TW202132439A - Manufacturing method of b-stage coat, manufacturing method of three-dimensional molded body - Google Patents

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 DEG 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

B-stage coating film, laminated film, three-dimensional molded body and their manufacturing method

The present invention relates to a B-level coating film and a manufacturing method of the B-level coating film. More specifically, the present invention relates to a Class B coating film, a laminated film, a three-dimensional molded body, and methods for manufacturing the same.

Previously, in order to impart functions such as surface hardness and abrasion resistance to molded bodies such as housings of household appliances and information electronic equipment, and automobile dashboards, acrylic resin, melamine resin, and isocyanate were often coated on the surface of the matrix of the molded body. Hardening resin paint such as resin and urethane resin to form a hardened coating film.

As a method of forming the above-mentioned hardened coating film, a method of first forming the above-mentioned substrate, using methods such as dip coating, spraying, spin coating, and pneumatic knife coating on the surface of the obtained substrate, and applying the above-mentioned hardened resin coating for hardening is widely used. method. On the other hand, the above method has the following problems: especially when the above-mentioned base has a three-dimensional shape/three-dimensional shape (for example, an overall curved shape, a shape with irregularities on the surface, etc.), there are the following various inconveniences, for example, It is difficult to apply the above-mentioned hardened resin coating on the surface of the above-mentioned substrate to make the thickness uniform; after coating, the above-mentioned hardened resin coating flows before hardening, which easily leads to uneven thickness of the hardened coating film/appearance defect; and due to the application on each substrate Lack of productivity due to paint.

Therefore, the following methods have been proposed: roll-to-roll methods such as roll coating, gravure coating, reverse coating, and rigid die coating are used to apply coatings with high productivity to form a Class B coating on the surface of the thermoplastic resin film. , After giving the obtained laminated film a predetermined shape by a method such as hot press molding, the above-mentioned Class B coating film is completely cured; the above-mentioned laminated film is inserted into the injection molding mold, and the above-mentioned laminated film is heated and softened to give the predetermined shape, After injecting the desired thermoplastic resin into the above-mentioned molding die, the above-mentioned Class B coating film is completely cured (for example, refer to Patent Documents 1 and 2). However, in these technologies, it is difficult to industrially produce a Class B coating film stably, and it is particularly difficult to stably maintain the hardening of the wet coating film to the Class B state and the hardening of the wet coating film at the B state in the industry. The balance between level states. In addition, the three-dimensional moldability (difficulty of causing defects such as cracks and whitening when imparting a three-dimensional shape) of the coating film at the B-level is insufficient. In addition, the surface hardness and abrasion resistance after the coating film is completely hardened cannot be sufficiently satisfied. [Prior Art Literature]

[Patent Literature] [Patent Document 1] Japanese Special Form No. 2012-521476 Bulletin [Patent Document 2] Japanese Patent Application Publication No. 2016-221922

The subject of the present invention is to provide a new type of B-level coating film manufacturing method. Another subject of the present invention is to provide a new class B coating film. Another subject of the present invention is to provide a Class B coating film with good three-dimensional moldability (difficulty of causing cracks, cracks, and appearance defects (for example, whitening) when imparting a three-dimensional shape) and a manufacturing method thereof. Another subject of the present invention is to provide a coating film with good three-dimensional moldability in class B, and good surface hardness, abrasion resistance, and chemical resistance after being completely cured (in class C), and a laminated film with the coating film , A molded body containing the above-mentioned coating film or the laminated film, and the manufacturing method thereof.

As a result of intensive research, the inventor found that the above-mentioned problem can be achieved by a specific method.

That is, the aspects of the present invention are as follows. [1]. A manufacturing method of Class B coating film, which includes the following steps: (1) On at least one surface of the film substrate, a wet coating film is formed using a coating material containing (A) an effective electric energy ray hardening resin and (B) a photopolymerization initiator; (2) Pre-drying the wet coating film formed in the above step (1) to form a dry coating film; and (3) High-pressure processing is performed on the above-mentioned dry coating film formed in the above-mentioned step (2). [2]. The method described in the above item [1], further comprising the following steps: after the above step (2) and before the above step (3), on the surface of the dry coating film formed in the above step (2) Stack the protective film and temporarily paste it. [3]. In the method described in [1] or [2] above, the high-pressure treatment of the above step (3) is carried out under the conditions of a pressure of 0.15 to 1 MPa and a temperature of 23 to 100°C for 1 to 60 minutes. [4]. The method described in any one of the above [1] to [3], further comprising the following step: performing an aging treatment after the above step (3). [5]. The method according to any one of the above [1] to [4], wherein the coating further contains (C) fine particles. [6]. The method according to the above item [5], wherein the component (C) microparticles include microparticles that function as an antibacterial agent or an antiviral agent. [7]. The method according to any one of the above [1] to [6], wherein the paint further contains (D) a water repellent. [8]. The method according to any one of the above [1] to [7], wherein the coating does not contain a thermal polymerization initiator. [9]. The method described in any one of the above [1] to [8], wherein the (A) effective electric energy ray hardening resin contains (A1) urethane (meth)acrylate. [10]. The method described in any one of the above [1] to [9], wherein the (A) effective electric energy ray hardening resin includes (A2) (a1) polyfunctional (meth)acrylate and (a2) Multifunctional mercaptan copolymer. [11]. The method described in any one of the above [1] to [10], further comprising the step of: transcribing the high-pressure treated coating film on the thin film substrate formed in the above step (3) To a substrate other than the film substrate. [12]. A method for manufacturing a three-dimensional molded body, which includes the following steps: (P) By the method described in any one of items [1] to [11], a B-grade coating film suitable for use on the above-mentioned film substrate or a B-grade film transcribed onto a substrate other than the above-mentioned film substrate is obtained Coating (Q) imparting a three-dimensional shape to the B-level coating film suitable for use on the film substrate or the B-level coating film transcribed on a substrate other than the film substrate obtained in the above step (P); and (R) Completely harden the above-mentioned Class B coating film given the three-dimensional shape in the above-mentioned step (Q). [Effects of the invention]

According to the manufacturing method of the present invention, a Class B coating film can be stably manufactured industrially. With the preferred manufacturing method of the present invention, it is possible to stably manufacture a Class B coating film with good three-dimensional formability in the industry. The Class B coating film of the present invention has good three-dimensional moldability. The preferred grade B coating film of the present invention has good three-dimensional formability in grade B, and has good surface hardness, abrasion resistance and chemical resistance after being completely cured (in grade C). Therefore, the surface hardness, abrasion resistance, and chemical resistance of the molded body formed by using the Class B coating film of the present invention and the laminated film of the present invention having the Class B coating film are good, and the surface appearance is also good (no cracks, cracks, and Appearance defects (for example, whitening) and other undesirable phenomena). Therefore, in order to impart functions such as surface hardness, abrasion resistance, and chemical resistance to the surface of molded objects having three-dimensional shapes/three-dimensional shapes, such as housings of household appliances and information electronic equipment, and automobile instrument panels, etc., The B-level coating film of the present invention and the laminated film of the present invention having the B-level coating film can be preferably used.

In this specification, the term "resin" is used as a term that also includes a resin mixture including two or more resins and a resin composition including components other than resin. In this specification, the term "film" and "sheet" can be used interchangeably or instead of each other. In this specification, the terms "film" and "sheet" are used for those that can be industrially wound into rolls. The term "board" is used for those that cannot be wound into rolls in the industry. In addition, in this specification, laminating a certain layer and another layer in sequence includes both directly laminating these layers and laminating one or more other layers such as an anchor coat between the layers.

In this specification, the term "above" in the numerical range is used with the meaning of a certain value or exceeding a certain value. For example, 20% or more means 20% or more than 20%. The term "below" in the numerical range is used to mean a certain value or less than a certain value. For example, 20% or less means 20% or less than 20%. Furthermore, the symbol "～" in the numerical range is used with the meaning of a certain value, exceeding a certain value and less than another certain value, or another certain value. Here, a certain other value is a value greater than a certain value. For example, 10 to 90% means 10%, more than 10% and less than 90%, or 90%. Furthermore, the upper limit and the lower limit of the numerical range are those that can be combined arbitrarily, and the embodiments of any combination can be read. For example, from the numerical range of a certain characteristic "usually 10% or more, preferably 20% or more. On the other hand, it is usually 40% or less, preferably 30% or less" and "usually 10-40%, which is more The description of "preferably 20-30%" shows that the numerical range of a certain characteristic can be read as 10-40%, 20-30%, 10-30%, or 20-40% in one embodiment.

In addition to the examples, or unless otherwise specified, all numerical values used in this specification and the scope of application rights should be understood as modified by the term "about." There is no need to limit the application of the theory of equalization of the scope of application rights. Each value should be interpreted by referring to valid figures and applying the usual rounding method.

In this specification, the term "B grade" refers to the meaning specified in JIS K6800-1985 for thermosetting resins, that is, "thermosetting resins are in a moderately hardened state. The resin in this state will soften if heated, and if it is Solvent will expand, but will not melt or dissolve completely.” It is used for the meaning of “effective electric energy ray hardening resin moderately hardened state. The resin in this state will soften if heated, if it is A certain solvent will swell when it comes in contact with it, but it will not completely melt or dissolve. "It means to use.

In this specification, the term "C-level" refers to the meaning specified in JIS K6800-1985 for any of the thermosetting resin and the effective electric energy ray curing resin, which means the final state of the curing reaction of the curing resin. The resin in this state It neither melts nor dissolves. The hardened resin in the completely hardened coating film is in this state. "It means to use.

1. The manufacturing method of Class B coating film The manufacturing method of the present invention includes the following steps: (1) On at least one surface of the film substrate, use a coating containing (A) an effective electric energy ray hardening resin and (B) a photopolymerization initiator (hereinafter, sometimes Abbreviated as "B-grade coating film formation paint") to form a wet coating film; (2) to pre-dry the wet coating film formed in the above step (1) to form a dry coating film; and (3) to perform the above step ( 2) The above-mentioned dry coating film formed in the process is subjected to high pressure treatment.

In the above step (1), on at least one surface of the film substrate, a wet coating film is formed using the above-mentioned B-level coating film forming paint. In the above step (1), usually, a wet coating film is formed on the surface of the film substrate by using the above-mentioned B-grade coating film forming paint.

The film substrate used in the above step (1) is not particularly limited, and any film can be used as the film substrate. As the film substrate used in the above step (1), the film substrate described in the following "3. Class B Coating Laminated Film" and the like can be preferably used. As the paint for forming the B-level coating film used in the above step (1), the paint described in the following "2. B-level coating film" and the like can be preferably used.

In the above step (1), the method of forming a wet coating film using the above-mentioned Class B coating film forming paint on the surface of the film substrate is not particularly limited, and a well-known winding application method can be used. As the above-mentioned winding application method, from the viewpoint of applying the coating material with higher productivity by the roll-to-roll method, for example, bar coating, roll coating, gravure coating, reversal coating, kiss reversal coating are preferred. Methods such as cloth and rigid die coating.

In the above step (2), the wet coating film formed in the above step (1) is pre-dried to form a dry coating film. By pre-drying the wet coating film as the dry coating film, in the above step (3), manufacturing problems such as coating film blistering can be suppressed. The above-mentioned pre-drying is, for example, by passing the rolled foil paper at a linear velocity of about 0.5-10 minutes, preferably 1-5 minutes, from the inlet to the outlet, and the set temperature is usually about 23-150°C. It is preferably carried out in a drying furnace at 50 to 130°C, more preferably 70 to 120°C.

Preferably, after the step (2) and before the step (3), a protective film is superimposed on the surface of the dried coating film formed in the step (2) and temporarily pasted. It can suppress manufacturing problems such as scratches on the pre-coating film (dry coating film or B-class coating film) before fully curing (changing to C-level). In addition, after three-dimensional molding, effective electric energy rays are irradiated to the coating film, and in the step of changing from B-level to C-level, manufacturing problems such as hardening defects caused by oxidative damage can be suppressed.

An example of a method of temporarily attaching the protective film on the surface of the dried coating film will be described with reference to FIG. 1. Fig. 1 is a schematic diagram showing an example of an apparatus for temporarily attaching the protective film on the surface of the dried coating film. The laminated body 1 obtained in the above step (2) (the laminated body with the above-mentioned dry coating film on one side surface of the film substrate) is placed on a rotating drum 3, so that the laminated body 1 and The surface on the opposite side of the above-mentioned dry coating film becomes the drum 3 side. In addition, the protective film 2 is placed on the surface of the above-mentioned dry coating film of the laminate 1 and is pressed by a pressure roller 4. The laminated body 5 with the protective film 2 superimposed on the surface of the above-mentioned dry coating film and temporarily pasted is separated from the drum 3 by the guide roller 6 and sent to step (3). The drum 3 can be preheated to a desired temperature. The temperature of the drum 3 can usually be room temperature (about 23°C) to about 100°C, preferably room temperature (about 23°C) to about 50°C.

As the above-mentioned protective film, one having effective electric energy ray permeability (hereinafter, sometimes referred to as "effective electric energy ray transmitting protective film") is preferable. When the B-grade coating film of the present invention is completely cured (to be C-grade), even if the protective film is not peeled off, effective electric energy rays can be irradiated, so manufacturing problems can be suppressed. In addition, the thickness of the protective film is not particularly limited. For example, it may be in the range of about 10 μm to about 600 μm, and preferably in the range of 20 μm to 250 μm.

Here, "having effective electrical energy ray transmittance" means that the effective electrical energy ray transmittance of the film is usually 70% or more, preferably 80% or more. In this specification, the effective power line transmittance is the integral area of the transmission spectrum of the effective power line at a wavelength of 200 to 600 nanometers relative to the assumption that the transmittance of the effective power line in the entire range of the wavelength 200 to 600 nanometers is 100% The ratio of the integrated area of the transmission spectrum. The above-mentioned transmission spectrum was measured using a spectrophotometer, and light was incident on the film at an incident angle of 0°. As the above-mentioned spectrophotometer, for example, a spectrophotometer "SolidSpec-3700" (trade name) manufactured by Shimadzu Corporation can be used.

Examples of the above-mentioned effective electric energy ray-transmissive protective film include, for example, polyethylene terephthalate resin film, polypropylene resin film, aromatic polycarbonate resin film, and fluororesin film.

The bonding surface of the protective film and the dried coating film may be those subjected to easy peeling treatment, may be those not subjected to easy peeling treatment, or may be subjected to easy adhesion treatment. The above-mentioned easy peeling treatment may be any known treatment method such as forming a peeling layer by silicone resin or the like, for example. The above-mentioned easy adhesion treatment may be any known treatment methods such as corona discharge treatment, plasma treatment, and anchor coating formation, for example.

As the above-mentioned protective film, the adhesive surface with the above-mentioned dry coating film is easily peeled off, typically, even if there is an embossed pattern on the adhesive surface, the shape is transferred to the above-mentioned protective film. When the coating film is dried to form an imprint pattern on the surface of the dried coating film, it is also possible to suppress peeling and remove the manufacturing problem when the protective film is removed.

