KR101481228B1 - Transfer film for the exterior, method for preparing the same and in-mold injection moulded article - Google Patents

Abstract

There is provided a multilayer structure external transfer film comprising a substrate layer, a release layer, a hard coat layer, an embossed layer having an uneven pattern formed on one surface thereof, and an adhesive layer in this order.

Description

TECHNICAL FIELD [0001] The present invention relates to a transfer film for external use, a method for manufacturing a transfer film for external use, and an in-mold injection molded product. BACKGROUND ART < RTI ID = 0.0 >

A transfer film for exterior use, a method for manufacturing an external transfer film, and an in-mold injection molded article.

Called in-mold injection is widely used in manufacturing front windows for washing machines and air conditioners, LCD windows for computers and mobile phones, and the like. Inmold injection refers to a method in which a transfer film printed with a pattern is mounted between a fixed mold and a moving mold of an injection mold, and a molten resin is injected so that the pattern printed on the transfer film is transferred to the injection mold simultaneously with injection. By using such an in-mold injection method, injection and transfer including injection, vacuum deposition, adhesion, and the like can be shortened to one-step process, and the production cost of the injection-molded product can be reduced and the defect rate can be considerably reduced.

In this in-mold injection, the transfer film has a great influence on the quality of the injection-molded article. Conventionally, a surface is formed by coating an ultraviolet ray-curable resin on a surface, and then a two-dimensional decorative effect is imparted by a monochromatic front printing method, a partial logos only deposition method, or a pattern printing method, The method is only for print and pearl effect, so only the planar design is implemented.

An embodiment of the present invention provides a transfer film for external use capable of imparting a steric effect.

Another embodiment of the present invention provides a method for manufacturing a transfer film for external use capable of imparting the steric effect.

Another embodiment of the present invention provides an in-mold injection molded article to which the above-mentioned exterior transfer film is applied.

In one embodiment of the present invention, there is provided a multilayer structure external transfer film comprising a substrate layer, a release layer, a hardcoat layer, an emboss layer having a concavo-convex pattern formed on one surface thereof, and an adhesive layer in this order.

The embossed layer may include a cured product of a photocurable resin composition comprising a photoreactive monomer and a photoreactive oligomer.

The photocurable resin composition may contain the photoreactive monomer and the photoreactive oligomer at a weight ratio of about 1: 1 to about 1: 1.5.

The photoreactive monomer and the photoreactive oligomer may be monomers and oligomers selected from the group consisting of epoxy acrylate type, urethane acrylate type, polyester acrylate type, polyether acrylate type, acryl type, and combinations thereof.

The emboss layer may have a thickness of about 10 [mu] m to about 30 [mu] m.

The concavo-convex pattern of the emboss layer may be formed on one surface of the hard coating layer opposite to the hard coating layer.

The hard coat layer is selected from an acrylic resin, a melamine resin, a urethane resin, a urethane-acrylic copolymer resin, an acryl-melamine copolymer resin, a phenol resin, a urea resin, an alkyd resin, an unsaturated polyester resin, an epoxy resin or a silicon resin, And may include a cured product of at least one thermosetting resin.

A primer layer may be interposed between the emboss layer and the hard coating layer.

The primer layer may comprise one selected from the group consisting of polyurethane, polystyrene, and combinations thereof.

At least one selected from a vapor deposition layer, a printing layer, or a combination thereof may be further stacked between the emboss layer and the adhesive layer.

The exterior transfer film may be used for in-mold injection molding or injection molding.

In another embodiment of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: forming a release layer on a substrate layer; Applying a composition for forming a hard coating layer of one thermosetting resin composition on the release layer to form a hard coating layer; Forming a primer layer on the hard coat layer; Applying a composition for forming an embossed layer of a photocurable resin composition on the primer layer, and forming an uneven pattern; Partially curing the embossed layer on which the concavo-convex pattern is formed; Sequentially forming an evaporation layer and a printing layer on the embossed layer on which the concavo-convex pattern is formed; And forming an adhesive layer on the printing layer. The present invention also provides a method for manufacturing a transfer film for external use.

