KR20180101212A - Decoration film and method for preparing decoration film - Google Patents

Abstract

The present invention provides a decoration film which sequentially includes a hard coating layer, a printing layer, and a base material layer, and includes a concave-convex pattern. The base material layer includes a cured mixed resin composition, wherein the mixed resin composition contains: a first resin comprising an acrylonitrile-butadiene-styrene (ABS) copolymer; a second resin comprising a thermoplastic olefin resin; and a third resin comprising a styrene-butadiene-styrene (SBS) copolymer or a derivative thereof. The present invention also provides a method for preparing the decoration film. The decoration film can be applied to injection-molded products with various shapes.

Description

TECHNICAL FIELD [0001] The present invention relates to a decorative film and a decorative film,

A decorative film and a decorative film.

In general, for the various decorations, the surface of the injection mold is given a design using painting, water transferring method, insert molding method and the like. However, the water transfer method or the insert mold method has a limitation in providing the surface texture by forming the emboss pattern on the surface, so that it is difficult to realize various designs. As a method for imparting the surface texture, a decoration sheet or a decor sheet can be used. Such decoration sheet or decor sheet can be attached to an injection object through an adhesive or the like to realize various designs. When a surface texture is desired to be imparted through the embossing pattern, such decorating sheet or decor sheet has an embossing pattern, and the embossing pattern is usually heated to pass through an embossing roll, It may be formed by a method of foaming. In order for the finished article with decoration sheet or deco sheet to have a good surface texture, it is important not to damage the embroidered pattern during the molding process, so that the final article is firmly adhered to the decorative sheet or deco sheet, It is one of the physical properties required to make.

One embodiment of the present invention provides a decorative film that maintains excellent surface texture even under processing in harsh environments and realizes high elongation.

Another embodiment of the present invention provides a unique method of manufacturing a decorative film having the above advantages.

In one embodiment of the present invention, the base layer sequentially includes a hard coat layer, a print layer, and a base layer, and the base layer includes a cured product of the mixed resin composition, A first resin comprising a nitrile-butadiene-styrene (ABS) copolymer; A second resin comprising a thermoplastic olefin resin; And a third resin comprising a styrene-butadiene-styrene (SBS) copolymer or a derivative thereof.

In another embodiment of the present invention, a first resin comprising an acrylonitrile-butadiene-styrene (ABS) copolymer, a second resin comprising a thermoplastic olefinic resin, and a styrene-butadiene-styrene (SBS) Preparing a substrate layer from a mixed resin composition comprising a third resin including a derivative thereof; Preparing a printing layer and a hard coat layer on the base layer; Heating and pressing the hard coat layer side to form a concave-convex pattern; And irradiating the electron beam energy to the decorative film.

The decorative film is applicable to an injection molding of various shapes. When applied to an injection molding, the decorative film maintains excellent surface texture even when processed in a severe environment such as high temperature and vacuum, and exhibits excellent moldability based on high elongation.

The method for producing the decorative film can provide an efficient method for producing a decorative film having the above-described advantages.

1 schematically shows a cross section of a decorative film according to an embodiment of the present invention.
2 schematically shows a cross section of a decorative film according to another embodiment of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The above and other features and advantages of the present invention will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings in which: These embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art to which the invention pertains. Only.

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. Like reference numerals refer to like elements throughout the specification.

It will also be understood that when a layer, film, region, plate, or the like is referred to as being "on" or "over" another portion, . Conversely, when a part is "directly over" another part, it means that there is no other part in the middle. In addition, when a layer, film, region, plate, or the like is referred to as being "under" or "under" another portion, . Conversely, when a part is "directly underneath" another part, it means that there is no other part in the middle.

In one embodiment of the present invention, there is provided a decorative film comprising a hard coating layer, a printing layer and a substrate layer sequentially and including a rugged pattern. In this case, the base layer includes a cured product of the mixed resin composition, and the mixed resin composition includes a first resin including an acrylonitrile-butadiene-styrene (ABS) copolymer; A second resin comprising a thermoplastic olefin resin; And a third resin comprising a styrene-butadiene-styrene (SBS) copolymer or derivative thereof.

