JP2016141122A - Jet-black transfer foil using carbon nanotube - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transfer foil used for decoration of various plastic molded products which is more excellent in jet-blackness.SOLUTION: In a transfer foil in which a peeling layer, an active energy ray-curable resin layer, a primer layer, a black pattern layer and an adhesive layer are sequentially laminated on a base material sheet, a pattern layer containing a carbon nanotube is inserted between the primer layer and the black pattern layer or the carbon nanotube is added to the primer layer, and thereby a transfer foil excellent in jet-blackness and a molded product obtained by transferring the transfer foil can be provided.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative molding transfer foil, and more particularly, to provide a decorative molded product excellent in jet blackness by being inserted into a molding die and transferred to an injection molded product by in-mold transfer or vacuum molding. The present invention relates to a decorative molding transfer foil and a molded product transferred from the foil.

Various plastic molded articles, for example, molded articles by injection molding, can be used for many things such as equipment bodies such as daily necessities and daily necessities, automobile parts, containers for food and various articles, and housings for electronic equipment and office supplies. It is used. Conventionally, in order to increase the design of these molded products, a printing film or a transfer film on which a pattern layer has been printed is inserted into a mold at the time of injection molding, and painting is performed simultaneously with injection molding. In general, a structure composed of a release layer, an active energy ray-curable resin layer, a primer layer, a pattern layer, and an adhesive layer is mainly used on a substrate sheet.
As one of the challenges of high design, a molded product with excellent jetness is required to enhance the high-quality feeling of the molded product. This is a jet black expression such as “Piano Black” or “Crow's Wet Feather”.
Various carbon blacks are used to enhance the jetness, but there is a problem that the jetness obtained by the difference in primary particle size at the time of dispersion changes, and the hiding property also changes, that is, primary particles. When the diameter is reduced, the jetness is improved, but the hiding property is inferior. Conversely, when the primary particle diameter is increased, the hiding property is improved but the jetness is inferior.
It was difficult to improve jetness easily.

JP 2001-179176 A JP 2004-098033 A JP-A-6-15223

  Therefore, in order to improve the jetness of the molded product, a transfer foil with more excellent jetness is required.

  That is, an object of the present invention is to provide a transfer foil that is more excellent in jetness in a transfer foil that imparts designability to the surface of various molded articles, and a molded product that has been transferred.

  Therefore, as a result of diligent investigations to solve the above problems, the present inventors, as a result, a release layer, an active energy ray curable resin layer, a primer layer, a black pattern layer, and an adhesive layer in order on the base sheet. In the laminated configuration, a pattern layer containing carbon nanotubes between the primer layer and the black pattern layer, that is, a carbon nanotube-containing primer layer is inserted or a carbon nanotube-containing primer layer in which carbon nanotubes are added to the primer layer. As a result, a transfer foil excellent in jetness was obtained, and a molding using the transfer foil was also found to be excellent in jetness, and the present invention was completed.

  That is, the first invention of the present invention comprises a release layer (A), an active energy ray-curable resin layer (B), a primer layer (C), a carbon nanotube (hereinafter referred to as CNT) -containing layer (D) on a base sheet. The present invention relates to a transfer foil excellent in jetness, characterized by sequentially laminating a black pattern layer (E) and an adhesive layer (F).

  Furthermore, 2nd invention of this invention is a peeling layer (A), an active energy ray hardening resin layer (B), a CNT containing primer layer (G), a black pattern layer (E), an adhesive layer ( F) It is related with the transfer foil excellent in jetness characterized by laminating | stacking one by one.

  Moreover, 3rd invention of this invention is related with the transfer foil excellent in jetness characterized by the lightness (L value) in the color difference measured from the base material sheet side of the said transfer foil being 4 or less. .

  Furthermore, the fourth invention of the present invention relates to a molded product having excellent jetness obtained by transferring the transfer foil.