The method for manufacturing a transfer film for external use is characterized in that the external transfer film having a multilayer structure including a substrate layer, a release layer, a hard coat layer, an emboss layer having a concavo-convex pattern formed on one surface, Transferring the toner to an injection product, and then secondary curing the toner.

According to another embodiment of the present invention, there is provided an in-mold injection-molded article in which a decorative coating layer is formed on the surface of an injection molded article in the order of a hard coating layer, an embossed layer having a concavo-convex pattern formed on one surface thereof, an adhesive layer and an injection molded product.

The decorative surface treatment layer may further include a vapor deposition layer and a printing layer laminated between the emboss layer and the adhesive layer.

The external transfer film may be transferred to the exterior of the article to realize a stereoscopic effect.

1 is a schematic cross-sectional view of an external transfer film according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

In the drawings, the thickness is enlarged to clearly represent the layers and regions. In the drawings, for the convenience of explanation, the thicknesses of some layers and regions are exaggerated.

Hereinafter, the formation of any structure in the "upper (or lower)" or the "upper (or lower)" of the substrate means that any structure is formed in contact with the upper surface (or lower surface) of the substrate However, the present invention is not limited to not including other configurations between the substrate and any structure formed on (or under) the substrate.

In one embodiment of the present invention, there is provided a multilayer structure external transfer film comprising a substrate layer, a release layer, a hardcoat layer, an emboss layer having a concavo-convex pattern formed on one surface thereof, and an adhesive layer in this order.

The exterior transfer film is applied to a transfer method by an in-mold injection process or an injection process, and can be applied as a decorative material for various home appliances or electronic products such as a mobile phone or a notebook, or as an exterior material for various interior construction materials.

1 shows a multilayer structure transfer film 10 including a base layer 1, a release layer 2, a hard coat layer 3, an emboss layer 5 having a concavo-convex pattern formed on one surface thereof, and an adhesive layer 8 Fig.

The exterior transfer film 10 is transferred to the injection molding 9 by an in-mold injection process or an injection process to form an exterior of the injection molding. Thereafter, the base layer 1 and the release layer 2 are removed, and the hard coat layer 2 is formed as the outermost surface of the injection-molded article. In the casing of the injection-molded product thus formed, the emboss layer 5 having a high elongation at the lower portion of the hard coat layer 3 and not disappearing at the time of molding is present, thereby realizing a more stereoscopic visual effect, A sense of depth can be given.

 The embossed layer 5 can realize a decorative effect by combining various metal effects using three-dimensional feeling, depth feeling, hologram diffused reflection effect, and deposition through various embossing effects.

First, a release layer 2 is formed on a base material layer 1 as a carrier film, and a hard coat layer 3 to be formed on the outermost surface of the injection molded article is formed thereon. The base material layer 1 and the release layer The emboss layer 5, the print layer 7, the adhesive layer 9, and the like can be protected after the removal of the emboss layer 2.

The hard coat layer 3 is a material used as a surface layer of an injection molded article, and can be used without limitation with materials having excellent durability, abrasion resistance, scratch resistance, and appropriate hardness so as not to be deformed during the manufacturing process. For example, the hard coat layer 3 is formed using a thermosetting resin. Specifically, the thermosetting resin that can be applied to the hard coating layer 3 may be an acrylic resin, a melamine resin, a urethane resin, a urethane-acrylic copolymer resin, an acryl-melamine copolymer resin, a phenol resin, a urea resin, an alkyd resin, , An epoxy resin, or a silicon resin, or a resin composition containing two or more kinds of resin components. Since the hard coating layer 3 is transparent as an acrylic resin and is acrylic thermosetting resin, it is softer than the photo-curable resin, so that it is advantageous in suppressing cracks and the like even after the final curing of the injection molded article, and excellent physical properties can be realized.

Further, in the thermosetting resin composition for forming the hard coat layer (3), an additive such as a crosslinking agent or a curing agent may be added in addition to the above-mentioned resin component, and if necessary, a releasing agent for releasability, Various functional additives may be added in consideration of the properties, hardness, flexibility, elongation and dimensional stability. The type and content of the crosslinking agent, the releasing agent and the functional additive are not particularly limited, and the general components and compositions used for the production of the thermosetting resin composition can be employed without any limitation in consideration of the characteristics of the final cured product.