As the above-mentioned protective film, by using the one that has not been subjected to easy peeling treatment on the bonding surface with the above-mentioned dried coating film, in particular, even if the above-mentioned B-grade coating film formation paint only exhibits no stickiness when the coating film is dried In the case of flexibility, it is also possible to maintain the adhesiveness of the dry coating film and the protective film at the minimum required level during the winding process. The "non-sticky" here means the difficulty of scratches and appearance defects caused by contact between the coating film and the transfer roller during the winding process.

As the above-mentioned protective film, use the one that has been subjected to easy adhesion treatment on the bonding surface of the above-mentioned dry coating film, and the one that performs easy peeling treatment on the surface of the B-grade coating film formed as the film substrate used in the above step (1) In this case, an embodiment is more practical. In this case, the B-grade coating film is usually transcribed from the film substrate used in the above step (1) to the above-mentioned protective film and used. In addition, in this case, of course, "temporary pasting" can be understood technically as "fitting, bonding".

The bonding surface of the protective film and the dried coating film may be highly smooth, satin, or embossed. By using a protective film with a highly smooth bonding surface, the fully hardened (C-level) coating film formed using the B-level coating film of the present invention becomes one with high gloss. By using a protective film with a satin-grained bonding surface, the fully hardened (C-level) coating film formed by the B-level coating film of the present invention becomes a matte surface (those with low gloss). By using the protective film on the bonding surface with the embossed pattern, the fully cured (level C) coating film formed using the B-level coating film of the present invention becomes one with the embossed pattern.

In the above step (3), the dry coating film formed in the above step (2) is subjected to high pressure treatment. Through the above-mentioned step (3), when a three-dimensional molded body is produced using the layered body with the B-level coating film of the present invention, for example, in the step of imparting a three-dimensional shape to the B-level coating film of the present invention and the step of making the B-level coating film of the present invention It is possible to suppress manufacturing problems such as coating film blistering in the process of complete curing of the coating film (to become C-level). In addition, in the embodiment using the above-mentioned protective film, by the above-mentioned step (3), the shape of the bonding surface of the above-mentioned protective film and the above-mentioned dry coating film can be transcribed to the surface of the above-mentioned dry coating film. In addition, in the embodiment using the above-mentioned protective film, by the above-mentioned step (3), even if air is trapped between the above-mentioned protective film and the above-mentioned dry coating film, the air can be exhausted and appearance defects can be prevented.

The above step (3) can be carried out according to the following steps. In a typical embodiment, first, the dry coating film formed in the above step (2) (a laminate having the dry coating film on at least one surface of the film substrate is placed on at least one surface of the film substrate; A laminated body with the above-mentioned dry coating film on at least one surface of the above-mentioned film substrate, and then the above-mentioned protective film is laminated on the surface and temporarily pasted; or a winding body of the laminated bodies; hereinafter, in this paragraph Same), and close the lid of the above-mentioned high-pressure processing device. Next, the inside of the high-pressure processing device is increased in temperature and pressure to a predetermined temperature and pressure, and after reaching the temperature and pressure, the temperature and pressure are maintained for a predetermined time (hereinafter, sometimes referred to as “holding time”). Next, after the pressure is reduced to normal pressure, preferably the temperature is also reduced to near room temperature, the lid of the high-pressure processing apparatus is opened, and the dried coating film formed in the step (2) can be taken out.

As the above-mentioned high-pressure processing device, there is no particular limitation, and any known high-pressure processing device can be used. In consideration of the characteristics of the coating used to form the Class B coating film of the present invention and the above-mentioned film substrate, the temperature, pressure, and holding time of the high-pressure treatment can be appropriately selected. In the embodiment using the above-mentioned protective film, the temperature, pressure, and holding time of the high-pressure treatment can be appropriately selected in consideration of the characteristics of the paint used to form the Class B coating film of the present invention, the above-mentioned film substrate, and the above-mentioned protective film. The pressure of the high-pressure treatment may generally be a pressure higher than normal pressure (0.1 MPa), preferably 0.15 to 1 MPa, more preferably 0.2 to 0.7 MPa, and still more preferably 0.3 to 0.6 MPa. The temperature of the high-pressure treatment may generally be room temperature (about 23°C) to 100°C, preferably 30 to 80°C, more preferably 40 to 60°C. The retention time of the high-pressure treatment can be usually 1 to 60 minutes, preferably 3 to 30 minutes, more preferably 5 to 20 minutes.

Preferably, the aging treatment is performed after the above step (3). It is possible to stabilize the characteristics of the Class B coating film of the present invention. In addition, when manufacturing a three-dimensional molded body using the layered film having the Class B coating film of the present invention, for example, in the step of imparting a three-dimensional shape to the Class B coating film of the present invention and completely hardening (changing) the Class B coating film of the present invention. In the steps of Class C), the risk of causing manufacturing problems such as coating film blistering can be further suppressed. The conditions of the above-mentioned aging treatment are not subject to special restrictions. The temperature of the above-mentioned aging treatment may usually be about 23 to 150°C, preferably the temperature is 50 to 120°C, and more preferably 70 to 100°C. The time of the above-mentioned aging treatment can be usually about 10 minutes to 10 hours, preferably 30 minutes to 4 hours, more preferably 1 to 3 hours.

There is no intention to be bound by theory, but it can be observed that the heat during the pre-drying in the above step (2), the heat when the protective film is stacked and temporarily pasted in the embodiment using the above protective film, the above step ( 3) The heat and pressure during the medium and high pressure treatment, and (in the case of implementation) the heat during the aging treatment, the coating film gradually hardens due to the heat and becomes a Class B state.

2. Grade B coating film The B-level coating film of the present invention uses the above-mentioned B-level coating film forming coating (a coating containing the above-mentioned component (A) effective electric energy ray hardening resin and the above-mentioned component (B) photopolymerization initiator), and by any method And formed. The B-grade coating film of the present invention preferably uses the above-mentioned B-grade coating film forming coating (a coating containing the above-mentioned component (A) effective electric energy ray hardening resin and the above-mentioned component (B) photopolymerization initiator), and It is formed by the manufacturing method of the present invention. Hereinafter, the above-mentioned B-grade coating film formation paint (a paint containing the above-mentioned component (A) effective electric energy ray hardening resin and the above-mentioned component (B) photopolymerization initiator) will be described.

(A) Effective power line hardening resin The above-mentioned component (A) effective electric energy ray hardening resin plays a role of forming a coating film by polymerization and hardening of effective electric energy rays such as ultraviolet rays and electron beams.

Examples of the component (A) effective electric energy ray hardening resin include, for example, urethane (meth)acrylate (or polyurethane (meth)acrylate), polyester (meth)acrylate, and polyacrylic acid. (Meth)acrylate, epoxy (meth)acrylate, polyalkylene glycol poly(meth)acrylate, and polyether (meth)acrylate, etc. containing (meth)acrylic acid Polymer or oligomer.

Examples of the component (A) effective electric energy ray hardening resin include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, hexyl (meth)acrylate, and hexyl (meth)acrylate. Base) acrylate, 2-ethylhexyl ((meth)acrylate, lauryl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, bicyclic Pentenoxyethyl (meth)acrylate, phenyl (meth)acrylate, benzene cellosolve (meth)acrylate, 2-methoxyethyl (meth)acrylate, hydroxyethyl (meth)acrylate Base) acrylate, hydroxypropyl (meth)acrylate, 2-phthaloyloxyoxyethyl hydrogen, dimethylaminoethyl (meth)acrylate, trifluoroethyl (meth) Monofunctional reactive monomers containing (meth)acrylic acid groups such as acrylate and trimethylsilyloxyethyl methacrylate; monofunctional reactive monomers such as N-vinylpyrrolidone and 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)acryloxypolyethyleneoxyphenyl)propane, and 2,2'-bis(4-(meth)acryloxypolypropyleneoxyphenyl)propane, etc. Bifunctional reactive monomers containing (meth)acrylic acid groups; trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, etc., containing (meth)acrylic acid groups The trifunctional reactive monomer; pentaerythritol tetra(meth)acrylate and other tetrafunctional reactive monomers containing (meth)acrylic acid; dipentaerythritol hexaacrylate, etc., containing (meth)acrylic hexafunctional Reactive monomers; octafunctional reactive monomers containing (meth)acrylic acid groups such as tripentaerythritol octaacrylate; and, prepolymers or oligomers with one or more of these as constituent monomers.

Examples of the component (A) effective electric energy ray hardening resin include, for example, 1,2-ethanedithiol, ethylene glycol bis(3-mercaptopropionate), and diethylene glycol bis(3-mercaptopropane). Acid ester), 1,4-bis(3-mercaptobutoxy)butane, and tetraethylene glycol bis(3-mercaptopropionate), etc., compounds having two thiol groups in one molecule; 1 ,3,5-Tris(3-mercaptobutyroxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tri(3- Mercaptobutyrate), trimethylolethane tris(3-mercaptobutyrate), and tris[(3-mercaptopropoxy)ethyl]isocyanurate, etc. have 3 sulfur in one molecule Alcohol-based compounds; pentaerythritol tetra(3-mercaptopropionate), and pentaerythritol tetra(3-mercaptobutyrate) and other compounds having 4 thiol groups in one molecule; and, dipentaerythritol hexa(3- Mercaptopropionate) and other compounds having 6 thiol groups in one molecule.

As the above-mentioned component (A) effective electric energy ray hardening resin, a mixture of one or more of these or a copolymer of two or more specific of these can be used. In addition, in this specification, (meth)acrylate means acrylate or methacrylate.

As said component (A) effective electric energy ray hardening resin, it is preferable to use what contains (A1) urethane (meth)acrylate. By this, it is possible to balance the three-dimensional moldability of the B-level coating film, and the surface hardness, abrasion resistance, and chemical resistance after being fully cured (in the C-level).

In the case of using a urethane (meth)acrylate containing the above component (A1) as the component (A) effective electric energy ray curing resin, from the viewpoint of surely obtaining the use effect of the component (A1), The blending ratio of the above-mentioned component (A1), based on the total of the above-mentioned components (A) as 100% by mass, may be usually 10% by mass or more, preferably 25% by mass or more, and more preferably 40% by mass or more. On the other hand, from the viewpoint of surface hardness, the blending ratio of the above-mentioned component (A1) can be generally 99% by mass or less, preferably 95% by mass or less, more preferably 93% by mass or less, and still more preferably 85 Mass% or less, preferably 65% by mass or less. In the case of paying special attention to the environmental resistance measured in accordance with the environmental test of test (iv) and test (v) of the following examples, the blending ratio of the above-mentioned component (A1) shall be the sum of the above-mentioned components (A) as 100 The mass% may preferably be 65-100% by mass, more preferably 75-100% by mass.

As the component (A) effective electric energy ray hardening resin, it is preferable to use (A2) a copolymer containing (a1) a polyfunctional (meth)acrylate and (a2) a polyfunctional thiol. By this, it is possible to improve the surface hardness, abrasion resistance, and chemical resistance after being completely cured (in the C grade). In addition, in the embodiment in which the Class B coating film of the present invention is formed only on one side surface of the above-mentioned film substrate, curling and warping of the laminate can be suppressed.

As the above-mentioned component (A) effective electric energy ray hardening resin, when the above-mentioned component (A2) contains (a1) a copolymer of polyfunctional (meth)acrylate and (a2) polyfunctional mercaptan, it can be reliably obtained From the viewpoint of the effect of the above-mentioned component (A2), the blending ratio of the above-mentioned component (A2), based on the total of the above-mentioned components (A) as 100% by mass, can usually be 1% by mass or more, preferably 5% by mass or more , More preferably, it is 7 mass% or more. On the other hand, from the viewpoint of crack resistance after fully hardened (in class C), the blending ratio of the above-mentioned component (A2) can usually be 90% by mass or less, preferably 75% by mass or less, more preferably It is 60% by mass or less.

As the above-mentioned component (A) effective electric energy ray hardening resin, it is more preferable to use the above-mentioned component (A1) urethane (meth)acrylate and the above-mentioned component (A2) containing (a1) polyfunctional (meth)acrylate and (A2) Copolymers of multifunctional mercaptans. It can more evenly improve the three-dimensional formability of the B-grade coating film, and the surface hardness, abrasion resistance and chemical resistance after being fully cured (in the C-grade).

As the above-mentioned component (A) effective electric energy ray hardening resin, the above-mentioned component (A1) urethane (meth)acrylate and the above-mentioned component (A2) include (a1) polyfunctional (meth)acrylate and (a2) ) In the case of multifunctional mercaptan copolymers, the balance of the three-dimensional moldability in the B-level coating film and the surface hardness after fully hardening (in the C-level), abrasion resistance and chemical resistance From the point of view, the blending ratio of the above-mentioned component (A1) and the above-mentioned component (A2) (the mass of the above-mentioned component (A1) / the mass of the above-mentioned component (A2)) can usually be 99/1 to 10/90, preferably It is 95/5 to 25/75, more preferably 93/7 to 40/60. In the case of paying particular attention to the environmental resistance measured according to the environmental test of test (iv) and test (v) of the following examples, the blending ratio may be preferably 99/1 to 65/35, more preferably 95/5～75/25, more preferably 93/7～75/25.

As the above-mentioned component (A) effective electric energy ray hardening resin, the above-mentioned component (A1) urethane (meth)acrylate and the above-mentioned component (A2) include (a1) polyfunctional (meth)acrylate and (a2) ) In the case of multifunctional mercaptan copolymers, the balance of the three-dimensional moldability in the B-level coating film and the surface hardness after fully hardening (in the C-level), abrasion resistance and chemical resistance From this point of view, the sum of the blending amount of the above-mentioned component (A1) and the blending amount of the above-mentioned component (A2), based on the sum of the above-mentioned components (A) as 100% by mass, may usually be 80% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 98-100% by mass.

(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 having more than one (meth)acrylic acid The base compound. The above-mentioned component (A1) urethane (meth)acrylate is not particularly limited. Typically, it may be a compound having two or more isocyanate groups (-N=C=O) in one molecule, or a polybasic Alcohol compounds and those that use hydroxyl-containing (meth)acrylates can be considered to contain structural units derived from these compounds.

Examples of the compound having two or more isocyanate groups in one molecule include, for example, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, and methylene bis(4 -Cyclohexyl isocyanate) and other compounds having two isocyanate groups in one molecule. As other examples of the above-mentioned compound having two or more isocyanate groups in one molecule, trimethylolpropane adduct of toluene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, and isocyanate Trimethylolpropane adduct of phorone diisocyanate, isocyanurate of toluene diisocyanate, isocyanurate of hexamethylene diisocyanate, isocyanurate of isophorone diisocyanate, and Biuret and other polyisocyanates of hexamethylene diisocyanate.

As the above-mentioned compound having two or more isocyanate groups in one molecule, one or a mixture of two or more of these can be used.

As said polyol compound, polyether polyol, polyester polyol, polycarbonate polyol, etc. are mentioned.

Examples of the above-mentioned polyether polyol include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol; polyalkylene oxides such as polyethylene oxide and polypropylene oxide; Copolymer of ethylene oxide and propylene oxide; Copolymer of ethylene oxide and tetrahydrofuran; Copolymer of dihydric phenol compound and polyoxyalkylene glycol; and Dihydric phenol and alkylene oxide with 2 to 4 carbon atoms (For example, ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,4-butylene oxide, etc.) copolymers of one or more types.

