WO2013021498A1

WO2013021498A1 - Transfer foil

Info

Publication number: WO2013021498A1
Application number: PCT/JP2011/068327
Authority: WO
Inventors: 光紀小松
Original assignee: 日東技研株式会社; 長瀬産業株式会社
Priority date: 2011-08-10
Filing date: 2011-08-10
Publication date: 2013-02-14
Also published as: JPWO2013021498A1; JP5867751B2

Abstract

A transfer foil which is obtained by sequentially laminating a releasing layer, a self-healing resin layer, an anchor layer and an adhesive layer on a base film. The releasing layer is not transferred but is closely adhered to the base film, while having properties of being releasable from the self-healing resin layer. The anchor layer is formed of a polyvinyl chloride copolymer resin, an acrylic urethane resin, a vinyl chloride-vinyl acetate copolymer resin, a polyester resin or a thermosetting resin.

Description

Transfer foil

The present invention relates to a transfer foil.

Recently, paints called self-healing resin paints are commercially available (see, for example, Patent Documents 1 to 3). This self-healing resin paint is made of a resin having a high elastic restoring force, and when this paint is applied to the surface of the coated body by a spray method or the like, even if the surface of the coated body is scratched once It is confirmed to disappear.

JP 2000-342127 A JP-A-11-228905 JP 2001-2744 A

However, when the self-healing resin paint is applied, the application range is limited because the paint is scattered around and there are environmental problems and it is difficult to mirror the application surface.

By the way, there is known a transfer foil used for a processing method in which a transfer object such as a resin molded product is transferred through an adhesive layer by thermal transfer or in-mold molding. According to this transfer foil, it is possible to protect the surface of the transfer object, to provide an antistatic function, or to decorate it with any color or pattern, so that home appliances, automotive interior / exterior products, acoustic products, Widely used in furniture furniture products.

The present inventors expect that if the above-mentioned self-healing resin paint can be made into a transfer foil, problems such as paint scattering and the difficulty of mirror finishing can be solved, and the application will be further expanded. The transfer foil of self-healing resin paint was studied. However, conventionally known transfer foil forming methods have not been able to form a self-healing resin paint into a transfer foil.

Therefore, an object of the present invention is to provide a transfer foil obtained by forming a self-healing resin paint into a transfer foil.

The present invention is a transfer foil in which a release layer, a self-healing resin layer, an anchor layer and an adhesive layer are sequentially laminated on a base film, and the release layer does not transfer and adheres to the base film. In addition, the anchor layer has an acrylic urethane resin, vinyl acetate resin (vinyl chloride / vinyl acetate copolymer resin), polyester resin, or thermosetting resin. A transfer foil is provided.

According to the transfer foil of the present invention, since the self-healing resin layer is formed as a transfer foil, the paint can be easily placed on the surface by being transferred to the transfer target, and the paint is scattered around. There is no worry. Furthermore, when the transfer foil of the present invention is used for in-mold molding, the surface layer of the self-healing resin can be easily mirror-finished by mirror-treating the surface of the mold.

The self-healing resin layer is preferably made of a thermosetting resin or a UV curable resin. The adhesive layer is preferably made of an acrylic resin, a vinyl acetate resin, an olefin resin or a composite resin thereof, or a thermosetting resin.

It is preferable that an antistatic layer made of a surfactant type, metal compound type or polymer type antistatic agent is laminated on the surface of the base film opposite to the surface on which the release layer is laminated. It is also preferred that the base film contains an antistatic agent.

The self-healing resin layer is preferably made of a thermosetting resin containing a polydimethylsiloxane copolymer, and the release layer is preferably made of a mixture of a polyether-modified silicone and an ionizing radiation curable resin.

The self-healing resin layer is preferably made of a UV curable resin containing a urethane (meth) acrylate oligomer, and the release layer is preferably made of a vinyl resin.

According to the transfer foil of the present invention, since the self-healing resin layer is formed as a transfer foil, the coating can be easily placed on the surface by transferring to the transfer target, and the coating is scattered around. There is no worry. Furthermore, when the transfer foil of the present invention is used for in-mold molding, the surface layer of the self-healing resin can be easily mirror-finished by mirror-treating the surface of the mold.
Furthermore, the transfer foil of the present invention can be used in the same manner as a conventional transfer foil because it can be laminated with a decorative ink or the like in the same manner as a conventional transfer foil.

It is a schematic cross section of the transfer foil according to an embodiment of the present invention. It is a manufacturing apparatus of transfer foil concerning one embodiment of the present invention. It is a photograph showing the disappearance process of the scratches attached to the in-mold molded product.

Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted.

First, the laminated structure of the transfer foil 1 according to an embodiment of the present invention will be described with reference to the schematic cross-sectional view of FIG. The transfer foil 1 can be suitably used as a transfer foil for transferring by applying heat and pressure, such as for in-mold molding, roll type or hot stamping type thermal transfer.