A primer layer 4 may be introduced to laminate the embossed layer 5 on the hard coat layer 3. That is, the primer layer 4 may be laminated on the hard coat layer 3, and then the emboss layer 5 may be laminated on the primer layer 4. The primer layer 4 may be formed using a material having high toughness such as polyurethane or polystyrene to serve as a buffer layer when the emboss layer 5 is formed after the lamination. The embossed layer 5 may then be laminated.

The emboss layer 5 may be formed by forming a coating layer of the photocurable resin composition for forming the emboss layer 5 on the primer layer 4.

The photocurable resin means a composition which is cured by irradiation with electromagnetic waves. In the above, the electromagnetic wave includes microwaves, infrared rays (IR), ultraviolet rays (UV), X- particle beam, particle beam, proton beam, neutron beam, and electron beam.

The photocurable resin composition for forming the embossed layer 5 may include, for example, a photoreactive monomer, a photoreactive oligomer, a diluting monomer, and a photoinitiator, and may be appropriately added with various functional additives including a release agent have.

Specifically, the photocurable resin composition for forming the embossed layer 5 may be prepared by mixing the photoreactive monomer and the oligomer having a weight average molecular weight of about 1,000 to about 100,000 at a weight ratio of about 1: 1 to about 1: 1.5. The photocurable resin composition for forming the emboss layer 5 is mixed with the embossing mold at the embossing ratio in the above range to form the embossing mold at the time of embossing, It is possible to prevent deterioration of physical properties which may be deteriorated.

Examples of the photoreactive monomer and photoreactive oligomer that can be used in the above may include epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate and / or acrylic monomers and oligomers, and the like. And most of the general types used in the production of the photocurable resin composition can be used.

The diluent monomer may control the viscosity of the composition and, if necessary, be inserted into the main chain at the time of polymerization. The specific kind of the diluting monomer is not particularly limited, and for example, a monofunctional or multifunctional acrylic monomer may be used. The diluting monomer may contain an appropriate amount of the polyfunctional acrylic monomer in order to secure the proper hardness of the emboss layer 5, but the present invention is not limited thereto.

The type of the photoinitiator is not particularly limited, and examples thereof include a benzoin compound, a benzoin ether compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a peroxide compound and a benzophenone compound Conventional photoinitiators such as one kind or mixture of two or more kinds can be used.

The specific type and content of each component of the photocurable resin composition for forming the embossed layer 5 are not particularly limited and may be appropriately selected in consideration of the physical properties of the desired cured product. For example, the photocurable resin composition may be set to a non-solvent type, specifically, a solid content concentration of 100% by weight from the viewpoint of improving the efficiency in forming a concavo-convex pattern, but the present invention is not limited thereto.

The photocurable resin composition for forming the embossed layer 5 is coated on the primer layer 4 to form a layer, and then embossed into embossed three-dimensional type to form a pattern. As described above, the emboss layer 5 is formed on the pattern after being coated on the primer layer 4, so that the concave-convex pattern of the emboss layer 5 can be formed on the opposite side of the hard coating layer 3 .

The method of forming the concavo-convex pattern of the emboss layer is not particularly limited. For example, the photocurable resin composition for forming the emboss layer 5 is coated to form a layer on the film, and then the coating liquid is partially cured in contact with a roll or a mold having a concavo-convex pattern formed thereon, Alternatively, the concavo-convex pattern may be formed by various printing methods such as gravure printing, rotary screen printing, offset printing, (silk) screen printing, or inkjet printing.

The specific shape of the concavo-convex pattern formed as described above is not particularly limited. The pattern may be a three-dimensional pattern such as a lens, a hologram, or the like. For example, the concavo-convex pattern may be configured to include convex portions and concave portions, and concretely, it may be a pattern composed of regular and repetitive convex portions and concave portions.

The shape of the concavo-convex pattern may be variously changed depending on the application to which the external transfer film is applied.