Examples of the above-mentioned polyester polyols include, for example, poly(ethylene adipate), poly(butylene adipate), poly(neopentyl adipate), poly(hexamethylene adipate), and poly(hexamethylene adipate). Diester), poly(butene azelate), poly(butene sebacate) and polycaprolactone, etc.

As said polycarbonate polyol, poly (butanediol carbonate), poly (hexanediol carbonate), poly (nonanediol carbonate), etc. are mentioned, for example.

As the above-mentioned polyol compound, one kind or a mixture of two or more kinds of these can be used.

Examples of the hydroxyl-containing (meth)acrylates include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (methyl) ) Acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 2-hydroxy-3-(meth)acryloxypropyl (meth)acrylate, etc. Hydroxyalkyl (meth)acrylate; dipropylene glycol (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate and other glycol series (meth) Acrylic esters; glycerol-based (meth)acrylates such as glycerol di(meth)acrylate; fatty acid modification-modified glycidyl (meth)acrylates such as glycidyl (meth)acrylate; containing 2-hydroxyl (Meth) acrylic acid esters of ethylene propylene phosphate, etc.; 2-(meth)acrylic acid oxyethyl-2-hydroxypropyl phthalate and other esters or ester derivatives of (meth)acrylic acid Products; pentaerythritol tri(meth)acrylate, pentaerythritol penta(meth)acrylate, ethylene oxide modified pentaerythritol tri(meth)acrylate, and ethylene oxide modified pentaerythritol penta(meth)acrylic acid Esters and other pentaerythritol-based (meth)acrylates; and, caprolactone-modified 2-hydroxyethyl (meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, and caprolactone-modified Caprolactones such as pentaerythritol penta(meth)acrylate are modified (meth)acrylates.

As the above-mentioned hydroxyl group-containing (meth)acrylate, one kind or a mixture of two or more kinds of these can be used.

From the viewpoint of three-dimensional moldability, and in the embodiment using the protective film, the adhesiveness between the dry coating film and the protective film is kept to the minimum required level during the winding process, from the viewpoint of The differential molecular weight distribution curve (hereinafter, sometimes abbreviated as "GPC curve") measured by gel permeation chromatography (hereinafter, sometimes abbreviated as "GPC") of the above component (A1) urethane (meth)acrylate ) The number-average molecular weight (Mn) in terms of polystyrene obtained can be usually 500 or more, preferably 1000 or more. On the other hand, from the viewpoint of coatability, the number average molecular weight (Mn) may be usually 30,000 or less, and preferably 20,000 or less.

From the viewpoint of three-dimensional moldability, and in the embodiment using the protective film, the adhesiveness between the dry coating film and the protective film is kept to the minimum required level during the winding process, from the viewpoint of The mass average molecular weight (Mw) in terms of polystyrene calculated from the GPC curve of the GPC measurement of the above-mentioned component (A1) urethane (meth)acrylate can be usually 1000 or more, preferably 2000 or more. On the other hand, from the viewpoint of coatability, the mass average molecular weight (Mw) may be usually 100,000 or less, and preferably 50,000 or less.

From the point of view of winding maneuverability, and the surface hardness after fully hardening (in the C grade), scratch resistance and chemical resistance, the above-mentioned component (A1) urethane (meth)acrylate The number of (meth)acrylic groups possessed per 1000 polystyrene conversion number average molecular weight (Mn) calculated from the GPC curve may be usually 2 or more, preferably 3 or more. On the other hand, from the viewpoint of three-dimensional moldability, the number of (meth)acrylic groups may be generally 20 or less, preferably 12 or less, and more preferably 10 or less. The winding maneuverability here is the same as the above, which means the difficulty of scratches or appearance defects caused by contact between the coating film and the conveyance roller during the winding process.

From the viewpoint of three-dimensional moldability, and in the embodiment using the protective film, the adhesiveness between the dry coating film and the protective film is kept to the minimum required level during the winding process, from the viewpoint of The Z average molecular weight (Mz) in terms of polystyrene obtained from the GPC curve of the GPC measurement of the above-mentioned component (A1) urethane (meth)acrylate may be usually 1500 or more, preferably 2500 or more. On the other hand, from the viewpoint of coatability, the Z average molecular weight (Mz) may be usually 150,000 or less, preferably 100,000 or less.

For GPC measurement, Tosoh Corporation’s high-performance liquid chromatography system "HLC-8320" (trade name) (including degasser, liquid feed pump, autosampler, column oven, and RI (differential Reflecting refractive index) detector system). As the GPC column, two GPC columns "KF-806L" (trade name), "KF-802" (trade name) and "KF-801" (trade name) from Shodex are used ) 1 each, 4 in total, connected to KF-806L, KF-806L, KF-802, and KF-801 in order from the upstream side. Use Wako Pure Chemical Industries, Ltd.'s tetrahydrofuran for high-performance liquid chromatography (excluding Stabilizer) as the mobile phase; it can be performed under the conditions of a flow rate of 1.0 ml/min, a column temperature of 40°C, a sample concentration of 1 mg/ml, and a sample injection volume of 100 microliters. The amount of elution in each holding capacity can be determined from the detection amount of the RI detector without the dependence of the refractive index of the measurement sample on the molecular weight. In addition, the calibration curve from holding capacity to polystyrene conversion molecular weight can be made using commercially available standard polystyrene. At this time, care should be taken to appropriately select standard polystyrene so that the measured value can be interpolated to the calibration curve. The analysis program can use "TOSOH HLC-8320GPC EcoSEC" (trade name) of Tosoh Corporation. In addition, for the theory and measurement of actual GPC, please refer to "High Performance Liquid Chromatography of Particle Size Screening Chromatography for Polymers" by Kyoritsu Publishing Co., Ltd., Author: Mori Masao, first edition, first printing December 10, 1991 "Synthetic Polymer Chromatography", OHM Co., Ltd., edited by Otani Hajime, Takarazaki Tatsuya (the upper part of "Saki" is "立"), the first edition first printed July 25, 2013 and other reference books .

Fig. 2 shows the differential molecular weight distribution curve of the following component (A1-1) used in the examples. Two sharp peaks can be confirmed in a region with a relatively low molecular weight, and the molecular weights in terms of polystyrene at the peak top positions are 280 and 610 in order from the low molecular weight side. The peak of the main component can be confirmed on the higher molecular weight side than these two peaks, and the molecular weight in terms of polystyrene at the peak top position is 2,400. In addition, the total average molecular weight (Mn) was 1,000, the mass average molecular weight (Mw) was 2,900, and the Z average molecular weight (Mz) was 4,700. In addition, the number of (meth)acrylic groups per molecule is two, so the number of (meth)acrylic groups per 1000 polystyrene conversion number average molecular weight (Mn) calculated from the GPC curve For two.

(A2) (a1) Copolymer of multifunctional (meth)acrylate and (a2) multifunctional mercaptan The above component (A2) is a copolymer of (a1) a polyfunctional (meth)acrylate and (a2) a polyfunctional mercaptan. Since the above-mentioned component (a1) and the above-mentioned component (a2) are both polyfunctional monomers, the above-mentioned component (A2) is usually a copolymer having a highly branched structure, that is, a so-called dendritic structure.

The said component (a1) polyfunctional (meth)acrylate is a (meth)acrylate which has 2 or more (meth)acryloyl groups in 1 molecule. From the viewpoint of making the structure of the above-mentioned component (A2) copolymer have a so-called dendritic structure, the number of (meth)acrylic groups in one molecule of the above-mentioned component (a1) may preferably be 3 or more , More preferably 4 or more, still more preferably 5 or more. On the other hand, from the viewpoint of crack resistance after the coating film is completely cured (in class C), it may be generally 20 or less, preferably 12 or less.

Examples of the above-mentioned component (a1) polyfunctional (meth)acrylate include, for example, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanedi Alcohol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2,2'-bis(4-(meth)acryloyloxypolyethyleneoxyphenyl)propane, and, 2,2 '-Bis(4-(meth)acryloyloxypolypropyleneoxyphenyl)propane and other bifunctional reactive monomers containing (meth)acrylic acid groups; trimethylolpropane tris(meth)acrylate, trimethylolpropane Trifunctional reactive monomers containing (meth)acrylic acid groups such as hydroxymethylethane tri(meth)acrylate and epoxidized trimethylolpropane tri(meth)acrylate; ditrimethylolpropane four (Meth) acrylate and pentaerythritol tetramethacrylate and other tetrafunctional reactive monomers containing (meth)acrylic acid; dipentaerythritol hexaacrylate and other hexafunctional reactive monomers containing (meth)acrylic acid Monomers; octafunctional reactive monomers containing (meth)acrylic acid groups such as tripentaerythritol octaacrylate; and polymers (oligomers or prepolymers) using one or more of these as constituent monomers and Those having two or more (meth)acrylic groups in one molecule. In addition, as the above-mentioned component (a1), for example, polyurethane (meth)acrylate, polyester (meth)acrylate, polyacrylic (meth)acrylate, and polyepoxy (meth)acrylate can be cited. , Prepolymers or oligomers such as polyalkylene glycol, poly(meth)acrylate, and polyether (meth)acrylate, which have two or more (meth)acrylic acid groups in one molecule . As the above-mentioned component (a1), one or a mixture of two or more of these can be used.

The said component (a2) polyfunctional thiol is a compound which has 2 or more thiol groups in 1 molecule. From the viewpoint of making the structure of the above-mentioned component (A2) copolymer have a so-called dendritic structure, the number of thiol groups in one molecule of the above-mentioned component (a2) may preferably be 3 or more, more preferably 4 or more. On the other hand, from the viewpoint of crack resistance after the coating film is completely cured (in class C), it may be generally 20 or less, preferably 12 or less. From the viewpoint of the balance between reactivity and handling, the thiol group possessed by the above-mentioned component (a2) may preferably be a secondary thiol group.

The above-mentioned component (a2) polyfunctional thiol may be a polymerizable function other than thiol groups such as (meth)acrylic groups, vinyl groups, epoxy groups, and isocyanate groups having one or more (meth)acrylic groups, vinyl groups, epoxy groups, and isocyanate groups in one molecule Base. In this specification, a compound having two or more thiol groups and two or more (meth)acryloyl groups in one molecule is classified as the aforementioned component (a2).

As the above-mentioned component (a2) polyfunctional thiol, for example, 1,2-ethanedithiol, ethylene glycol bis(3-mercaptopropionate), diethylene glycol bis(3-mercaptopropionic acid Esters), 1,4-bis(3-mercaptobutoxy)butane, and tetraethylene glycol bis(3-mercaptopropionate) and other compounds having two thiol groups in one molecule; 1, 3,5-Tris(3-mercaptobutyroxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercapto Butyrate), trimethylolethane tris(3-mercaptobutyrate), and tris[(3-mercaptopropoxy)ethyl]isocyanurate, etc. have 3 mercaptans in one molecule Group compounds; pentaerythritol tetra (3-mercaptopropionate), and pentaerythritol tetra (3-mercaptobutyrate) and other compounds with 4 thiol groups in one molecule; dipentaerythritol hexa(3-mercaptopropionic acid Esters) and other compounds having 6 thiol groups in one molecule; and polymers (oligomers or prepolymers) using one or more of these as constituent monomers and having two in one molecule Above thiol group. As the aforementioned component (a2), one or a mixture of two or more of these can be used.

To the extent that the objective of the present invention is not violated, the above-mentioned component (A2) copolymer, in addition to the above-mentioned component (a1) polyfunctional (meth)acrylate and the above-mentioned component (a2) polyfunctional mercaptan, may be a source of inclusion It is the structural unit of monomers that can be copolymerized with these. The copolymerizable monomer is usually a compound having a carbon-carbon double bond, typically a compound having an ethylene double bond.

From the viewpoint of making the structure of the above-mentioned component (A2) copolymer have a so-called dendritic structure and the viewpoint of scratch resistance, the above-mentioned component (A2) copolymer is derived from the above-mentioned component (a1) polyfunctional (meth)acrylic acid The content of the structural units of the ester (hereinafter sometimes referred to as "(a1) content") is 100 mol% based on the total of the structural units derived from polymerizable monomers, and it can usually be 50 mol% or more, preferably It is 60 mol% or more, more preferably 70 mol% or more, and still more preferably 80 mol% or more. On the other hand, from the viewpoint of making the structure of the above-mentioned component (A2) copolymer have a so-called dendritic structure, and from the viewpoint of crack resistance and handling properties after the coating film is completely cured (in the C grade), it can be Generally, it is 99 mol% or less, preferably 97 mol% or less, more preferably 95 mol% or less, and still more preferably 93 mol% or less.

From the viewpoint of making the structure of the above component (A2) have a so-called dendritic structure, and from the viewpoint of crack resistance and handling properties after the coating film is completely cured (in the C grade), the above component (A2) copolymer The content of structural units derived from the above-mentioned component (a2) polyfunctional thiol (hereinafter, sometimes referred to as "(a2) content"), the sum of structural units derived from polymerizable monomers is 100 mol%, It may be generally 1 mol% or more, preferably 3 mol% or more, more preferably 5 mol% or more, and still more preferably 7 mol% or more. On the other hand, from the viewpoint of making the structure of the above-mentioned component (A2) copolymer to have a so-called dendritic structure, and from the viewpoint of scratch resistance, it may be usually 50 mol% or less, preferably 40 mol% or less , It is more preferably 30 mol% or less, and still more preferably 20 mol% or less.

Here, the sum of the content of (a1) polyfunctional (meth)acrylate and the content of polyfunctional thiol (a2) above is 100 mol% based on the sum of structural units derived from polymerizable monomers, which may usually be 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 99 mol% or more, and 100 mol% or less. In addition, "polymerizable monomer" means the above-mentioned component (a1), the above-mentioned component (a2), and a monomer copolymerizable with these. The copolymerizable monomer is usually a compound having a carbon-carbon double bond, typically a compound having an ethylene double bond.

From the viewpoint of making the content of the (a2) polyfunctional thiol in the above preferable range, the content of sulfur in the copolymer of the component (A2) can be usually 0.1 to 12% by mass, preferably 0.5 to 10% by mass, and more Preferably it is 1-7 mass %, More preferably, it is 1.5-5 mass %.

Here, the sulfur content refers to the ashing (wet decomposition) of a sample using a microwave device and a mixed acid of nitric acid and hydrochloric acid (volume ratio 8:2) by atomic absorption analysis, and then adding an aqueous hydrochloric acid solution to filter. The value of the measurement sample obtained by constant volume of the filtrate with purified water. At this time, yttrium is used as an internal standard. Also, since sulfur is easily combined with iron and the like to precipitate, care should be taken to prevent it from occurring. Specifically, the sulfur content can be measured in the same manner as the method described in paragraphs 0035 to 0039 of JP 2018-187924 A.

From the viewpoint of the balance between scratch resistance and crack resistance after the coating film is completely cured (in class C), it is calculated from the polystyrene conversion obtained from the GPC curve measured by the GPC of the above-mentioned component (A2) copolymer The mass average molecular weight (Mw) may preferably be 5,000 or more, more preferably 8,000 or more, and still more preferably 10,000 or more. On the other hand, from the viewpoint of the coatability of the coating containing the above-mentioned component (A2) copolymer, the mass average molecular weight (Mw) may be preferably 200,000 or less, more preferably 100,000 or less, and still more preferably Below 50,000.