  By using the transfer foil of the present invention, a molded product having excellent jetness can be obtained. Therefore, it is possible to use the transfer foil and molded product obtained in the present invention in various application fields where high jetness is required.

It is sectional drawing of transfer foil (I) which has a CNT content layer (D) between a primer layer (C) and a black pattern layer (E). It is sectional drawing of transfer foil (II) using a CNT containing primer layer (G). It is sectional drawing of transfer foil (III) which has several layers (C1, C2, C3) and a reflection layer (H) for a primer layer (C). It is sectional drawing of the molded article transcribe | transferred using the transfer foil of this invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
(Transfer foil)
The transfer foil of the present invention is roughly
Classification (1): A structure having a primer layer (C), and the primer layer (C) does not contain CNT.
Classification (2): A structure having a CNT-containing primer layer (G) containing CNTs.
More specifically, each (1): base material 11 / peeling layer (A) 12 / active energy ray curable resin layer (B) 13 / primer layer (C) 14 / CNT-containing layer (15) / black pattern Layer (E) 16 / Adhesive layer (F) 19. FIG. 1 shows a sectional view of the transfer foil (I).
Configuration (2): base material 11 / peeling layer (A) 12 / active energy ray-curable resin layer (B) 13 / CNT-containing primer layer (G) 17 / black pattern layer (E) 16 / adhesive layer (F) 19 . FIG. 2 shows a cross-sectional view of the transfer foil (II).

In the present invention, a configuration (3): including a reflective layer (H) or a plurality of primer layers (C) is also possible. More specifically, composition (3): base material 11 / peeling layer (A) 12 / active energy ray cured resin layer (B) 13 / primer layer (C1) 14-1 / CNT-containing layer (D) 15 / black Pattern layer (E) 16 / primer layer (C2) 14-2 / reflection layer (H) 18 / primer layer (C3) 14-3 / adhesion layer (F) 19. FIG. 3 shows a cross-sectional view of the transfer foil (III). Other configuration (4): base material 11 / peeling layer (A) 12 / active energy ray curable resin layer (B) 13 / CNT-containing primer layer (G) 17 / black pattern layer (E) 16 / primer layer (C1) 14-1 / reflective layer (H) 18 / primer layer (C2) 14-2 / adhesive layer (F) 19 and the like.

When it has a reflection layer (H) in classification (3), the reflection layer is usually formed partially. For example, composition (5): base material 11 / peeling layer (A) 12 / active energy ray cured resin layer (B) 13 / primer layer (C1) 14-1 / partially formed reflective layer (H) 18 / Primer layer (C2) 14-2 / CNT-containing layer (D) 15 / black pattern layer (E) 16 / adhesive layer (F) 19,
Configuration (6): substrate 11 / peeling layer (A) 12 / active energy ray curable resin layer (B) 13 / CNT-containing primer layer (G) 17 / partially formed reflective layer (H) 18 / primer Layer (C) 14 / Black pattern layer (E) 16 / Adhesion layer (F) 19.

The classification (1) which is the most basic configuration of the present invention will be mainly described.
(Base material)
As the base material, various materials can be applied depending on the application as long as they have heat resistance, mechanical strength, solvent resistance and the like. For example, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins such as nylon 6, polyolefin resins such as polyethylene, polypropylene and polymethylpentene, vinyl resins such as polyvinyl chloride, polymethyl methacrylate, etc. Examples include acrylic resins, polycarbonate, cellophane, and cellulose films such as cellulose acetate. Preferably, in terms of heat resistance and mechanical strength, polyethylene terephthalate is the most suitable for polyester resin films such as polyethylene terephthalate and polyethylene naphthalate. The thickness of the substrate is usually about 2.5 to 100 μm, but 4 to 50 μm is preferable in terms of transferability.