The thickness of the embossed layer 5 is not particularly limited. For example, the thickness of the embossed layer 5 may be about 10 탆 to about 30 탆. The thickness of the embossed layer 5 may mean the average thickness or the thickness of the thickest portion. The external transfer film 10 is formed by forming the embossed layer 5 having the above-mentioned thickness by surface hardness, adhesiveness, cracking, injection moldability and the like, so that the embossed layer intervenes as described above, . ≪ / RTI >

By forming the adhesive layer 8, the external transfer film 10 can be attached to the adherend. When the external transfer film 10 is applied to in-mold injection molding or injection molding, the adhesive agent 8 is attached to the injection article 9 since the agent is an injection product 9. The material of the adhesive layer 8 is not particularly limited and may be composed of, for example, an acrylic or vinyl adhesive. For example, the adhesive layer 8 is fused to the surface of the molded article 9 when the external transfer film 10 is heat-pressed on the molded article 9 in the transfer printing process. For example, the adhesive layer 8 can be formed by a gravure process using a mixture of polyvinyl chloride and acryl resin and diluted in an organic solvent.

At least one selected from a deposition layer 6, a print layer 7, or a combination thereof may be further formed between the emboss layer 5 and the adhesive layer 8 in the external transfer film 10 have.

The deposition layer 6 may be a transparent deposition layer or a metal layer deposition layer, and may be deposited on the surface of the emboss layer 5 on which the concavo-convex pattern is formed. The material used for the deposition layer 6 is not particularly limited and may be formed of a transparent vapor deposition layer using, for example, SiO ₂ or TiO ₂ , or may be formed of a material such as aluminum, stainless steel, copper, gold, silver, nickel, Chromium, or cobalt, a metal oxide, or an alloy. The method of forming the deposition layer 6 is not particularly limited and may be formed by, for example, a vacuum deposition method, a sputtering method, or the like.

The deposition layer 6 may be deformed in various combinations together with the pattern of the embossed layer 5 to realize various dimensional sensations.

The printing layer 7 may be laminated on the deposition layer 6. The printing layer 7 is made of, for example, acrylic resin, polyurethane resin, melamine resin, polyamide resin or the like, and may include various dyes and pigments. The print layer 7 may have a predetermined pattern and color, and may have a thickness of, for example, about 1 탆 to about 5 탆.

The exterior transfer film 10 can be embodied with a different esthetic feeling by applying a variety of embossing and deposition and printing in harmony. Specifically, as a transfer film for in-mold injection molding, the appearance can be expressed by a variety of metal effects using a three-dimensional feeling and a depth feeling through various embossing effects, a diffuse reflection effect through a hologram, and a deposition. For example, by applying the exterior transfer film 10 to the exterior of a notebook computer, it is possible to provide a simple flat but more dimensional feeling, and a visual sense of depth.

The kind of the base layer 1 is not particularly limited, but a material capable of withstanding heat and pressure when performing a process such as thermocompression bonding should be used. For example, a polyester film such as a polyethylene terephthalate (PET) film or a polyethylene terephthalate glycol (PETG) film, a poly (methyl methacrylate) film, a polyethylene film, a polypropylene film, a polyvinylidene chloride film, May be used, but the present invention is not limited thereto. The combination of two or more of the films listed above means a film made of a mixture of at least two or copolymer resins in a laminated film or a laminated resin. For example, the substrate layer 1 may comprise a polyester film. The thickness of the substrate layer 1 is not particularly limited and may be suitably changed in accordance with the intended effect.

The release layer 2 functions to separate the substrate layer 1 from the injection molded article after injection molding. The releasing layer 2 can be formed by applying a releasing agent containing at least one selected from wax, silicone, Teflon, melamine, urethane, or a combination thereof on the base layer 1. Specifically, a melamine-based or silicone-based releasing agent to which an additive having good slipperiness is added is thinly coated on the base layer 1 in a liquid phase to form the releasing layer 2, and the hard coating layer 3 is adhered. The release layer 2 and the hard coat layer 3 can be easily separated from each other after the hard coat layer 3 is completely cured.

The release layer 2 may be applied by a known method such as a gravure coating method, and the thickness of the release layer 2 may be about 0.5 탆 to about 1 탆.