From the viewpoint of the balance between the scratch resistance and the crack resistance after the coating film is completely cured (in the C level), the Z average molecular weight in terms of polystyrene ( Mz), may preferably be 5,000 or more, more preferably 10,000 or more, and still more preferably 30,000 or more. On the other hand, from the viewpoint of coating properties of a coating containing the above-mentioned component (A2) copolymer, the Z average molecular weight (Mz) may preferably be 200,000 or less, more preferably 150,000 or less, and still more preferably Below 120,000.

From the viewpoint of the balance between the scratch resistance and the crack resistance after the coating film is completely cured (in class C), the polystyrene conversion number average molecular weight ( Mn), may preferably be 300 or more, more preferably 500 or more. On the other hand, from the viewpoint of the coatability of a coating containing the above-mentioned component (A2) copolymer, the number average molecular weight (Mn) may be preferably 100,000 or less, more preferably 50,000 or less, and still more preferably Below 20,000.

The GPC measurement of the copolymer of the aforementioned component (A2) can be performed in the same manner as the aforementioned method in the description of the aforementioned component (A1).

Fig. 3 shows the differential molecular weight distribution curve of the following component (A2-1) used in the examples. Three clear peaks can be confirmed in a region with a relatively low molecular weight, and the polystyrene conversion molecular weight at the peak top position is 340, 570, and 970 in order from the low molecular weight side. In addition, it can be confirmed that multiple peaks overlapping each other on the high molecular weight side are wider than these three peaks, and it can be confirmed that the polystyrene conversion molecular weight of the component on the highest molecular weight side is about 200,000. In addition, the total 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) Initiator for photopolymerization The above-mentioned component (B) photopolymerization initiator is a compound that generates active species such as free radicals by irradiation with effective electric energy rays. The above-mentioned component (B) photopolymerization initiator plays the role of polymerizing and hardening the above-mentioned component (A) effective electric energy ray hardening resin by generating active species such as free radicals, and completely hardening the coating film (to C-level) .

Examples of the photopolymerization initiator include, for example, diphenyl ketone, methyl phthalate, 4-methyl diphenyl ketone, 4,4'-bis(diethylamine) two Phenyl ketone, methyl phthalate, 4-phenyl diphenyl ketone, 4-benzyl-4'-methyl diphenyl sulfide, 3,3',4,4'-tetra (Tertiary butylperoxycarbonyl) benzophenone and 2,4,6-trimethyldiphenyl ketone and other benzophenone compounds; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and biphenyl ketone Benzoin compounds such as benzophenone ketal; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, and 2-hydroxypropoxy-1-{ Acetophenone compounds such as 4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propane-1-one, α-hydroxyalkylphenone Series compounds, and alkyl phenone series compounds such as acetophenone dimethyl acetal; anthraquinone series compounds such as methylanthraquinone, 2-ethylanthraquinone and 2-pentanthraquinone; thioxanthone (Thioxanthone), 2, Thioxanthone compounds such as 4-diethylthioxanthone and 2,4-diisopropylthioxanthone; phosphine oxide compounds; biimidazole compounds; titanocene compounds; oxime ester compounds; oximes Phenyl acetate-based compounds; hydroxyketone-based compounds; triazine-based compounds; and aminobenzoate-based compounds, etc. In addition, the above term "alkylphenone compound" is defined as a compound having an acetophenone skeleton (benzene ring-CO-alkyl) or a structure derived from the acetophenone skeleton. Among the alkylphenone-based compounds, a compound that maintains the carbonyl group C=O derived from the acetophenone skeleton corresponds to the term "acetophenone-based compound" described above. That is, "acetophenone-based compound" is a subordinate concept included in "alkylphenone-based compound".

From the viewpoint of ensuring that the coating film is completely hardened (to C-level) after three-dimensional molding, the above-mentioned component (B) photopolymerization initiator is preferably a compound that generates free radicals by irradiation with effective electric energy rays. From the viewpoint of stably maintaining the coating film in the B-stage state until three-dimensional molding, the photopolymerization initiator of the above-mentioned component (B) is preferably an alkyl phenone compound such as an acetophenone compound, and more preferably Hydroxyalkylphenone compounds (phenone compounds having a hydroxyalkyl group) such as hydroxyacetophenone compounds (acetophenone compounds having a hydroxyl group). In addition, from the viewpoint of suppressing the volatilization of the photopolymerization initiator caused by heat during three-dimensional molding, one with low volatility is preferred. Examples of the low-volatile photopolymerization initiator include, for example, 1-hydroxycyclohexyl-phenyl ketone, 2-hydroxypropoxy-1-{4-[4-(2-hydroxy-2-methyl -Propyl)-benzyl]phenyl}-2-methyl-propan-1-one. As the aforementioned component (B), one or a mixture of two or more of these can be used.

Comprehensively consider the viewpoints of curing the coating film to the B-level state, the viewpoints of maintaining the curing of the coating film in the B-level state, the viewpoints of stably maintaining the coating film in the B-level state until three-dimensional molding, and the three-dimensional molding. From the viewpoint of class C), the blending amount of the above-mentioned component (B) photopolymerization initiator can be appropriately selected. From the viewpoint of curing the coating film into a B-level state and from the viewpoint that it is completely cured (to C-level) after three-dimensional molding, the blending amount of the above-mentioned component (B) photopolymerization initiator is relative to the above-mentioned component (A). ) 100 parts by mass of the effective electric energy ray hardening resin may usually be 1 part by mass or more, preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and still more preferably 4 parts by mass or more. On the other hand, from the viewpoint of maintaining the curing of the coating film in the B-level state and the viewpoint of stably maintaining the coating film in the B-level state until three-dimensional molding, the blending amount of the above-mentioned component (B) photopolymerization initiator , Can be generally 20 parts by mass or less, preferably 15 parts by mass or less, more preferably 12 parts by mass or less, and still more preferably 10 parts by mass or less

(C) Particles The paint for forming a Class B coating film may preferably further contain fine particles of the component (C). The above-mentioned component (C) fine particles play a role in increasing the surface hardness of the molded body (coating film is C grade) obtained by using the B grade coating film of the present invention.

Examples of the fine particles of the component (C) include inorganic fine particles and organic fine particles. Examples of the above-mentioned inorganic particles include, for example, silica (silica); aluminum oxide, zirconium oxide, titanium dioxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide, antimony oxide, and metals such as cerium oxide. Oxide particles; metal fluoride particles such as magnesium fluoride and sodium fluoride; metal sulfide particles; metal nitride particles; and metal particles.

Examples of the aforementioned organic particles include resin particles such as silicone resins, styrene resins, acrylic resins, fluororesins, polycarbonate resins, vinyl resins, and cured resins of amino compounds and formaldehyde.

Among them, from the viewpoint of obtaining higher surface hardness, silica and alumina particles are preferred, and silica particles are more preferred. As commercially available products of silica fine particles, SNOWTEX (trade name) of Nissan Chemical Industry Co., Ltd., QUARTTRON (trade name) of Fuso Chemical Industry Co., Ltd., and the like can be cited.

Preferably, a silane coupling agent such as vinyl silane and amino silane; titanate coupling agent; aluminate coupling agent; Organic compounds with reactive functional groups such as unsaturated bond groups and epoxy groups; and surface treatment agents such as fatty acids and fatty acid metal salts, etc., on the surface of the above-mentioned component (C) fine particles, especially when inorganic compounds are used as the above-mentioned component (C) In the case of fine particles, the surface of the inorganic fine particles is treated. By treating the surface in this way, the dispersibility in the coating of the above-mentioned inorganic particles can be improved or the surface hardness can be improved.

In one embodiment, the component (C) fine particles may be those containing fine particles that function as an antibacterial agent or an antiviral agent (hereinafter, sometimes referred to as “functional fine particles”). As part or all of the above-mentioned component (C) particles (that is, the amount of component (C) exceeding 0% by mass to 100% by mass), by using the above-mentioned functional particles, it is possible to impart antibacterial properties and resistance to the coating film of the present invention. Viral. In the embodiment using the above-mentioned functional fine particles, the ratio of the above-mentioned functional fine particles in the above-mentioned component (C) fine particles may generally be 10% by mass or more and 100% by mass or less, preferably 30% by mass or more and 100% by mass. Below, more preferably 50% by mass or more and 100% by mass or less. Examples of the above-mentioned functional particles include, for example, copper compounds, silver compounds, tin compounds, molybdenum compounds, zinc compounds, and other inorganic particles that function as antibacterial or antiviral agents (hereinafter, sometimes referred to as "functional inorganic Particles") and so on. Examples of the above-mentioned copper compounds include, for example, cuprous halides such as cuprous chloride (CuCl), cuprous bromide (CuBr), and cuprous iodide (CuI), and cuprous thiocyanate (CuSCN). Copper compounds; copper compounds such as copper carbonate (CuCO ₃ ), copper oxide (CuO), and copper chloride (CuCl ₂ ). As said silver compound, silver halide compounds, such as silver iodide (AgI), etc. are mentioned, for example. Examples of the tin compound include tin halide compounds such as tin _{tetraiodide (SnI 4 ).} Examples of the molybdenum compound include molybdenum oxide compounds such as molybdenum oxide (MoO ₃ ), molybdenum-silver composite oxide, molybdenum-zinc composite oxide, and molybdenum-copper composite oxide. As said zinc compound, zinc oxide compounds, such as zinc oxide (ZnO), etc. are mentioned, for example. As the above-mentioned functional particles, in addition to these, for example, aluminum potassium 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/phosphate/borate glass (FCN registration number 432 of the US Food and Drug Administration), silver/zinc/magnesium/aluminum/calcium/sodium/boric acid/phosphate glass (FCN of the US Food and Drug Administration) Registration number 476), silver/magnesium/sodium/phosphate glass (FCN registration number 434 of the US Food and Drug Administration), silver/magnesium/zinc/aluminum/calcium/sodium/boric acid/phosphate glass (US Food and Drug Administration FCN registration number 1981), silver zeolite (CAS number 0130328-18-6), silver-copper zeolite (CAS number 0130328-19-7), silver-zinc zeolite (CAS number 0130328-20-0), copper-tin alloy and other functions Sexual inorganic particles.

As the above-mentioned component (C) fine particles, one or a mixture of two or more of these can be used. For example, as the above-mentioned 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. In addition, for example, as the above-mentioned component (C) fine particles, one or a mixture of two or more kinds of functional fine particles and other fine particles (organic fine particles and/or inorganic fine particles) can be used.

From the standpoint of maintaining the transparency of the coating film and the standpoint of ensuring the hardness improvement effect, the average particle size of the fine particles of the component (C) may be generally 300 nm or less, preferably 200 nm or less, and more preferably 120 nm or less. On the other hand, there is no particular limitation on the lower limit of the average particle diameter, and generally the fine particles that can be obtained are as fine as about 1 nm at most.

In this specification, in the particle size distribution curve measured by the laser diffraction/scattering method using a laser diffraction/scattering particle size analyzer, the average particle size of the particles is 50% by mass from the smaller particles. Particle size. As the above-mentioned laser diffraction/scattering particle size analyzer, for example, “MT3200II” (trade name) of Nikkiso Co., Ltd. can be used.

Since the blending amount of the above-mentioned component (C) fine particles is an optional component, it is not particularly limited. From the viewpoint of surface hardness and crack resistance after being fully cured (to C-level), the blending amount of the above-mentioned component (C) fine particles can be appropriately selected. From the viewpoint of the surface hardness after being completely cured (to C level), the blending amount of the above-mentioned component (C) can be preferably 10 parts by mass relative to 100 parts by mass of the above-mentioned component (A) effective electric energy ray hardening resin Above, more preferably 80 parts by mass or more, still more preferably 120 parts by mass or more, most preferably 150 parts by mass or more. On the other hand, from the viewpoint of crack resistance after being completely cured (to C grade), the blending amount of the fine particles of the above component (C) may be preferably 500 parts by mass or less, more preferably 400 parts by mass or less, It is still more preferably 300 parts by mass or less, and most preferably 250 parts by mass or less.

In the embodiment in which the fine particles of the component (C) include the functional fine particles, the above is appropriately determined from the viewpoint of surely showing the antibacterial and antiviral properties and the viewpoint that the total amount of the above component (C) does not exceed the above range The blending amount of functional particles. From the viewpoint of realizing antibacterial and antiviral properties, the blending amount of the functional particles can be generally 1 part by mass or more, preferably more than 100 parts by mass of the component (A) effective electric energy ray hardening resin. 4 parts by mass or more, more preferably 7 parts by mass or more, still more preferably 10 parts by mass or more. On the other hand, from the viewpoint of crack resistance after being fully cured (to C-grade), the blending amount of the above-mentioned functional fine particles may be preferably 500 parts by mass or less, more preferably 400 parts by mass or less, and still more. It is preferably 300 parts by mass or less, and most preferably 250 parts by mass or less. In other embodiments, from the above viewpoint, 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. .

(D) Water repellent The paint for forming a Class B coating film may preferably further contain the component (D) water-repellent agent. By using the above-mentioned component (D) water repellent, it is possible to improve the abrasion resistance, stain adhesion prevention and stain wiping properties of the molded body (coating film is C grade) obtained by using the B-grade coating film of the present invention.

As the above-mentioned component (D) water repellent, for example, wax water repellents such as paraffin wax, polyethylene wax, and propylene-ethylene copolymer wax; silicone oil, silicone resin, polydimethylsiloxane, alkylbenzene Silicone water repellents such as base ketones; fluorine-containing water repellents such as fluoropolyether water repellents, fluoropolyalkyl water repellents, etc.

Among these, as the component (D) water-repellent agent, from the viewpoint of rub resistance and water-repellent performance, a fluorine-containing water-repellent agent is preferred. As the above component (D) water repellent agent, it prevents the above component ( D) From the viewpoint of overflow and other issues, it is more preferable to be a fluorine-containing water-repellent and a (meth)acrylic-based water-repellent (hereinafter, sometimes referred to as "(meth)acrylic-based fluorine water-repellent) Agent"). Here, the fluorine water-repellent agent containing (meth)acryloyl groups has one or more (meth)acryloyl groups in the molecule, and has one or more, preferably three or more, more preferably five in the molecule. A compound that has more than one fluorine-carbon bond (typically, a structure in which one or more hydrogen atoms of an organic functional group such as a hydrocarbyl group are substituted with fluorine atoms) and exerts a water-repellent function.

Examples of the above-mentioned (meth)acryloyl group-containing fluorine water-repellent agent include, for example, (meth)acryloyl group-containing fluoroether water-repellent agent, and (meth)acryloyl group-containing halothane water-repellent agent Agent, fluoroalkene water repellent containing (meth)acrylic acid group, fluoropolyether water-repellent containing (meth)acrylic acid group, fluoropolyalkylene water repellent containing (meth)acrylic acid group, and (Meth) acryl-based fluoropolyene water repellent, etc.

