アクリレート、ポリエポキシ(メタ)アクリレート、ポリアルキレングリコールポリ(メタ)アクリレート、及び、ポリエーテル(メタ)アクリレートなどのプレポリマー又はオリゴマーであって、1分子中に2個以上の(メタ)アクリロイル基を有するものあげることができる。上記成分(a1)としては、これらの1種又は2種以上の混合物を用いることができる。
Examples of the component (a1) polyfunctional (meth) acrylate 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. 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) in one molecule. Those having an acryloyl group can be mentioned. Examples of the component (a1) 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. As the component (a1), one kind or a mixture of two or more kinds of these can be used.
上記成分(a2)多官能チオールは、1分子中に2個以上チオール基を有する化合物である。上記成分(a2)の1分子中のチオール基の数は、上記成分(A2)共重合体の構造を所謂デンドリマー構造を有するものにする観点から、好ましくは3個以上、より好ましくは4個以上であってよい。一方、塗膜を完全硬化後(Cステージにおいて)の耐クラック性の観点から、通常20個以下、好ましくは12個以下であってよい。上記成分(a2)の有するチオール基は、反応性と取扱性のバランスの観点から、好ましくは2級チオール基であってよい。
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. On the other hand, from the viewpoint of crack resistance after the coating film is completely cured (in the C stage), 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.
上記成分(a2)多官能チオールは、1分子中に1個又は2個以上の(メタ)アクリロイル基、ビニル基、エポキシ基、及びイソシアネート基などのチオール基以外の重合性官能基を有するものであってもよい。本明細書において、1分子中に2個以上のチオール基を有し、かつ2個以上の(メタ)アクリロイル基を有する化合物は、上記成分(a2)に分類されるものとする。
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. In the present specification, 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).
上記成分(a2)多官能チオールとしては、例えば、1,2-エタンジチオール、エチレングリコールビス(3-メルカプトプロピオネート)、ジエチレングリコールビス(3-メルカプトプロピオネート)、1,4-ビス(3-メルカプトブチリルオキシ)ブタン、及びテトラエチレングリコールビス(3-メルカプトプロピオネート)等の1分子中に2個のチオール基を有する化合物;1,3,5-トリス(3-メルカプトブチリルオキシエチル)-1,3,5-トリアジン-2,4,6(1H,3H,5H)-トリオン、トリメチロールプロパントリス(3-メルカプトブチレート)、トリメチロールエタントリス(3-メルカプトブチレート)、及びトリス[(3-メルカプトプロピオニルオキシ)エチル]イソシアヌレート等の1分子中に3個のチオール基を有する化合物;ペンタエリスリトールテトラキス(3-メルカプトプロピオネート)、及びペンタエリスリトールテトラキス(3-メルカプトブチレート)等の1分子中に4個のチオール基を有する化合物;ジペンタエリスリトールヘキサキス(3-メルカプトプロピオネート)等の1分子中に6個のチオール基を有する化合物;及び、これらの1種以上を構成モノマーとする重合体(オリゴマーやプレポリマー)であって、1分子中に2個以上チオール基を有するものをあげることができる。上記成分(a2)としては、これらの1種又は2種以上の混合物を用いることができる。
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). -Compounds having two thiol groups in one molecule, such as mercaptobutyryloxy) butane and tetraethylene glycolbis (3-mercaptopropionate); 1,3,5-tris (3-mercaptobutyryloxy) Ethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropanetris (3-mercaptobutyrate), trimethylol ethanetris (3-mercaptobutyrate), And tris [(3-mercaptopropionyloxy) ethyl] isocyanurate and other compounds having three thiol groups in one molecule; pentaerythritol tetrakis (3-mercaptopropionate), and pentaerythritol tetrakis (3-mercaptobuty). Compounds having 4 thiol groups in 1 molecule such as rate); compounds having 6 thiol groups in 1 molecule such as dipentaerythritol hexakis (3-mercaptopropionate); and 1 of these Examples of polymers (oligomers and prepolymers) having seeds or more as constituent monomers and having two or more thiol groups in one molecule can be mentioned. As the component (a2), one kind or a mixture of two or more kinds of these can be used.
上記成分(A2)共重合体は、本発明の目的に反しない限度において、上記成分(a1)多官能(メタ)アクリレートと上記成分(a2)多官能チオール以外に、これらと共重合可能なモノマーに由来する構成単位を含むものであってよい。該共重合可能なモノマーは、通常、炭素・炭素二重結合を有する化合物であり、典型的にはエチレン性二重結合を有する化合物である。
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.
上記成分(A2)共重合体中の上記成分(a1)多官能(メタ)アクリレートに由来する構成単位の含有量(以下、「(a1)含有量」と略すことがある)、は、重合性モノマーに由来する構成単位の総和を100モル%として、上記成分(A2)共重合体の構造を所謂デンドリマー構造を有するものにする観点、及び耐擦傷性の観点から、通常50モル%以上、好ましくは60モル%以上、より好ましくは70モル%以上、更に好ましくは80モル%以上であってよい。一方、上記成分(A2)共重合体の構造を所謂デンドリマー構造を有するものにする観点、及び塗膜を完全硬化後(Cステージにおいて)の耐クラック性やハンドリング性の観点から、通常99モル%以下、好ましくは97モル%以下、より好ましくは95モル%以下、更に好ましくは93モル%以下であってよい。
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. From the viewpoint of making the structure of the above-mentioned component (A2) copolymer having a so-called dendrimer structure, and from the viewpoint of scratch resistance, 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. On the other hand, from the viewpoint of making 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%. Hereinafter, it may be preferably 97 mol% or less, more preferably 95 mol% or less, still more preferably 93 mol% or less.
上記成分(A2)共重合体中の上記成分(a2)多官能チオールに由来する構成単位の含有量(以下、「(a2)含有量」と略すことがある)は、重合性モノマーに由来する構成単位の総和を100モル%として、上記成分(A)の構造を所謂デンドリマー構造を有するものにする観点、及び塗膜を完全硬化後(Cステージにおいて)の耐クラック性やハンドリング性の観点から、通常1モル%以上、好ましくは3モル%以上、より好ましくは5モル%以上、更に好ましくは7モル%以上であってよい。一方、上記成分(A2)共重合体の構造を所謂デンドリマー構造を有するものにする観点、及び耐擦傷性の観点から、通常50モル%以下、好ましくは40モル%以下、より好ましくは30モル%以下、更に好ましくは20モル%以下であってよい。
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. From the viewpoint of making the structure of the above component (A) having a so-called dendrimer structure by setting the total of the constituent units to 100 mol%, and from the viewpoint of crack resistance and handleability after the coating film is completely cured (in the C stage). , Usually 1 mol% or more, preferably 3 mol% or more, more preferably 5 mol% or more, still more preferably 7 mol% or more. On the other hand, from the viewpoint of making the structure of the above component (A2) copolymer having a so-called dendrimer structure and from the viewpoint of scratch resistance, it is usually 50 mol% or less, preferably 40 mol% or less, more preferably 30 mol%. Hereinafter, it may be more preferably 20 mol% or less.
ここで上記(a1)多官能(メタ)アクリレート含有量と上記(a2)多官能チオール含有量との和は、重合性モノマーに由来する構成単位の総和を100モル%として、通常80モル%以上、好ましくは90モル%以上、より好ましくは95モル%以上、更に好ましくは99モル%以上、100モル%以下であってよい。なお「重合性モノマー」とは、上記成分(a1)、上記成分(a2)、及びこれらと共重合可能なモノマーを意味する。該共重合可能なモノマーは、通常、炭素・炭素二重結合を有する化合物であり、典型的にはエチレン性二重結合を有する化合物である。
Here, 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.
上記成分(A2)共重合体中の硫黄含有量は、上記(a2)多官能チオール含有量を上述の好ましい範囲にする観点から、通常0.1~12質量%、好ましくは0.5~10質量%、より好ましくは1~7質量%、更に好ましくは1.5~5質量%であってよい。
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.
ここで硫黄含有量は、マイクロウェーブ装置を使用し、硝酸と塩酸の混合酸(体積比8:2)を用いて、試料の灰化(湿式分解)を行った後、塩酸水溶液を加えて濾過し、濾過液を精製水で定容して得た測定サンプルを、原子吸光分析法で測定した値である。このとき内部標準としてイットリウムを用いる。また硫黄は鉄等と結合して沈殿し易いので、これを防止すべきことに留意する。具体的には、特開2018-187924号公報の段落0035~0039に記載の方法と同様にして、硫黄含有量の測定を行うことができる。
Here, 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. In addition, it should be noted that sulfur should be prevented because it binds to iron and the like and easily precipitates. Specifically, 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.
上記成分(A2)共重合体のGPCにより測定したGPC曲線から求めたポリスチレン換算の質量平均分子量(Mw)は、塗膜を完全硬化後(Cステージにおいて)の耐擦傷性と耐クラック性のバランスの観点から、好ましくは5千以上、より好ましくは8千以上、更に好ましくは1万以上であってよい。一方、この質量平均分子量(Mw)は、上記成分(A2)共重合体を含む塗料の塗工性の観点から、好ましくは20万以下、より好ましくは10万以下、更に好ましくは5万以下であってよい。
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.
上記成分(A2)共重合体のGPC曲線から求めたポリスチレン換算のZ平均分子量(Mz)は、塗膜を完全硬化後(Cステージにおいて)の耐擦傷性と耐クラック性のバランスの観点から、好ましくは5千以上、より好ましくは1万以上、更に好ましくは3万以上であってよい。一方、このZ平均分子量(Mz)は、上記成分(A2)共重合体を含む塗料の塗工性の観点から、好ましくは20万以下、より好ましくは15万以下、更に好ましくは12万以下であってよい。
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.
上記成分(A2)共重合体のGPC曲線から求めたポリスチレン換算の数平均分子量(Mn)は、塗膜を完全硬化後(Cステージにおいて)の耐擦傷性と耐クラック性のバランスの観点から、好ましくは300以上、より好ましくは500以上であってよい。一方、この数平均分子量(Mn)は、上記成分(A2)共重合体を含む塗料の塗工性の観点から、好ましくは10万以下、より好ましくは5万以下、更に好ましくは2万以下であってよい。
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.
上記成分(A2)共重合体のGPC測定は、上記成分(A1)の説明において上述した方法と同様にして行うことができる。
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).
図3に実施例で用いた下記成分(A2-1)の微分分子量分布曲線を示す。相対的に低分子量の領域に3本の明確なピークが認められ、そのピークトップ位置のポリスチレン換算分子量は、低分子量側から順に、340、570、及び970である。またこれらの3本のピークよりも高分子量側に、重なりあいブロードになった複数のピークが認められ、最も高分子量側の成分のポリスチレン換算分子量は20万程度と認められる。そして全体の数平均分子量(Mn)は940、質量平均分子量(Mw)は1万2千、Z平均分子量(Mz)は7万3千である。
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.
(B)光重合開始剤
上記成分(B)光重合開始剤は、活性エネルギー線の照射によりラジカルなどの活性種を発生する化合物である。上記成分(B)光重合開始剤は、ラジカルなどの活性種を発生することにより、上記成分(A)活性エネルギー線硬化性樹脂を重合・硬化させ、塗膜を完全硬化(Cステージに)する働きをする。 (B) Photopolymerization Initiator 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.
上記成分(B)光重合開始剤は、活性エネルギー線の照射によりラジカルなどの活性種を発生する化合物である。上記成分(B)光重合開始剤は、ラジカルなどの活性種を発生することにより、上記成分(A)活性エネルギー線硬化性樹脂を重合・硬化させ、塗膜を完全硬化(Cステージに)する働きをする。 (B) Photopolymerization Initiator 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.
上記成分(B)光重合開始剤としては、例えば、ベンゾフェノン、メチル-o-ベンゾイルベンゾエート、4-メチルベンゾフェノン、4,4’-ビス(ジエチルアミノ)ベンゾフェノン、o-ベンゾイル安息香酸メチル、4-フェニルベンゾフェノン、4-ベンゾイル-4’-メチルジフェニルサルファイド、3,3’,4,4’-テトラ(tert-ブチルパーオキシカルボニル)ベンゾフェノン、及び2,4,6-トリメチルベンゾフェノンなどのベンゾフェノン系化合物;ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、及びベンジルメチルケタールなどのベンゾイン系化合物;アセトフェノン、2,2-ジメトキシ-2-フェニルアセトフェノン、1-ヒドロキシシクロヘキシルフェニルケトン、及び2-ヒロドキシ-1-{4-[4-(2-ヒドロキシ-2-メチル-プロピオニル)-ベンジル]フェニル}-2-メチル-プロパン-1-オン等のアセトフェノン系化合物、α-ヒドロキシアルキルフェノン系化合物、並びにアセトフェノンジメチルアセタールなどのアルキルフェノン系化合物;メチルアントラキノン、2-エチルアントラキノン、及び2-アミルアントラキノンなどのアントラキノン系化合物;チオキサントン、2,4-ジエチルチオキサントン、及び2,4-ジイソプロピルチオキサントンなどのチオキサントン系化合物;アシルフォスフィンオキサイド系化合物;ビイミダゾール化合物;チタノセン系化合物;オキシムエステル系化合物;オキシムフェニル酢酸エステル系化合物;ヒドロキシケトン系化合物;トリアジン系化合物;並びに、アミノベンゾエート系化合物などをあげることができる。
なお、上記用語「アルキルフェノン系化合物」は、アセトフェノン骨格(ベンゼン環-CO-アルキル基)またはアセトフェノン骨格に由来する構造を有する化合物であると定義される。このアルキルフェノン系化合物の中で、アセトフェノン骨格に由来するカルボニル基C=Oが保たれている化合物が上記用語「アセトフェノン系化合物」に当たる。つまり、「アセトフェノン系化合物」は「アルキルフェノン系化合物」に包含される下位概念である。 Examples of the component (B) photopolymerization initiator include benzophenone, methyl-o-benzoylbenzoate, 4-methylbenzophenone, 4,4'-bis (diethylamino) benzophenone, methyl o-benzoylbenzoate, and 4-phenylbenzophenone. , 4-Benzoyl-4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, and benzophenone compounds such as 2,4,6-trimethylbenzophenone; benzoin, Benzophenone compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl methyl ketal; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, and 2-hirodoxy-1-{ Acetphenone compounds such as 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, α-hydroxyalkylphenone compounds, acetphenone dimethylacetal, etc. Alkylphenone compounds; anthraquinone 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.
The above term "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. Among the alkylphenone compounds, the compound in which the carbonyl group C = O derived from the acetophenone skeleton is maintained corresponds to the above term "acetophenone compound". That is, "acetophenone-based compound" is a subordinate concept included in "alkylphenone-based compound".
なお、上記用語「アルキルフェノン系化合物」は、アセトフェノン骨格(ベンゼン環-CO-アルキル基)またはアセトフェノン骨格に由来する構造を有する化合物であると定義される。このアルキルフェノン系化合物の中で、アセトフェノン骨格に由来するカルボニル基C=Oが保たれている化合物が上記用語「アセトフェノン系化合物」に当たる。つまり、「アセトフェノン系化合物」は「アルキルフェノン系化合物」に包含される下位概念である。 Examples of the component (B) photopolymerization initiator include benzophenone, methyl-o-benzoylbenzoate, 4-methylbenzophenone, 4,4'-bis (diethylamino) benzophenone, methyl o-benzoylbenzoate, and 4-phenylbenzophenone. , 4-Benzoyl-4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, and benzophenone compounds such as 2,4,6-trimethylbenzophenone; benzoin, Benzophenone compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl methyl ketal; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, and 2-hirodoxy-1-{ Acetphenone compounds such as 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, α-hydroxyalkylphenone compounds, acetphenone dimethylacetal, etc. Alkylphenone compounds; anthraquinone 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.
The above term "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. Among the alkylphenone compounds, the compound in which the carbonyl group C = O derived from the acetophenone skeleton is maintained corresponds to the above term "acetophenone compound". That is, "acetophenone-based compound" is a subordinate concept included in "alkylphenone-based compound".
上記成分(B)光重合開始剤としては、三次元成形後、塗膜を確実に完全硬化(Cステージに)する観点から、活性エネルギー線の照射によりラジカルを発生する化合物が好ましい。上記成分(B)光重合開始剤としては、三次元成形を行うまで塗膜をBステージ状態に安定的に保持する観点から、アセトフェノン系化合物などのアルキルフェノン系化合物が好ましく、ヒドロキシアセトフェノン系化合物(水酸基を有するアセトフェノン系化合物)などのヒドロキシアルキルフェノン系化合物(水酸基を有するアルキルフェノン系化合物)がより好ましい。また三次元成形時の熱による光重合開始剤の揮発を抑制する観点から、揮発性の低いものが好ましい。揮発性の低い光重合開始剤としては、例えば、1-ヒドロキシシクロヘキシル-フェニルケトン、2-ヒロドキシ-1-{4-[4-(2-ヒドロキシ-2-メチル-プロピオニル)-ベンジル]フェニル}-2-メチル-プロパン-1-オンをあげることができる。上記成分(B)としては、これらの1種又は2種以上の混合物を用いることができる。
As 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. As the component (B) photopolymerization initiator, 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 (alkylphenone compound having a hydroxyl group) 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.
上記成分(B)光重合開始剤の配合量は、塗膜をBステージ状態に硬化させる観点、塗膜の硬化をBステージ状態に留める観点、三次元成形を行うまで塗膜をBステージ状態に安定的に保持する観点、及び三次元成形後、確実に完全硬化(Cステージに)する観点を総合的に勘案して適宜選択すればよい。上記成分(B)光重合開始剤の配合量は、上記成分(A)活性エネルギー線硬化性樹脂100質量部に対して、塗膜をBステージ状態に硬化させる観点、及び三次元成形後、確実に完全硬化(Cステージに)する観点から、通常1質量部以上、好ましくは2質量部以上、より好ましくは3質量部以上、更に好ましくは4質量部以上であってよい。一方、上記成分(B)光重合開始剤の配合量は、塗膜の硬化をBステージ状態に留める観点、及び三次元成形を行うまで塗膜をBステージ状態に安定的に保持する観点から、通常20質量部以下、好ましくは15質量部以下、より好ましくは12質量部以下、更に好ましくは10質量部以下であってよい。
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. From 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. On the other hand, 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.
(C)微粒子
上記Bステージ塗膜形成用塗料は、好ましくは更に上記成分(C)微粒子を含むものであってよい。上記成分(C)微粒子は、本発明のBステージ塗膜を用いて得られる成形体(塗膜はCステージ)の表面硬度を高める働きをする。 (C) Fine Particles 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.
上記Bステージ塗膜形成用塗料は、好ましくは更に上記成分(C)微粒子を含むものであってよい。上記成分(C)微粒子は、本発明のBステージ塗膜を用いて得られる成形体(塗膜はCステージ)の表面硬度を高める働きをする。 (C) Fine Particles 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.