  The substrate may be a copolymer resin containing these resins as a main component, a mixture (including an alloy), or a laminate composed of a plurality of layers. The substrate may be a stretched film or an unstretched film, but a film stretched in a uniaxial direction or a biaxial direction is preferable for the purpose of improving the strength. The substrate is used as a film, sheet or board formed of at least one layer of these resins. Prior to application, the substrate is subjected to corona discharge treatment, plasma treatment, ozone treatment, flame treatment, primer (also called an anchor coat, adhesion promoter, or easy adhesive) application treatment, pre-heat treatment, dust removal treatment. Alternatively, easy adhesion treatment such as vapor deposition treatment or alkali treatment may be performed. If necessary, the base material may contain additives such as a filler, a plasticizer, a colorant, and an antistatic agent.

(Peeling layer (A))
Examples of the release layer (A) include a release resin, a resin containing a release agent, and a curable resin that is cross-linked by ionizing radiation. In the present invention, it is preferable to use a melamine resin. By using the melamine-based resin, stable peelability is exhibited with respect to the active energy ray-curable resin layer (B) described later.

  The release layer (A) is formed by dispersing or dissolving the resin in a solvent, coating and drying to form a coating film. The thickness of the release layer (A) is usually about 0.01 μm to 5 μm, preferably about 0.1 μm to 3 μm. The thinner the thickness is, the better. However, when the thickness is 0.1 μm or more, better film formation is obtained and the peeling force is more stable.

(Active energy ray cured resin layer (B))
The active energy ray-curable resin layer (B) is preferably formed from an active energy ray-curable resin composition containing (1) a polymerizable oligomer and (2) an inert resin. Moreover, when (3) a filler is contained, tackiness can be further improved and printability can be imparted.
Examples of the curing method of the active energy ray-curable resin composition include electron beam curing and ultraviolet curing. Any method may be used, but when UV curing is performed, 4) a photopolymerization initiator is required for curing.

  (1) As the polymerizable oligomer, an oligomer having a radical polymerizable unsaturated group in the molecule, for example, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate The system etc. are mentioned. Here, the epoxy (meth) acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. . Further, a carboxyl-modified epoxy (meth) acrylate oligomer obtained by partially modifying this epoxy (meth) acrylate oligomer with a dibasic carboxylic acid anhydride can also be used. The urethane (meth) acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. Polyester (meth) acrylate oligomers include, for example, esterifying hydroxyl groups of polyester oligomers having hydroxyl groups at both ends obtained by condensation of polycarboxylic acid and polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a carboxylic acid with (meth) acrylic acid. The polyether (meth) acrylate oligomer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.

  In the present invention, it is preferable to use a urethane (meth) acrylate having a weight average molecular weight of 1,000 to 100,000. Further, the urethane (meth) acrylate is 45 to 90 weight in the active energy ray-curable resin composition. % Is preferable in terms of heat followability at the time of injection molding.

  (2) An inert resin is a resin that does not participate in radical polymerization by irradiation of active energy rays, that is, a resin that does not undergo radical polymerization by active energy rays. There is no limit. Specific examples of the inert resin include polyurethane resin, amino resin, phenol resin, polyamide, cellulose derivative, fluorine resin, diallyl phthalate resin, vinyl resin, polyolefin, natural rubber derivative, acrylic resin, vinyl chloride / vinyl acetate copolymer. , Epoxy resin, polyester, polystyrene, alkyd resin, rosin-modified alkyd resin, linseed oil-modified alkyd resin, cellulose derivative, fluororesin, and the like. These can be used alone or in admixture of two or more. . Of these, acrylic resins, vinyl chloride / vinyl acetate copolymers, cellulose derivatives, and fluororesins are preferred because of their excellent adhesion, moldability, and hard coat properties.