The component (D) water repellent is more preferably a fluoropolyether water repellent containing a (meth)acryloyl group (a compound containing a (meth)acryloyl group and a fluoropolyether group in the molecule). As the above-mentioned component (D) water repellent, from the proper adjustment of the above-mentioned component (D) and the above-mentioned component (A) the chemical bond and interaction of the effective electric energy ray hardening resin, it exhibits good abrasion resistance while maintaining high transparency and From the viewpoint of water repellency and prevention of the above-mentioned component (D) from overflowing, it is most preferable to be a mixture of a fluoropolyether water repellent containing an acrylic group and a fluoropolyether water repellent containing a methacryl group.

As the said component (D) water repellent, these 1 type or the mixture of 2 or more types can be used.

Since the blending amount of the above-mentioned component (D) water repellent is an optional component, it is not particularly limited. From the viewpoint of good abrasion resistance, stain adhesion prevention, and stain wiping performance after being fully cured (to C-level), the blending amount of the above-mentioned component (D) water repellent can be appropriately determined. From the viewpoint of obtaining the effect of the above-mentioned component (D), the blending amount of the above-mentioned component (D) water repellent can be generally 0.01 parts by mass or more relative to 100 parts by mass of the above-mentioned component (A) effective electric energy ray hardening resin , Preferably it is 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and still more preferably 0.2 parts by mass or more. On the other hand, from the viewpoint of preventing the above-mentioned component (D) from overflowing, the blending amount of the above-mentioned component (D) water repellent can be generally 7 parts by mass or less, preferably 4 parts by mass or less, more preferably 2 parts by mass or less, more preferably 1 part by mass or less.

Within the scope that does not violate the purpose of the present invention, if necessary, the above-mentioned Class B coating film formation coating (coating containing the above-mentioned component (A) effective electric energy ray hardening resin and the above-mentioned component (B) photopolymerization initiator can be used ) Containing one or more compounds having two or more isocyanate groups in one molecule, antistatic agents, surfactants, leveling agents, thixotropic agents, antifouling agents, printability improvers, antioxidants, Weather resistance stabilizers, light resistance stabilizers, ultraviolet absorbers, heat stabilizers, inorganic particles, inorganic colorants, organic particles, organic colorants, and dispersants (for example, phosphate salts of high molecular weight copolymers with polyamine structures) And other amine-based dispersants) and other additives. In the case of using these additives, the blending amount is not particularly limited. For example, relative to 100 parts by mass of the effective electric energy ray hardening resin of the above component (A), from the viewpoint of obtaining the effect of the additive, it can usually be 0.001 Part by mass or more, from the viewpoint of not impairing the desired effect of the present invention, it may usually be 10 parts by mass or less.

The paint for forming the B-stage coating film may preferably be one that does not contain a thermal polymerization initiator. Since the paint for forming a Class B coating film does not contain the thermal polymerization initiator, it is easy to maintain the formed coating film in a Class B state, and it is easy to maintain the coating film in a Class B state stably until it is three-dimensionally formed. Here, "does not contain" means that the above-mentioned thermal polymerization initiator is not intentionally blended. In the case where the thermal polymerization initiator described above is intentionally blended, it is usually blended at 0.01 parts by mass or more with respect to 100 parts by mass of the effective electric energy ray hardening resin of the aforementioned component (A). Therefore, the so-called "the coating for forming a coating film of class B does not contain the thermal polymerization initiator", in other words, the content of the thermal polymerization initiator is relative to 100 parts by mass of the component (A) effective electric energy ray hardening resin 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.

The thermal polymerization initiator is a compound that generates active species such as free radicals by heating. In addition, in this specification, compounds that generate active species such as free radicals by effective electric energy ray irradiation (or light irradiation) or 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)); benzene peroxide Organic peroxides such as formazan; and benzenesulfonates such as p-toluenesulfonate cyclohexyl.

In order to dilute to a concentration that is easy to coat, the above-mentioned paint for forming a Class B coating film may contain a solvent as needed. The solvent is not particularly limited as long as it does not react with the above-mentioned component (A), the above-mentioned component (B), and other optional components, or catalyze (promote) the self-reaction (including deterioration reaction) of these components. As said solvent, 1-methoxy-2-propanol, ethyl acetate, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, acetone, etc. are mentioned, for example. As the above-mentioned solvent, one or a mixture of two or more of these can be used.

The above-mentioned paint for forming a Class B coating film can be obtained by mixing and stirring these components.

The thickness of the Class B coating film of the present invention is not particularly limited. From the viewpoints of surface hardness, abrasion resistance, and chemical resistance after being completely cured (changed to grade C), the thickness of the grade B coating film of the present invention can be generally 0.5 μm or more, preferably 1 μm or more, It is more preferably 5 μm or more, and still more preferably 10 μm or more. On the other hand, from the viewpoint of three-dimensional moldability, the thickness of the Class B coating film may be generally 100 μm or less, preferably 50 μm or less, more preferably 30 μm or less, and still more preferably 20 μm or less.

From the viewpoint of three-dimensional moldability, the tensile elongation of the Class B coating film of the present invention can be generally 10% or more, preferably 20% or more, more preferably 25% or more, and still more preferably 30% or more. Higher tensile elongation is better. Here, the tensile elongation is based on JIS K7127:1999, using two types of test specimens (width 15mm) collected so that the width direction of the B-class coating film or the laminated film with the B-class coating film coincides with the stretching direction , Total length 150mm), the value measured under the conditions of gauge length 50mm, initial distance between chucks 100mm, and test speed 10mm/min.

The surface pencil hardness of the B-grade coating film of the present invention after being completely cured (changed to C-grade) can be generally H or higher (1H or higher), preferably 3H or higher, more preferably 4H or higher, and even more preferably 5H or higher, The best is 6H or more. Higher pencil hardness is better. Here, the pencil hardness is a value measured under the conditions of a test length of 25 mm and a load of 750 g in accordance with JIS K5600-5-4:1999.

3. B-level coating laminated film The B-level coating film laminated film of the present invention includes the B-level coating film of the present invention. The B-grade coating film laminated film of the present invention has the B-grade coating film of the present invention on at least one surface of the film substrate. The B-grade coating laminated film of the present invention usually has the B-grade coating film of the present invention on one side surface of the film substrate, and the B-grade coating film forms the surface.

The B-level coating film laminate film of the present invention can use the above-mentioned B-level coating film forming coating (a coating containing the above-mentioned component (A) effective electric energy ray hardening resin and the above-mentioned component (B) photopolymerization initiator), by Optional method and manufactured by forming the B-grade coating film of the present invention on at least one surface of the above-mentioned film substrate. The B-level coating film laminate film of the present invention preferably uses the above-mentioned B-level coating film forming paint, by the B-level coating film manufacturing method of the present invention and by forming the present invention on at least one surface of the above-mentioned film substrate Manufactured by the Class B coating film.

The manufacturing method of the B-grade coating film of the present invention has been described in the item "1. B-grade coating film manufacturing method". In the item "2. B-level coating film", the above-mentioned B-level coating film formation coating (coating containing the above-mentioned component (A) effective electric energy ray hardening resin and the above-mentioned component (B) photopolymerization initiator) has been described .

Film substrate The above-mentioned film substrate is a film that becomes a substrate on which the Class B coating film of the present invention is formed on at least one surface thereof.

As the above-mentioned film base material, there is no particular limitation, and any film can be used as the film base material. Examples of the above-mentioned film include polyester resins such as aromatic polyesters and aliphatic polyesters; acrylic resins; polycarbonate resins; poly(meth)acrylimide resins; polyethylene, polypropylene, and Polyolefin resins such as poly-4-methylpentene-1; cellulose resins such as cellophane, triacetyl cellulose, diacetyl cellulose, and acetyl cellulose butyrate; polystyrene, acrylonitrile butadiene Ethylene-styrene copolymer resin (ABS resin), styrene-ethylene-butadiene-styrene copolymer, styrene-ethylene-propylene-styrene copolymer, and styrene-ethylene-ethylene-propylene-styrene copolymer Styrene resin; polyvinyl chloride resin; polyvinylidene chloride resin; fluorine resin such as polyvinylidene fluoride; others, polyvinyl alcohol, ethylene-vinyl alcohol, polyether ether ketone, nylon, polyamide, polyvinyl Resin films such as imide, polyurethane, polyetherimide, polyether, and polyether. These films include unoriented films, uniaxially oriented films, and biaxially oriented films. In addition, it includes a laminated film in which one or more of these and two or more layers are laminated. In addition, these films can be transparent or opaque, can be hidden, colored, or inherently colored.

When the film substrate is used as one of the constituent materials of the molded body When the above-mentioned film substrate is used as one of the constituent materials of the molded article of the present invention (described in the item "4. Molded article" below), the improvement of the film substrate and the B-level coating film of the present invention From the viewpoint of adhesion, the coating film forming surface of the above-mentioned film substrate may be subjected to easy adhesion treatments such as corona discharge treatment, plasma treatment, and anchor coating formation.

When the above-mentioned film substrate is used as one of the constituent materials of the molded article of the present invention, the thickness of the above-mentioned film substrate can be appropriately determined in consideration of the application of the molded article. When the above-mentioned film substrate is used as one of the materials constituting the molded article of the present invention, the thickness of the above-mentioned film substrate may be generally 20 μm or more, preferably 50 μm or more from the viewpoint of handling properties. From the viewpoint of the strength of the molded body, the thickness of the film substrate may be generally 100 μm or more, preferably 150 μm or more. On the other hand, from the viewpoint of reducing the weight of the molded body, the thickness of the above-mentioned film substrate may be generally 2000 μm or less, preferably 800 μm or less, and more preferably 600 μm or less.

When the above-mentioned film base material is used as one of the materials constituting the molded article of the present invention, it is preferable to use a material having high transparency and no color as the above-mentioned film base material. Thereby, the B-grade coating film laminated film of the present invention can be preferably used as articles that require higher transparency and colorlessness, for example, vehicle parts such as vehicle dashboards. Examples of such films include cellulose ester resins such as triacetyl cellulose; polyester resins such as polyethylene terephthalate; cyclic hydrocarbon resins such as ethylene norbornene copolymer; polymethacrylic acid Acrylic resins such as methyl ester, polyethyl methacrylate, and vinyl cyclohexane-(meth)methyl acrylate copolymer; aromatic polycarbonate resin; polypropylene, and poly 4-methylpentene-1, etc. Polyolefin resins; polyamide resins; polyarylate resins; polymeric urethane acrylate resins; and transparent resin films such as polyimide resins. These films include unoriented films, uniaxially oriented films, and biaxially oriented films. In addition, these thin films include a laminated film in which one or more of these two or more layers are laminated.

When the B-level coating film of the present invention is used for articles that require high transparency and colorlessness, the total light transmittance of the B-level coating film of the present invention is sufficient to harden the B-level coating film. After (becoming C-level), it may be usually 80% or more, preferably 85% or more, more preferably 88% or more, and still more preferably 90% or more. The higher the total light transmittance, the better. Here, the total light transmittance is a value measured in accordance with JIS K7361-1:1997. As the turbidity meter, for example, the turbidity meter "NDH2000" (trade name) of Nippon Denshoku Industries Co., Ltd. can be used.

In the case of using the B-level coating film laminate film of the present invention for articles that require higher transparency and colorlessness, and when clear transparency is desired, the haze of the B-level coating film laminate film of the present invention is After the B-grade coating film is completely cured (changed to C-grade), it can usually be 3% or less, preferably 2% or less, and more preferably 1% or less. From the viewpoint of obtaining clear transparency, the lower the haze, the better.

In the case of using the Class B coating film laminate film of the present invention for articles that require higher transparency and colorlessness, and when anti-glare is desired, the haze of the Class B coating film laminate film of the present invention is lower than After the B-grade coating film is completely cured (changed to C-grade), it also depends on the desired anti-glare level, but it can usually be 3-30%, preferably 5-25%, more preferably 7- 20%.

In the case of using the Class B coating film laminate film of the present invention for articles that require higher transparency and colorlessness, the yellow index of the Class B coating film laminate film of the present invention can be generally 5 or less, preferably 3 or less, It is more preferably 2 to -2, and still more preferably 1 to -1. Here, the yellow index is a value measured in accordance with JIS K7105:1981. As the colorimeter, for example, the colorimeter "SolidSpec-3700" (trade name) of Shimadzu Corporation can be used.

The above-mentioned transparent resin film may preferably be a transparent resin film of acrylic resin. Examples of the above-mentioned acrylic resin include, for example, (meth)acrylate (co)polymers, which mainly contain structural units derived from (meth)acrylate (usually 50 mol% or more, preferably 65 mol%). Ear% or more, more preferably 70 mol% or more) copolymers, and these modified products. In addition, (meth)acrylic acid means acrylic acid or methacrylic acid. In addition, (co)polymer means polymer or copolymer.

As the above-mentioned (meth)acrylate (co)polymer, for example, polymethyl(meth)acrylate, polyethyl(meth)acrylate, poly(meth)acrylate, poly(meth)acrylate, poly(meth)acrylate, poly(meth)acrylate, poly(meth)acrylate, poly(meth)acrylate, poly(meth)acrylate, Base) butyl acrylate, methyl (meth)acrylate-butyl (meth)acrylate copolymer, and ethyl (meth)acrylate-butyl (meth)acrylate copolymer, etc.

As a copolymer mainly containing structural units derived from the above-mentioned (meth)acrylate, for example, ethylene-methyl (meth)acrylate copolymer, styrene-methyl (meth)acrylate copolymer, Copolymerization of vinyl cyclohexane-methyl (meth)acrylate copolymer, maleic anhydride-methyl (meth)acrylate copolymer and N-substituted maleimide-methyl (meth)acrylate Things and so on.

Examples of the above-mentioned modified body include, for example, a polymer in which a lactone ring structure is introduced by an intramolecular cyclization reaction; a polymer in which glutaric anhydride is introduced by an intramolecular cyclization reaction; An imidizing agent (for example, methylamine, cyclohexylamine, ammonia, etc.) reacts to introduce a polymer having an imine structure, and the like.

Examples of the above-mentioned transparent resin film of acrylic resin include films of one kind or a mixture of two or more kinds of these. In addition, these thin films include a laminated film in which one or more of these two or more layers are laminated.

As the above-mentioned transparent resin film, the copolymerization of (meth)acrylate such as N-substituted maleimide-methyl (meth)acrylate copolymer and polymerizable monomer having an imine structure is more preferable And, by reacting an acrylic resin with an imidizing agent to introduce a polymer of imide structure (hereinafter, these may be collectively referred to as "poly(meth)acryl imide resin") transparent A thin film, a transparent multilayer film including one or more layers formed using the above-mentioned poly(meth)acrylimide resin. By using the transparent film or the transparent multilayer film as the film substrate of the Class B coating film laminate film of the present invention, the molded body formed by using the Class B coating film laminate film of the present invention can have surface hardness, abrasion resistance, and transparency. , Surface smoothness, appearance, rigidity, heat resistance and heat-resistant dimensional stability are good.