In the transfer foil 1, a release layer 5, a self-healing resin layer 7, an anchor layer 9 and an adhesive layer 11 are sequentially laminated on one surface of the base film 3, and an antistatic layer is further formed on the other surface of the base film 3. 13 is laminated. In FIG. 1, the thickness of each layer is substantially the same, but of course, the thickness of the layer can be adjusted as appropriate. Further, a decorative layer (not shown) and an adhesive layer (not shown) may be further laminated on the adhesive layer 11.

The base film 3 is made of a flexible film. The material constituting this is not particularly limited as long as it has desired heat resistance, mechanical strength, etc., and known materials that have been used for conventional general in-mold molding and thermal transfer can be used. Specific examples of the base film 3 include stretched or unstretched transparent plastics such as polyethylene terephthalate (PET), polybutylene terephthalate, polypropylene, polyethylene, nylon, polymethyl acrylate, polymethyl methacrylate, polycarbonate, and polyurethane. , Paper, metal, and composites thereof, and polyethylene terephthalate having good heat resistance and mechanical strength is particularly preferable.
The thickness of the base film 3 is usually about 10 to 200 μm.

The release layer 5 is a layer that enables the base film 3 and the self-healing resin layer 7 to be separated and does not transfer. As a material constituting the release layer 5, known materials that have been used for conventional general in-mold molding and thermal transfer can be used. Examples of the material constituting the release layer 5 include a release resin, a resin to which a release agent is added or copolymerized, or a material containing a curable resin that is cured by a crosslinking reaction. Examples of release resins and resins containing release agents include fluororesins, silicone resins, melamine resins, waxes, acrylic resins with added or copolymerized release agents such as various waxes, and vinyl resins Examples of curable resins that can be cured by crosslinking reaction (by irradiation with ionizing radiation) include epoxy-modified acrylate resins, urethane-modified acrylate resins, acrylic-modified polyester resins, and polyether-modified resins. A silicone resin, an acrylic resin, etc. are mentioned. These can be used alone or in combination. When the self-healing resin layer 7 is a thermosetting resin (particularly, polydimethylsiloxane copolymer or polycarbonate diol type), the release layer 5 has a polyether-modified silicone and an ionizing radiation curable resin (preferably, A mixture of acrylic resins) (for example, a polyether-modified silicone content of 10 to 70% by mass) is preferable. In the case of a UV curable resin (particularly a urethane (meth) acrylic oligomer), a vinyl type is used. Resins are preferred. According to these combinations, the self-healing resin layer 7 and the release layer 5 can be released more easily.

The thickness of the release layer 5 is usually about 0.01 to 20 μm, preferably about 0.1 to 10 μm, considering the film formability and ease of release.

The release layer 5 is prepared by dispersing or dissolving the above-described materials in a solvent, roll coating, reverse roll coating, gravure coating, micro gravure coating, reverse gravure coating, bar coating, rod coating, kiss coating, knife coating, die coating, comma. It is applied on the base film 3 by a known method such as a coating method such as coating, flow coating, spray coating, or a coating method, followed by drying by heating. Moreover, it can be hardened | cured by irradiating electromagnetic radiation depending on the hardening type.

The self-healing resin layer 7 has a three-dimensional structure, and is made of a self-healing resin having an elastic shape recovery function that elastically restores to its original shape over time even when deformed.
Examples of self-healing resins include acrylic resins, urethane resins, polycarbonate resins, polycarbonate diol resins, polystyrene resins, polyester resins, silicone resins, fluorine resins, and their copolymers or blends, which are relatively soft. There are elastic and easily deformable.
As the self-healing resin, for example, an ultraviolet (UV) curable or thermosetting paint sold as “Self-healing clear” (manufactured by NATCO CORPORATION) can be suitably used. As the thermosetting type, as shown in JP-A-11-228905, those using polydimethylsiloxane copolymers, such as those containing polydimethylsiloxane copolymers, polycaprolactone and polysiloxane are typical. As an ultraviolet curable type, as shown in JP-A No. 2001-2744, a urethane (meth) acrylate oligomer, for example, a urethane (meth) acrylate oligomer and a photoinitiator are used. What is included is typical.

The self-healing resin is also preferably a resin (polycarbonate diol type) containing acrylic polyol, polycarbonate diol and polyisocyanate.

The film thickness of the self-healing resin layer 7 is usually about 3 to 100 μm in consideration of recoverability. The self-healing resin layer 7 can be formed in the same manner as the release layer 5 in the case of the thermosetting type. In the case of the ultraviolet curable type, ultraviolet rays are further irradiated.