  (3) As the filler, particles made of inorganic substances such as polyethylene wax, silica, alumina, aluminosilicate, calcium carbonate, barium sulfate, acrylic polymers, organic polymers such as polyethylene, and the like are used. Among these, silica that has an effect of reducing tackiness and is easy to handle is preferable, and colloidal silica is more preferable. The colloidal silica is not particularly limited, and a commercially available product using an organic solvent or the like as a dispersion medium can be used. The average primary particle diameter of colloidal silica is preferably about 6 to 100 nm, and more preferably 10 to 80 nm. When the average primary particle diameter is less than 6 nm, the surface hardness tends to be insufficient and the scratch resistance tends to be lowered, and when it exceeds 100 nm, the storage stability tends to be insufficient, and the adhesion and transparency tend to be deteriorated. The average primary particle diameter is a value determined by a dynamic light scattering method. Specific examples of the colloidal silica component include, for example, Snowtex (manufactured by Nissan Chemical Industries, Ltd.), Quartron (manufactured by Fuso Chemical Industries, Ltd.), Aerosil (manufactured by Nippon Aerosil Co., Ltd.), and Sildex (Asahi Glass). And Silysia 470 (manufactured by Fuji Silysia Chemical Co., Ltd.). In order to simplify the production, it is preferable to use an organosilica sol dispersed in an organic solvent in advance, for example, IPA-ST, IPA-ST-L, IPA-ST-ZL, IPA-ST-UP (above , Respectively, isopropanol dispersion manufactured by Nissan Chemical Industries, Ltd.), MA-ST-M (methanol dispersion manufactured by Nissan Chemical Industries, Ltd.), Quattron PL-2-IPA (isopropanol dispersion manufactured by Fuso Chemical Industries, Ltd.) Etc.

  (4) The photopolymerization initiator is used when the active energy ray-curable resin composition is cured with ultraviolet rays. As a photoinitiator, it does not specifically limit and can use a well-known thing. As photoinitiators, acetophenones such as diacetoxyacetophenone and 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzoin ethers such as isobutyl benzoin ether and isopropyl benzoin ether, benzyl dimethyl ketal and hydroxycyclohexyl phenyl ketone Benzyl ketals such as benzophenone and ketones such as 2-chlorothioxanthone. Specifically, for example, 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl -Propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1propan-1-one, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine Oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 4-methylbenzophenone, etc.These may be used alone or in combination of two or more. Although the usage-amount in the case of using a photoinitiator is not specifically limited, Usually, it is preferable to set it as about 1-10 weight part with respect to 100 weight part of ultraviolet curing components. In the case of electron beam curing type, a photoinitiator is not always necessary.

  In addition to the above components, a polymerization inhibitor, a viscosity modifier, a surfactant, an antifoaming agent, an organometallic coupling agent, and the like can be added to the active energy ray curable resin composition as necessary. .

When actually performing ultraviolet curing, the ultraviolet irradiation dose is cured at 50 mJ / cm 2 to 1200 mJ / cm 2 using a high-pressure mercury lamp, and preferably 100 to 1000 mJ / cm 2. In the case of curing with an electron beam, a conventionally known curing apparatus can be used, and the irradiation dose is preferably 10 kGy to 200 kGy, and more preferably 30 kGy to 100 kGy.
The irradiation may be divided according to the required formability, that is, pre-molding curing and post-molding curing. The thickness of the active energy ray-curable resin layer (B) is about 0.5 to 20 μm, preferably 1 to 10 μm. In the present invention, a curing method using ultraviolet rays is preferred.

(Primer layer (C))
The primer layer is used to improve the adhesive strength between the upper and lower layers. For example, polyurethane resin, polyester resin, polyamide resin, polyvinyl chloride resin, acid-modified, depending on the adhesion with the upper and lower layers Known and publicly used resins such as polyolefin resins, (methacrylic resins, polyethyleneimine compounds, isocyanate compounds, chlorinated rubber resins, etc. can be used. If necessary, add a filler, plasticizer, dispersant, lubricant, antistatic agent, antioxidant, antifungal agent, etc. The primer layer (C) has a thickness of about 0.05 to 10 μm, preferably 0.1 to 5 μm.