The above-mentioned poly(meth)acrylimide resin can also be defined as a thermoplastic resin having two structures, an acrylic structure and an amide structure. Due to its acrylic structure, the above-mentioned poly(meth)acrylimide resin has the characteristics of high transparency, high surface hardness, and high rigidity of acrylic resin. In addition, due to the polyimide structure, the poly(meth)acrylimide resin has the characteristics of good heat resistance and dimensional stability of polyimide. In addition, the above-mentioned poly(meth)acrylimide resin is usually improved from the shortcomings of polyimide coloring from light yellow to reddish brown.

From the viewpoint of heat resistance, the glass transition temperature of the poly(meth)acrylimide resin can be generally 110°C or higher, preferably 115°C or higher, more preferably 120°C or higher, and still more preferably 130°C Above, and more preferably above 140°C. On the other hand, from the viewpoint of three-dimensional moldability, the glass transition temperature of the poly(meth)acrylimide resin can be generally 170°C or lower, preferably 165°C or lower, more preferably 160°C or lower, and more More preferably, it is 155°C or less. Here, the glass transition temperature is, in accordance with JIS K7121-1987, from holding at 250°C for 3 minutes, cooling at 10°C/min to 20°C, holding at 20°C for 3 minutes, and raising temperature at 10°C/min to 250°C The glass transition temperature at the middle point of the curve calculation of the final heating process measured by the program. As the differential scanning calorimeter, for example, Diamond DSC of PerkinElmer Japan Co., Ltd. can be used.

The yellow index of the poly(meth)acrylimide resin may be usually 5 or less, preferably 3 or less, more preferably 2 to -2, and still more preferably 1 to -1. By using a poly(meth)acrylimide resin with a yellow index of 5 or less, it is possible to obtain a Class B coating layered film suitable for the hue of vehicle parts such as vehicle dashboards and molded products using these. Here, the yellow index is a value measured in accordance with JIS K7105:1981. As the colorimeter, for example, the colorimeter "SolidSpec-3700" (trade name) of Shimadzu Corporation can be used.

From the viewpoint of extrusion load and melt film stability during film production, the melt mass flow rate of the above poly(meth)acrylimide resin (measured under the conditions of 260°C and 98.07N in accordance with ISO1133), It may be preferably 0.1 to 20 g/10 minutes, more preferably 0.5 to 10 g/10 minutes.

As far as the purpose of the present invention is not violated, the above-mentioned poly(meth)acrylimide resin may further contain thermoplastic resins other than poly(meth)acrylimide resin; pigments, inorganic fillers, organic Fillers, resin fillers; lubricants, antioxidants, weather resistance stabilizers, heat stabilizers, mold release agents, antistatic agents, surfactants and other additives. The blending amount of these optional components is usually 10 parts by mass or less or about 0.01-10 parts by mass when the poly(meth)acrylimide resin is 100 parts by mass.

The above-mentioned transparent resin film may preferably be a transparent multilayer film in which an acrylic resin layer (α) and an aromatic polycarbonate resin layer (β) are directly laminated in the above order. The above-mentioned transparent resin film may more preferably be a transparent multilayer film in which the first acrylic resin layer (α1), the aromatic polycarbonate resin layer (β), and the second acrylic resin layer (α2) are directly laminated in the above order.

Although acrylic resins have good surface hardness, they tend to be insufficient in machinability. On the other hand, aromatic polycarbonate resins have better machinability but tend to be insufficient in surface hardness. Therefore, by using the transparent multilayer film composed of the above-mentioned layers, the shortcomings of the two can be compensated for each other. After the B-grade coating film is completely cured (C-grade), it is easy to obtain B-grade with better surface hardness and machinability. Laminated film coating.

Hereinafter, as a B-level coating film formed on the side of the α1 layer, the first acrylic resin layer (α1), the aromatic polycarbonate resin layer (β), and the second acrylic resin layer (α2) are directly laminated in the above order. The resulting transparent multilayer film will be described.

The thickness of the above-mentioned α1 layer is not particularly limited, but from the viewpoint of the surface hardness of the B-grade coating film (grade C) after being completely cured, it can be generally 20 μm or more, preferably 40 μm or more, more preferably 50 μm or more, More preferably, it is 80 μm or more.

The layer thickness of the α2 layer is not particularly limited, but from the viewpoint of curl resistance, it is preferably the same layer thickness as the α1 layer.

In addition, the so-called "same layer thickness" herein should not be interpreted as the same layer thickness in a strict physical and chemical sense. It should be interpreted as the same layer thickness within the amplitude range of the steps and quality management commonly implemented in the industry. This is because as long as it is the same layer thickness within the amplitude range of the steps and quality control generally implemented in the industry, the curl resistance of the multilayer film can be maintained well. In the case of a co-extruded polyolefin film formed by a T-die co-extrusion method, the steps and quality control are usually carried out in the range of -5～+5μm, so it should be interpreted as, for example, the layer thickness is 65μm and 75μm is the same.

The layer thickness of the above β layer is not particularly limited, but from the viewpoint of machinability, it may be generally 20 μm or more, preferably 70 μm or more.

The acrylic resin used in the above-mentioned α1 layer and the above-mentioned α2 layer has been described above.

In addition, the acrylic resin used for the α1 layer and the acrylic resin used for the α2 layer may also use different resin characteristics, for example, acrylic resins with different types, melt mass flow rates, and glass transition temperatures. From the viewpoint of the curl resistance of the hard coating laminated film, it is preferable to use the same resin characteristics. For example, using the same level and the same batch is one of the preferred embodiments.

As the aromatic polycarbonate resin used for the above β layer, for example, bisphenol A, dimethyl bisphenol A, 1,1-bis(4-hydroxyphenyl)- Polymers of aromatic dihydroxy compounds such as 3,3,5-trimethylcyclohexane and phosgene; bisphenol A, dimethyl bisphenol A, 1,1-bis(4-hydroxyl Phenyl) One or a mixture of two or more aromatic polycarbonate resins such as polymers of aromatic dihydroxy compounds such as 3,3,5-trimethylcyclohexane and carbonic acid diesters such as diphenyl carbonate.

As a preferable optional component that can be contained in the above-mentioned aromatic polycarbonate resin, a core-shell rubber can be cited. When the total of the aromatic polycarbonate resin and the core-shell rubber is taken as 100 parts by mass, 0 to 30 parts by mass (100 to 70 parts by mass of the aromatic polycarbonate resin), preferably 0 to 10 parts by mass The core-shell rubber is used in the amount of parts (100-90 parts by mass of aromatic polycarbonate resin), which can further improve the machinability and impact resistance.

Examples of the above-mentioned core-shell rubber include, for example, methacrylate-styrene/butadiene rubber graft copolymer, acrylonitrile-styrene/butadiene rubber graft copolymer, and acrylonitrile-styrene graft copolymer. /Ethylene-propylene rubber graft copolymer, acrylonitrile-styrene/acrylate graft copolymer, methacrylate/acrylate rubber graft copolymer, methacrylate-styrene/acrylate rubber graft copolymer As well as core-shell rubbers such as methacrylate-acrylonitrile/acrylate rubber graft copolymer. As the above-mentioned core-shell rubber, one or a mixture of two or more of these can be used.

In addition, as long as the purpose of the present invention is not violated, the above-mentioned aromatic polycarbonate resin may further include aromatic polycarbonate resin and thermoplastic resins other than core-shell rubber; pigments, inorganic fillers, organic fillers, Resin fillers; additives such as lubricants, antioxidants, weather resistance stabilizers, heat stabilizers, mold release agents, antistatic agents, and surfactants. The blending amount of these optional components is usually 10 parts by mass or less or about 0.01-10 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 above-mentioned transparent resin film is not particularly limited. As the above-mentioned transparent resin film, the first poly(meth)acrylimide resin layer (α1), the aromatic polycarbonate resin layer (β), and the second poly(meth)acrylimide resin layer ( α2) A preferable manufacturing method in the case of a transparent multi-layer film directly laminated in the above order can be exemplified by the method described in Japanese Patent Application Laid-Open No. 2015-083370. In addition, when forming the above-mentioned Class B coating film, in order to improve the adhesion strength with the above-mentioned Class B coating film, corona discharge treatment, plasma treatment, and anchor coating formation may be performed on one or both sides of the transparent resin film in advance. Easy bonding process.

The total light transmittance of the above-mentioned transparent resin film may usually be 85% or more, preferably 88% or more, and more preferably 90% or more. The higher the total light transmittance, the better. By using a transparent resin film with a total light transmittance of 85% or more, it is possible to obtain articles that require higher transparency, such as a Class B coating laminated film suitable for vehicle parts such as vehicle dashboards and molded products using these. Here, the total light transmittance is a value measured in accordance with JIS K7361-1:1997. As the turbidity meter, for example, the turbidity meter "NDH2000" (trade name) of Nippon Denshoku Industries Co., Ltd. can be used.

The yellow index of the above-mentioned transparent resin film may usually be 5 or less, preferably 3 or less, more preferably 2 to -2, and still more preferably 1 to -1. By using a transparent resin film with a yellow index of 5 or less, articles that require high colorlessness can be obtained, for example, a B-level coating laminated film suitable for vehicle parts such as vehicle dashboards and molded articles using these. Here, the yellow index is a value measured in accordance with JIS K7105:1981. As the colorimeter, for example, the colorimeter "SolidSpec-3700" (trade name) of Shimadzu Corporation can be used.

The retardation of the above-mentioned transparent resin film may generally be 75 nm or less, preferably 50 nm, more preferably 40 nm or less, still more preferably 30 nm or less, even more preferably 20 nm or less, and most preferably 15 nm or less. The lower the delay, the better. By using a transparent resin film with a retardation of 75nm or less, it is possible to obtain articles that require clarity and transparency, for example, a Class B coating laminated film suitable for vehicle parts such as vehicle dashboards and molded products using these. Here, the retardation is a value measured by the parallel Nikkor rotation method. As the measuring device, for example, a phase difference measuring device "KOBRA-WR" (trade name) by the parallel Nikkor rotation method of Oji Measurement Instruments Co., Ltd. can be used.

Transcribing the formed B-level coating film to other substrates for use When the B-grade coating film of the present invention formed on the surface of the above-mentioned film substrate is transcribed to other substrates (for example, films, sheets, plates, and substrates of arbitrary shapes, etc.) (that is, when the film substrate does not constitute In the case of a molded body), the coating film forming surface of the above-mentioned film substrate may be one that has undergone easy peeling treatment.

When the B-grade coating film of the present invention formed on the surface of the above-mentioned film substrate is transcribed to other substrates for use, the thickness of the above-mentioned film substrate is not particularly limited. In the case of transcribing the B-grade coating film of the present invention formed on the surface of the above-mentioned film substrate to another substrate for use, from the viewpoint of handling, the thickness of the above-mentioned film substrate may generally be 20 μm or more, preferably More than 30μm. On the other hand, in this case, from the viewpoint of economy, the thickness of the above-mentioned film substrate may be generally 100 μm or less, preferably 75 μm or less.

When the B-grade coating film of the present invention formed on the surface of the above-mentioned film substrate is transcribed to another substrate for use, the above-mentioned film substrate is preferably, for example, polyester such as polyethylene terephthalate Biaxially oriented film of resin and biaxially oriented film of polypropylene resin, etc.

4. Molded body The molded body of the present invention has a coating film (Class C) that completely hardens the Class B coating film of the present invention. The molded body of the present invention usually consists of a coating film (C level) that completely hardens the B-level coating film of the present invention to form part or all of the surface of the molded body. The molded body of the present invention can be produced by completely curing the B-level coating film (to C-level) after imparting a desired shape to the B-level coating film (and base material) of the present invention. Examples of such molded articles include, for example, films, sheets, and plates (molded articles that maintain a flat shape) having a coating film (Class C) that completely hardens the Class B coating film of the present invention; A grade B coating film or sheet is formed into a desired shape by thermoforming such as vacuum forming, pressure molding, and thermoforming, and then the B grade coating film is completely cured (to C grade); and , The film or sheet with the B-grade coating film of the present invention is inserted into the mold as the skin material, and after injecting any thermoplastic resin as the core material, the B-grade coating film is completely hardened (changed to C-grade) to obtain a composite molding体等。 Body and so on.

Taking vacuum forming as an example, for the B-grade coating film laminated film of the present invention (the coating film is B-grade), after applying vacuum forming and vacuum pressure forming and other three-dimensional molding methods to give a three-dimensional shape, the B-grade coating The method of manufacturing the molded body of the present invention by completely curing the film (becoming C-level) will be described.

Fig. 4 is a schematic diagram showing an example of a vacuum forming apparatus. First, as shown in (a) of FIG. 4, a heating device 8 such as an infrared heater is used to heat and soften the B-stage coating film laminated film 7. Then, remove the B-level coating film build-up film 7 from the heating device 8, and quickly cover the molding die 9 so that the side opposite to the B-level coating film side of the B-level coating film build-up film 7 becomes the molding die 9 side (Figure 4(b)). At this time, the molding die 9 may also be preheated. Next, depressurize the space 10 between the B-level coating film build-up film 7 and the molding die 9, so that the B-level coating film build-up film 7 is adhered to the molding die 9, and the shape of the molding die 9 is transcribed to the B-level coating film build-up. Film 7 was formed into molded body 11 (coating film was grade B) (FIG. 4( c )). Before the molded body 11 is released from the molding die 9, the molding die 9 may be cooled. Next, the molded body of the present invention can be manufactured by using any effective electric energy ray irradiation device to completely harden the B-level coating film of the molded body 11 (change to C-level).

From the viewpoint that there is no need to allow air to remain between the B-class coating film layered film 7 and the molding die 9 for sufficient adhesion, the pressure of the space 10 may be preferably 10 KPa or less, more preferably 1 Kpa or less. In addition, although the pressure in the space 10 is smaller, the adhesive force is larger, but considering that the pressure is reduced, the cost will be increased quickly, and the mechanical strength of the B-grade coating layer film 7, in fact, the lower limit of the pressure in the space 10 can be 10 ^-5 Around KPa.

From the point of view that sufficient exposure is required to completely harden the B-level coating film (to C-level), the above-mentioned effective electric energy ray exposure can be appropriately selected and determined. The irradiation dose of the above-mentioned effective electric energy rays can be usually about 10 to 10000 mJ/cm ² , preferably 200 to 2000 mJ/cm ² , more preferably 300 to 700 mJ/cm ² .

In one embodiment, the molded body of the present invention may be one having a coating film (C-level) that completely hardens the B-level coating film of the present invention and any substrate. The molded body of this embodiment, for example, can be obtained by using the above-mentioned base in place of the molding die 9 and adhering the B-level coating film laminated film 7 to the above-mentioned base, and integrating the B-level coating film to completely harden (becoming C-level). manufacture. As the above-mentioned matrix, for example, a matrix composed of wood, plywood, laminated board, wood particle board, cardboard and other wooden materials; composed of polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS Resin), polycarbonate, polyester, polyvinyl chloride, polyolefin and other resin materials; matrix composed of metal materials such as iron and aluminum; and matrix composed of mineral materials such as gypsum and calcium silicate.