上記成分(C)微粒子としては、無機微粒子、及び有機微粒子をあげることができる。上記無機微粒子としては、例えば、シリカ(二酸化珪素);酸化アルミニウム、ジルコニア、チタニア、酸化亜鉛、酸化ゲルマニウム、酸化インジウム、酸化スズ、インジウムスズ酸化物、酸化アンチモン、及び酸化セリウム等の金属酸化物微粒子;弗化マグネシウム、及び弗化ナトリウム等の金属弗化物微粒子;金属硫化物微粒子;金属窒化物微粒子;及び金属微粒子などをあげることができる。
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.
上記有機微粒子としては、例えば、シリコーン系樹脂、スチレン系樹脂、アクリル系樹脂、弗素系樹脂、ポリカーボネート系樹脂、エチレン系樹脂、及びアミノ系化合物とホルムアルデヒドとの硬化樹脂などの樹脂微粒子をあげることができる。
Examples of the organic fine particles 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.
これらの中でより高い表面硬度を得る観点から、シリカや酸化アルミニウムの微粒子が好ましく、シリカの微粒子がより好ましい。シリカ微粒子の市販品としては、日産化学工業株式会社のスノーテックス(商品名)、扶桑化学工業株式会社のクォートロン(商品名)などをあげることができる。
Among these, 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.
上記成分(C)微粒子の表面を、特に上記成分(C)として無機微粒子を用いる場合に当該無機微粒子の表面を、ビニルシラン、及びアミノシラン等のシラン系カップリング剤;チタネート系カップリング剤;アルミネート系カップリング剤;(メタ)アクリロイル基、ビニル基、及びアリル基等のエチレン性不飽和結合基やエポキシ基などの反応性官能基を有する有機化合物;及び脂肪酸、脂肪酸金属塩等の表面処理剤などにより処理したものを用いることは好ましい。このように表面を処理することによって上記無機微粒子の塗料中での分散性を高めたり、表面硬度を高めたりすることができる。
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. Coupling agents; organic compounds having reactive functional groups such as ethylenically unsaturated bonding groups such as (meth) acryloyl groups, vinyl groups, and allyl groups and epoxy groups; and surface treatment agents such as fatty acids and fatty acid metal salts. It is preferable to use the one treated by the above. By treating the surface in this way, it is possible to increase the dispersibility of the inorganic fine particles in the paint and increase the surface hardness.
上記成分(C)微粒子は、実施形態の1つにおいて、抗菌剤又は抗ウィルス剤として機能する微粒子(以下、「機能性微粒子」と呼ぶことがある)を含むものであってよい。
上記成分(C)微粒子の一部又は全部として(すなわち、成分(C)の0質量%超から100質量%以下の量で)上記機能性微粒子を用いることにより、本発明の塗膜に抗菌性や抗ウィルス性を付与することができる。上記機能性微粒子を用いる実施形態において、上記成分(C)微粒子中の上記機能性微粒子の割合は、通常10質量%以上から100質量%以下、好ましくは30質量%以上から100質量%以下、より好ましくは50質量%以上から100質量%以下であってよい。
上記機能性微粒子としては、例えば、銅化合物、銀化合物、錫化合物、モリブデン化合物、及び亜鉛化合物などの抗菌剤又は抗ウィルス剤として機能する無機微粒子(以下、「機能性無機微粒子」と呼ぶことがある)などをあげることができる。
上記銅化合物としては、例えば、塩化第一銅(CuCl)、臭化第一銅(CuBr)、及びヨウ化第一銅(CuI)等のハロゲン化第一銅、及びチオシアン酸第一銅(CuSCN)などの第一銅化合物;炭酸第二銅(CuCO3)、酸化第二銅(CuO)、及び塩化第二銅(CuCl2)などの第二銅化合物をあげることができる。
上記銀化合物としては、例えば、ヨウ化第一銀(AgI)などハロゲン化銀化合物などをあげることができる。
上記錫化合物としては、例えば、四ヨウ化錫(SnI4)などのハロゲン化錫化合物などをあげることができる。
上記モリブデン化合物としては、例えば、酸化モリブデン(MoO3)、モリブデン・銀複合酸化物、モリブデン・亜鉛複合酸化物、及びモリブデン・銅複合酸化物などの酸化モリブデン化合物などをあげることができる。
上記亜鉛化合物としては、例えば、酸化亜鉛(ZnO)などの酸化亜鉛化合物などをあげることができる。
上記機能性微粒子としてはその他に、例えば、硫酸アルミニウムカリウム、銀・ナトリウム・水素・リン酸ジルコニウム、銀・マグネシウム・アルミニウム・リン酸ガラス(アメリカ食品医薬品局のFCN登録番号433)、銀・マグネシウム・カルシウム・リン酸・硼酸ガラス(アメリカ食品医薬品局のFCN登録番号432)、銀・亜鉛・マグネシウム・アルミニウム・カルシウム・ナトリウム・硼酸・リン酸ガラス(アメリカ食品医薬品局のFCN登録番号476)、銀・マグネシウム・ナトリウム・リン酸ガラス(アメリカ食品医薬品局のFCN登録番号434)、銀・マグネシウム・亜鉛・アルミニウム・カルシウム・ナトリウム・硼酸・リン酸ガラス(アメリカ食品医薬品局のFCN登録番号1981)、銀ゼオライト(CAS番号0130328-18-6)、銀銅ゼオライト(CAS番号0130328-19-7)、銀亜鉛ゼオライト(CAS番号0130328-20-0)、及び銅錫合金などの機能性無機微粒子をあげることができる。 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.
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. In the embodiment using the functional fine particles, 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"). There is) and so on.
Examples of the copper compound include cuprous halide such as cuprous chloride (CuCl), cuprous bromide (CuBr), and cuprous iodide (CuI), and cuprous thiocyanate (CuSCN). ) And the like; 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.
上記成分(C)微粒子の一部又は全部として(すなわち、成分(C)の0質量%超から100質量%以下の量で)上記機能性微粒子を用いることにより、本発明の塗膜に抗菌性や抗ウィルス性を付与することができる。上記機能性微粒子を用いる実施形態において、上記成分(C)微粒子中の上記機能性微粒子の割合は、通常10質量%以上から100質量%以下、好ましくは30質量%以上から100質量%以下、より好ましくは50質量%以上から100質量%以下であってよい。
上記機能性微粒子としては、例えば、銅化合物、銀化合物、錫化合物、モリブデン化合物、及び亜鉛化合物などの抗菌剤又は抗ウィルス剤として機能する無機微粒子(以下、「機能性無機微粒子」と呼ぶことがある)などをあげることができる。
上記銅化合物としては、例えば、塩化第一銅(CuCl)、臭化第一銅(CuBr)、及びヨウ化第一銅(CuI)等のハロゲン化第一銅、及びチオシアン酸第一銅(CuSCN)などの第一銅化合物;炭酸第二銅(CuCO3)、酸化第二銅(CuO)、及び塩化第二銅(CuCl2)などの第二銅化合物をあげることができる。
上記銀化合物としては、例えば、ヨウ化第一銀(AgI)などハロゲン化銀化合物などをあげることができる。
上記錫化合物としては、例えば、四ヨウ化錫(SnI4)などのハロゲン化錫化合物などをあげることができる。
上記モリブデン化合物としては、例えば、酸化モリブデン(MoO3)、モリブデン・銀複合酸化物、モリブデン・亜鉛複合酸化物、及びモリブデン・銅複合酸化物などの酸化モリブデン化合物などをあげることができる。
上記亜鉛化合物としては、例えば、酸化亜鉛(ZnO)などの酸化亜鉛化合物などをあげることができる。
上記機能性微粒子としてはその他に、例えば、硫酸アルミニウムカリウム、銀・ナトリウム・水素・リン酸ジルコニウム、銀・マグネシウム・アルミニウム・リン酸ガラス(アメリカ食品医薬品局のFCN登録番号433)、銀・マグネシウム・カルシウム・リン酸・硼酸ガラス(アメリカ食品医薬品局のFCN登録番号432)、銀・亜鉛・マグネシウム・アルミニウム・カルシウム・ナトリウム・硼酸・リン酸ガラス(アメリカ食品医薬品局のFCN登録番号476)、銀・マグネシウム・ナトリウム・リン酸ガラス(アメリカ食品医薬品局のFCN登録番号434)、銀・マグネシウム・亜鉛・アルミニウム・カルシウム・ナトリウム・硼酸・リン酸ガラス(アメリカ食品医薬品局のFCN登録番号1981)、銀ゼオライト(CAS番号0130328-18-6)、銀銅ゼオライト(CAS番号0130328-19-7)、銀亜鉛ゼオライト(CAS番号0130328-20-0)、及び銅錫合金などの機能性無機微粒子をあげることができる。 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.
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. In the embodiment using the functional fine particles, 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"). There is) and so on.
Examples of the copper compound include cuprous halide such as cuprous chloride (CuCl), cuprous bromide (CuBr), and cuprous iodide (CuI), and cuprous thiocyanate (CuSCN). ) And the like; 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.
上記成分(C)微粒子としては、これらの1種又は2種以上の混合物を用いることができる。例えば、上記成分(C)微粒子として、有機微粒子および無機微粒子の1種又は2種以上の混合物を用いることができる。また、例えば、上記成分(C)微粒子として、機能性微粒子ならびにそれ以外の微粒子(有機微粒子および/または無機微粒子)の1種又は2種以上の混合物を用いることができる。
As the component (C) fine particles, one or a mixture of two or more of these can be used. For example, as the 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. Further, for example, as the 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.
上記成分(C)微粒子の平均粒子径は、塗膜の透明性を保持する観点、及び硬度改良効果を確実に得る観点から、通常300nm以下、好ましくは200nm以下、より好ましくは120nm以下であってよい。一方、平均粒子径の下限は特にないが、通常入手可能な微粒子は細かくてもせいぜい1nm程度である。
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. On the other hand, although there is no particular lower limit on the average particle size, the fine particles that are usually available are at most about 1 nm.
本明細書において、微粒子の平均粒子径は、レーザー回折・散乱式粒度分析計を使用し、レーザー回折・散乱法で測定した粒子径分布曲線において、粒子の小さい方からの累積が50質量%となる粒子径である。上記レーザー回折・散乱式粒度分析計としては、例えば、日機装株式会社の「MT3200II」(商品名)などを使用することができる。
In the present specification, 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. As the laser diffraction / scattering type particle size analyzer, for example, "MT3200II" (trade name) manufactured by Nikkiso Co., Ltd. can be used.
上記成分(C)微粒子の配合量は、任意成分であるから特に制限されない。上記成分(C)微粒子の配合量は、完全硬化(Cステージにした)後の表面硬度と耐クラック性の観点から適宜選択すればよい。上記成分(C)の配合量は、上記成分(A)活性エネルギー線硬化性樹脂100質量部に対して、完全硬化(Cステージにした)後の表面硬度の観点から、好ましくは10質量部以上、より好ましくは80質量部以上、更に好ましくは120質量部以上、最も好ましくは150質量部以上であってよい。一方、上記成分(C)微粒子の配合量は、完全硬化(Cステージにした)後の耐クラック性の観点から、好ましくは500質量部以下、より好ましくは400質量部以下、更に好ましくは300質量部以下、最も好ましくは250質量部以下であってよい。
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. On the other hand, 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.
上記成分(C)微粒子が上記機能性微粒子を含む実施形態において、上記機能性微粒子の配合量は、抗菌性や抗ウィルス性を確実に発現させる観点、及び上記成分(C)の総量が上述の範囲を超えないようにする観点から適宜決定する。
上記機能性微粒子の配合量は、抗菌性や抗ウィルス性を確実に発現させる観点から、上記成分(A)活性エネルギー線硬化性樹脂100質量部に対して、通常1質量部以上、好ましくは4質量部以上、より好ましくは7質量部以上、更に好ましくは10質量部以上であってよい。一方、上記機能性微粒子の配合量は、完全硬化(Cステージにした)後の耐クラック性の観点から、好ましくは500質量部以下、より好ましくは400質量部以下、更に好ましくは300質量部以下、最も好ましくは250質量部以下であってよい。他の実施形態において、上記機能性微粒子の配合量は、上述の観点から、10質量部以上200質量部以下であってよく、または10質量部以上100質量部以下、または10質量部以上50質量部以下であってよい。 In the embodiment in which the fine particles of the component (C) include the functional fine particles, 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. On the other hand, 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.
上記機能性微粒子の配合量は、抗菌性や抗ウィルス性を確実に発現させる観点から、上記成分(A)活性エネルギー線硬化性樹脂100質量部に対して、通常1質量部以上、好ましくは4質量部以上、より好ましくは7質量部以上、更に好ましくは10質量部以上であってよい。一方、上記機能性微粒子の配合量は、完全硬化(Cステージにした)後の耐クラック性の観点から、好ましくは500質量部以下、より好ましくは400質量部以下、更に好ましくは300質量部以下、最も好ましくは250質量部以下であってよい。他の実施形態において、上記機能性微粒子の配合量は、上述の観点から、10質量部以上200質量部以下であってよく、または10質量部以上100質量部以下、または10質量部以上50質量部以下であってよい。 In the embodiment in which the fine particles of the component (C) include the functional fine particles, 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. On the other hand, 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.
(D)撥水剤
上記Bステージ塗膜形成用塗料は、好ましくは更に上記成分(D)撥水剤を含むものであってよい。上記成分(D)撥水剤を用いることによって、本発明のBステージ塗膜を用いて得られる成形体(塗膜はCステージ)の耐擦傷性、汚れの付着防止性、及び汚れの拭取り性を向上させることができる。 (D) Water-repellent agent The paint for forming a B-stage coating film may preferably further contain the above-mentioned component (D) water-repellent agent. By using the above component (D) water repellent, 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.
上記Bステージ塗膜形成用塗料は、好ましくは更に上記成分(D)撥水剤を含むものであってよい。上記成分(D)撥水剤を用いることによって、本発明のBステージ塗膜を用いて得られる成形体(塗膜はCステージ)の耐擦傷性、汚れの付着防止性、及び汚れの拭取り性を向上させることができる。 (D) Water-repellent agent The paint for forming a B-stage coating film may preferably further contain the above-mentioned component (D) water-repellent agent. By using the above component (D) water repellent, 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.
上記成分(D)撥水剤としては、例えば、パラフィンワックス、ポリエチレンワックス、及びアクリル・エチレン共重合体ワックス等のワックス系撥水剤;シリコーンオイル、シリコーン樹脂、ポリジメチルシロキサン、アルキルアルコキシシラン等のシリコーン系撥水剤;フルオロポリエーテル系撥水剤、フルオロポリアルキル系撥水剤等の含弗素系撥水剤などをあげることができる。
Examples of the component (D) water repellent 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.
これらの中で、上記成分(D)撥水剤としては、耐擦傷性、及び撥水性能の観点から、含弗素系撥水剤が好ましい。上記成分(D)撥水剤としては、耐擦傷性、撥水性能、及び上記成分(D)を上記成分(A)活性エネルギー線硬化性樹脂と化学結合ないしは強く相互作用させ、上記成分(D)がブリードアウトするなどのトラブルを防止する観点から、含弗素系撥水剤であって(メタ)アクリロイル基を含有する撥水剤(以下、「(メタ)アクリロイル基含有弗素系撥水剤」と略すことがある)がより好ましい。ここで(メタ)アクリロイル基含有弗素系撥水剤は、分子内に1個以上の(メタ)アクリロイル基を有し、かつ分子内に1個以上、好ましくは3個以上、より好ましくは5個以上の弗素・炭素結合(典型的には炭化水素基などの有機官能基の1個又は2個以上の水素原子が弗素原子に置換された構造)を有し、撥水機能を発現する化合物である。
Among these, as the component (D) water repellent, 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). ) Is a fluorine-containing water repellent and contains a (meth) acryloyl group (hereinafter, "(meth) acryloyl group-containing fluorine-based water repellent") from the viewpoint of preventing troubles such as bleeding out. May be abbreviated as) is more preferable. Here, 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) and exhibits a water-repellent function. is there.
上記(メタ)アクリロイル基含有弗素系撥水剤としては、例えば、(メタ)アクリロイル基含有フルオロエーテル系撥水剤、(メタ)アクリロイル基含有フルオロアルキル系撥水剤、(メタ)アクリロイル基含有フロオロアルケニル系撥水剤、(メタ)アクリロイル基含有フルオロポリエーテル系撥水剤、(メタ)アクリロイル基含有フルオロポリアルキル系撥水剤、及び(メタ)アクリロイル基含有フロオロポリアルケニル系撥水剤などをあげることができる。
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. Oroalkenyl water repellent, (meth) acryloyl group-containing fluoropolyether water repellent, (meth) acryloyl group-containing fluoropolyalkyl water repellent, and (meth) acryloyl group-containing fluoropolyalkenyl water repellent And so on.
上記成分(D)撥水剤としては、(メタ)アクリロイル基含有フルオロポリエーテル系撥水剤(分子内に(メタ)アクリロイル基とフルオロポリエーテル基とを含有する化合物)が更に好ましい。上記成分(D)撥水剤としては、上記成分(D)と上記成分(A)活性エネルギー線硬化性樹脂との化学結合ないしは相互作用を適宜調節し、透明性を高く保ちつつ良好な耐擦傷性、及び撥水性を発現させ、かつ上記成分(D)のブリードアウトを防止性する観点から、アクリロイル基含有フルオロポリエーテル系撥水剤とメタアクリロイル基含有フルオロポリエーテル系撥水剤との混和物が最も好ましい。
As the component (D) water repellent, 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. As 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. Mixing of acryloyl group-containing fluoropolyether-based water repellent and metaacryloyl group-containing fluoropolyether-based water repellent from the viewpoint of exhibiting properties and water repellency and preventing bleed-out of the above component (D). The thing is the most preferable.
上記成分(D)撥水剤としては、これらの1種又は2種以上の混合物を用いることができる。
As the component (D) water repellent, one or a mixture of two or more of these can be used.
上記成分(D)撥水剤の配合量は、任意成分であるから特に制限されない。上記成分(D)撥水剤の配合量は、完全硬化(Cステージにした)後の耐擦傷性、汚れの付着防止性、及び汚れの拭取り性を良好なものにする観点から適宜決定すればよい。上記成分(D)撥水剤の配合量は、上記成分(A)活性エネルギー線硬化性樹脂100質量部に対して、上記成分(D)の使用効果を得るという観点から、通常0.01質量部以上、好ましくは0.05質量部以上、より好ましくは0.1質量部以上、更に好ましくは0.2質量部以上であってよい。一方、上記成分(D)撥水剤の配合量は、上記成分(D)がブリードアウトするなどのトラブルを防止する観点から、通常7質量部以下、好ましくは4質量部以下、より好ましくは2質量部以下、更に好ましくは1質量部以下であってよい。
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. On the other hand, 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.