(CNT-containing primer layer (G))
The CNT-containing primer layer (G) is a composition in which the primer layer (14) contains CNT (carbon nanotubes).
The shape of the CNT may be any shape such as a needle shape, a cylindrical tube shape, a fish bone shape (fishbone, cup-laminated type), a trump shape (platelet), or a coil shape. Specific examples include graphite whiskers, filamentous carbon, graphite fibers, ultrafine carbon tubes, carbon tubes, carbon fibrils, carbon microtubes, and carbon nanofibers. These forms can be used in the form of one or a combination of two or more.

  The CNT used in the present invention has a shape in which one surface of graphite is wound into a cylindrical shape, and the single-layer CNT having a structure in which the graphite layer is wound in one layer, a multilayer in which two or more layers are wound. CNTs may be mixed, but multilayer CNTs are preferable from the viewpoint of cost and coloring effect. Further, CNTs having an amorphous structure on the side walls of the CNTs can be used instead of the graphite structure. The primer layer has a thickness of about 0.05 to 10 μm, preferably 0.1 to 5 μm.

  The fiber diameter of the CNT is preferably 1 to 500 nm, more preferably 5 to 50 nm, from the viewpoint of easy dispersion and hue.

  The fiber length of CNT is preferably from 0.1 to 150 μm, more preferably from 1 to 50 μm, from the viewpoint of ease of dispersion and hue.

  The carbon purity of CNT is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more in 100% by mass of CNT.

  CNT generally exists as secondary particles. The secondary particle shape may be, for example, a state in which CNTs, which are general primary particles, are intricately intertwined, or may be an aggregate of CNTs that are easily loosened and linearized. Secondary particles which are aggregates of linear CNTs are preferable because they have better dispersibility than those intertwined.

  The CNT may be a surface-treated one or a CNT derivative provided with a functional group such as a carboxyl group. In addition, CNT containing an organic compound, a metal atom, fullerene, or the like can also be used. Further, the content of CNT is preferably 0.1 wt% to 10 wt%, more preferably 1 to 5 wt% in the layer. When it is less than 0.1% by weight, the jet black feeling is inferior, and when it is more than 10% by weight, the flow state of the CNT-containing primer forming the CNT-containing primer layer is inferior and the printing state is deteriorated. The thickness of the CNT-containing primer layer (G) is about 0.05 to 10 μm, preferably 0.1 to 5 μm.

(CNT-containing layer (D))
The CNT-containing layer (D) is a mixture of CNTs by removing the pigment from the black pattern layer described later. In this case, the content of CNT is the same as that of the CNT-containing primer layer (G), and is preferably 0.1 wt% to 10 wt%, more preferably 1 to 5 wt% in the layer. When the amount is less than 0.1% by weight, the jet black feeling is inferior. The CNT-containing layer (D) can be the same CNT as the CNT-containing primer layer (G), but a different binder resin is used. In addition, unlike the primer layer (C) and the CNT-containing primer layer (G), the CNT-containing layer (D) tends to have poor adhesion to the active energy ray-curable resin layer (B) having a hard coat property. Direct contact with the energy ray curable resin layer (B) is not preferable. The thickness of the CNT-containing layer (D) is about 0.05 to 10 μm, preferably 0.1 to 5 μm.

(Black pattern layer (E))
The black pattern layer (E) is obtained by dispersing black pigments (excluding CNT) such as carbon black, perylene black, titanium rack, and graphite, which are publicly known and used, in the publicly known resins and solvents described in the explanation of the primer layer. It is. When a black pigment is not used, it is possible to express black by mixing three kinds of pigments, yellow, red and indigo. The thickness of the black pattern layer is about 0.05 to 10 μm, preferably 1 to 5 μm. In addition, from the viewpoint of design properties, a pattern layer of another hue (yellow, red, indigo, white, etc.) may be further formed. If necessary, additives such as fillers, plasticizers, dispersants, lubricants, antistatic agents, antioxidants, antifungal agents and the like may be included. The thickness of the black pattern layer (E) is about 0.05 to 10 μm, preferably 0.1 to 5 μm.