Since the molded body of the present invention has preferable characteristics as described above, it can be preferably used as an article (part including an article). Examples of the above-mentioned articles include, for example, image display devices such as liquid crystal displays, plasma displays, and electroluminescence displays, and parts such as display panels, transparent conductive substrates, and casings; TVs, personal computers, and tablet computers -Type information equipment, smart phones, and parts such as their casings and display panels; furthermore, refrigerators, washing machines, cabinets, wardrobes, and panels constituting them; doors and windows of buildings, etc.; vehicles, car windows, and windshields Glass, roof windows, dashboards, etc.; head-up displays, electronic signs, and protective panels for these; showcases; solar cells, their casings, and front panels, etc. [Example]

Hereinafter, the present invention will be described with examples, but the present invention is not limited to these.

Measurement and evaluation method of physical properties (i) Three-dimensional moldability 1 After preheating the laminated film (coating film is grade B) with an infrared heater, unfold and stack the laminated film on a molding die preheated to 130°C ( Referring to Fig. 5), the side opposite to the coating film surface of the laminated film is made the above-mentioned molding die side. Figure 5(a) is a front view of the molding die. Here, the height (h) is 10mm, and the radius of curvature (R) of the surrounding curved part is 16.25mm. Figure 5(b) is a plan view of the molding die, where the outer diameter (φ) is 90mm. As described above, after waiting for 30 seconds with the laminated film unfolded and stacked on the molding die, the space between the laminated film and the molding die is reduced to a pressure of 1.0×10 ^-3 KPa, and the pressure is reduced to 1.0×10 -3 KPa. The shape of the molding die is transcribed to the above-mentioned laminated film to obtain a molded body (coating film is grade B). By using a high-pressure mercury lamp type ultraviolet irradiation device, irradiating ^{under the condition of a cumulative light amount of 600mJ/cm 2} , the B-level coating film of the molded body is completely cured (changed to C-level), and a molded body (coating film is C-level) ). If the corrected vision is 1.0, use the naked eye or a magnifying glass (10 times) to visually observe the appearance of the molded body (coating film is Grade C), and evaluate according to the following standards. In addition, when the above-mentioned laminated film has a protective film, after the B-class coating film is completely cured by ultraviolet irradiation, the protective film is peeled off and used for visual observation. A: Even with a magnifying glass, no cracks, cracks, and appearance defects were seen. B: Even if a magnifying glass is used, no cracks and cracks are seen. However, when observed through light at close range, a slight turbidity can be seen. C: If a magnifying glass is used, slight cracks and cracks can be seen in the surrounding curve. D: Cracks and cracks are also visible with the naked eye.

(Ii) Three-dimensional formability 2 As the molding die, 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 diameter (φ) of 90 mm were used. Except for this, the molding was performed in the same manner as in the above test (i) Three-dimensional moldability 1. Manufacturing, observation and evaluation.

(Iii) Tensile elongation (tensile elongation of laminated film with B-grade coating film) According to JIS K7127:1999, use two types of test specimens (width 15mm, total length 150mm) collected from a laminate film with a Class B coating film so that the width direction of the laminate film coincides with the stretching direction, at a gauge length of 50mm , The initial distance between the chucks is 100mm and the test speed is 10mm/min. The tensile elongation is measured. In the tensile test, the test piece was visually observed, and the instantaneous elongation at which cracks occurred in the coating film of the test piece was taken as the tensile elongation of the laminated film. In addition, technically, it can be considered that the value of the tensile elongation in the test (iii) is equivalent to the tensile elongation of the Class B coating film possessed by the laminated film. In addition, when the laminated film has a protective film, after collecting the test piece, the protective film is peeled off and used for a test.

(Iv) Environmental test 1 The molded body (coating film is Grade C) obtained in the above test (ii) was treated in a gear oven at a temperature of 90°C for 4 hours, and those with a corrected vision of 1.0 were visually observed with the naked eye or a magnifying glass (10 times). (The coating film is Grade C) The appearance is evaluated according to the following standards. In addition, when the above-mentioned laminated film has a protective film, the protective film is peeled off after the gear oven treatment and used for visual observation. A: Even with a magnifying glass, no cracks, cracks, and appearance defects were seen. B: Even if a magnifying glass is used, no cracks and cracks are seen. However, when observed through light at close range, a slight turbidity can be seen. C: If a magnifying glass is used, slight cracks and cracks can be seen in the surrounding curve. D: Cracks and cracks are also visible with the naked eye.

(V) Environmental test 2 Except that the temperature of the gear oven was changed to 130°C, the processing, observation, and evaluation of the molded body were performed in the same manner as in the test (iv) Environmental Test 1 above.

In the following (vi) pencil hardness, (vii) total light transmittance, (viii) haze, (ix) chemical resistance, (x) checkerboard test, (xi) checkerboard test after wet heat treatment, and (xii) ) In the abrasion resistance test, a high-pressure mercury lamp type ultraviolet irradiation device is used to irradiate the B-level coating film of the laminated film with the B-level coating film under the condition of a ^{cumulative light amount of 600mJ/cm 2 and it will be completely cured (become C-level)} The person is used as a sample. For those with a protective film, peel off the protective film and use it for testing.

(Vi) Pencil hardness According to JIS K 5600-5-4:1999, under the conditions of a test length of 25mm and a load of 750g, the pencil hardness of the coating film surface of the above sample was measured using the pencil "UNI" (trade name) of Mitsubishi Pencil Co., Ltd. Regarding whether scratches are generated, determine by visually observing the surface of the sample under the fluorescent lamp at a distance of 50 cm from the fluorescent lamp.

(Vii) Total light transmittance In accordance with JIS K7361-1:1997, the total light transmittance of the above-mentioned sample was measured using the turbidity meter "NDH2000" (trade name) of Nippon Denshoku Industries Co., Ltd.

(Viii) Haze In accordance with JIS K7136: 2000, the haze of the above-mentioned sample was measured with a turbidity meter "NDH2000" (trade name) of Nippon Denshoku Industries Co., Ltd.

(Ix) Chemical resistance 20 ml of "Neutrogena Ultra Sheer Dry-Touch Sunblock" (trade name) of Johnson & Johnson's sunscreen and 10 drops of "Pilot ink red" (trade name) of Pilot Co., Ltd. were mixed to prepare a test liquid. A test piece with a size of 100mm×100mm is collected from the above sample, and a paper wiper ("Kimwipe" (product of Nippon Paper Crecia Co., Ltd.) ("Kimwipe" (product Name)), use a dropper to evenly drop 10 drops of the test solution on the paper cloth. After the dripping, use tweezers to remove the air bubbles between the paper wipe and the test piece. After the paper wipe and the test piece are adhered, the paper wipes are stored in an environment with a temperature of 23° C. and a relative humidity of 50%. The storage was carried out for 72 hours, and the operation of adding 10 drops of the above test liquid and removing air bubbles to make it sticky was repeated every 24 hours of storage time. After a predetermined period of time, remove the paper cloth containing the test liquid on the test piece, wipe the test piece with a paper cloth soaked in water, and dry it with a dry paper cloth to remove the test liquid adhering to the surface of the test piece. Then, those with a corrected visual acuity of 1.0 visually observe the above test piece with the naked eye or a magnifying glass (10 times), and evaluate it according to the following criteria. A: Even if a magnifying glass is used, no cracks are seen. There was no color difference in the parts where the coating film surface of the above-mentioned laminated film was in contact with the above-mentioned test liquid and the parts not in contact with each other. B: Even if a magnifying glass is used, no cracks are seen. However, the color difference was seen in the parts where the coating film surface of the above-mentioned laminated film was in contact with the above-mentioned test liquid and the parts not in contact with each other. (Compared with the untouched part, the touched part is slightly red.) C: No cracks were seen with naked eyes. But if you use a magnifying glass, cracks are visible. D: Cracks are visible even with naked eyes.

(X) Checkerboard test (coating film adhesion) According to JIS K5600-5-6:1999, after adding 100 grids (1 grid = 1mm×1mm) of the cut marks of a checkerboard from the side of the coating film of the sample, stick the test tape to the checkerboard and comb it with your fingers and peel it off . The evaluation standard complies with Table 1 of the above-mentioned standard of JIS. Category 0: The cutting edge is completely flat, and all grids are not peeled off. Classification 1: The coating film in the cutting intersection has a small peeling. The area affected by the cross cut part does not significantly exceed 5%. Category 2: The coating film peels off along the cutting edge and/or at the intersection. The affected area of the cross-cut part obviously exceeds 5% but not more than 15%. Classification 3: The coating film is peeled off partly or as a whole along the cutting edge and/or partly or wholly peeled off in each part of the grid. The affected area of the cross-cut part obviously exceeds 15% but not more than 35%. Classification 4: The coating film is peeled off partially or entirely along the cutting edge and/or partially or entirely peeled off in multiple places. The affected area of the cross-cut part obviously exceeds 35% but not more than 65%. Category 5: The case where the degree of peeling exceeds Category 4 is this category.

(Xi) Checkerboard test after wet heat treatment (damp heat test) After the above sample was subjected to 72 hours of wet heat treatment at a temperature of 85°C and a relative humidity of 85%, the same test as the above test (x) checkerboard test was carried out to evaluate the adhesion.

(Xii) Scratch resistance (steel wool resistance) According to the size of 150mm in length and 50mm in width, the test piece collected so that the machine direction of the laminated film becomes the longitudinal direction of the test piece is placed on the Gakushin Tester (Friction Tester Type 2) of JIS L0849:2013 to make the coating The film becomes the surface. Then, after installing #0000 steel wool on the friction terminal of the Gakushin type testing machine, load a 250g load, and wipe the coating surface of the test piece 5 times at a moving speed of 300mm/min and a moving distance of 30mm at the friction terminal. Then visually observe the friction part. In the case of no scratches, repeat the operation of visually observing the rubbed part after 5 reciprocating wiping, and evaluate according to the following standards. A: No scratches were seen after 15 reciprocations. B: No scratches were seen after 10 reciprocations, but scratches were seen after 15 reciprocations. C: No scratches were seen after 5 reciprocations, but scratches were seen after 10 reciprocations. D: Scratches are visible after reciprocating 5 times.

Raw materials used (A) Effective power line hardening resin (A1) Urethane (meth)acrylate (A1-1) Multifunctional urethane (meth)acrylate "EBECRYL284" (trade name) of DAICEL-ALLNEX Corporation. The solid content is 100% by mass, the number of functional groups is 2, the number average molecular weight is 1,000, the mass average molecular weight is 2,900, and the Z average molecular weight is 4,700. (A1-2) Multifunctional urethane (meth)acrylate "EBECRYL4101" (trade name) of DAICEL-ALLNEX Corporation. The solid content is 100% by mass, the number of functional groups is 3, the number average molecular weight is 1,100, the mass average molecular weight is 2,800, and the Z average molecular weight is 4,900. (A1-3) "ART RESIN-952" (trade name), a diluent of multifunctional urethane (meth)acrylate produced by Nekami Kogyo Co., Ltd. The solid content is 60% by mass, the number of functional groups is 10, the number average molecular weight is 2500, the mass average molecular weight is 9100, and the Z average molecular weight is 23,000. (A1-4) "ART RESIN-954" (trade name), a diluent of multifunctional urethane (meth)acrylate produced by Nejo Industrial Co., Ltd. The solid content is 60% by mass, the number of functional groups is 6, the number average molecular weight is 2000, the mass average molecular weight is 4800, and the Z average molecular weight is 9600.

(A2) (a1) Copolymer of multifunctional (meth)acrylate and (a2) multifunctional mercaptan (A2-1) "SIRIUS-501" (trade name) of Osaka Organic Chemical Industry Co., Ltd. A diluent of the so-called dendritic structure copolymer of dipentaerythritol hexaacrylate and 4-functional mercaptan. The solid content is 50% by mass, the sulfur content is 2.2% by mass, the mass average molecular weight is 12,000, the number average molecular weight is 940, and the Z average molecular weight is 73,000.

(B) Initiator for photopolymerization (B-1) Acetophenone photopolymerization initiator from IGM Resins (2-hydroxypropoxy-1-{4-[4-(2-hydroxy-2-methyl-propanol)-benzyl ]Phenyl}-2-methyl-propan-1-one) "Omnirad127" (trade name). (B-2) Acetophenone photopolymerization initiator (1-hydroxycyclohexyl-phenone) "Omnirad 184" (trade name) from IGM Resins.

(C) Particles (C-1) Nissan Chemical Co., Ltd.'s propylene glycol monomethyl ether dispersion of silica particles "PGM-AC-2140Y" (trade name). The solid content is 42% by mass and the average particle size is 15nm. (C-2) NBC Meshtec's antiviral agent (ethanol suspension of cuprous iodide particles), the average particle size of cuprous iodide particles (in the particle size distribution measured by the laser diffraction/scattering method) In the curve, the particle size from the smaller particle is 50% by mass) 120nm and the solid content is 11% by mass.

(D) Water repellent (D-1) Shin-Etsu Chemical Industry Co., Ltd.'s diluent "KY-1203" (trade name) of fluoropolyether water repellent containing acrylic groups. The solid content is 20% by mass. (D-2) The fluoroalkane water repellent containing acrylic group (2-(perfluorobutyl) ethyl acrylate) "CHEMINOXFAAC-4" (trade name) of Unimatec Co., Ltd. The solid content is 100% by mass.

(E) Other ingredients (E-1) Amine-based dispersant "DISPERBY K-145" (trade name) of BYK Japan Co., Ltd. Phosphate salt of high molecular weight copolymer with polyamine structure. The amine value is 71mgKOH/g. The solid content is 100% by mass.

(H) Class B coating film formation paint (H-1) Mix and stir 50 parts by mass of the above-mentioned component (A1-1), 100 parts by mass of the above-mentioned component (A2-1) (50 parts by mass in terms of solid content), 5 parts by mass of the above-mentioned component (B-1), and the above-mentioned component (C-1) 555 parts by mass (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 isobutyl ketone (described as "MIBK" in the table) 233 parts by mass to obtain a paint for forming a Class B coating film. In addition, the table describes all solid content conversion values except for solvents.

(H-2～H-11) As shown in any one of Tables 1 to 3, except for changing the blending, the paint was obtained in the same manner as in the above (H-1). In addition, the table describes all solid content conversion values except for solvents.

(P) Transparent resin film (P-1) Use a co-extrusion T-die with two types of three-layer multi-manifolds, and the first mirror roll (roller with the molten film sent to the next conveying roll) and the second mirror roll to mold the molten film The device of the stretch winding machine of the mechanism, as the two outer layers (α1 layer and α2 layer) of the two types of three-layer multilayer resin film ), as the intermediate layer (β layer), the aromatic polycarbonate "CALIBER301-4" (trade name) of Sumika Styron Polycarbonate Co., Ltd. was continuously co-extruded from the co-extrusion T-die to make the α1 layer become the first mirror surface On the roll side, it is fed between the rotating first mirror roll and the second mirror roll, and is molded to obtain a total thickness of 170μm, the layer thickness of the α1 layer is 50μm, the layer thickness of the β layer is 70μm, and the layer thickness of the α2 layer is 50μm. Resin film. At this time, the setting conditions are 300°C set temperature of the T-shaped mold, 130°C set temperature of the first mirror roll, 120°C set temperature of the second mirror roll, and 9.5 m/min of pulling speed.