上記Bステージ塗膜形成用塗料(上記成分(A)活性エネルギー線硬化性樹脂と上記成分(B)光重合開始剤を含む塗料)には、本発明の目的に反しない限度において、所望により、1分子中に2個以上のイソシアネート基を有する化合物、帯電防止剤、界面活性剤、レベリング剤、チクソ性付与剤、汚染防止剤、印刷性改良剤、酸化防止剤、耐候性安定剤、耐光性安定剤、紫外線吸収剤、熱安定剤、無機粒子、無機着色剤、有機粒子、有機着色剤、及び分散剤(例えば、ポリアミン構造を有する高分子量共重合体のリン酸エステル塩などのアミン系分散剤)などの添加剤を1種又は2種以上含ませることができる。これらの添加剤を使用する場合の配合量は、特に制限されないが、例えば上記成分(A)活性エネルギー線硬化性樹脂100質量部に対して、添加剤の使用効果を得るという観点から通常0.001質量部以上であってよく、本発明による所望の効果を妨げない観点から通常10質量部以下であってよい。
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.
上記Bステージ塗膜形成用塗料は、好ましくは熱重合開始剤を含まないものであってよい。上記Bステージ塗膜形成用塗料が上記熱重合開始剤を含まないことにより、形成される塗膜をBステージ状態に留めること、及び三次元成形を行うまで塗膜をBステージ状態に安定的に保持することが容易になる。ここで「含まない」とは、上記熱重合開始剤を意図的に配合していないことを意味する。上記熱重合開始剤を意図的に配合する場合、上記成分(A)活性エネルギー線硬化性樹脂100質量部に対して、通常0.01質量部以上を配合する。従って、「上記Bステージ塗膜形成用塗料が上記熱重合開始剤を含まない」とは、上記熱重合開始剤の含有量が、上記成分(A)活性エネルギー線硬化性樹脂100質量部に対して、通常0.01質量部未満、好ましくは0.005質量部以下、より好ましくは0.001質量部以下、更に好ましくは0.0005質量部以下、最も好ましくは約0質量部と言い換えることもできる。
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. Here, "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). Therefore, "the paint for forming a B-stage coating film does not contain the thermal polymerization initiator" means that the content of the thermal polymerization initiator is 100 parts by mass with respect to the component (A) active energy ray-curable resin. In other words, it is usually less than 0.01 parts by mass, preferably 0.005 parts by mass or less, more preferably 0.001 parts by mass or less, still more preferably 0.0005 parts by mass or less, and most preferably about 0 parts by mass. it can.
上記熱重合開始剤は、加熱によりラジカルなどの活性種を発生する化合物である。なお本明細書において、活性エネルギー線の照射(または光照射)によっても、加熱によってもラジカルなどの活性種を発生する化合物は、熱重合開始剤に分類するものとする。上記熱重合開始剤としては、2,2’-アゾビスイソブチロニトリル(2,2’-アゾビス(2-メチルプロピオニトリル))などのアゾ化合物;過酸化ベンゾイルなどの有機過酸化物;及び、p-トルエンスルホン酸シクロヘキシルなどのベンゼンスルホン酸エステルなどを例示することができる。
The thermal polymerization initiator is a compound that generates active species such as radicals by heating. In the present specification, 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. Examples of 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.
上記Bステージ塗膜形成用塗料には、塗工し易い濃度に希釈するため、所望により、溶剤を含ませてもよい。上記溶剤は上記成分(A)、上記成分(B)、及びその他の任意成分と反応したり、これらの成分の自己反応(劣化反応を含む)を触媒(促進)したりしないものであれば、特に制限されない。上記溶剤としては、例えば、1-メトキシ-2-プロパノール、酢酸エチル、酢酸n-ブチル、トルエン、メチルエチルケトン、メチルイソブチルケトン、ダイアセトンアルコール、及びアセトンなどをあげることができる。上記溶剤としては、これらの1種又は2種以上の混合物を用いることができる。
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. As long as the 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. There are no particular restrictions. Examples of 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. As the solvent, one kind or a mixture of two or more kinds of these can be used.
上記Bステージ塗膜形成用塗料は、これらの成分を混合攪拌することにより得ることができる。
The above B-stage coating film forming paint can be obtained by mixing and stirring these components.
本発明のBステージ塗膜の厚みは、特に限定されない。本発明のBステージ塗膜の厚みは、完全硬化(Cステージにした)後の表面硬度、耐擦傷性、及び耐薬品性の観点から、通常0.5μm以上、好ましくは1μm以上、より好ましくは5μm以上、更に好ましくは10μm以上であってよい。一方、Bステージ塗膜の厚みは、三次元成形性の観点から、通常100μm以下、好ましくは50μm以下、より好ましくは30μm以下、更に好ましくは20μm以下であってよい。
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 μm or more, preferably 1 μm or more, more preferably 1 μm or more, from the viewpoint of surface hardness, scratch resistance, and chemical resistance after complete curing (C stage). It may be 5 μm or more, more preferably 10 μm or more. On the other hand, the thickness of the B-stage coating film may be usually 100 μm or less, preferably 50 μm or less, more preferably 30 μm or less, and further preferably 20 μm or less from the viewpoint of three-dimensional moldability.
本発明のBステージ塗膜の引張伸びは、三次元成形性の観点から、通常10%以上、好ましくは20%以上、より好ましくは25%以上、更に好ましくは30%以上であってよい。引張伸びはより高い方が好ましい。ここで引張伸びは、JIS K7127:1999に準拠し、Bステージ塗膜又はBステージ塗膜を有する積層フィルムの幅方向と引張方向とが一致するように採取した試験片タイプ2(幅15mm、全長150mm)の試験片を用い、標線間距離50mm、チャック間の初期距離100mm、及び試験速度10mm/分の条件で測定した値である。
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. Here, 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.
本発明のBステージ塗膜の完全硬化(Cステージにした)後の表面の鉛筆硬度は、通常H以上(1H以上)、好ましくは3H以上、より好ましくは4H以上、更に好ましくは5H以上、最も好ましくは6H以上であってよい。鉛筆硬度はより高い方が好ましい。ここで鉛筆硬度は、JIS K5600-5-4:1999に従い、試験長さ25mm、及び荷重750gの条件で測定される値である。
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. Here, 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.
3.Bステージ塗膜積層フィルム
本発明のBステージ塗膜積層フィルムは、本発明のBステージ塗膜を含む。本発明のBステージ塗膜積層フィルムは、フィルム基材の少なくとも一方の面の上に本発明のBステージ塗膜を有する。本発明のBステージ塗膜積層フィルムは、通常は、フィルム基材の片面の上に本発明のBステージ塗膜を有し、該Bステージ塗膜が表面を形成する。 3. 3. B-stage coating film laminated film 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.
本発明のBステージ塗膜積層フィルムは、本発明のBステージ塗膜を含む。本発明のBステージ塗膜積層フィルムは、フィルム基材の少なくとも一方の面の上に本発明のBステージ塗膜を有する。本発明のBステージ塗膜積層フィルムは、通常は、フィルム基材の片面の上に本発明のBステージ塗膜を有し、該Bステージ塗膜が表面を形成する。 3. 3. B-stage coating film laminated film 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.
本発明のBステージ塗膜積層フィルムは、上記Bステージ塗膜形成用塗料(上記成分(A)活性エネルギー線硬化性樹脂と上記成分(B)光重合開始剤を含む塗料)を用い、任意の方法により、上記フィルム基材の少なくとも一方の面の上に本発明のBステージ塗膜を形成することにより、製造することができる。本発明のBステージ塗膜積層フィルムは、好ましくは、上記Bステージ塗膜形成用塗料を用い、本発明のBステージ塗膜製造方法により、上記フィルム基材の少なくとも一方の面の上に本発明のBステージ塗膜を形成することにより、製造することができる。
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.
本発明のBステージ塗膜製造方法については、「1.Bステージ塗膜の製造方法」の項において説明した。上記Bステージ塗膜形成用塗料(上記成分(A)活性エネルギー線硬化性樹脂と上記成分(B)光重合開始剤を含む塗料)については、「2.Bステージ塗膜」の項において説明した。
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". ..
フィルム基材
上記フィルム基材は、その少なくとも一方の面の上に本発明のBステージ塗膜を形成するための基材となるフィルムである。 Film base material 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.
上記フィルム基材は、その少なくとも一方の面の上に本発明のBステージ塗膜を形成するための基材となるフィルムである。 Film base material 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.
上記フィルム基材としては、特に制限されず、任意のフィルムをフィルム基材として用いることができる。上記フィルムとしては、例えば、芳香族ポリエステル、脂肪族ポリエステルなどのポリエステル系樹脂;アクリル系樹脂;ポリカーボネート系樹脂;ポリ(メタ)アクリルイミド系樹脂;ポリエチレン、ポリプロピレン、及びポリ4-メチルペンテン-1などのポリオレフィン系樹脂;セロファン、トリアセチルセルロース、ジアセチルセルロース、及びアセチルセルロースブチレートなどのセルロース系樹脂;ポリスチレン、アクリロニトリル・ブタジエン・スチレン共重合樹脂(ABS樹脂)、スチレン・エチレン・ブタジエン・スチレン共重合体、スチレン・エチレン・プロピレン・スチレン共重合体、及びスチレン・エチレン・エチレン・プロピレン・スチレン共重合体などのスチレン系樹脂;ポリ塩化ビニル系樹脂;ポリ塩化ビニリデン系樹脂;ポリフッ化ビニリデンなどの含弗素系樹脂;その他、ポリビニルアルコール、エチレンビニルアルコール、ポリエーテルエーテルケトン、ナイロン、ポリアミド、ポリイミド、ポリウレタン、ポリエーテルイミド、ポリスルフォン、ポリエーテルスルフォン等の樹脂フィルムをあげることができる。これらのフィルムは、無延伸フィルム、一軸延伸フィルム、及び二軸延伸フィルムを包含する。またこれらの1種以上を2層以上積層した積層フィルムを包含する。更にこれらのフィルムは透明であってもよく、不透明であってもよく、隠蔽性を有するものであってもよく、着色されたものであってもよく、固有の色を有するものであってもよい。
The film base material is not particularly limited, and any film can be used as the film base material. Examples of 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; cellulose-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. 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.
フィルム基材が成形体の構成材料の1つとして用いられる場合
上記フィルム基材が、本発明の成形体(「4.成形体」の項において後述する)の構成材料の1つとして用いられる場合には、上記フィルム基材と本発明のBステージ塗膜との密着性を高める観点から、上記フィルム基材の塗膜形成面は、コロナ放電処理、プラズマ処理、及びアンカーコート形成などの易接着処理が施されたものであってよい。 When the film base material is used as one of the constituent materials of the molded product When 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") From the viewpoint of enhancing the adhesion between the film substrate and the B-stage coating film of the present invention, 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.
上記フィルム基材が、本発明の成形体(「4.成形体」の項において後述する)の構成材料の1つとして用いられる場合には、上記フィルム基材と本発明のBステージ塗膜との密着性を高める観点から、上記フィルム基材の塗膜形成面は、コロナ放電処理、プラズマ処理、及びアンカーコート形成などの易接着処理が施されたものであってよい。 When the film base material is used as one of the constituent materials of the molded product When 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") From the viewpoint of enhancing the adhesion between the film substrate and the B-stage coating film of the present invention, 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.
上記フィルム基材が本発明の成形体の構成材料の1つとして用いられる場合、上記フィルム基材の厚みは成形体の用途を勘案して適宜決定される。上記フィルム基材が本発明の成形体の構成材料の1つとして用いられる場合、上記フィルム基材の厚みは、ハンドリング性の観点から、通常20μm以上、好ましくは50μm以上であってよい。上記フィルム基材の厚みは、成形体の強度の観点から、通常100μm以上、好ましくは150μm以上であってよい。一方、上記フィルム基材の厚みは、成形体の軽量化の観点から、通常2000μm以下、好ましくは800μm以下、より好ましくは600μm以下であってよい。
When the film base material is used as one of the constituent materials of the molded product of the present invention, the thickness of the film base material is appropriately determined in consideration of the use of the molded product. When the film base material is used as one of the constituent materials of the molded product of the present invention, the thickness of the film base material may be usually 20 μm or more, preferably 50 μm or more from the viewpoint of handleability. The thickness of the film base material may be usually 100 μm or more, preferably 150 μm or more, from the viewpoint of the strength of the molded product. On the other hand, the thickness of the film base material may be usually 2000 μm or less, preferably 800 μm or less, and more preferably 600 μm or less from the viewpoint of weight reduction of the molded product.
上記フィルム基材が本発明の成形体の構成材料の1つとして用いられる場合、上記フィルム基材として高い透明性を有し、かつ色のないものを用いることは好ましい。それによって、本発明のBステージ塗膜積層フィルムを、高い透明性及び無色性が要求される物品、例えば、車両のインストルメントパネルなどの車両用部材として好適に用いることができるようになる。このようなフィルムとしては、例えば、トリアセチルセルロース等のセルロースエステル系樹脂;ポリエチレンテレフタレート等のポリエステル系樹脂;エチレンノルボルネン共重合体等の環状炭化水素系樹脂;ポリメタクリル酸メチル、ポリメタクリル酸エチル、及びビニルシクロヘキサン・(メタ)アクリル酸メチル共重合体等のアクリル系樹脂;芳香族ポリカーボネート系樹脂;ポリプロピレン、及びポリ4-メチルペンテン-1等のポリオレフィン系樹脂;ポリアミド系樹脂;ポリアリレート系樹脂;ポリマー型ウレタンアクリレート系樹脂;及びポリイミド系樹脂などの透明樹脂フィルムをあげることができる。これらのフィルムは無延伸フィルム、一軸延伸フィルム、及び二軸延伸フィルムを包含する。またこれらのフィルムは、これらの1種又は2種以上を、2層以上積層した積層フィルムを包含する。
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. As a result, 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. Examples of such 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. And 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.
本発明のBステージ塗膜積層フィルムを高い透明性及び無色性が要求される物品に用いる場合、本発明のBステージ塗膜積層フィルムの全光線透過率は、そのBステージ塗膜を完全硬化(Cステージにした)後において、通常80%以上、好ましくは85%以上、より好ましくは88%以上、更に好ましくは90%以上であってよい。全光線透過率は高いほど好ましい。ここで全光線透過率はJIS K7361-1:1997に従い測定した値である。濁度計としては、例えば、日本電色工業株式会社の濁度計「NDH2000」(商品名)を使用することができる。
When the B-stage coating film laminated film of the present invention is used for an article that requires high transparency and colorlessness, 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 higher the total light transmittance, the more preferable. Here, 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.
本発明のBステージ塗膜積層フィルムを高い透明性及び無色性が要求される物品に用いる場合であって、すっきりとした透明感を所望する場合、本発明のBステージ塗膜積層フィルムのヘーズは、そのBステージ塗膜を完全硬化(Cステージにした)後において、通常3%以下、好ましくは2%以下、より好ましくは1%以下であってよい。すっきりとした透明感を得る観点から、ヘーズは低い方が好ましい。
When the B-stage coating film laminated film of the present invention is used for an article that requires high transparency and colorlessness, and a clean transparency is desired, the haze of the B-stage coating film laminated film of the present invention is used. After the B-stage coating film is completely cured (C-stage), it 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.
本発明のBステージ塗膜積層フィルムを高い透明性及び無色性が要求される物品に用いる場合であって、防眩性を所望する場合、本発明のBステージ塗膜積層フィルムのヘーズは、そのBステージ塗膜を完全硬化(Cステージにした)後において、所望する防眩性のレベルにもよるが、通常3~30%、好ましくは5~25%、より好ましくは7~20%であってよい。
When the B-stage coating film laminated film of the present invention is used for an article that requires high transparency and colorlessness, and antiglare is desired, the haze of the B-stage coating film laminated film of the present invention is the same. After 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.
本発明のBステージ塗膜積層フィルムを高い透明性及び無色性が要求される物品に用いる場合、本発明のBステージ塗膜積層フィルムの黄色度指数は、通常5以下、好ましくは3以下、より好ましくは2~-2、更に好ましくは1~-1であってよい。ここで黄色度指数はJIS K7105:1981に従い測定した値である。色度計としては、例えば、株式会社島津製作所の色度計「SolidSpec-3700」(商品名)を使用することができる。
When the B-stage coating film laminated film of the present invention is used for an article requiring high transparency and colorlessness, 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. Here, the yellowness index is a value measured according to JIS K7105: 1981. As the chromaticity meter, for example, a chromaticity meter "SolidSpec-3700" (trade name) manufactured by Shimadzu Corporation can be used.
上記透明樹脂フィルムは、好ましくは、アクリル系樹脂の透明樹脂フィルムであってよい。上記アクリル系樹脂としては、例えば、(メタ)アクリル酸エステル(共)重合体、(メタ)アクリル酸エステルに由来する構成単位を主として(通常50モル%以上、好ましくは65モル%以上、より好ましくは70モル%以上)含む共重合体、及びこれらの変性体などをあげることができる。なお、(メタ)アクリルとは、アクリル又はメタクリルの意味である。また(共)重合体とは、重合体又は共重合体の意味である。
The transparent resin film is preferably a transparent resin film made of an acrylic resin. As 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. Further, the (co) polymer means a polymer or a copolymer.
上記(メタ)アクリル酸エステル(共)重合体としては、例えば、ポリ(メタ)アクリル酸メチル、ポリ(メタ)アクリル酸エチル、ポリ(メタ)アクリル酸プロピル、ポリ(メタ)アクリル酸ブチル、(メタ)アクリル酸メチル・(メタ)アクリル酸ブチル共重合体、及び(メタ)アクリル酸エチル・(メタ)アクリル酸ブチル共重合体などをあげることができる。
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.
上記(メタ)アクリル酸エステルに由来する構成単位を主として含む共重合体としては、例えば、エチレン・(メタ)アクリル酸メチル共重合体、スチレン・(メタ)アクリル酸メチル共重合体、ビニルシクロヘキサン・(メタ)アクリル酸メチル共重合体、無水マレイン酸・(メタ)アクリル酸メチル共重合体、及びN-置換マレイミド・(メタ)アクリル酸メチル共重合体などをあげることができる。
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.
上記変性体としては、例えば、分子内環化反応によりラクトン環構造が導入された重合体;分子内環化反応によりグルタル酸無水物が導入された重合体;及び、イミド化剤(例えば、メチルアミン、シクロヘキシルアミン、及びアンモニアなどをあげることができる)と反応させることによりイミド構造が導入された重合体などをあげることができる。
Examples of the modified product 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). By reacting with amine, cyclohexylamine, ammonia, etc.), a polymer having an imide structure introduced therein can be mentioned.