The anchor layer 9 is provided for protecting the self-healing resin layer 7 and interposing between the cured self-healing resin layer 7 and the adhesive layer 11 to be laminated next, so as to adhere to each layer. It is. It is difficult for the self-healing resin to adhere an adhesive layer or a decorative layer thereon, and the insertion of the anchor layer 9 is important.
Examples of the material constituting the anchor layer 9 include acrylic urethane resin, vinyl chloride resin, polyester resin, melamine resin, and epoxy thermosetting resin. The material constituting the anchor layer 9 is preferably a material harder than the self-healing resin in order to exhibit the performance of the self-healing resin to a higher degree. In addition, the hardness of resin can be confirmed by the nanoindentation method, for example.
The film thickness of the anchor layer 9 is usually about 1 to 2 μm in consideration of adhesion.
The anchor layer 9 can be formed in the same manner as the release layer 5.

When the decorative layer is provided, the adhesive layer 11 is in close contact with the decorative ink, and when directly placed on the transferred material, the adhesive layer 11 is in close contact with the transferred material.
Therefore, as a material constituting the adhesive layer 11, when a decorative layer is provided, a material having an affinity with a decorating material with the other side to be in close contact is appropriately selected and used, and is directly placed on the transferred object. In this case, a compatible, heat-sensitive, and pressure-sensitive resin suitable for the other-side transferred object is appropriately selected and used. Examples of the material constituting the adhesive layer 11 include resins such as acrylic resins, vinyl acetate resins, olefin resins, composite resins thereof, and thermosetting resins.
The film thickness of the adhesive layer 11 is usually about 0.1 to 5.0 μm in consideration of adhesion.
The adhesive layer 11 can be formed in the same manner as the release layer 5.

The decorative layer can be formed by a known printing method such as a gravure printing method, an offset printing method, a screen printing method, a letterpress printing method, or a metal vapor deposition using various printing inks containing a known pigment or dye. It can be formed by transferring a film. When the decorative layer is provided, it is possible to place the decorative layer on the transfer target by further providing an adhesive layer thereon.

The antistatic layer 13 is provided in order to prevent dust from adhering to the foil, and is preferably provided because the self-healing paint is easily charged.
The antistatic layer 13 preferably has a surface electrical resistance of 10 ¹¹ Ω / □ or less, and can withstand the heat treatment during the production of the transfer foil 1 and is not deteriorated at a high temperature of about 170 ° C. for about 5 minutes. Those that can withstand are preferred.
Examples of the material constituting the antistatic layer 13 include surfactant, metal compound, and polymer antistatic agents. These can be used alone or in combination.
The antistatic layer 13 can be formed in the same manner as the release layer 5.
Instead of providing the antistatic layer 13, the base film 3 may contain the above components to impart an antistatic function.

The material of each layer described above can be applied by dissolving in a solvent such as toluene, methyl ethyl ketone, methyl isobutyl ketone, butyl acetate or cyclohexanone.

The transfer foil 1 can be manufactured using a normal transfer foil manufacturing apparatus 14, for example, as shown in FIG.
The base film 3 is wound around the unrolling roller 15. The base film 3 is unwound from the unwinding side roller 15 and is transported along a predetermined path by the transport rollers 29a to 29e and 31a to 31e. The roller 17 is wound up. A container 19 containing a coating material such as a releasable resin is disposed on the upstream side of the transport path of the base film 3 so that the above-described layers are formed by gravure printing using the coating roller 27. It has become. Further, drying furnaces 21a to 21f are provided on the downstream side thereof. If necessary, a corona treatment unit 25 may be provided on the upstream side of the manufacturing apparatus 14, or an ionizing radiation or UV irradiation unit 23 may be provided on the downstream side.

Each time the above-described transfer foil manufacturing apparatus is passed once, one layer is laminated. That is, the paint contained in the container 19 is applied on the base film 3 unwound from the unwinding roller 15 and dried in the drying furnaces 21a to 21f, and then wound on the unwinding roller 17. Thus, a film in which one layer is newly formed is obtained. When laminating the next layer, the roller 17 on the take-up side and the roller 15 on the take-out side are exchanged, and the roller on the take-up side may be arranged on the unwind side in the previous layer formation. In this way, each layer can be sequentially stacked.
Usually, in consideration of dust resistance, after forming the antistatic layer 13 on one side of the base film 3, the release layer 5 and the like are formed and laminated on the other side.

(Example 1)
As the base film 3, polyethylene terephthalate (manufactured by Toyobo Co., Ltd., trade name: E-5100, thickness: 38 μm) is prepared, and the transfer of Example 1 is performed through the following steps 1 to 7 using the manufacturing apparatus 14. A foil was produced. In addition, it shows in following Table 1 about the coating conditions and coating material of each layer.