(Reflective layer (H))
Examples of the reflective layer (H) include a metallic luster reflective layer, a white reflective layer, a transparent reflective layer, and a high-brightness ink reflective layer. The metallic glossy reflective layer may be provided by depositing a metal thin film such as aluminum, gold, silver, or copper by a vacuum thin film method such as vapor deposition, sputtering, or ion plating. As the transparent reflective layer, for example, a transparent metal compound having a refractive index different from that of the unevenness forming layer can be applied, and examples thereof include ZnS, TiO2, Al2O3, Sb2S3, SiO, SnO2, ITO, LiF, MgF2, and AlF3. In the present invention, a vapor deposition layer of aluminum or titanium oxide is particularly preferable. The transparent metal compound may be formed by a vacuum thin film method such as vapor deposition, sputtering, or ion plating so that the thickness is about 0.01 to 0.2 μm, preferably 0.03 to 0.1 μm. .

(Adhesive layer (F))
The adhesive layer (F) is a layer for adhering to the transfer molded body, and when heated, it melts or softens and exhibits an adhesive effect. Specific examples include known and publicly used resins such as vinyl chloride / vinyl acetate copolymer resins, acrylic resins, and polyester resins, and are appropriately selected depending on the type of molded article to be transferred. The material resin is dissolved or dispersed in a solvent, and additives such as a filler, a plasticizer, a dispersant, a lubricant, an antistatic agent, an antioxidant, and an antifungal agent may be added as necessary. It is well applied and dried, and the thickness is preferably about 0.1 to 10 μm, more preferably 0.5 to 3 μm.

  For the production of the transfer foil, various general printing methods are suitably used, and gravure printing, screen printing, flexographic printing, gravure offset printing, inkjet printing, and the like can be applied.

(Transfer molding)
Transfer to the molded product is performed by in-mold injection molding or vacuum molding. An example of in-mold molding will be shown. (1) a step of preparing a transfer foil, (2) a step of inserting the transfer foil into an injection mold, and (3) injection-molding a resin to the injection mold and closely contacting the mold. A step of transferring the transfer foil to the surface of the resin, and (4) a step of releasing the mold after cooling, peeling the base material of the transfer foil and the release layer (A) and taking out the injection molded product, Through the injection molding method, an injection molded product in which the adhesive layer (F) is transferred from the active energy ray-curable resin layer (B) to the three-dimensional surface can be manufactured.

  As a resin used in the injection molding method, various materials can be applied according to a desired application. For example, polyester resins such as polyethylene terephthalate, polyolefin resins such as polyethylene, polypropylene, polymethylpentene, and cyclic polyolefin resins, acrylic resins such as polyacrylate, polymethacrylate, and polymethyl methacrylate, engineering resins, polycarbonate, AS Resin, styrene resin such as acrylic nitrile butadiene styrene (ABS resin), and the like, and these copolymers may be used alone or in combination. An acrylic resin, a polycarbonate resin, or a cyclic polyolefin resin having excellent optical characteristics is preferable, and an acrylic resin or a polycarbonate resin is more preferable.

  Also, when transferring by vacuum molding, press the transfer foil against a convex or concave mold, create a state close to vacuum by sucking the air between the transfer foil and the mold, close the transfer foil to the mold, and the intended shape In recent years, a method of directly adhering to a molded body such as a TOM method has been performed.

  In the TOM method, (1) a step of preparing a transfer foil, (2) a step of inserting the transfer foil into a vacuum forming stage, (3) a molded product to be deposited, and (4) a transfer foil by heating A step of transferring the transfer foil to the surface of the molded product by fusing, bonding, and adhering the molded product, and (5) after cooling, the transfer foil substrate and release layer (A ) And removing the injection molded product, an injection molded product in which the adhesive layer (F) is transferred from the active energy ray-curable resin layer (B) to the three-dimensional surface can be produced.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, it is not limited to this. In addition, except a solvent, each composition of each layer is a mass part of solid content conversion.