上記アクリル系樹脂の透明樹脂フィルムとしては、これらの1種又は2種以上の混合物のフィルムをあげることができる。またこれらのフィルムは、これらの1種又は2種以上を、2層以上積層した積層フィルムを包含する。
Examples of the transparent resin film of the acrylic resin 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.
上記透明樹脂フィルムとしては、N-置換マレイミド・(メタ)アクリル酸メチル共重合体などの(メタ)アクリル酸エステルとイミド構造を有する重合性モノマーとの共重合体;及び、アクリル系樹脂をイミド化剤と反応させることによりイミド構造が導入された重合体(以下、これらを総称して「ポリ(メタ)アクリルイミド系樹脂」ということがある)の透明フィルム、上記ポリ(メタ)アクリルイミド系樹脂を用いて形成された層を1層以上含む透明多層フィルムがより好ましい。該透明フィルムや該透明多層フィルムを、本発明のBステージ塗膜積層フィルムのフィルム基材として用いることにより、本発明のBステージ塗膜積層フィルムを用いて形成される成形体は、表面硬度、耐擦傷性、透明性、表面平滑性、外観、剛性、耐熱性、及び耐熱寸法安定性に優れたものになり得る。
Examples of the transparent resin film 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. By using the transparent film or the transparent multilayer film as the film base material of the B-stage coating film laminated film of the present invention, 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.
上記ポリ(メタ)アクリルイミド系樹脂はアクリル構造とイミド構造の両方の構造を有する熱可塑性樹脂と定義することもできる。上記ポリ(メタ)アクリルイミド系樹脂は、アクリル構造を有することから、アクリル系樹脂の高透明性、高表面硬度、高剛性という特徴を有する。また上記ポリ(メタ)アクリルイミド系樹脂は、イミド構造を有することから、ポリイミドの耐熱性や寸法安定性に優れるという特徴を有する。更に、上記ポリ(メタ)アクリルイミド系樹脂は、通常、ポリイミドの淡黄色から赤褐色に着色するという欠点が改良されている。
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.
上記ポリ(メタ)アクリルイミド系樹脂のガラス転移温度は、耐熱性の観点から、通常110℃以上、好ましくは115℃以上、より好ましくは120℃以上、更に好ましくは130℃以上、より更に好ましくは140℃以上であってよい。一方、上記ポリ(メタ)アクリルイミド系樹脂のガラス転移温度は、三次元成形性の観点から、通常170℃以下、好ましくは165℃以下、より好ましくは160℃以下、更に好ましくは155℃以下であってよい。ここでガラス転移温度は、JIS K7121-1987に従い、250℃で3分間保持し、10℃/分で20℃まで冷却し、20℃で3分間保持し、10℃/分で250℃まで昇温するプログラムで測定される最後の昇温過程の曲線から算出した中間点ガラス転移温度である。示差走査熱量計としては、例えば、株式会社パーキンエルマージャパンのDiamond DSCを使用することができる。
From the viewpoint of heat resistance, 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. On the other hand, 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. Here, the glass transition temperature is maintained at 250 ° C. for 3 minutes, cooled to 20 ° C. at 10 ° C./min, held at 20 ° C. for 3 minutes, and raised to 250 ° C. at 10 ° C./min according to JIS K7121-1987. It is the midpoint glass transition temperature calculated from the curve of the last heating process measured by the program. As the differential scanning calorimetry, for example, Diamond DSC of PerkinElmer Japan Co., Ltd. can be used.
上記ポリ(メタ)アクリルイミド系樹脂の黄色度指数は、通常5以下、好ましくは3以下、より好ましくは2~-2、更に好ましくは1~-1であってよい。黄色度指数が5以下のポリ(メタ)アクリルイミド系樹脂を用いることにより、車両のインストルメントパネルなどの車両用部材として好適な色調のBステージ塗膜積層フィルム、及びこれを用いた成形体を得ることができる。ここで黄色度指数はJIS K7105:1981に従い測定した値である。色度計としては、例えば、株式会社島津製作所の色度計「SolidSpec-3700」(商品名)を使用することができる。
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. By using 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. Here, the yellowness index is a value measured according to JIS K7105: 1981. As the chromaticity meter, for example, a chromaticity meter "SolidSpec-3700" (trade name) manufactured by Shimadzu Corporation can be used.
上記ポリ(メタ)アクリルイミド系樹脂のメルトマスフローレート(ISO1133に従い、260℃、98.07Nの条件で測定)は、フィルム製膜時の押出負荷や溶融フィルムの安定性の観点から、好ましくは0.1~20g/10分、より好ましくは0.5~10g/10分であってよい。
The melt mass flow rate of the poly (meth) acrylicimide-based resin (measured at 260 ° C. and 98.07N according to ISO1133) 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.
上記ポリ(メタ)アクリルイミド系樹脂には、本発明の目的に反しない限度において、所望により、ポリ(メタ)アクリルイミド系樹脂以外の熱可塑性樹脂;顔料、無機フィラー、有機フィラー、樹脂フィラー;滑剤、酸化防止剤、耐候性安定剤、熱安定剤、離型剤、帯電防止剤、及び界面活性剤等の添加剤などを更に含ませることができる。これらの任意成分の配合量は、上記ポリ(メタ)アクリルイミド系樹脂を100質量部としたとき、通常10質量部以下、あるいは0.01~10質量部程度である。
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.
上記透明樹脂フィルムは、好ましくは、アクリル系樹脂層(α);芳香族ポリカーボネート系樹脂層(β)が、この順に直接積層された透明多層フィルムであってよい。上記透明樹脂フィルムは、より好ましくは、第一アクリル系樹脂層(α1);芳香族ポリカーボネート系樹脂層(β);第二アクリル系樹脂層(α2)が、この順に直接積層された透明多層フィルムであってよい。
The transparent resin film is preferably a transparent multilayer film in which an acrylic resin layer (α); an aromatic polycarbonate resin layer (β) is directly laminated in this order. The transparent resin film is more preferably a transparent multilayer film in which a first acrylic resin layer (α1); an aromatic polycarbonate resin layer (β); and a second acrylic resin layer (α2) are directly laminated in this order. It may be.
アクリル系樹脂は表面硬度には優れているが、切削加工性が不十分になり易いのに対し、芳香族ポリカーボネート系樹脂は切削加工性には優れているが、表面硬度が不十分になり易い。そのため上記の層構成の透明多層フィルムを用いることにより、両者の弱点を補い合い、Bステージ塗膜を完全硬化後(Cステージ)において、表面硬度、及び切削加工性の何れにも優れたBステージ塗膜積層フィルムを容易に得ることができるようになる。
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.
以下、第一アクリル系樹脂層(α1);芳香族ポリカーボネート系樹脂層(β);第二アクリル系樹脂層(α2)が、この順に直接積層された透明多層フィルムについて、上記α1層側にBステージ塗膜が形成されるものとして説明する。
Hereinafter, the transparent multilayer film in which the first acrylic resin layer (α1); the aromatic polycarbonate resin layer (β); the second acrylic resin layer (α2) are directly laminated in this order is B on the α1 layer side. It will be described as assuming that a stage coating film is formed.
上記α1層の層厚みは、特に制限されないが、Bステージ塗膜を完全硬化後(Cステージ)の表面硬度の観点から、通常20μm以上、好ましくは40μm以上、より好ましくは50μm以上、更に好ましくは80μm以上であってよい。
The layer thickness of the α1 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 μm or more, preferably 40 μm or more, more preferably 50 μm or more, still more preferably. It may be 80 μm or more.
上記α2層の層厚みは、特に制限されないが、耐カール性の観点から、上記α1層と同じ層厚みであることが好ましい。
The layer thickness of the α2 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 α1 layer.
なおここで「同じ層厚み」とは、物理化学的に厳密な意味で同じ層厚みと解釈されるべきではない。工業的に通常行われる工程・品質管理の振れ幅の範囲内において同じ層厚みと解釈されるべきである。工業的に通常行われる工程・品質管理の振れ幅の範囲内において同じ層厚みであれば、多層フィルムの耐カール性を良好に保つことができるからである。Tダイ共押出法による無延伸多層フィルムの場合には、通常-5~+5μm程度の幅で工程・品質管理されるものであるから、例えば、層厚み65μmと同75μmとは同一と解釈されるべきである。
Here, "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. In the case of a non-stretched multilayer film produced by the T-die coextrusion method, the process and quality are usually controlled with a width of about -5 to +5 μm. Therefore, for example, a layer thickness of 65 μm and 75 μm are interpreted as the same. Should be.
上記β層の層厚みは、特に制限されないが、切削加工性の観点から、通常20μm以上、好ましくは70μm以上であってよい。
The layer thickness of the β layer is not particularly limited, but from the viewpoint of machinability, it may be usually 20 μm or more, preferably 70 μm or more.
上記α1層及び上記α2層に用いるアクリル系樹脂については、上述した。
The acrylic resin used for the α1 layer and the α2 layer is described above.
なお上記α1層に用いるアクリル系樹脂と、上記α2層に用いるアクリル系樹脂とは、異なる樹脂特性のもの、例えば種類、メルトマスフローレート、及びガラス転移温度などの異なるアクリル系樹脂を用いても良い。透明多層フィルムの耐カール性の観点から、同じ樹脂特性のものを用いることが好ましい。例えば、同一グレードの同一ロットを用いるのは、好ましい実施態様の一つである。
The acrylic resin used for the α1 layer and the acrylic resin used for the α2 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.
上記β層に用いる芳香族ポリカーボネート系樹脂としては、例えば、ビスフェノールA、ジメチルビスフェノールA、1,1-ビス(4-ヒドロキシフェニル)-3,3,5-トリメチルシクロヘキサンなどの芳香族ジヒドロキシ化合物とホスゲンとの界面重合法によって得られる重合体;ビスフェノールA、ジメチルビスフェノールA、1,1-ビス(4-ヒドロキシフェニル)-3,3,5-トリメチルシクロヘキサンなどの芳香族ジヒドロキシ化合物とジフェニルカーボネートなどの炭酸ジエステルとのエステル交換反応により得られる重合体などの芳香族ポリカーボネート系樹脂の1種又は2種以上の混合物を用いることができる。
Examples of the aromatic polycarbonate-based resin used for the β layer 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. 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.
上記芳香族ポリカーボネート系樹脂に含み得る好ましい任意成分としては、コアシェルゴムをあげることができる。芳香族ポリカーボネート系樹脂とコアシェルゴムとの合計を100質量部としたとき、コアシェルゴムを0~30質量部(芳香族ポリカーボネート系樹脂100~70質量部)、好ましくは0~10質量部(芳香族ポリカーボネート系樹脂100~90質量部)の量で用いることにより、切削加工性や耐衝撃性をより高めることができる。
As a preferable optional component that can be contained in the aromatic polycarbonate-based resin, core-shell rubber can be mentioned. When the total of the aromatic polycarbonate resin and the core shell rubber is 100 parts by mass, 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). By using the amount of the polycarbonate resin (100 to 90 parts by mass), the machinability and impact resistance can be further improved.
上記コアシェルゴムとしては、例えば、メタクリル酸エステル・スチレン/ブタジエンゴムグラフト共重合体、アクリロニトリル・スチレン/ブタジエンゴムグラフト共重合体、アクリロニトリル・スチレン/エチレン・プロピレンゴムグラフト共重合体、アクリロニトリル・スチレン/アクリル酸エステルグラフト共重合体、メタクリル酸エステル/アクリル酸エステルゴムグラフト共重合体、メタクリル酸エステル・スチレン/アクリル酸エステルゴムグラフト共重合体、及びメタクリル酸エステル・アクリロニトリル/アクリル酸エステルゴムグラフト共重合体などのコアシェルゴムをあげることができる。上記コアシェルゴムとしては、これらの1種又は2種以上の混合物を用いることができる。
Examples of the core-shell rubber 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.
また上記芳香族ポリカーボネート系樹脂には、本発明の目的に反しない限度において、所望により、芳香族ポリカーボネート系樹脂やコアシェルゴム以外の熱可塑性樹脂;顔料、無機フィラー、有機フィラー、樹脂フィラー;滑剤、酸化防止剤、耐候性安定剤、熱安定剤、離型剤、帯電防止剤、及び界面活性剤等の添加剤などを更に含ませることができる。これらの任意成分の配合量は、通常、芳香族ポリカーボネート系樹脂とコアシェルゴムとの合計を100質量部としたとき、通常10質量部以下、あるいは0.01~10質量部程度である。
Further, 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.
上記透明樹脂フィルムの製造方法は特に制限されない。上記透明樹脂フィルムが第一ポリ(メタ)アクリルイミド系樹脂層(α1);芳香族ポリカーボネート系樹脂層(β);第二ポリ(メタ)アクリルイミド系樹脂層(α2)が、この順に直接積層された透明多層フィルムである場合の好ましい製造方法としては、特開2015-083370号公報に記載された方法をあげることができる。また上記Bステージ塗膜を形成するに際し、上記透明樹脂フィルムの一方の面又は両面に、上記Bステージ塗膜との接着強度を高めるため、事前にコロナ放電処理、プラズマ処理、及びアンカーコート形成などの易接着処理を施してもよい。
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 (α1); the aromatic polycarbonate-based resin layer (β); and the second poly (meth) acrylicimide-based resin layer (α2). As a preferable manufacturing method in the case of the transparent multilayer film, the method described in JP-A-2015-0833370 can be mentioned. Further, when forming the B-stage coating film, 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.
上記透明樹脂フィルムの全光線透過率は、通常85%以上、好ましくは88%以上、より好ましくは90%以上であってよい。全光線透過率は高いほど好ましい。全光線透過率が85%以上の透明樹脂フィルムを用いることにより、高い透明性が要求される物品、例えば、車両のインストルメントパネルなどの車両用部材として好適なBステージ塗膜積層フィルム、及びこれを用いた成形体を得ることができる。ここで全光線透過率はJIS K7361-1:1997に従い測定した値である。濁度計としては、例えば、日本電色工業株式会社の濁度計「NDH2000」(商品名)を使用することができる。
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. By using 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. Here, 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.
上記透明樹脂フィルムの黄色度指数は、通常5以下、好ましくは3以下、より好ましくは2~-2、更に好ましくは1~-1であってよい。黄色度指数が5以下の透明樹脂フィルムを用いることにより、高い無色性が要求される物品、例えば、車両のインストルメントパネルなどの車両部材用として好適なBステージ塗膜積層フィルム、及びこれを用いた成形体を得ることができる。ここで黄色度指数はJIS K7105:1981に従い測定した値である。色度計としては、例えば、株式会社島津製作所の色度計「SolidSpec-3700」(商品名)を使用することができる。
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. By using 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. Here, the yellowness index is a value measured according to JIS K7105: 1981. As the chromaticity meter, for example, a chromaticity meter "SolidSpec-3700" (trade name) manufactured by Shimadzu Corporation can be used.
上記透明樹脂フィルムのレタデーションは、通常75nm以下、好ましくは50nm、より好ましくは40nm以下、更に好ましくは30nm以下、更により好ましくは20nm以下、最も好ましくは15nm以下であってよい。レタデーションは低いほど好ましい。レタデーションが75nm以下の透明樹脂フィルムを用いることにより、クリアな透明感の要求される物品、例えば、車両のインストルメントパネルなどの車両部材用として好適なBステージ塗膜積層フィルム、及びこれを用いた成形体を得ることができる。ここでレタデーションは平行ニコル回転法により測定した値である。測定装置としては、例えば、王子計測機器株式会社の平行ニコル回転法による位相差測定装置「KOBRA-WR」(商品名)を使用することができる。
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. The lower the retardation, the better. By using 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. Here, the retardation is a value measured by the parallel Nicol rotation method. As the measuring device, for example, the phase difference measuring device "KOBRA-WR" (trade name) by the parallel Nicol rotation method of Oji Measuring Instruments Co., Ltd. can be used.
形成されたBステージ塗膜を他の基材に転写して用いる場合
上記フィルム基材の面の上に形成された本発明のBステージ塗膜を他の基材(例えば、フィルム、シート、板、及び任意の形状の基体など)に転写して用いる場合(即ち、フィルム基材は成形体を構成しない場合)には、上記フィルム基材の塗膜形成面は易剥離処理がされたものであってよい。 When the formed B-stage coating film is transferred to another substrate for use 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). , And when used by transferring to a substrate of arbitrary shape (that is, when the film substrate does not form a molded body), the coating film-forming surface of the film substrate is easily peeled off. It may be there.
上記フィルム基材の面の上に形成された本発明のBステージ塗膜を他の基材(例えば、フィルム、シート、板、及び任意の形状の基体など)に転写して用いる場合(即ち、フィルム基材は成形体を構成しない場合)には、上記フィルム基材の塗膜形成面は易剥離処理がされたものであってよい。 When the formed B-stage coating film is transferred to another substrate for use 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). , And when used by transferring to a substrate of arbitrary shape (that is, when the film substrate does not form a molded body), the coating film-forming surface of the film substrate is easily peeled off. It may be there.
上記フィルム基材の面の上に形成された本発明のBステージ塗膜を他の基材に転写して用いる場合、上記フィルム基材の厚みは特に制限されない。上記フィルム基材の面の上に形成された本発明のBステージ塗膜を他の基材に転写して用いる場合、上記フィルム基材の厚みは、ハンドリング性の観点から、通常20μm以上、好ましくは30μm以上であってよい。一方、この場合、上記フィルム基材の厚みは、経済性の観点から、通常100μm以下、好ましくは75μm以下であってよい。
When the B-stage coating film of the present invention formed on the surface of the film base material is transferred to another base material and used, the thickness of the film base material is not particularly limited. When the B-stage coating film of the present invention formed on the surface of the film base material is transferred to another base material and used, the thickness of the film base material is usually preferably 20 μm or more from the viewpoint of handleability. May be 30 μm or more. On the other hand, in this case, the thickness of the film base material may be usually 100 μm or less, preferably 75 μm or less, from the viewpoint of economy.
上記フィルム基材の面の上に形成された本発明のBステージ塗膜を他の基材に転写して用いる場合、上記フィルム基材としては、例えば、ポリエチレンテレフタレートなどのポリエステル系樹脂の二軸延伸フィルム、及びポリプロピレン系樹脂の二軸延伸フィルムなどが好ましい。
When the B-stage coating film of the present invention formed on the surface of the film base material is transferred to another base material and used, 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.