(Q) Protective film (Q-1) Teijin Co., Ltd.'s aromatic polycarbonate resin film "PanLightFilm PC-2151" (trade name), with a thickness of 125 μm. (Q-2) The use of a stretch-winding mechanism including a single-layer T-die and a mechanism that clamps the molten film extruded from the single-layer T-die with the first cooling roll (mirror metal roller) and nip rollers (silicon rubber roller) The film forming device of the wire machine, and uses the copolymerized polyethylene terephthalate resin "PIFG5" (trade name) of BELL PET Co., Ltd., and the set temperature of the above T-shaped mold is 250 ℃, and the set temperature of the first cooling roll is 50. A resin film with a thickness of 75 μm was obtained under the conditions of ℃ and a drawing speed of 10.8 m/min. The surface (high-gloss surface) on the side of the first cooling roll of the resin film was used as the bonding surface with the coating film.

example 1 (1) Perform corona discharge treatment on both sides of the above (P-1). The wetness index of both sides is 64mN/m. (2) Then, use a steel die coating device to coat the side surface of the α1 layer of the above (P-1) to make the thickness of the above (H-1) completely hardened (become C grade), and A wet coating film is formed. (3) Next, the wet coating film is pre-dried through a drying furnace set to 90° C. in the furnace at a linear speed with a passage time of 2 minutes from the entrance to the exit to obtain a dry coating film. (4) Next, using the laminating device shown in Fig. 1, the laminate 1 with the dry coating film on the side surface of the α1 layer of (P-1) is placed on the rotating drum 3, and the laminate The opposite side of the above-mentioned dry coating film of the body 1 becomes the drum 3 side. At the same time, the protective film 2 of (Q-1) is stacked on the dry coating surface of the laminate 1 so that the protective film 2 of (Q-1) is on the side of the first cooling roll (high gloss The surface) becomes the side of the dry coating film, which is crimped by the pressure roller 4, and then detached from the drum 3 by the guide roller 6 to obtain the layer (Q -1) The protective film 2 and the laminated body 5 temporarily pasted. At this time, the temperature of the drum 3 is room temperature (23°C). (5) Next, use the high-pressure steam sterilization "YKP-500 type" (trade name) of Kurihara Manufacturing Co., Ltd., and let stand in the high-pressure steam sterilization with the above-mentioned (P-1), the above-mentioned dry coating film and the above-mentioned (Q- 1) After the laminated body in the order of 1), perform autoclave sterilization under the conditions of a temperature of 50°C, a pressure of 0.5 MPa, and a holding time of 10 minutes. (6) Next, perform an aging treatment at a temperature of 80°C for 2 hours to form a B-level coating film, and obtain a layered film having a B-level coating film on the surface of the α1 layer side of the above (P-1). (7) Perform the above tests (i) to (xii). The results are shown in Table 1.

Examples 2～10 As the coating material for forming a Class B coating film, the coating material shown in Table 1 or Table 2 was used instead of the above (H-1). In the same manner as in Example 1, a laminated film having a Class B coating film was obtained. Carry out the above tests (i) to (xii). The results are shown in Table 1 or Table 2.

Example 11 As a paint for forming a B-grade coating film, the above (H-11) was used instead of the above (H-1), and the above (Q-2) was used as a protective film instead of the above (Q-1), except that the same as Example 1 A build-up film with a B-level coating film is obtained. Carry out the above tests (i) to (xii). The results are shown in Table 2.

Example 12 When forming the wet coating film, coating was performed so that the thickness after being completely cured (to be C-level) was 13 μm, and except for this, a laminated film having a B-level coating film was obtained in the same manner as in Example 1. Carry out the above tests (i) to (xii). The results are shown in Table 3.

Example 13 Except that the pre-drying conditions were changed to the conditions shown in Table 1, the same as in Example 1 was carried out to obtain a laminated film having a Class B coating film. Carry out the above tests (i) to (xii). The results are shown in Table 3.

Examples 14-17 Except that the conditions of the high-pressure steam sterilization treatment were changed to the conditions shown in Table 1, the same as in Example 1 was carried out to obtain a laminated film having a Class B coating film. Carry out the above tests (i) to (xii). The results are shown in Table 3.

Example 18 Except for omitting the high-pressure steam sterilization treatment, a laminated film having a B-grade coating film was obtained in the same manner as in Example 1. The above test (i) was performed, and many appearance defects due to blistering of the coating film were observed in the obtained molded body. Therefore, experiments (ii) to (xii) are omitted.

[Table 1] example 1 Example 2 Example 3 Example 4 Example 4-2 Example 4-3 Example 5 coating H-1 H-2 H-3 H-4 H-4-2 H-4-3 H-5 Coating blending (parts by mass) A1-1 50 50 70 80 80 80 90 A1-2 - - - - - - - A1-3 - - - - - - - A1-4 - - - - - - - A2-1 50 50 30 20 20 20 10 B-1 5 10 5 5 5 - 5 B-2 - - - - - 5 - C-1 233 233 233 233 - 233 233 C-2 - - - - 11 - - D-1 0.25 0.25 0.25 0.25 0.25 0.25 0.25 D-2 - - - - - - - E-1 - - - - 5 - - MIBK 233 233 233 233 100 233 233 Film substrate P-1 P-1 P-1 P-1 P-1 P-1 P-1 Protective film Q-1 Q-1 Q-1 Q-1 Q-1 Q-1 Q-1 Grade C coating film thickness μm 18 18 18 18 18 18 18 Manufacturing conditions Pre-drying temperature ℃ 90 90 90 90 90 90 90 Pre-drying time min 2 2 2 2 2 2 2 High pressure steam sterilization temperature ℃ 50 50 50 50 50 50 50 Same as above pressure MPa 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Same as above holding time min 10 10 10 10 10 10 10 Aging temperature °C 80 80 80 80 80 80 80 Aging time hr 2 2 2 2 2 2 2 evaluation result Three-dimensional formability 1 A A A A A A A Three-dimensional formability 2 A A A A A A A Tensile elongation% 30 30 35 35 35 35 40 Environmental test 1 (90℃) A A A A A A A Environmental test 2 (130℃) D D C A A A A Pencil hardness 6H 6H 5H 5H 2H 5H 4H Total light transmittance% 91.4 91.4 91.4 91.4 84.4 91.1 91.4 Haze% 0.4 0.4 0.4 0.4 7.8 0.4 0.4 Chemical resistance A A A A A A A Checkerboard test Category 0 Category 0 Category 0 Category 0 Category 0 Category 0 Category 0 Damp heat test Category 0 Category 0 Category 0 Category 0 Category 0 Category 0 Category 0 Scratch resistance A A B B C B C

[Table 2] Example 5-2 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 coating H-5-2 H-6 H-7 H-8 H-9 H-10 H-11 Coating blending (parts by mass) A1-1 100 - - - 50 - 50 A1-2 - 50 - - - 90 - A1-3 - - 50 - - - - A1-4 - - - 50 - - - A2-1 - 50 50 50 50 10 50 B-1 5 5 5 5 5 5 5 B-2 - - - - - - - C-1 233 233 233 233 233 135 100 C-2 - - - - - - - D-1 0.25 0.25 0.25 0.25 - 0.25 0.25 D-2 - - - - 0.25 - - E-1 - - - - - - - MIBK 233 233 233 233 233 160 145 Film substrate P-1 P-1 P-1 P-1 P-1 P-1 P-1 Protective film Q-1 Q-1 Q-1 Q-1 Q-1 Q-1 Q-2 Grade C coating film thickness μm 18 18 18 18 18 18 18 Manufacturing conditions Pre-drying temperature ℃ 90 90 90 90 90 90 90 Pre-drying time min 2 2 2 2 2 2 2 High pressure steam sterilization temperature ℃ 50 50 50 50 50 50 50 Same as above pressure MPa 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Same as above holding time min 10 10 10 10 10 10 10 Aging temperature °C 80 80 80 80 80 80 80 Aging time hr 2 2 2 2 2 2 2 evaluation result Three-dimensional formability 1 A A A A A A A Three-dimensional formability 2 A A B A A A A Tensile elongation% 50 30 25 30 30 30 30 Environmental test 1 (90℃) A A A A A A A Environmental test 2 (130℃) A D D D D A A Pencil hardness 2H 6H 6H 6H 6H 3H 3H Total light transmittance% 91.5 91.4 91.4 91.4 91.4 91.4 91.4 Haze% 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Chemical resistance A A A A A A A Checkerboard test Category 0 Category 0 Category 0 Category 0 Category 0 Category 0 Category 0 Damp heat test Category 0 Category 0 Category 0 Category 0 Category 0 Category 0 Category 0 Scratch resistance C A A A A C C

[table 3] Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 coating H-1 H-1 H-1 H-1 H-1 H-1 Coating blending (parts by mass) A1-1 50 50 50 50 50 50 A1-2 - - - - - - A1-3 - - - - - - A1-4 - - - - - - A2-1 50 50 50 50 50 50 B-1 5 5 5 5 5 5 B-2 - - - - - - C-1 233 233 233 233 233 233 C-2 - - - - - - D-1 0.25 0.25 0.25 0.25 0.25 0.25 D-2 - - - - - - E-1 - - - - - - MIBK 233 233 233 233 233 233 Film substrate P-1 P-1 P-1 P-1 P-1 P-1 Protective film Q-1 Q-1 Q-1 Q-1 Q-1 Q-1 Grade C coating film thickness μm 13 18 18 18 18 18 Manufacturing conditions Pre-drying temperature ℃ 90 120 90 90 90 90 Pre-drying time min 2 1 2 2 2 2 High pressure steam sterilization temperature ℃ 50 50 30 70 50 50 Same as above pressure MPa 0.5 0.5 0.5 0.5 0.5 0.3 Same as above holding time min 10 10 10 10 5 10 Aging temperature °C 80 80 80 80 80 80 Aging time hr 2 2 2 2 2 2 evaluation result Three-dimensional formability 1 A A A A A A Three-dimensional formability 2 A A A A A A Tensile elongation% 30 30 30 30 30 30 Environmental test 1 (90℃) A A A A A A Environmental test 2 (130℃) D D D D D D Pencil hardness 6H 6H 6H 6H 6H 6H Total light transmittance% 91.5 91.4 91.4 91.4 91.4 91.4 Haze% 0.4 0.4 0.4 0.4 0.4 0.4 Chemical resistance A A A A A A Checkerboard test Category 0 Category 0 Category 0 Category 0 Category 0 Category 0 Damp heat test Category 0 Category 0 Category 0 Category 0 Category 0 Category 0 Scratch resistance A A A A A A

According to the manufacturing method of the present invention, a Class B coating film can be stably manufactured industrially. With the preferred manufacturing method of the present invention, a Class B coating film with good three-dimensional formability can be manufactured stably in industry. The preferred grade B coating film of the present invention has good three-dimensional moldability in grade B, and after fully hardened (in grade C) heat resistance, surface hardness, transparency, chemical resistance, coating film adhesion, and coating after damp heat test The film has good adhesion and scratch resistance. Therefore, in order to impart functions such as surface hardness, abrasion resistance, and chemical resistance to the surface of molded objects having three-dimensional shapes/three-dimensional shapes, such as housings of household appliances and information electronic equipment, and automobile dashboards, etc., The B-grade coating film of the present invention can be preferably used.

Examples of embodiments of the Class B coating film of the present invention are summarized as follows. [1]. A grade B coating film, It is formed by a coating containing (A) an effective electric energy line hardening resin and (B) a photopolymerization initiator; The tensile elongation of the above-mentioned Class B coating film is more than 10%. [2]. The Class B coating film described in [1], wherein the coating further comprises (C) fine particles with an average particle diameter of 1 to 300 nm. [3]. The Class B coating film described in [1] or [2], wherein the coating further contains (D) a water repellent. [4]. The Class B coating film described in any one of [1] to [3], wherein the coating does not contain a thermal polymerization initiator. [5]. In the Class B coating film described in any one of [1] to [4], the (A) effective electric energy ray hardening resin contains (A1) urethane (meth)acrylate. [6]. For the Class B coating film described in any one of [1] to [5], the above (A) effective electric energy ray hardening resin contains (A2) (a1) multifunctional (meth)acrylate and ( a2) Copolymer of multifunctional mercaptan.

1: A laminate with a dry coating film on one side of the film substrate 2: Protective film 3: turn bucket 4: pressure roller 5: Laminated body in which the protective film 2 is stacked on the dry coating film surface of the laminated body 1 and temporarily pasted 6: Guide roller 7: B-level coating laminated film 8: heating device 9: Forming mold 10: The space between the B-level coating film laminated film and the molding die 11: Molded body

Fig. 1 is a schematic diagram showing an example of a device for temporarily attaching a protective film on the surface of a dry coating film. Figure 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 schematic diagram illustrating vacuum forming. Fig. 5 is a front view (a) and a plan view (b) of the molding die used in the embodiment.

Claims (12)

A method for manufacturing Class B coating film, which is characterized in that it comprises the following steps: (1) On at least one surface of the film substrate, a wet coating film is formed using a coating material containing (A) an effective electric energy ray hardening resin and (B) a photopolymerization initiator; (2) Pre-drying the wet coating film formed in the above step (1) to form a dry coating film; and (3) Perform high-pressure steam sterilization on the dry coating film formed in the above step (2). The method according to claim 1, which further comprises, after the above step (2) and before the above step (3), stacking a protective film on the surface of the dried coating film formed in the above step (2) and temporarily sticking it的步。 The steps. The method according to claim 1 or 2, wherein the high-pressure steam sterilization treatment in the above step (3) is performed under the conditions of a pressure of 0.15 to 1 MPa and a temperature of 23 to 100°C for a period of 1 to 60 minutes. The method according to any one of claims 1 to 3, which further comprises a step of performing an aging treatment after the above step (3). The method according to any one of claims 1 to 4, wherein the paint further contains (C) fine particles. The method according to claim 5, wherein the fine particles of the component (C) include fine particles that function as an antibacterial agent or an antiviral agent. The method according to any one of claims 1 to 6, wherein the paint further contains (D) a water repellent. The method according to any one of claims 1 to 7, wherein the coating does not contain a thermal polymerization initiator. The method according to any one of claims 1 to 8, wherein the (A) effective electric energy ray hardening resin comprises (A1) urethane (meth)acrylate. The method according to any one of claims 1 to 9, wherein the above-mentioned (A) effective electric energy ray hardening resin comprises (A2) (a1) copolymerization of (a2) polyfunctional (meth)acrylate and (a2) polyfunctional mercaptan Things. The method according to any one of claims 1 to 10, which further comprises the following step: transcribing the high-pressure steam sterilized coating film on the film substrate formed in the above step (3) to the film substrate Other than the substrate. A method for manufacturing a three-dimensional molded body, which is characterized in that it comprises the following steps: (P) By the method described in any one of claims 1 to 11, obtain a B-grade coating film suitable for the above-mentioned film substrate or a B-grade coating film transcribed onto a substrate other than the above-mentioned film substrate; (Q) imparting a three-dimensional shape to the B-grade coating film obtained in the above step (P) and suitable for use on the film substrate or the B-grade coating film transcribed on a substrate other than the film substrate; and (R) Completely harden the above-mentioned Class B coating film given the three-dimensional shape in the above-mentioned step (Q).

Images