In another embodiment of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: forming a release layer on a substrate layer; Applying a composition for forming a hard coating layer of one thermosetting resin composition on the release layer to form a hard coating layer; Forming a primer layer on the hard coat layer; Applying a composition for forming an embossed layer of a photocurable resin composition on the primer layer, and forming an uneven pattern; Partially curing the embossed layer on which the concavo-convex pattern is formed; Sequentially forming an evaporation layer and a printing layer on the embossed layer on which the concavo-convex pattern is formed; And a step of forming an adhesive layer on the printing layer.

A multilayered external transfer film containing the substrate layer, the release layer, the hard coat layer, the emboss layer having the concavo-convex pattern formed on one side and the adhesive layer in this order is transferred to the injection mold, and then the secondary cured The method comprising the steps of: Thus, the final injection molded article can be manufactured after the secondary curing step.

In another embodiment of the present invention, there is provided an in-mold injection-molded article in which a decorated surface treatment layer is formed on the surface of an injection molded article in which a hard coating layer, an embossed layer formed on one surface with an embossed pattern, an adhesive layer and an injection molded body are laminated in this order.

The in-mold injection molded article may be obtained by applying the external transfer film to in-mold injection molding as described above, and then separating the release layer of the external transfer film to remove the base layer and the release layer. At this time, A hard coating layer transferred from the external transfer film, an embossed layer having a concave-convex pattern formed on one surface, an adhesive layer, and an embossed surface are laminated in this order.

The decorative surface treatment layer may further include a vapor deposition layer and a printing layer between the emboss layer and the adhesive layer in the same manner as in the above-mentioned external transfer film.

Hereinafter, examples and comparative examples of the present invention will be described. The following embodiments are only examples of the present invention, and the present invention is not limited to the following embodiments.

( Example )

Example  One

A mixture containing a melamine-based, melamine-acrylic-based resin and a toluene sulfonic acid-based curing agent in a weight ratio of 7: 3 was applied to the surface of a PET film (trade name: Toray Saehan F99) Layer. A hard coating layer having a thickness of about 6 탆 was formed on the release layer by a micro-coating method using an acrylic thermosetting resin composition. Next, an acryl-urethane-based primer was laminated to a thickness of 2 탆.

A polyester acrylate-based monomer and an oligomer were mixed on the primer layer at a weight ratio of 1: 1, and a embossed emboss was formed using a roll-type UV ember, and the resin was cured by UV light irradiation to form an emboss.

Sn was deposited on the formed embossed layer to form a metal deposition layer, and then a composition including a pigment was applied by gravure printing to form a print layer. An acrylic adhesive was used on the print layer, To form a transfer film.

Using a transfer film and a PC-ABS, a cover part for a notebook (10 inch) having a bent portion of R 2.0 mm at an injection temperature of 250 ° C and a pressure of 300 kg / cm 2 was in-mold injection-molded.

Comparative Example  One

Except that embossed layer formation was omitted in Example 1, a transfer film containing no embossed layer was prepared in the same manner as in the above example, and then the notebook cover portion was in-mold injection molded in the same manner.

evaluation

The notebook cover parts as the in-mold injection molded articles manufactured in Example 1 and Comparative Example 1 were evaluated for the following physical properties, and the results are shown in Table 1.

(Surface hardness)

The pencil hardened by a pencil hardness method was made at an angle of 45 °, and the surface was scratched while pressing the specimen at a load of 9.8 N to evaluate the strength according to pencil hardness.

(Embossed release)

The embossability of the embossed layer after embossing was evaluated according to the following criteria.

○: Smooth release

X: Some irregular patterns were deformed because they could not be smoothly released

(Adhesiveness)

The adhesion of the transfer film was evaluated according to the following criteria.

○: Strong adhesion between transfer film and PC-ABS

△: Part of the detached part between the transfer film and the PC-ABS, which is an injection product, was found

X: Detached part between transfer film and PC-ABS, which is an injection product, was found severely

 (Evaluation of crack occurrence)

Cracks were evaluated according to the following criteria.

?: The degree of cracking was reduced to a level comparable to that of commercially available hard coat layer of transfer film after in-mold injection.

[Delta]: Cracks to the extent that it can be commercialized to the hard coat layer of the transfer film after the in-mold injection.