4.成形体
本発明の成形体は、本発明のBステージ塗膜を完全硬化させた塗膜(Cステージ)を有する。本発明の成形体は、通常は、本発明のBステージ塗膜を完全硬化させた塗膜(Cステージ)が成形体の表面の一部又は全部を構成する。本発明の成形体は、本発明のBステージ塗膜(及び基材)に所望の形状を付与した後、該Bステージ塗膜を完全硬化(Cステージに)することにより製造することができる。このような成形体としては、例えば、本発明のBステージ塗膜を完全硬化させた塗膜(Cステージ)を有するフィルム、シート、及び板(平らな形状が維持された成形体);本発明のBステージ塗膜を有するフィルム、シートを用いて真空成形、圧空成形、及びプレス成形などの熱成形により所望の形状を付与した後、該Bステージ塗膜を完全硬化(Cステージに)して得られる成形体;及び、本発明のBステージ塗膜を有するフィルム、シートを表皮材として金型内にインサートし、任意の熱可塑性樹脂を芯材として射出した後、該Bステージ塗膜を完全硬化(Cステージに)して得られる複合成形体などをあげることができる。 4. Molded article 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. In the molded product 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. After imparting a desired shape by thermal molding such as vacuum molding, pressure molding, and press molding using a film or sheet having the B stage coating film, 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).
本発明の成形体は、本発明のBステージ塗膜を完全硬化させた塗膜(Cステージ)を有する。本発明の成形体は、通常は、本発明のBステージ塗膜を完全硬化させた塗膜(Cステージ)が成形体の表面の一部又は全部を構成する。本発明の成形体は、本発明のBステージ塗膜(及び基材)に所望の形状を付与した後、該Bステージ塗膜を完全硬化(Cステージに)することにより製造することができる。このような成形体としては、例えば、本発明のBステージ塗膜を完全硬化させた塗膜(Cステージ)を有するフィルム、シート、及び板(平らな形状が維持された成形体);本発明のBステージ塗膜を有するフィルム、シートを用いて真空成形、圧空成形、及びプレス成形などの熱成形により所望の形状を付与した後、該Bステージ塗膜を完全硬化(Cステージに)して得られる成形体;及び、本発明のBステージ塗膜を有するフィルム、シートを表皮材として金型内にインサートし、任意の熱可塑性樹脂を芯材として射出した後、該Bステージ塗膜を完全硬化(Cステージに)して得られる複合成形体などをあげることができる。 4. Molded article 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. In the molded product 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. After imparting a desired shape by thermal molding such as vacuum molding, pressure molding, and press molding using a film or sheet having the B stage coating film, 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).
本発明のBステージ塗膜積層フィルム(塗膜はBステージ)を用い、真空成形、及び真空圧空成形などの三次元成形法を適用して三次元形状を付与した後、該Bステージ塗膜を完全硬化(Cステージに)して本発明の成形体を製造する方法について、真空成形の場合の例を説明する。
Using the B-stage coating film laminated film of the present invention (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.
図4は真空成形装置の一例を示す概念図である。先ず図4(a)に示されるように、Bステージ塗膜積層フィルム7を赤外線ヒーターなどの加熱装置8を使用して加熱し、軟化させる。次に、Bステージ塗膜積層フィルム7を加熱装置8から外し、Bステージ塗膜積層フィルム7のBステージ塗膜側の面とは反対側の面が成形型9側となるように、速やかに成形型9を覆うように被せる(図4(b))。このとき成形型9は予熱しておいてもよい。続いて、Bステージ塗膜積層フィルム7と成形型9との間の空間10を減圧し、Bステージ塗膜積層フィルム7を成形型9に密着させて、成形型9の形状をBステージ塗膜積層フィルム7に転写し、成形体11(塗膜はBステージ)を得る(図4(c))。成形体11を成形型9から離型する前に、成形型9を冷却してもよい。続いて、成形体11のBステージ塗膜を、任意の活性エネルギー線照射装置を使用して完全硬化(Cステージに)することにより、本発明の成形体を製造することができる。
FIG. 4 is a conceptual diagram showing an example of a vacuum forming apparatus. First, as shown in FIG. 4A, the B-stage coating film laminated film 7 is heated and softened by using a heating device 8 such as an infrared heater. Next, 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)). At this time, the molding die 9 may be preheated. Subsequently, 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. Subsequently, 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.
上記空間10の圧力は、Bステージ塗膜積層フィルム7と成形型9との間に空気を残留させることなく、十分密着させる観点から、好ましく10KPa以下、より好ましくは1KPa以下であってよい。なお密着力は、空間10の圧力が小さいほど大きくなるが、圧力を小さくするのは加速度的にコストがかかること、及びBステージ塗膜積層フィルム7の機械強度を考慮すれば、実用的には、空間10の圧力の下限は10-5KPa程度であってよい。
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.
上記活性エネルギー線の照射量は、Bステージ塗膜を完全硬化(Cステージに)するのに必要十分な照射量とする観点から適宜選択して決定する。上記活性エネルギー線の照射量は、通常10~10000mJ/cm2程度、好ましくは200~2000mJ/cm2、より好ましくは300~700mJ/cm2であってよい。
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.
本発明の成形体は、実施形態の1つにおいて、本発明のBステージ塗膜を完全硬化させた塗膜(Cステージ)と任意の基体を有するものであってよい。該実施形態の成形体は、例えば、成形型9の代わりに上記基体を用い、Bステージ塗膜積層フィルム7を上記基体に密着、一体化した後、Bステージ塗膜を完全硬化(Cステージに)することにより製造することができる。
上記基体としては、例えば、木材、合板、集成材、パーチクルボード、及びハードボードなどの木質系材料からなる基体;ポリスチレン、アクリロニトリル・ブタジエン・スチレン共重合体(ABS樹脂)、ポリカーボネート、ポリエステル、ポリ塩化ビニル、及びポリオレフィンなどの樹脂系材料からなる基体;鉄、及びアルミニウムなどの金属系材料からなる基体;並びに、石膏、及びケイ酸カルシウムなどの鉱物系材料からなる基体等をあげることができる。 In one of the embodiments, 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. In the molded product of the embodiment, for example, the above-mentioned substrate is used instead of the molding die 9, and the B-stage coating film laminatedfilm 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.
Examples of the substrate 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.
上記基体としては、例えば、木材、合板、集成材、パーチクルボード、及びハードボードなどの木質系材料からなる基体;ポリスチレン、アクリロニトリル・ブタジエン・スチレン共重合体(ABS樹脂)、ポリカーボネート、ポリエステル、ポリ塩化ビニル、及びポリオレフィンなどの樹脂系材料からなる基体;鉄、及びアルミニウムなどの金属系材料からなる基体;並びに、石膏、及びケイ酸カルシウムなどの鉱物系材料からなる基体等をあげることができる。 In one of the embodiments, 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. In the molded product of the embodiment, for example, the above-mentioned substrate is used instead of the molding die 9, and the B-stage coating film laminated
Examples of the substrate 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.
本発明の成形体は、上述のように好ましい特性を有することから、物品(物品の部材を含む)として好適に用いることができる。上記物品としては、例えば、液晶ディスプレイ、プラズマディスプレイ、及びエレクトロルミネセンスディスプレイなどの画像表示装置、及びこれらのディスプレイ面板、透明導電性基板、及び筐体などの部材;テレビ、パソコン、タブレット型情報機器、スマートフォン、及びこれらの筐体やディスプレイ面板などの部材;更には冷蔵庫、洗濯機、食器棚、衣装棚、及びこれらを構成するパネル;建築物の窓や扉など;車両、車両の窓、風防、ルーフウインドウ、及びインストルメントパネルなど;ヘッドアップディスプレイ、電子看板、及びこれらの保護板;ショーウインドウ;太陽電池、及びその筐体や前面板などの部材等をあげることができる。
Since 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). Examples of 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.
以下、本発明を実施例により説明するが、本発明はこれらに限定されるものではない。
Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.
物性の測定・評価方法
(i)三次元成形性1
積層フィルム(塗膜はBステージ)を、赤外線ヒーターを使用して予熱した後、130℃に予熱した成形型(図5参照)の上に、上記積層フィルムを、該積層フィルムの塗膜面とは反対側の面が上記成形型側となるように広げて重ねた。図5(a)は成形型の正面図であり、ここで高さ(h)は10mm、周囲の曲線部の曲率半径(R)は16.25mmである。図5(b)は成形型の平面図であり、ここで外周の直径(φ)は90mmである。上述のように、この積層フィルムを上記成形型の上に広げて重ねた状態で30秒間待機した後、上記積層フィルムと上記成形型との間の空間を圧力1.0×10-3KPaに減圧し、上記成形型の形状を上記積層フィルムに転写し、成形体(塗膜はをBステージ)を得た。該成形体のBステージ塗膜を、高圧水銀灯タイプの紫外線照射装置を使用し、積算光量600mJ/cm2の条件で照射して、完全硬化(Cステージに)することにより、成形体(塗膜はCステージ)を得た。該成形体(塗膜はCステージ)の外観を、矯正視力1.0の者が肉眼で又はルーペ(10倍)を使用して目視観察し、以下の基準で評価した。なお上記積層フィルムが保護フィルムを有するものにあっては、Bステージ塗膜を紫外線照射により完全硬化後に保護フィルムを剥離し、目視観察に供した。
A:ルーペを使用しても、ヒビ、割れ、及び外観不良は認められなかった。
B:ルーペを使用しても、ヒビ、及び割れは認められなかった。しかし、間近に光を透かし見ると、僅かな曇感のある箇所があった。
C:ルーペを使用すると周囲の曲線部において、僅かなヒビや割れが認められた。
D:肉眼でもヒビ、及び割れが認められた。 Measurement / evaluation method of physical properties (i) Three-dimensional moldability 1
The laminated film (coating film is B stage) was preheated using an infrared heater, and then the laminated film was placed on a molding die (see FIG. 5) preheated to 130 ° C. with the coating film surface of the laminated film. Was spread out and stacked so that the opposite surface was on the molding die side. 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 (φ) is 90 mm. As described above, after waiting for 30 seconds in a state where the laminated film is spread on the molding die and stacked, 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 (the coating film 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. When 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.
(i)三次元成形性1
積層フィルム(塗膜はBステージ)を、赤外線ヒーターを使用して予熱した後、130℃に予熱した成形型(図5参照)の上に、上記積層フィルムを、該積層フィルムの塗膜面とは反対側の面が上記成形型側となるように広げて重ねた。図5(a)は成形型の正面図であり、ここで高さ(h)は10mm、周囲の曲線部の曲率半径(R)は16.25mmである。図5(b)は成形型の平面図であり、ここで外周の直径(φ)は90mmである。上述のように、この積層フィルムを上記成形型の上に広げて重ねた状態で30秒間待機した後、上記積層フィルムと上記成形型との間の空間を圧力1.0×10-3KPaに減圧し、上記成形型の形状を上記積層フィルムに転写し、成形体(塗膜はをBステージ)を得た。該成形体のBステージ塗膜を、高圧水銀灯タイプの紫外線照射装置を使用し、積算光量600mJ/cm2の条件で照射して、完全硬化(Cステージに)することにより、成形体(塗膜はCステージ)を得た。該成形体(塗膜はCステージ)の外観を、矯正視力1.0の者が肉眼で又はルーペ(10倍)を使用して目視観察し、以下の基準で評価した。なお上記積層フィルムが保護フィルムを有するものにあっては、Bステージ塗膜を紫外線照射により完全硬化後に保護フィルムを剥離し、目視観察に供した。
A:ルーペを使用しても、ヒビ、割れ、及び外観不良は認められなかった。
B:ルーペを使用しても、ヒビ、及び割れは認められなかった。しかし、間近に光を透かし見ると、僅かな曇感のある箇所があった。
C:ルーペを使用すると周囲の曲線部において、僅かなヒビや割れが認められた。
D:肉眼でもヒビ、及び割れが認められた。 Measurement / evaluation method of physical properties (i) Three-
The laminated film (coating film is B stage) was preheated using an infrared heater, and then the laminated film was placed on a molding die (see FIG. 5) preheated to 130 ° C. with the coating film surface of the laminated film. Was spread out and stacked so that the opposite surface was on the molding die side. 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 (φ) is 90 mm. As described above, after waiting for 30 seconds in a state where the laminated film is spread on the molding die and stacked, 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 (the coating film 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. When 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.
(ii)三次元成形性2
成形型として高さ(h)13.5mm、周囲の曲線部の曲率半径(R)13.5mm、及び外周の直径(φ)90mmのものを使用したこと以外は、上記試験(i)三次元成形性1と同様に成形体の作成ならびに観察および評価を行った。 (Ii) Three-dimensional moldability 2
The above test (i) three-dimensional, except that a molding die having a height (h) of 13.5 mm, a radius of curvature (R) of the surrounding curved portion (R) of 13.5 mm, and an outer peripheral diameter (φ) of 90 mm was used. The molded product was prepared, observed and evaluated in the same manner as inFormability 1.
成形型として高さ(h)13.5mm、周囲の曲線部の曲率半径(R)13.5mm、及び外周の直径(φ)90mmのものを使用したこと以外は、上記試験(i)三次元成形性1と同様に成形体の作成ならびに観察および評価を行った。 (Ii) Three-
The above test (i) three-dimensional, except that a molding die having a height (h) of 13.5 mm, a radius of curvature (R) of the surrounding curved portion (R) of 13.5 mm, and an outer peripheral diameter (φ) of 90 mm was used. The molded product was prepared, observed and evaluated in the same manner as in
(iii)引張伸び(Bステージ塗膜を有する積層フィルムの引張伸び)
JIS K7127:1999に準拠し、Bステージ塗膜を有する積層フィルムから、該積層フィルムの幅方向と引張方向とが一致するように採取した試験片タイプ2(幅15mm、全長150mm)の試験片を用い、標線間距離50mm、チャック間の初期距離100mm、及び試験速度10mm/分の条件で引張伸びを測定した。引張試験中、上記試験片を目視観察し、上記試験片の塗膜にクラックが生じた瞬間の伸びを、上記積層フィルムの引張伸びとした。なお技術的に、上記試験(iii)引張伸びの値は、上記積層フィルムが有しているBステージ塗膜の引張伸びに相当すると考えられる。また上記積層フィルムが保護フィルムを有するものにあっては、上記試験片を採取後に保護フィルムを剥離し、試験に供した。 (Iii) Tension elongation (tensile elongation of a laminated film having a B-stage coating film)
A test piece of test piece type 2 (width 15 mm,total length 150 mm) collected from a laminated film having a B-stage coating film in accordance with JIS K7127: 1999 so that the width direction and the tensile direction of the laminated film coincide with each other. The tensile elongation was measured 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. During the tensile test, 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. Technically, 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. When the laminated film had a protective film, the protective film was peeled off after collecting the test piece and used for the test.
JIS K7127:1999に準拠し、Bステージ塗膜を有する積層フィルムから、該積層フィルムの幅方向と引張方向とが一致するように採取した試験片タイプ2(幅15mm、全長150mm)の試験片を用い、標線間距離50mm、チャック間の初期距離100mm、及び試験速度10mm/分の条件で引張伸びを測定した。引張試験中、上記試験片を目視観察し、上記試験片の塗膜にクラックが生じた瞬間の伸びを、上記積層フィルムの引張伸びとした。なお技術的に、上記試験(iii)引張伸びの値は、上記積層フィルムが有しているBステージ塗膜の引張伸びに相当すると考えられる。また上記積層フィルムが保護フィルムを有するものにあっては、上記試験片を採取後に保護フィルムを剥離し、試験に供した。 (Iii) Tension elongation (tensile elongation of a laminated film having a B-stage coating film)
A test piece of test piece type 2 (width 15 mm,
(iv)環境試験1
上記試験(ii)で得た成形体(塗膜はCステージ)を温度90℃にしたギアオーブン中で4時間処理した後、上記成形体(塗膜はCステージ)の外観を矯正視力1.0の者が肉眼で又はルーペ(10倍)を使用して目視観察し、以下の基準で評価した。なお上記積層フィルムが保護フィルムを有するものにあっては、ギアオーブン処理をした後に保護フィルムを剥離し、目視観察に供した。
A:ルーペを使用しても、ヒビ、割れ、及び外観不良は認められなかった。
B:ルーペを使用しても、ヒビ、及び割れは認められなかった。しかし、間近に光を透かし見ると、僅かな曇感のある箇所があった。
C:ルーペを使用すると周囲の曲線部において、僅かなヒビや割れが認められた。
D:肉眼でもヒビ、及び割れが認められた。 (Iv)Environmental test 1
After treating the molded product (coating film is C stage) obtained in the above test (ii) in a gear oven at a temperature of 90 ° C. for 4 hours, the appearance of the molded product (coating film is C stage) is corrected. Persons with 0 were visually observed with the naked eye or using a loupe (10 times), and evaluated according to the following criteria. When the laminated film had a protective film, the protective film was peeled off after being subjected to a gear oven treatment 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.
上記試験(ii)で得た成形体(塗膜はCステージ)を温度90℃にしたギアオーブン中で4時間処理した後、上記成形体(塗膜はCステージ)の外観を矯正視力1.0の者が肉眼で又はルーペ(10倍)を使用して目視観察し、以下の基準で評価した。なお上記積層フィルムが保護フィルムを有するものにあっては、ギアオーブン処理をした後に保護フィルムを剥離し、目視観察に供した。
A:ルーペを使用しても、ヒビ、割れ、及び外観不良は認められなかった。
B:ルーペを使用しても、ヒビ、及び割れは認められなかった。しかし、間近に光を透かし見ると、僅かな曇感のある箇所があった。
C:ルーペを使用すると周囲の曲線部において、僅かなヒビや割れが認められた。
D:肉眼でもヒビ、及び割れが認められた。 (Iv)
After treating the molded product (coating film is C stage) obtained in the above test (ii) in a gear oven at a temperature of 90 ° C. for 4 hours, the appearance of the molded product (coating film is C stage) is corrected. Persons with 0 were visually observed with the naked eye or using a loupe (10 times), and evaluated according to the following criteria. When the laminated film had a protective film, the protective film was peeled off after being subjected to a gear oven treatment 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.
(v)環境試験2
上記ギアオーブンの温度を130℃に変更したこと以外は、上記試験(iv)環境試験1と同様に成形体の処理ならびに観察および評価を行った。 (V)Environmental test 2
The molded product was treated, observed and evaluated in the same manner as in Test (iv)Environmental Test 1 except that the temperature of the gear oven was changed to 130 ° C.
上記ギアオーブンの温度を130℃に変更したこと以外は、上記試験(iv)環境試験1と同様に成形体の処理ならびに観察および評価を行った。 (V)
The molded product was treated, observed and evaluated in the same manner as in Test (iv)
以下の(vi)鉛筆硬度、(vii)全光線透過率、(viii)ヘーズ、(ix)耐薬品性、(x)碁盤目試験、(xi)湿熱処理後の碁盤目試験、及び(xii)耐擦傷性の試験には、Bステージ塗膜を有する積層フィルムのBステージ塗膜を、高圧水銀灯タイプの紫外線照射装置を使用し、積算光量600mJ/cm2の条件で照射して、完全硬化(Cステージに)したものをサンプルとして使用した。保護フィルムを有するものについては、該保護フィルムを剥離してから試験に供した。
The following (vi) pencil hardness, (vii) total light transmittance, (viii) haze, (ix) chemical resistance, (x) grid test, (xi) grid test after wet heat treatment, and (xii) For the scratch resistance test, 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.