(Example)
Each layer in the present invention is as follows.
Release layer (A) : A release agent (A) using TCM01 medium (manufactured by Dainippon Ink Co., Ltd., trade name of melamine resin) was applied and dried to form.
Active energy ray cured resin layer (B) :
Urethane acrylate (EB220 manufactured by Daicel UCB) 50 parts Trimethylolpropane triacrylate (TMPTA-N, manufactured by Daicel UCB) 19 parts Photopolymerization initiator (Darocur 1173, manufactured by Ciba Specialty Chemicals) 1 part Vinyl chloride / acetic acid Vinyl copolymer solution (VAGH, manufactured by Dow Chemical Co., 25% methyl ethyl ketone solution) An active energy ray-curable resin composition (B) composed of 30 parts was coated, dried and cured to form.
Primer layer (C) :
Acrylic resin (Hydroxyl value 52 mgKOH / g, Dainar LR1927, manufactured by Mitsubishi Rayon) 90 parts curing agent (Sumijoule L75, manufactured by Sumitomo Bayer Urethane) A primer (C) consisting of 10 parts was coated and thermally cured.
CNT-containing primer layer (G) :
The primer (C) was coated with a CNT-containing primer (G) in which carbon nanotubes (manufactured by Toyo Ink Co., Ltd., characteristic) were blended so that the solid content ratio was 5%, and heat-cured to form.
CNT-containing layer (D) :
Urethane resin (Rio Urethane JRU520, manufactured by Toyo Ink, solid content 30%) A CNT-containing composition (D) consisting of 1.5 parts of 100 parts carbon nanotubes (manufactured by Toyo Ink) was coated and dried to form.
Black pattern layer (E1) :
Urethane resin (Rio Urethane JRU520, manufactured by Toyo Ink, solid content 30%) 55 parts carbon black (Regal 99R, manufactured by Cabot) 10 parts ethyl acetate 27 parts methyl ethyl ketone 8 parts black pattern ink (E1) is applied and dried. Formed.
Black pattern layer (E2) :
In the black pattern layer (E1), black pattern ink (E2) in which carbon black was changed to (MCF-88, manufactured by Mitsubishi Chemical) was applied and dried.
Adhesive layer (F) :
An adhesive (F) using a vinyl chloride / vinyl acetate copolymer (VMCH, manufactured by Dow Chemical Company, 25% methyl ethyl ketone solution) was applied and dried to form.

In Comparative Example 3, the carbon black-containing layer (j) having the same amount of carbon black as the CNT of the CNT-containing layer (D) is included.
Carbon black-containing layer (J) : urethane resin (Rio Urethane JRU520, Toyo Ink, solid content 30%) 100 parts carbon black (Regal 99R, manufactured by Cabot) 1.5 parts carbon black-containing composition (J) It was formed by coating and drying.

(Example 1)
The manufacturing process of a transfer foil is shown below. In forming each layer, an organic solvent is appropriately added to adjust the printing viscosity.
A PET film having a thickness of 50 μm was used as a base material, and the release agent (A) was applied to one surface of the base material by a gravure coating method so that the film thickness after drying was 2 μm, and dried. Baking was performed for 20 seconds to form a release layer (A).

  The active energy ray-curable resin composition (B) is applied to the surface of the release layer (A) with a gravure reverse coater so that the thickness after drying is 5 μm, dried at 80 ° C., and cured with 80 W ultraviolet rays. The lamp was passed once (line speed was 30 m / min) and cured with ultraviolet rays to form an active energy ray cured resin layer (B).

  Next, the primer (C) is applied to the surface of the active energy ray-curable resin layer (B) with a gravure coater so that the coating amount after drying is 1 μm, and dried at 80 ° C. Formed.