X: Severe cracking occurred.

division Surface hardness Embo Diffusion Attachment rapping Evaluation of crack occurrence Example 1 HB to F ○ ○ ○ ○ Comparative Example 1 HB ○ △ ○ ○

From the above results, it can be seen that Example 1 achieves the same level of physical properties as Comparative Example 1, which implements the steric effect by the embossed layer, but does not realize the steric effect. In particular, It can be confirmed that the evaluation is excellent.

1: base layer 2: release layer
3: hard coat layer 4: primer layer
5: emboss layer 6: deposition layer
7: print layer 8: adhesive layer
9: Injection product 10: Transfer film for external use

Claims (15)

A substrate layer, a release layer, a hard coat layer, an emboss layer having a concavo-convex pattern formed on one surface thereof, and an adhesive layer,
Wherein the emboss layer comprises a cured product of a photocurable resin composition comprising a photoreactive monomer and a photoreactive oligomer,
Wherein the photocurable resin composition comprises the photoreactive monomer and the photoreactive oligomer in a weight ratio of 1: 1 to 1: 1.5. delete delete The method according to claim 1,
The photoreactive monomer and the photoreactive oligomer may be monomers and oligomers selected from the group consisting of epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, acrylic, and combinations thereof.
Exterior transfer film. The method according to claim 1,
Wherein the emboss layer has a thickness of 10 mu m to 30 mu m
Exterior transfer film. The method according to claim 1,
The embossed pattern of the emboss layer is formed on one surface of the hard coating layer opposite to the hard coating layer
Exterior transfer film. The method according to claim 1,
The hard coat layer is selected from an acrylic resin, a melamine resin, a urethane resin, a urethane-acrylic copolymer resin, an acryl-melamine copolymer resin, a phenol resin, a urea resin, an alkyd resin, an unsaturated polyester resin, an epoxy resin or a silicon resin, Comprising a cured product of at least one thermosetting resin
Exterior transfer film. The method according to claim 1,
And a primer layer interposed between the embossed layer and the hard coat layer,
Exterior transfer film. 9. The method of claim 8,
Wherein the primer layer comprises one selected from the group consisting of polyurethane, polystyrene, and combinations thereof
Exterior transfer film. The method according to claim 1,
At least one selected from a vapor deposition layer, a printing layer, or a combination thereof is further formed between the emboss layer and the adhesive layer
Exterior transfer film. The method according to claim 1,
The exterior transfer film is used for in-mold injection molding or injection molding
Exterior transfer film. Forming a release layer on the base layer;
Applying a composition for forming a hard coating layer of one thermosetting resin composition on the release layer to form a hard coating layer;
Forming a primer layer on the hard coat layer;
Applying a composition for forming an embossed layer of a photocurable resin composition on the primer layer, and forming an uneven pattern;
Partially curing the embossed layer on which the concavo-convex pattern is formed;
Sequentially forming an evaporation layer and a printing layer on the embossed layer on which the concavo-convex pattern is formed; And
Forming an adhesive layer on the print layer;
Lt; / RTI >
Wherein the emboss layer comprises a cured product of a photocurable resin composition comprising a photoreactive monomer and a photoreactive oligomer,
The photocurable resin composition comprises the photoreactive monomer and the photoreactive oligomer in a weight ratio of 1: 1 to 1: 1.5
A method for manufacturing a transfer film for external use. 13. The method of claim 12,
Transferring the exterior transfer film having a multilayer structure including the base layer, the release layer, the hard coat layer, the emboss layer having the concavo-convex pattern formed on one surface thereof, and the adhesive layer in this order to the injection product and then secondary-
A method for manufacturing a transfer film for external use. A decorated surface treatment layer is formed on the surface of the hard coat layer, the emboss layer having the concavo-convex pattern formed on one side, the adhesive layer,
Wherein the emboss layer comprises a cured product of a photocurable resin composition comprising a photoreactive monomer and a photoreactive oligomer,
Wherein the photocurable resin composition comprises the photoreactive monomer and the photoreactive oligomer in a weight ratio of 1: 1 to 1: 1.5. 15. The method of claim 14,
Wherein the decorative surface treatment layer further comprises a vapor deposition layer and a printing layer laminated between the emboss layer and the adhesive layer
Inmold injection molding.

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