(vi)鉛筆硬度
JIS K 5600-5-4:1999に従い、試験長さ25mm、及び荷重750gの条件で、三菱鉛筆株式会社の鉛筆「ユニ」(商品名)を用い、上記サンプルの塗膜面について鉛筆硬度を測定した。傷跡が生じたか否かの判定は、蛍光灯下、蛍光灯から50cm離れた位置において、上記サンプルの表面を目視観察することにより行った。 (Vi) Pencil hardness According to JIS K 5600-5-4: 1999, under the conditions of a test length of 25 mm and a load of 750 g, a pencil "Uni" (trade name) of Mitsubishi Pencil Co., Ltd. was used, and the coated surface of the above sample was used. The pencil hardness was measured. Whether or not a scar was generated was determined by visually observing the surface of the sample under a fluorescent lamp at aposition 50 cm away from the fluorescent lamp.
JIS K 5600-5-4:1999に従い、試験長さ25mm、及び荷重750gの条件で、三菱鉛筆株式会社の鉛筆「ユニ」(商品名)を用い、上記サンプルの塗膜面について鉛筆硬度を測定した。傷跡が生じたか否かの判定は、蛍光灯下、蛍光灯から50cm離れた位置において、上記サンプルの表面を目視観察することにより行った。 (Vi) Pencil hardness According to JIS K 5600-5-4: 1999, under the conditions of a test length of 25 mm and a load of 750 g, a pencil "Uni" (trade name) of Mitsubishi Pencil Co., Ltd. was used, and the coated surface of the above sample was used. The pencil hardness was measured. Whether or not a scar was generated was determined by visually observing the surface of the sample under a fluorescent lamp at a
(vii)全光線透過率
JIS K7361-1:1997に従い、日本電色工業株式会社の濁度計「NDH2000」(商品名)を使用して、上記サンプルの全光線透過率を測定した。 (Vii) Total light transmittance According to JIS K7361-1: 1997, the total light transmittance of the above sample was measured using a turbidity meter "NDH2000" (trade name) manufactured by Nippon Denshoku Kogyo Co., Ltd.
JIS K7361-1:1997に従い、日本電色工業株式会社の濁度計「NDH2000」(商品名)を使用して、上記サンプルの全光線透過率を測定した。 (Vii) Total light transmittance According to JIS K7361-1: 1997, the total light transmittance of the above sample was measured using a turbidity meter "NDH2000" (trade name) manufactured by Nippon Denshoku Kogyo Co., Ltd.
(viii)ヘーズ
JIS K7136:2000に従い、日本電色工業株式会社の濁度計「NDH2000」(商品名)を使用して、上記サンプルのヘーズを測定した。 (Viii) Haze The haze of the above sample was measured using a turbidity meter "NDH2000" (trade name) manufactured by Nippon Denshoku Kogyo Co., Ltd. in accordance with JIS K7136: 2000.
JIS K7136:2000に従い、日本電色工業株式会社の濁度計「NDH2000」(商品名)を使用して、上記サンプルのヘーズを測定した。 (Viii) Haze The haze of the above sample was measured using a turbidity meter "NDH2000" (trade name) manufactured by Nippon Denshoku Kogyo Co., Ltd. in accordance with JIS K7136: 2000.
(ix)耐薬品性
ジョンソン・エンド・ジョンソン社の日焼け止め「ニュートロジーナ ウルトラシアー ドライタッチサンブロック」(商品名)20mlに対し、株式会社パイロットの赤色インキ「パイロットインキレッド」(商品名)を10滴の割合で混合し試験液とした。上記サンプルから100mm×100mmの大きさの試験片を採取し、該試験片の塗膜面に30mm×40mmの大きさにカットした紙ワイパー(日本製紙クレシア株式会社の「キムワイプ」(商品名))を広げて置き、スポイトを使用して、上記試験液10滴を上記紙ワイパーの上に均一に滴下した。滴下後、ピンセットを使用して、上記紙ワイパーと上記試験片との間の気泡を抜き、上記紙ワイパーと上記試験片とを密着させた後、温度23℃、相対湿度50%の環境下で保管した。該保管は、保管時間24時間毎に、上記試験液10滴を滴下し、気泡を抜いて密着させる操作を繰り返しながら72時間行った。所定時間経過後、上記試験片上の上記試験液を含んだ上記紙ワイパーを除去し、上記試験片を、水を染み込ませた紙ワイパーで水拭きし、更に乾いた紙ワイパーで乾拭きし、上記試験片の表面に付着した上記試験液を取除いた。その後、上記試験片を矯正視力1.0の者が肉眼で又はルーペ(10倍)を使用して目視観察し、以下の基準で評価した。
A:ルーペを使用しても、クラックは認められなかった。上記積層フィルムの塗膜面の上記試験液に接触した箇所と接触していない箇所とで、色調に差は認められなかった。
B:ルーペを使用しても、クラックは認められなかった。しかし、上記積層フィルムの塗膜面の上記試験液に接触した箇所と接触していない箇所とで、色調に差があった。(接触箇所は、非接触箇所と比較して赤みがあった。)
C:肉眼ではクラックは認められなかった。しかし、ルーペを使用すると、クラックが認められた。
D:肉眼でもクラックが認められた。 (Ix) Chemical resistance Johnson & Johnson sunscreen "Neutrogena Ultra Shear Dry Touch Sunblock" (trade name) 20 ml, 10 drops of Pilot Ink Red (trade name) Was mixed to prepare a test solution. A paper wiper having a size of 100 mm × 100 mm was collected from the above sample and cut into a size of 30 mm × 40 mm on the coated surface of the test piece (“Kimwipe” (trade name) of Nippon Paper Crecia Co., Ltd.). Was spread out, and 10 drops of the test solution were uniformly dropped onto the paper wiper using a dropper. After dropping, air bubbles between the paper wiper and the test piece are removed using tweezers, the paper wiper and the test piece are brought into close contact with each other, and then the temperature is 23 ° C. and the relative humidity is 50%. I kept it. The storage was carried out for 72 hours while repeating the operation of dropping 10 drops of the above test solution every 24 hours of storage time to remove air bubbles and bring them into close contact with each other. After a lapse of a predetermined time, the paper wiper containing the test solution on the test piece is removed, the test piece is wiped with a paper wiper soaked with water, and further wiped dry with a dry paper wiper to perform the above test. The above test solution adhering to the surface of the piece was removed. Then, 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.
A: No cracks were observed even when the loupe was used. No difference in color tone was observed between the portion of the coating film surface of the laminated film that was in contact with the test solution and the portion that was not in contact with the test solution.
B: No cracks were observed even when the loupe was used. However, there was a difference in color tone between the portion of the coating film surface of the laminated film that was in contact with the test solution and the portion that was not in contact with the test solution. (The contact area was reddish compared to the non-contact area.)
C: No cracks were observed with the naked eye. However, when using the loupe, cracks were observed.
D: Cracks were also observed with the naked eye.
ジョンソン・エンド・ジョンソン社の日焼け止め「ニュートロジーナ ウルトラシアー ドライタッチサンブロック」(商品名)20mlに対し、株式会社パイロットの赤色インキ「パイロットインキレッド」(商品名)を10滴の割合で混合し試験液とした。上記サンプルから100mm×100mmの大きさの試験片を採取し、該試験片の塗膜面に30mm×40mmの大きさにカットした紙ワイパー(日本製紙クレシア株式会社の「キムワイプ」(商品名))を広げて置き、スポイトを使用して、上記試験液10滴を上記紙ワイパーの上に均一に滴下した。滴下後、ピンセットを使用して、上記紙ワイパーと上記試験片との間の気泡を抜き、上記紙ワイパーと上記試験片とを密着させた後、温度23℃、相対湿度50%の環境下で保管した。該保管は、保管時間24時間毎に、上記試験液10滴を滴下し、気泡を抜いて密着させる操作を繰り返しながら72時間行った。所定時間経過後、上記試験片上の上記試験液を含んだ上記紙ワイパーを除去し、上記試験片を、水を染み込ませた紙ワイパーで水拭きし、更に乾いた紙ワイパーで乾拭きし、上記試験片の表面に付着した上記試験液を取除いた。その後、上記試験片を矯正視力1.0の者が肉眼で又はルーペ(10倍)を使用して目視観察し、以下の基準で評価した。
A:ルーペを使用しても、クラックは認められなかった。上記積層フィルムの塗膜面の上記試験液に接触した箇所と接触していない箇所とで、色調に差は認められなかった。
B:ルーペを使用しても、クラックは認められなかった。しかし、上記積層フィルムの塗膜面の上記試験液に接触した箇所と接触していない箇所とで、色調に差があった。(接触箇所は、非接触箇所と比較して赤みがあった。)
C:肉眼ではクラックは認められなかった。しかし、ルーペを使用すると、クラックが認められた。
D:肉眼でもクラックが認められた。 (Ix) Chemical resistance Johnson & Johnson sunscreen "Neutrogena Ultra Shear Dry Touch Sunblock" (trade name) 20 ml, 10 drops of Pilot Ink Red (trade name) Was mixed to prepare a test solution. A paper wiper having a size of 100 mm × 100 mm was collected from the above sample and cut into a size of 30 mm × 40 mm on the coated surface of the test piece (“Kimwipe” (trade name) of Nippon Paper Crecia Co., Ltd.). Was spread out, and 10 drops of the test solution were uniformly dropped onto the paper wiper using a dropper. After dropping, air bubbles between the paper wiper and the test piece are removed using tweezers, the paper wiper and the test piece are brought into close contact with each other, and then the temperature is 23 ° C. and the relative humidity is 50%. I kept it. The storage was carried out for 72 hours while repeating the operation of dropping 10 drops of the above test solution every 24 hours of storage time to remove air bubbles and bring them into close contact with each other. After a lapse of a predetermined time, the paper wiper containing the test solution on the test piece is removed, the test piece is wiped with a paper wiper soaked with water, and further wiped dry with a dry paper wiper to perform the above test. The above test solution adhering to the surface of the piece was removed. Then, 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.
A: No cracks were observed even when the loupe was used. No difference in color tone was observed between the portion of the coating film surface of the laminated film that was in contact with the test solution and the portion that was not in contact with the test solution.
B: No cracks were observed even when the loupe was used. However, there was a difference in color tone between the portion of the coating film surface of the laminated film that was in contact with the test solution and the portion that was not in contact with the test solution. (The contact area was reddish compared to the non-contact area.)
C: No cracks were observed with the naked eye. However, when using the loupe, cracks were observed.
D: Cracks were also observed with the naked eye.
(x)碁盤目試験(塗膜密着性)
JIS K5600-5-6:1999に従い、サンプルの塗膜面側から碁盤目の切れ込みを100マス(1マス=1mm×1mm)入れた後、密着試験用テープを碁盤目へ貼り付けて指でしごいた後、剥がした。評価基準はJISの上記規格の表1に従った。
分類0:カットの縁が完全に滑らかで、どの格子の目にも剥れがなかった。
分類1:カットの交差点において塗膜の小さな剥れがあった。クロスカット部分で影響を受けた面積は、明確に5%を上回ることはなかった。
分類2:塗膜がカットの縁に沿って、及び/又は交差点において剥れていた。クロスカット部分で影響を受けた面積は、明確に5%を超えるが15%を上回ることはなかった。
分類3:塗膜がカットの縁に沿って、部分的又は全面的に大剥れを生じており、及び/又は目のいろいろな部分が、部分的又は全面的に剥れていた。クロスカット部分で影響を受けた面積は、明確に15%を超えるが35%を上回ることはなかった。
分類4:塗膜がカットの縁に沿って、部分的又は全面的に大剥れを生じており、及び/又は数箇所の目が、部分的又は全面的に剥れていた。クロスカット部分で影響を受けた面積は、明確に35%を超えるが65%を上回ることはなかった。
分類5:剥れの程度が分類4を超える場合を本分類とした。 (X) Go board test (coating film adhesion)
According to JIS K5600-5-6: 1999, make 100 squares (1 square = 1 mm x 1 mm) of cuts in the grid from the coating surface side of the sample, and then attach the adhesion test tape to the grid and use your finger. After squeezing, it was peeled off. The evaluation criteria were in accordance with Table 1 of the above JIS standards.
Classification 0: The edges of the cut were perfectly smooth and there was no peeling in any of the grids.
Classification 1: There was a small peeling of the coating film at the intersection of the cuts. The area affected by the cross-cut portion did not clearly exceed 5%.
Category 2: The coating was peeled off along the edges of the cut and / or at the intersection. The area affected by the cross-cut portion clearly exceeded 5% but never exceeded 15%.
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 exceedsCategory 4 is defined as this category.
JIS K5600-5-6:1999に従い、サンプルの塗膜面側から碁盤目の切れ込みを100マス(1マス=1mm×1mm)入れた後、密着試験用テープを碁盤目へ貼り付けて指でしごいた後、剥がした。評価基準はJISの上記規格の表1に従った。
分類0:カットの縁が完全に滑らかで、どの格子の目にも剥れがなかった。
分類1:カットの交差点において塗膜の小さな剥れがあった。クロスカット部分で影響を受けた面積は、明確に5%を上回ることはなかった。
分類2:塗膜がカットの縁に沿って、及び/又は交差点において剥れていた。クロスカット部分で影響を受けた面積は、明確に5%を超えるが15%を上回ることはなかった。
分類3:塗膜がカットの縁に沿って、部分的又は全面的に大剥れを生じており、及び/又は目のいろいろな部分が、部分的又は全面的に剥れていた。クロスカット部分で影響を受けた面積は、明確に15%を超えるが35%を上回ることはなかった。
分類4:塗膜がカットの縁に沿って、部分的又は全面的に大剥れを生じており、及び/又は数箇所の目が、部分的又は全面的に剥れていた。クロスカット部分で影響を受けた面積は、明確に35%を超えるが65%を上回ることはなかった。
分類5:剥れの程度が分類4を超える場合を本分類とした。 (X) Go board test (coating film adhesion)
According to JIS K5600-5-6: 1999, make 100 squares (1 square = 1 mm x 1 mm) of cuts in the grid from the coating surface side of the sample, and then attach the adhesion test tape to the grid and use your finger. After squeezing, it was peeled off. The evaluation criteria were in accordance with Table 1 of the above JIS standards.
Classification 0: The edges of the cut were perfectly smooth and there was no peeling in any of the grids.
Classification 1: There was a small peeling of the coating film at the intersection of the cuts. The area affected by the cross-cut portion did not clearly exceed 5%.
Category 2: The coating was peeled off along the edges of the cut and / or at the intersection. The area affected by the cross-cut portion clearly exceeded 5% but never exceeded 15%.
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
(xi)湿熱処理後の碁盤目試験(湿熱試験)
上記サンプルに対して温度85℃、相対湿度85%の条件で72時間の湿熱処理をした後、上記試験(x)碁盤目試験と同様に試験し、密着性を評価した。 (Xi) Go board test after moist heat treatment (wet heat test)
The sample was subjected to a wet heat treatment for 72 hours under the conditions of a temperature of 85 ° C. and a relative humidity of 85%, and then tested in the same manner as in the above test (x) grid test to evaluate the adhesion.
上記サンプルに対して温度85℃、相対湿度85%の条件で72時間の湿熱処理をした後、上記試験(x)碁盤目試験と同様に試験し、密着性を評価した。 (Xi) Go board test after moist heat treatment (wet heat test)
The sample was subjected to a wet heat treatment for 72 hours under the conditions of a temperature of 85 ° C. and a relative humidity of 85%, and then tested in the same manner as in the above test (x) grid test to evaluate the adhesion.
(xii)耐擦傷性(耐スチールウール性)
縦150mm、横50mmの大きさで、積層フィルムのマシン方向が試験片の縦方向となるように採取した試験片を、塗膜が表面になるようにJIS L0849:2013の学振形試験機(摩擦試験機2形)に置いた。続いて、学振形試験機の摩擦端子に#0000のスチールウールを取り付けた後、250g荷重を載せ、摩擦端子の移動速度300mm/分、移動距離30mmの条件で、試験片の塗膜面を往復5回擦った後、当該摩擦箇所を目視観察した。傷が認められない場合には、更に往復5回擦った後、当該摩擦箇所を目視観察する作業を繰り返し、以下の基準で評価した。
A:往復15回後でも傷は認められなかった。
B:往復10回後では傷は認められなかったが、往復15回後には傷を認めることができた。
C:往復5回後では傷は認められなかったが、往復10回後には傷を認めることができた。
D:往復5回後で傷を認めることができた。 (Xii) Scratch resistance (steel wool resistance)
A test piece with a size of 150 mm in length and 50 mm in width and collected so that the machine direction of the laminated film is the vertical direction of the test piece, and the JIS L0849: 2013 Gakushin type tester (JIS L0849: 2013) so that the coating film is on the surface. It was placed in a friction tester type 2). Subsequently, after attaching # 0000 steel wool to the friction terminal of the Gakushin type tester, a load of 250 g was placed on the coated surface of the test piece under the conditions of the friction terminal moving speed of 300 mm / min and moving distance of 30 mm. After rubbing 5 times back and forth, the friction point was visually observed. When no scratches were found, after rubbing 5 times back and forth, the work of visually observing the rubbed portion was repeated and evaluated according to the following criteria.
A: No scratches were found even after 15 round trips.
B: No scratches were found after 10 round trips, but scratches were found after 15 round trips.
C: No scratches were found after 5 round trips, but scratches were found after 10 round trips.
D: The scratch was found after 5 round trips.
縦150mm、横50mmの大きさで、積層フィルムのマシン方向が試験片の縦方向となるように採取した試験片を、塗膜が表面になるようにJIS L0849:2013の学振形試験機(摩擦試験機2形)に置いた。続いて、学振形試験機の摩擦端子に#0000のスチールウールを取り付けた後、250g荷重を載せ、摩擦端子の移動速度300mm/分、移動距離30mmの条件で、試験片の塗膜面を往復5回擦った後、当該摩擦箇所を目視観察した。傷が認められない場合には、更に往復5回擦った後、当該摩擦箇所を目視観察する作業を繰り返し、以下の基準で評価した。
A:往復15回後でも傷は認められなかった。
B:往復10回後では傷は認められなかったが、往復15回後には傷を認めることができた。
C:往復5回後では傷は認められなかったが、往復10回後には傷を認めることができた。
D:往復5回後で傷を認めることができた。 (Xii) Scratch resistance (steel wool resistance)
A test piece with a size of 150 mm in length and 50 mm in width and collected so that the machine direction of the laminated film is the vertical direction of the test piece, and the JIS L0849: 2013 Gakushin type tester (JIS L0849: 2013) so that the coating film is on the surface. It was placed in a friction tester type 2). Subsequently, after attaching # 0000 steel wool to the friction terminal of the Gakushin type tester, a load of 250 g was placed on the coated surface of the test piece under the conditions of the friction terminal moving speed of 300 mm / min and moving distance of 30 mm. After rubbing 5 times back and forth, the friction point was visually observed. When no scratches were found, after rubbing 5 times back and forth, the work of visually observing the rubbed portion was repeated and evaluated according to the following criteria.