Step 1: Coating an antistatic layer on one surface of polyethylene terephthalate so that the surface electrical resistance is 10 ¹¹ Ω / □ or less.
Process 2: A release layer is coated on the other surface of polyethylene terephthalate.
Step 3: A self-healing resin layer is applied on the release layer.
Step 4: Corona treatment of the self-healing resin layer at a discharge density of 50 to 100 W / m ² .
Step 5: An anchor layer is applied on the corona-treated self-healing resin layer.
Step 6: Corona treatment of the anchor layer at a discharge density of 50 to 100 W / m ² .
Step 7: An adhesive layer is applied on the corona-treated anchor layer.

(Example 2)
As the base film 3, polyethylene terephthalate (manufactured by Toyobo, trade name: A4100, thickness 50 μm) is prepared, and the transfer foil of Example 2 is manufactured through the following steps 1 to 6 using the manufacturing apparatus 14 described above. did. In addition, it shows in Table 2 about the coating conditions and coating material of each layer.

Step 1: Coating an antistatic layer on one surface of polyethylene terephthalate so that the surface electrical resistance is 10 ¹¹ Ω / □ or less.
Process 2: A release layer is coated on the other surface of polyethylene terephthalate.
Step 3: A self-healing resin layer is applied on the release layer.
Step 4: Corona treatment of the self-healing resin layer at a discharge density of 50 to 100 W / m ² .
Step 5: An anchor layer is applied on the corona-treated self-healing resin layer.
Process 6: Applying an adhesive layer on the anchor layer.

(Example 3)
Polyethylene terephthalate (trade name: E-5100, thickness: 38 μm, manufactured by Toyobo Co., Ltd.) is prepared as the base film 3, and the transfer of Example 3 is performed through the following steps 1 to 5 using the manufacturing apparatus 14 described above. A foil was produced. In addition, it shows in Table 3 about the coating conditions and coating material of each layer.

Step 1: Coating an antistatic layer on one surface of polyethylene terephthalate so that the surface electrical resistance is 10 ¹¹ Ω / □ or less.
Process 2: A release layer is coated on the other surface of polyethylene terephthalate.
Step 3: A self-healing resin layer is applied on the release layer.
Step 4: An anchor layer is applied on the self-healing resin layer.
Process 5: Applying an adhesive layer on the anchor layer.

(Comparative Example 1)
A transfer foil of Comparative Example 1 was produced in the same manner as Example 2 except that no anchor layer was formed.

[Evaluation of transfer foil]
A resin molded product was produced by using the transfer foil obtained in Example 1 for in-mold molding, scratches were made with a brass brush, and disappearance, that is, recovery power was confirmed. As shown in FIG. It was confirmed that it recovered. Moreover, when the same evaluation was performed using the transfer foils obtained in Examples 2 and 3, it was confirmed that the scratches were recovered in the same manner as in Example 1 shown in FIG.
On the other hand, with respect to the transfer foil obtained in Comparative Example 1, delamination occurred and in-mold molding could not be performed.

The transfer foil of the present invention can be used in the same manner as a conventional transfer foil.

DESCRIPTION OF SYMBOLS 1 ... Transfer foil, 3 ... Base film, 5 ... Release layer, 7 ... Self-healing resin layer, 9 ... Anchor layer, 11 ... Adhesive layer, 13 ... Antistatic layer, 14 ... Transfer foil manufacturing apparatus, 15, 17 DESCRIPTION OF SYMBOLS ... Roller, 19 ... Paint container, 21a-21f ... Drying furnace, 23 ... Irradiation part, such as ionizing radiation, 25 ... Corona treatment part, 27 ... Coating roller, 29a-29e, 31a-31e ... Conveyance roller.

Claims

A transfer foil in which a release layer, a self-healing resin layer, an anchor layer and an adhesive layer are sequentially laminated on a base film,
The release layer does not transfer transfer, adheres to the base film, and has the ability to release from the self-healing resin layer,
The anchor layer is a transfer foil made of an acrylic urethane resin, a vinyl chloride resin, a polyester resin, or a thermosetting resin.
The self-healing resin layer is made of a thermosetting resin or a UV curable resin,
The transfer foil according to claim 1, wherein the adhesive layer is made of an acrylic resin, a vinyl acetate resin, an olefin resin or a composite resin thereof, or a thermosetting resin.
An antistatic layer made of a surfactant-based, metal compound-based or polymer-based antistatic agent is laminated on the surface of the base film opposite to the surface on which the release layer is laminated, or the base film The transfer foil according to claim 1 or 2, comprising an antistatic agent.
The self-healing resin layer is made of a thermosetting resin containing a polydimethylsiloxane copolymer, and the release layer is made of a mixture of a polyether-modified silicone and an ionizing radiation curable resin. The transfer foil according to any one of the above.
The transfer foil according to any one of claims 1 to 3, wherein the self-healing resin layer is made of a UV curable resin containing a urethane (meth) acrylate oligomer, and the release layer is made of a vinyl resin. .