  Next, the CNT-containing composition (D) is applied onto the surface of the primer layer (C) with a gravure coater so that the coating amount after drying is 1 μm, and dried at 80 ° C. to form the CNT-containing layer (D). Formed.

  Next, the black pattern ink (E1) was applied to the surface of the CNT-containing layer (1) with a gravure coater so that the coating amount after drying was 1 μm, and dried at 80 ° C. to obtain the black pattern layer (E1). Formed.

Finally, the adhesive (F) is applied to the black pattern layer (E1) surface with a gravure coater so that the coating amount after drying is 1 μm and dried at 80 ° C. to form the adhesive layer (F). did.
Through the above steps, from the substrate / release layer (A) / active energy ray curable resin layer (B) / primer layer (C) / CNT-containing layer (D) / black pattern layer (E1) / adhesive layer (F) A transfer foil (1) was obtained.

[Examples 2 and 3, Comparative Examples 1 to 3]
With the configuration shown in Table 1, transfer foils (2) to (6) were obtained in the same manner as in Example 1.
In Examples 2 and 3 and Comparative Examples 1 to 3, the coating amount of each layer was adjusted to be the same as the coating amount of the corresponding layer in Example 1. In addition, the coating amount of the carbon black containing layer in Comparative Example 3 is the same as the coating amount of the CNT containing layer (D).

(Manufacture of molded products)
Using the transfer foil obtained in each Example and Comparative Example, the transfer foil was placed in a mold by injection molding, and acrylic nitrile butadiene styrene was injected to perform simultaneous molding and obtain a molded product. It was.
The evaluation method and evaluation criteria are shown below.

(Evaluation of jetness: measurement of brightness)
The brightness (L value) of the transfer foil obtained from each of the Examples and Comparative Examples and the molded product was measured with a spectral densitometer (X-Rite 939 manufactured by X-Rite Co., Ltd.), and the jet blackness was evaluated. Excellent jetness means that the brightness is 4 or less. More preferably, it is 3.8 or less.
In addition, it measured from the base material side in the case of transfer foil, and measured in the state which removed the base material in the case of the molding.

  Table 1 summarizes the formulations and evaluation results of Examples and Comparative Examples.

  In Examples, by providing the CNT-containing layer (D) or the CNT-containing primer layer (G), a transfer foil and a molded product having low brightness and excellent jetness were obtained. In a comparative example, when it was set as the layer which contains the same amount of carbon black instead of CNT, it was inferior to jet blackness.

  Various plastic molded articles, for example, molded articles by injection molding, are used to improve the design of equipment bodies such as daily necessities and daily necessities, automobile parts, containers for food and various articles, and casings for electronic equipment and office supplies. It is valid.

10: Transfer foil 11: Base material 12: Release layer (A)
13: Active energy ray cured resin layer (B)
14 (-1, 2, 3): Primer layer (C)
15: CNT-containing layer (D)
16: Black pattern layer (E)
17: CNT-containing primer layer (G)
18: Reflective layer (H)
19: Adhesive layer (F)
20: Injection molding resin 21: Transfer foil (I)
22: Transfer foil (II)
23: Transfer foil (III)
30: Molded product

Claims (4)

  A release layer (A), an active energy ray curable resin layer (B), a primer layer (C), a carbon nanotube (hereinafter referred to as CNT) -containing layer (D), a black pattern layer (E), and an adhesive layer ( A transfer foil excellent in jetness, characterized in that F) are sequentially laminated. A release layer (A), an active energy ray curable resin layer (B), a CNT-containing primer layer (G), a black pattern layer (E), and an adhesive layer (F) are sequentially laminated on a base sheet. Transfer foil with excellent jetness. The brightness (L value) in the color difference measured from the base sheet side is 4 or less, The transfer foil excellent in jetness according to claim 1 or 2. A molded article excellent in jetness obtained by transferring the transfer foil according to any one of claims 1 to 3.

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