A: No scratches were found even after 15 round trips.
B: No scratches were found after 10 round trips, but scratches were found after 15 round trips.
C: No scratches were found after 5 round trips, but scratches were found after 10 round trips.
D: The scratch was found after 5 round trips.
使用した原材料
(A)活性エネルギー線硬化性樹脂
(A1)ウレタン(メタ)アクリレート
(A1-1)ダイセル・オルネクス株式会社の多官能ウレタン(メタ)アクリレート「EBECRYL284」(商品名)。固形分100質量%、官能基数2、数平均分子量1000、質量平均分子量2900、Z平均分子量4700。
(A1-2)ダイセル・オルネクス株式会社の多官能ウレタン(メタ)アクリレート「EBECRYL4101」(商品名)。固形分100質量%、官能基数3、数平均分子量1100、質量平均分子量2800、Z平均分子量4900。
(A1-3)根上工業株式会社の多官能ウレタン(メタ)アクリレートの希釈液「アートレジンUN-952」(商品名)。固形分60質量%、官能基数10、数平均分子量2500、質量平均分子量9100、Z平均分子量23000。
(A1-4)根上工業株式会社の多官能ウレタン(メタ)アクリレートの希釈液「アートレジンUN-954」(商品名)。固形分60質量%、官能基数6、数平均分子量2000、質量平均分子量4800、Z平均分子量9600。 Raw materials used (A) Active energy ray-curable resin (A1) Urethane (meth) acrylate (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.
(A1-3) Diluted solution of polyfunctional urethane (meth) acrylate of Negami Kogyo Co., Ltd. "Art Resin UN-952" (trade name). Solid content 60% by mass, number offunctional groups 10, number average molecular weight 2500, mass average molecular weight 9100, Z average molecular weight 23000.
(A1-4) Diluted solution of polyfunctional urethane (meth) acrylate of Negami Kogyo Co., Ltd. "Art Resin UN-954" (trade name). Solid content 60% by mass, number offunctional groups 6, number average molecular weight 2000, mass average molecular weight 4800, Z average molecular weight 9600.
(A)活性エネルギー線硬化性樹脂
(A1)ウレタン(メタ)アクリレート
(A1-1)ダイセル・オルネクス株式会社の多官能ウレタン(メタ)アクリレート「EBECRYL284」(商品名)。固形分100質量%、官能基数2、数平均分子量1000、質量平均分子量2900、Z平均分子量4700。
(A1-2)ダイセル・オルネクス株式会社の多官能ウレタン(メタ)アクリレート「EBECRYL4101」(商品名)。固形分100質量%、官能基数3、数平均分子量1100、質量平均分子量2800、Z平均分子量4900。
(A1-3)根上工業株式会社の多官能ウレタン(メタ)アクリレートの希釈液「アートレジンUN-952」(商品名)。固形分60質量%、官能基数10、数平均分子量2500、質量平均分子量9100、Z平均分子量23000。
(A1-4)根上工業株式会社の多官能ウレタン(メタ)アクリレートの希釈液「アートレジンUN-954」(商品名)。固形分60質量%、官能基数6、数平均分子量2000、質量平均分子量4800、Z平均分子量9600。 Raw materials used (A) Active energy ray-curable resin (A1) Urethane (meth) acrylate (A1-1) Polyfunctional urethane (meth) acrylate "EBECRYL284" (trade name) manufactured by Daicel Ornex Co., Ltd.
(A1-2) Polyfunctional urethane (meth) acrylate "EBECRYL4101" (trade name) of Daicel Ornex Co., Ltd.
(A1-3) Diluted solution of polyfunctional urethane (meth) acrylate of Negami Kogyo Co., Ltd. "Art Resin UN-952" (trade name). Solid content 60% by mass, number of
(A1-4) Diluted solution of polyfunctional urethane (meth) acrylate of Negami Kogyo Co., Ltd. "Art Resin UN-954" (trade name). Solid content 60% by mass, number of
(A2)(a1)多官能(メタ)アクリレートと(a2)多官能チオールとの共重合体
(A2-1)大阪有機化学工業株式会社の「SIRIUS-501」(商品名)。ジペンタエリスリトールヘキサアクリレートと4官能チオールとの所謂デンドリマー構造を有する共重合体の希釈液。固形分50質量%、硫黄含有量2.2質量%、質量平均分子量1万2千、数平均分子量940、Z平均分子量7万3千。 (A2) (a1) Copolymer of polyfunctional (meth) acrylate and (a2) polyfunctional thiol (A2-1) "SIRIUS-501" (trade name) of Osaka Organic Chemical Industry Co., Ltd. A diluent of a copolymer having a so-called dendrimer structure of dipentaerythritol hexaacrylate and a tetrafunctional thiol.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.
(A2-1)大阪有機化学工業株式会社の「SIRIUS-501」(商品名)。ジペンタエリスリトールヘキサアクリレートと4官能チオールとの所謂デンドリマー構造を有する共重合体の希釈液。固形分50質量%、硫黄含有量2.2質量%、質量平均分子量1万2千、数平均分子量940、Z平均分子量7万3千。 (A2) (a1) Copolymer of polyfunctional (meth) acrylate and (a2) polyfunctional thiol (A2-1) "SIRIUS-501" (trade name) of Osaka Organic Chemical Industry Co., Ltd. A diluent of a copolymer having a so-called dendrimer structure of dipentaerythritol hexaacrylate and a tetrafunctional thiol.
(B)光重合開始剤
(B-1)IGM Resins社のアセトフェノン系光重合開始剤(2-ヒロドキシ-1-{4-[4-(2-ヒドロキシ-2-メチル-プロピオニル)-ベンジル]フェニル}-2-メチル-プロパン-1-オン)「Omnirad127」(商品名)。
(B-2)IGM Resins社のアセトフェノン系光重合開始剤(1-ヒドロキシシクロヘキシル-フェニルケトン)「Omnirad 184」(商品名)。 (B) Photopolymerization Initiator (B-1) Acetophenone-based Photopolymerization Initiator from IGM Resins (2-Hyrodoxy-1- {4- [4- (2-Hydroxy-2-methyl-propionyl) -benzyl] phenyl } -2-Methyl-Propane-1-one) "Omnirad 127" (trade name).
(B-2) IGM Resins' acetophenone-based photopolymerization initiator (1-hydroxycyclohexyl-phenylketone) "Omnirad 184" (trade name).
(B-1)IGM Resins社のアセトフェノン系光重合開始剤(2-ヒロドキシ-1-{4-[4-(2-ヒドロキシ-2-メチル-プロピオニル)-ベンジル]フェニル}-2-メチル-プロパン-1-オン)「Omnirad127」(商品名)。
(B-2)IGM Resins社のアセトフェノン系光重合開始剤(1-ヒドロキシシクロヘキシル-フェニルケトン)「Omnirad 184」(商品名)。 (B) Photopolymerization Initiator (B-1) Acetophenone-based Photopolymerization Initiator from IGM Resins (2-Hyrodoxy-1- {4- [4- (2-Hydroxy-2-methyl-propionyl) -benzyl] phenyl } -2-Methyl-Propane-1-one) "Omnirad 127" (trade name).
(B-2) IGM Resins' acetophenone-based photopolymerization initiator (1-hydroxycyclohexyl-phenylketone) "Omnirad 184" (trade name).
(C)微粒子
(C-1)日産化学株式会社のシリカ微粒子のプロピレングリコールモノメチルエーテル分散液「PGM-AC-2140Y」(商品名)。固形分42質量%、平均粒子径15nm。
(C-2)株式会社NBCメッシュテックの抗ウィルス剤(ヨウ化第一銅微粒子のエタノール懸濁液)、ヨウ化第一銅微粒子の平均粒子径(レーザー回折・散乱法により測定した粒子径分布曲線において、粒子の小さい方からの累積が50質量%となる粒子径)120nm、固形分11質量%。 (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.
(C-1)日産化学株式会社のシリカ微粒子のプロピレングリコールモノメチルエーテル分散液「PGM-AC-2140Y」(商品名)。固形分42質量%、平均粒子径15nm。
(C-2)株式会社NBCメッシュテックの抗ウィルス剤(ヨウ化第一銅微粒子のエタノール懸濁液)、ヨウ化第一銅微粒子の平均粒子径(レーザー回折・散乱法により測定した粒子径分布曲線において、粒子の小さい方からの累積が50質量%となる粒子径)120nm、固形分11質量%。 (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)撥水剤
(D-1)信越化学工業株式会社のアクリロイル基含有フルオロポリエーテル系撥水剤の希釈液「KY-1203」(商品名)。固形分20質量%。
(D-2)ユニマテック株式会社のアクリロイル基含有フルオロアルキル系撥水剤(2-(パーフルオロブチル)エチルアクリレート)「CHEMINOXFAAC-4」(商品名)。固形分100質量%。 (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.
(D-1)信越化学工業株式会社のアクリロイル基含有フルオロポリエーテル系撥水剤の希釈液「KY-1203」(商品名)。固形分20質量%。
(D-2)ユニマテック株式会社のアクリロイル基含有フルオロアルキル系撥水剤(2-(パーフルオロブチル)エチルアクリレート)「CHEMINOXFAAC-4」(商品名)。固形分100質量%。 (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.
(E)その他の成分
(E-1)ビッグケミー・ジャパン株式会社のアミン系分散剤「DISPERBY K-145」(商品名)。ポリアミン構造を有する高分子量共重合体のリン酸エステル塩。アミン価71mgKOH/g。固形分100質量%。 (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.
(E-1)ビッグケミー・ジャパン株式会社のアミン系分散剤「DISPERBY K-145」(商品名)。ポリアミン構造を有する高分子量共重合体のリン酸エステル塩。アミン価71mgKOH/g。固形分100質量%。 (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.
(H)Bステージ塗膜形成用塗料
(H-1)上記成分(A1-1)50質量部、上記成分(A2-1)100質量部(固形 分換算50質量部)、上記成分(B-1)5質量部、上記成分(C-1)555質量部(固形分換算233質量部)、上記成分(D-1)1.25質量部(固形分換算0.25質量部)、及びメチルイソブチルケトン(表には「MIBK」と記載)233質量部を混合攪拌し、Bステージ塗膜形成用塗料を得た。なお表には、溶剤を除き、全て固形分換算の値を記載した。 (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. In the table, all the values in terms of solid content are shown except for the solvent.
(H-1)上記成分(A1-1)50質量部、上記成分(A2-1)100質量部(固形 分換算50質量部)、上記成分(B-1)5質量部、上記成分(C-1)555質量部(固形分換算233質量部)、上記成分(D-1)1.25質量部(固形分換算0.25質量部)、及びメチルイソブチルケトン(表には「MIBK」と記載)233質量部を混合攪拌し、Bステージ塗膜形成用塗料を得た。なお表には、溶剤を除き、全て固形分換算の値を記載した。 (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. In the table, all the values in terms of solid content are shown except for the solvent.
(H-2~H-11)
表1~3の何れか1に示すように配合を変更したこと以外は、上記(H-1)と同様にして塗料を得た。なお表には、溶剤を除き、全て固形分換算の値を記載した。 (H-2 to H-11)
A paint was obtained in the same manner as in (H-1) above, except that the formulation was changed as shown in any one of Tables 1 to 3. In the table, all the values in terms of solid content are shown except for the solvent.
表1~3の何れか1に示すように配合を変更したこと以外は、上記(H-1)と同様にして塗料を得た。なお表には、溶剤を除き、全て固形分換算の値を記載した。 (H-2 to H-11)
A paint was obtained in the same manner as in (H-1) above, except that the formulation was changed as shown in any one of Tables 1 to 3. In the table, all the values in terms of solid content are shown except for the solvent.
(P)透明樹脂フィルム
(P-1)2種3層マルチマニホールド方式の共押出Tダイ、及び第一鏡面ロール(溶融フィルムを抱いて次の移送ロールへと送り出す側のロール)と第二鏡面ロールとで溶融フィルムを押圧する機構を有する引巻取機を備えた装置を使用し、2種3層多層樹脂フィルムの両外層(α1層とα2層)としてエボニック社のポリ(メタ)アクリルイミド「PLEXIMID TT50」(商品名)を、中間層(β層)として住化スタイロンポリカーボネート株式会社の芳香族ポリカーボネート「カリバー301-4」(商品名)を、共押出Tダイから連続的に共押出し、α1層が第一鏡面ロール側となるように、回転する第一鏡面ロールと第二鏡面ロールとの間に供給投入し、押圧して、全厚み170μm、α1層の層厚み50μm、β層の層厚み70μm、α2層の層厚み50μmの透明樹脂フィルムを得た。このとき設定条件は、Tダイの設定温度300℃、第一鏡面ロールの設定温度130℃、第二鏡面ロールの設定温度120℃、引取速度9.5m/分であった。 (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 Using a device equipped with a winder having a mechanism for pressing the molten film with a roll, Ebonic's poly (meth) acrylicimide is used as both outer layers (α1 layer and α2 layer) of a two-kind three-layer multilayer resin film. Using "PLEXIMID TT50" (trade name) as an intermediate layer (β layer), the aromatic polycarbonate "Calibre 301-4" (trade name) of Sumika Stylon Polycarbonate Co., Ltd. was continuously co-extruded from the co-extruded T-die. The α1 layer is supplied and charged between the rotating first mirror surface roll and the second mirror surface roll so that the α1 layer is on the first mirror surface roll side, and pressed to obtain a total thickness of 170 μm, a layer thickness of the α1 layer of 50 μm, and a β layer. A transparent resin film having a layer thickness of 70 μm and an α2 layer thickness of 50 μm was obtained. At this time, 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.
(P-1)2種3層マルチマニホールド方式の共押出Tダイ、及び第一鏡面ロール(溶融フィルムを抱いて次の移送ロールへと送り出す側のロール)と第二鏡面ロールとで溶融フィルムを押圧する機構を有する引巻取機を備えた装置を使用し、2種3層多層樹脂フィルムの両外層(α1層とα2層)としてエボニック社のポリ(メタ)アクリルイミド「PLEXIMID TT50」(商品名)を、中間層(β層)として住化スタイロンポリカーボネート株式会社の芳香族ポリカーボネート「カリバー301-4」(商品名)を、共押出Tダイから連続的に共押出し、α1層が第一鏡面ロール側となるように、回転する第一鏡面ロールと第二鏡面ロールとの間に供給投入し、押圧して、全厚み170μm、α1層の層厚み50μm、β層の層厚み70μm、α2層の層厚み50μmの透明樹脂フィルムを得た。このとき設定条件は、Tダイの設定温度300℃、第一鏡面ロールの設定温度130℃、第二鏡面ロールの設定温度120℃、引取速度9.5m/分であった。 (P) Transparent resin film (P-1)
(Q)保護フィルム
(Q-1)帝人株式会社の芳香族ポリカーボネート系樹脂フィルム「パンライトフィルムPC-2151」(商品名)、厚み125μm。
(Q-2)単層Tダイ、及び第1チルロール(鏡面金属ロール)とニップロール(シリコンゴムロール)とで上記単層Tダイから押出された溶融状態のフィルムをニップする機構を有する引巻取機を備えたフィルム製膜装置を使用し、株式会社ベルポリエステルプロダクツの共重合ポリエチレンテレフタレート樹脂「PIFG5」(商品名)を用い、上記Tダイの設定温度250℃、第1チルロールの設定温度50℃、引取速度10.8m/分の条件で厚み75μmの樹脂フィルムを得た。該樹脂フィルムの第1チルロール側の面(高光沢の面)を塗膜との貼合面とした。 (Q) Protective film (Q-1) Teijin Limited's aromatic polycarbonate-based resin film "Panlite Film PC-2151" (trade name), thickness 125 μm.
(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). Using a film-forming device equipped with the above-mentioned T-die using the copolymerized polyethylene terephthalate resin "PIFG5" (trade name) of Bell Polyester Products Co., Ltd., 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 μm 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.
(Q-1)帝人株式会社の芳香族ポリカーボネート系樹脂フィルム「パンライトフィルムPC-2151」(商品名)、厚み125μm。
(Q-2)単層Tダイ、及び第1チルロール(鏡面金属ロール)とニップロール(シリコンゴムロール)とで上記単層Tダイから押出された溶融状態のフィルムをニップする機構を有する引巻取機を備えたフィルム製膜装置を使用し、株式会社ベルポリエステルプロダクツの共重合ポリエチレンテレフタレート樹脂「PIFG5」(商品名)を用い、上記Tダイの設定温度250℃、第1チルロールの設定温度50℃、引取速度10.8m/分の条件で厚み75μmの樹脂フィルムを得た。該樹脂フィルムの第1チルロール側の面(高光沢の面)を塗膜との貼合面とした。 (Q) Protective film (Q-1) Teijin Limited's aromatic polycarbonate-based resin film "Panlite Film PC-2151" (trade name), thickness 125 μm.
(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). Using a film-forming device equipped with the above-mentioned T-die using the copolymerized polyethylene terephthalate resin "PIFG5" (trade name) of Bell Polyester Products Co., Ltd., 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 μm 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.
例1
(1)上記(P-1)の両面にコロナ放電処理を行った。両面とも濡れ指数は64mN/mであった。
(2)次に、上記(P-1)のα1層側の面の上に、ダイ方式の塗工装置を使用して、上記(H-1)を完全硬化(Cステージにした)後の厚みが18μmとなるように塗布し、ウェット塗膜を形成した。
(3)次に、炉内温度90℃に設定した乾燥炉を、入口から出口までパスするのに要する時間が2分間となるライン速度でパスさせて、上記ウェット塗膜を予備乾燥し、乾燥塗膜にした。
(4)次に、図1に概念図を示すラミネート装置を使用し、上記(P-1)のα1層側の面の上に上記乾燥塗膜を有する積層体1を、該積層体1の上記乾燥塗膜とは反対側の面が回転ドラム3側となるように、回転する回転ドラム3の上に載せた。これと同時に、上記(Q-1)の保護フィルム2を、上記積層体1の上記乾燥塗膜面の上に、上記(Q-1)の保護フィルム2の第一チルロール側の面(高光沢の面)が上記乾燥塗膜面側となるように重ね、圧着ロール4により圧着し、次いでガイドロール6により回転ドラム3からリリースして、上記積層体1の上記乾燥塗膜面の上に、上記(Q-1)の保護フィルム2を重ねて仮貼りした積層体5を得た。このとき回転ドラム3の温度は、室温(23℃)にした。
(5)次に、株式会社栗原製作所のオートクレーブ「YKP-500型」(商品名)を使用し、該オートクレーブ内に上記(P-1)、上記乾燥塗膜、及び上記(Q-1)をこの順に有する積層体を静置した後、温度50℃、圧力0.5MPa、及び保持時間10分間の条件でオートクレーブ処理を行った。
(6)続いて、温度80℃で2時間のエージング処理をして、Bステージ塗膜を形成し、上記(P-1)のα1層側の面の上にBステージ塗膜を有する積層フィルムを得た。
(7)上記試験(i)~(xii)を行った。結果を表1に示す。 Example 1
(1) Corona discharge treatment was performed on both sides of the above (P-1). The wettability index was 64 mN / m on both sides.
(2) Next, after the above (H-1) is completely cured (made into a C stage) by using a die-type coating device on the surface of the above (P-1) on the α1 layer side. It was applied so as to have a thickness of 18 μm to form a wet coating film.
(3) Next, 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.
(4) Next, using the laminating apparatus shown in the conceptual diagram in FIG. 1, thelaminated body 1 having the dry coating film on the surface on the α1 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. At the same time, 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. At this time, the temperature of the rotating drum 3 was set to room temperature (23 ° C.).
(5) Next, using the autoclave "YKP-500 type" (trade name) manufactured by Kurihara Seisakusho Co., Ltd., the above (P-1), the above dry coating film, and the above (Q-1) are placed in the autoclave. After allowing the laminates held in this order to stand still, 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.
(6) Subsequently, an aging treatment is carried out at a temperature of 80 ° C. for 2 hours to form a B-stage coating film, and a laminated film having the B-stage coating film on the surface on the α1 layer side of (P-1) above. Got
(7) The above tests (i) to (xii) were performed. The results are shown in Table 1.
(1)上記(P-1)の両面にコロナ放電処理を行った。両面とも濡れ指数は64mN/mであった。
(2)次に、上記(P-1)のα1層側の面の上に、ダイ方式の塗工装置を使用して、上記(H-1)を完全硬化(Cステージにした)後の厚みが18μmとなるように塗布し、ウェット塗膜を形成した。
(3)次に、炉内温度90℃に設定した乾燥炉を、入口から出口までパスするのに要する時間が2分間となるライン速度でパスさせて、上記ウェット塗膜を予備乾燥し、乾燥塗膜にした。
(4)次に、図1に概念図を示すラミネート装置を使用し、上記(P-1)のα1層側の面の上に上記乾燥塗膜を有する積層体1を、該積層体1の上記乾燥塗膜とは反対側の面が回転ドラム3側となるように、回転する回転ドラム3の上に載せた。これと同時に、上記(Q-1)の保護フィルム2を、上記積層体1の上記乾燥塗膜面の上に、上記(Q-1)の保護フィルム2の第一チルロール側の面(高光沢の面)が上記乾燥塗膜面側となるように重ね、圧着ロール4により圧着し、次いでガイドロール6により回転ドラム3からリリースして、上記積層体1の上記乾燥塗膜面の上に、上記(Q-1)の保護フィルム2を重ねて仮貼りした積層体5を得た。このとき回転ドラム3の温度は、室温(23℃)にした。
(5)次に、株式会社栗原製作所のオートクレーブ「YKP-500型」(商品名)を使用し、該オートクレーブ内に上記(P-1)、上記乾燥塗膜、及び上記(Q-1)をこの順に有する積層体を静置した後、温度50℃、圧力0.5MPa、及び保持時間10分間の条件でオートクレーブ処理を行った。
(6)続いて、温度80℃で2時間のエージング処理をして、Bステージ塗膜を形成し、上記(P-1)のα1層側の面の上にBステージ塗膜を有する積層フィルムを得た。
(7)上記試験(i)~(xii)を行った。結果を表1に示す。 Example 1
(1) Corona discharge treatment was performed on both sides of the above (P-1). The wettability index was 64 mN / m on both sides.
(2) Next, after the above (H-1) is completely cured (made into a C stage) by using a die-type coating device on the surface of the above (P-1) on the α1 layer side. It was applied so as to have a thickness of 18 μm to form a wet coating film.
(3) Next, 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.
(4) Next, using the laminating apparatus shown in the conceptual diagram in FIG. 1, the
(5) Next, using the autoclave "YKP-500 type" (trade name) manufactured by Kurihara Seisakusho Co., Ltd., the above (P-1), the above dry coating film, and the above (Q-1) are placed in the autoclave. After allowing the laminates held in this order to stand still, 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.
(6) Subsequently, an aging treatment is carried out at a temperature of 80 ° C. for 2 hours to form a B-stage coating film, and a laminated film having the B-stage coating film on the surface on the α1 layer side of (P-1) above. Got
(7) The above tests (i) to (xii) were performed. The results are shown in Table 1.
例2~10
Bステージ塗膜形成用塗料として、上記(H-1)の替わりに表1又は2に示す塗料を用いたこと以外は、例1と同様にしてBステージ塗膜を有する積層フィルムを得た。上記試験(i)~(xii)を行った。結果を表1又は2に示す。 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.
Bステージ塗膜形成用塗料として、上記(H-1)の替わりに表1又は2に示す塗料を用いたこと以外は、例1と同様にしてBステージ塗膜を有する積層フィルムを得た。上記試験(i)~(xii)を行った。結果を表1又は2に示す。 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.
例11
Bステージ塗膜形成用塗料として、上記(H-1)の替わりに上記(H-11)を用い、保護フィルムとして上記(Q-1)の替わりに上記(Q-2)を用いたこと以外は、例1と同様にしてBステージ塗膜を有する積層フィルムを得た。上記試験(i)~(xii)を行った。結果を表2に示す。 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.
Bステージ塗膜形成用塗料として、上記(H-1)の替わりに上記(H-11)を用い、保護フィルムとして上記(Q-1)の替わりに上記(Q-2)を用いたこと以外は、例1と同様にしてBステージ塗膜を有する積層フィルムを得た。上記試験(i)~(xii)を行った。結果を表2に示す。 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.
例12
ウェット塗膜を形成する際に、完全硬化(Cステージにした)後の厚みが13μmとなるように塗布したこと以外は、例1と同様にしてBステージ塗膜を有する積層フィルムを得た。上記試験(i)~(xii)を行った。結果を表3に示す。 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 μm. The above tests (i) to (xii) were performed. The results are shown in Table 3.
ウェット塗膜を形成する際に、完全硬化(Cステージにした)後の厚みが13μmとなるように塗布したこと以外は、例1と同様にしてBステージ塗膜を有する積層フィルムを得た。上記試験(i)~(xii)を行った。結果を表3に示す。 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 μm. The above tests (i) to (xii) were performed. The results are shown in Table 3.
例13
予備乾燥条件を表1に示す条件に変更したこと以外は、例1と同様にしてBステージ塗膜を有する積層フィルムを得た。上記試験(i)~(xii)を行った。結果を表3に示す。 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.
予備乾燥条件を表1に示す条件に変更したこと以外は、例1と同様にしてBステージ塗膜を有する積層フィルムを得た。上記試験(i)~(xii)を行った。結果を表3に示す。 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.
例14~17
オートクレーブ処理条件を表1に示す条件に変更したこと以外は、例1と同様にしてBステージ塗膜を有する積層フィルムを得た。上記試験(i)~(xii)を行った。結果を表3に示す。 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.
オートクレーブ処理条件を表1に示す条件に変更したこと以外は、例1と同様にしてBステージ塗膜を有する積層フィルムを得た。上記試験(i)~(xii)を行った。結果を表3に示す。 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.
例18
オートクレーブ処理を省略したこと以外は、例1と同様にしてBステージ塗膜を有する積層フィルムを得た。上記試験(i)を行ったところ、得られた成形体に、塗膜の発泡による外観不良が多数認められた。そのため試験(ii)~(xii)は省略した。 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. When 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.
オートクレーブ処理を省略したこと以外は、例1と同様にしてBステージ塗膜を有する積層フィルムを得た。上記試験(i)を行ったところ、得られた成形体に、塗膜の発泡による外観不良が多数認められた。そのため試験(ii)~(xii)は省略した。 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. When 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.
本発明の製造方法により、Bステージ塗膜を工業的に安定して製造することができた。本発明の好ましい製造方法により、三次元成形性に優れたBステージ塗膜を工業的に安定して製造することができた。本発明の好ましいBステージ塗膜は、Bステージにおいては三次元成形性に優れ、完全硬化後(Cステージにおいて)は耐熱性、表面硬度、透明性、耐薬品性、塗膜密着性、湿熱試験後の塗膜密着性、及び耐擦傷性に優れていた。従って、本発明のBステージ塗膜は、三次元形状/立体的形状を有する成形体、例えば、家電製品や情報電子機器の筐体等、及び自動車のインスツルメントパネル等の成形体の表面に表面硬度、耐擦傷性、及び耐薬品性などの機能を付与するために好適に用いることができる。
By the production method of the present invention, the B stage coating film could be industrially stably produced. By the preferred production method of the present invention, 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. Therefore, the B-stage coating film of the present invention is applied to the surface of a molded body having a three-dimensional shape / three-dimensional shape, for example, a housing of a home appliance or an information electronic device, and a molded body such as an instrument panel of an automobile. It can be suitably used to impart functions such as surface hardness, scratch resistance, and chemical resistance.
本発明のBステージ塗膜の実施形態の例は、以下のように要約される。
[1].
Bステージ塗膜であって、
(A)活性エネルギー線硬化性樹脂と(B)光重合開始剤を含む塗料を用いて形成され;
上記Bステージ塗膜の引張伸びが10%以上である;
上記Bステージ塗膜。
[2].
上記塗料が更に(C)平均粒子径1~300nmの微粒子を含む、[1]項に記載のBステージ塗膜。
[3].
上記塗料が更に(D)撥水剤を含む、[1]項又は[2]項に記載のBステージ塗膜。
[4].
上記塗料が熱重合開始剤を含まない、[1]~[3]項の何れか1項に記載のBステージ塗膜。
[5].
上記(A)活性エネルギー線硬化性樹脂が(A1)ウレタン(メタ)アクリレートを含む、[1]~[4]項の何れか1項に記載のBステージ塗膜。
[6].
上記(A)活性エネルギー線硬化性樹脂が(A2)(a1)多官能(メタ)アクリレートと(a2)多官能チオールとの共重合体を含む、[1]~[5]項の何れか1項に記載のBステージ塗膜。 Examples of embodiments of the B-stage coating film of the present invention are summarized as follows.
[1].
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 item [1], wherein the coating material further contains (C) fine particles having an average particle size of 1 to 300 nm.
[3].
The B-stage coating film according to item [1] or [2], wherein the coating material further contains (D) a water repellent.
[4].
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 any one of [1] to [4], wherein the (A) active energy ray-curable resin contains (A1) urethane (meth) acrylate.
[6].
Any one of items [1] to [5], wherein the (A) active energy ray-curable resin contains a copolymer of (A2) (a1) polyfunctional (meth) acrylate and (a2) polyfunctional thiol. The B stage coating film according to the section.
[1].
Bステージ塗膜であって、
(A)活性エネルギー線硬化性樹脂と(B)光重合開始剤を含む塗料を用いて形成され;
上記Bステージ塗膜の引張伸びが10%以上である;
上記Bステージ塗膜。
[2].
上記塗料が更に(C)平均粒子径1~300nmの微粒子を含む、[1]項に記載のBステージ塗膜。
[3].
上記塗料が更に(D)撥水剤を含む、[1]項又は[2]項に記載のBステージ塗膜。
[4].
上記塗料が熱重合開始剤を含まない、[1]~[3]項の何れか1項に記載のBステージ塗膜。
[5].
上記(A)活性エネルギー線硬化性樹脂が(A1)ウレタン(メタ)アクリレートを含む、[1]~[4]項の何れか1項に記載のBステージ塗膜。
[6].
上記(A)活性エネルギー線硬化性樹脂が(A2)(a1)多官能(メタ)アクリレートと(a2)多官能チオールとの共重合体を含む、[1]~[5]項の何れか1項に記載のBステージ塗膜。 Examples of embodiments of the B-stage coating film of the present invention are summarized as follows.
[1].
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 item [1], wherein the coating material further contains (C) fine particles having an average particle size of 1 to 300 nm.
[3].
The B-stage coating film according to item [1] or [2], wherein the coating material further contains (D) a water repellent.
[4].
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 any one of [1] to [4], wherein the (A) active energy ray-curable resin contains (A1) urethane (meth) acrylate.
[6].
Any one of items [1] to [5], wherein the (A) active energy ray-curable resin contains a copolymer of (A2) (a1) polyfunctional (meth) acrylate and (a2) polyfunctional thiol. The B stage coating film according to the section.
1:フィルム基材の一方の面の上に乾燥塗膜を有する積層体
2:保護フィルム
3:回転ドラム
4:圧着ロール
5:積層体1の乾燥塗膜の面の上に保護フィルム2を重ね、仮貼りされた積層体
6:ガイドロール
7:Bステージ塗膜積層フィルム
8:加熱装置
9:成形型
10:Bステージ塗膜積層フィルムと成形型との間の空間
11:成形体
1: Laminated body having a dry coating film on one surface of the film substrate 2: Protective film 3: Rotating drum 4: Crimping roll 5: Laminating theprotective film 2 on the surface of the dry coating film of the laminated body 1. , Temporarily pasted laminate 6: Guide roll 7: B stage coating film laminated film 8: Heating device 9: Molding mold 10: Space between B stage coating film laminated film and molding mold 11: Molded body
2:保護フィルム
3:回転ドラム
4:圧着ロール
5:積層体1の乾燥塗膜の面の上に保護フィルム2を重ね、仮貼りされた積層体
6:ガイドロール
7:Bステージ塗膜積層フィルム
8:加熱装置
9:成形型
10:Bステージ塗膜積層フィルムと成形型との間の空間
11:成形体
1: Laminated body having a dry coating film on one surface of the film substrate 2: Protective film 3: Rotating drum 4: Crimping roll 5: Laminating the
Claims (12)
- Bステージ塗膜の製造方法であって、
(1)フィルム基材の少なくとも一方の面の上に、(A)活性エネルギー線硬化性樹脂及び(B)光重合開始剤を含む塗料を用いてウェット塗膜を形成する工程;
(2)上記工程(1)で形成された上記ウェット塗膜を予備乾燥し、乾燥塗膜を形成する工程;ならびに、
(3)上記工程(2)で形成された上記乾燥塗膜をオートクレーブ処理する工程
を含む上記方法。 This is a method for manufacturing a B-stage coating film.
(1) A step of forming a wet coating film on at least one surface of a film substrate using a coating material containing (A) an active energy ray-curable resin and (B) a photopolymerization initiator;
(2) A step of pre-drying the wet coating film formed in the above step (1) to form a dry coating film;
(3) The above method including the step of autoclaving the above dry coating film formed in the above step (2). - 更に、上記工程(2)の後、上記工程(3)の前に、上記工程(2)で形成された上記乾燥塗膜の面の上に、保護フィルムを重ね、仮貼りする工程を含む、請求項1に記載の方法。 Further, after the step (2) and before the step (3), 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. The method according to claim 1.
- 上記工程(3)のオートクレーブ処理が、圧力0.15~1MPa、温度23~100℃で1~60分間の時間保持する条件で行われる、請求項1又は2に記載の方法。 The method according to claim 1 or 2, wherein the autoclave treatment in the above step (3) is performed under the condition that the autoclave treatment is carried out at a pressure of 0.15 to 1 MPa and a temperature of 23 to 100 ° C. for 1 to 60 minutes.
- 更に、上記工程(3)の後、エージング処理をする工程を含む、請求項1~3の何れか1項に記載の方法。 The method according to any one of claims 1 to 3, further comprising a step of performing an aging treatment after the above step (3).
- 上記塗料が更に(C)微粒子を含む、請求項1~4の何れか1項に記載の方法。 The method according to any one of claims 1 to 4, wherein the coating material further contains (C) fine particles.
- 上記成分(C)微粒子が、抗菌剤又は抗ウィルス剤として機能する微粒子を含む請求項5に記載の方法。 The method according to claim 5, wherein the fine particles of the component (C) contain fine particles that function as an antibacterial agent or an antiviral agent.
- 上記塗料が更に(D)撥水剤を含む、請求項1~6の何れか1項に記載の方法。 The method according to any one of claims 1 to 6, wherein the coating material further contains (D) a water repellent.
- 上記塗料が熱重合開始剤を含まない、請求項1~7の何れか1項に記載の方法。 The method according to any one of claims 1 to 7, wherein the coating material does not contain a thermal polymerization initiator.
- 上記(A)活性エネルギー線硬化性樹脂が(A1)ウレタン(メタ)アクリレートを含む、請求項1~8の何れか1項に記載の方法。 The method according to any one of claims 1 to 8, wherein the (A) active energy ray-curable resin contains (A1) urethane (meth) acrylate.
- 上記(A)活性エネルギー線硬化性樹脂が(A2)(a1)多官能(メタ)アクリレートと(a2)多官能チオールとの共重合体を含む、請求項1~9の何れか1項に記載の方法。 The method according to any one of claims 1 to 9, wherein the (A) active energy ray-curable resin contains a copolymer of (A2) (a1) polyfunctional (meth) acrylate and (a2) polyfunctional thiol. the method of.
- 上記工程(3)で形成された上記フィルム基材上のオートクレーブ処理済み塗膜を、このフィルム基材以外の基材上に転写する工程を更に含む、請求項1~10の何れか1項に記載の方法。 The item according to any one of claims 1 to 10, further comprising a step of transferring the autoclaved coating film on the film substrate formed in the step (3) onto a substrate other than the film substrate. The method described.
- 三次元成形体の製造方法であって、
(P)請求項1~11の何れか1項に記載の方法により、上記フィルム基材上に適用されたBステージ塗膜、または上記フィルム基材以外の基材上に転写されたBステージ塗膜を得る工程;
(Q)上記工程(P)で得た、上記フィルム基材上に適用された上記Bステージ塗膜、または上記フィルム基材以外の基材上に転写された上記Bステージ塗膜に三次元形状を付与する工程;及び、
(R)上記工程(Q)で三次元形状を付与された上記Bステージ塗膜を完全硬化させる工程を含む上記方法。 It is a method of manufacturing a three-dimensional molded product.
(P) 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 by the method according to any one of claims 1 to 11. The process of obtaining a 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).
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JP2016221922A (en) * | 2015-06-03 | 2016-12-28 | Dic株式会社 | Film for processing, processed film, and method for producing them |
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2020
- 2020-12-18 WO PCT/JP2020/047446 patent/WO2021140874A1/en active Application Filing
- 2020-12-18 JP JP2021569807A patent/JPWO2021140874A1/ja active Pending
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JPS52152941A (en) * | 1976-06-15 | 1977-12-19 | Matsushita Electric Works Ltd | Method for forming inorganic cured coating layer |
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