1 schematically shows a cross section of a decorative film according to an embodiment of the present invention. 1, the decorative film 100 includes a substrate layer 10, a printing layer 20 and a hard coat layer 30 sequentially from the bottom. Specifically, the decorative film 100 includes a hard coat layer 30, And the base layer 10 may be in contact with the print layer 20 immediately below the print layer 20. [

Referring to FIG. 1, the decorative film 10 includes a concave-convex pattern A. FIG. The concave-convex pattern (A) serves to impart a surface texture to the decorative film.

Specifically, the concavo-convex pattern A may be formed over the entire hard coat layer 30, the print layer 20, and the base layer 10. More specifically, the uneven pattern A has a first uneven pattern A1 on the hard coat layer 30, a second uneven pattern A2 on the interface between the hard coat layer 30 and the print layer 20, And a third uneven pattern A3 at the interface between the print layer 20 and the base layer 10. [ At this time, the surface of the hard coat layer 30 refers to one surface opposite to the print layer 20 side.

Further, the first irregular pattern A1, the second irregular pattern A2, and the third irregular pattern A3 may be mutually compliant. That is, as shown in Fig. 1, the recessed portions and the convex portions of the first uneven pattern A1, the second uneven pattern A2, and the third uneven pattern A3 are present at positions corresponding to each other , The average depth and the average spacing may be the same or similar to an error range of 占 1 占 퐉.

Referring to FIG. 1, the first irregular pattern A1, the second irregular pattern A2, and the third irregular pattern A3 may have an average depth h of about 10 μm to about 200 μm, , And the average spacing (d) may be between about 50 μm and about 5 mm. Through such average depth h, the average spacing d, the decorative film 100 can achieve a good surface texture. It is also possible to obtain the advantage that the decorative film having such concave-convex patterns maintains the depth and interval of the surface well during post-processing through heat-forming, that is, the film having excellent average depth retention ratio is formed.

Referring to FIG. 1, the substrate layer 10 serves to support the hard coat layer 30 and the print layer 20, and includes a cured product of the mixed resin composition. At this time, the mixed resin composition includes the first resin, the second resin, and the third resin in a mixed state, whereby the base layer can be provided with improved support performance, heat resistance, and moldability through the cured product. Even if the decorative film 100 is placed in a harsh environment in the subsequent processing, it is possible to maintain the depth and spacing of the concave / convex patterns included in the decorative film, thereby giving excellent surface texture and decorative property. Accordingly, it can be more useful as a decorative sheet for automobiles.

The first resin comprises an acrylonitrile-butadiene-styrene (ABS) copolymer. The ABS copolymer is a copolymer prepared through a polymerization reaction from a monomer component containing acrylonitrile, butadiene and styrene. By including the ABS copolymer in the first resin, an improved elongation, heat resistance and moldability can be secured as compared with the case of using other kinds of resins such as polyethylene terephthalate (PET) and polyacrylate, Which is advantageous in terms of processability.

Specifically, the ABS copolymer may contain about 5 mol% to about 35 mol% of butadiene-derived constituent units. That is, the ABS copolymer may contain a constituent unit derived from butadiene in a molar ratio within the above range, and a constituent unit derived from an acrylonitrile and a styrene derived constituent unit may be composed of about 65 mol% to about 95 mol%. By satisfying the content ratio of the constituent units of the ABS copolymer, the reactivity to electron beam crosslinking can be greatly improved, and excellent heat resistance can be exhibited. As a result, not only small-sized uneven patterns but also large- It can be implemented with excellent performance.

The second resin includes a thermoplastic olefin-based resin. The thermoplastic polyolefin-based resin is a polymer or copolymer based on an olefin compound while having a thermoplastic property which is repeatedly flowable at a high temperature. The second resin may include a thermoplastic olefin-based resin to improve the curing density in the substrate layer containing the thermoplastic olefin-based resin. The average depth retention ratio of the concavo-convex pattern can be improved through the combination of the first resin and the third resin. Specifically, the thermoplastic olefin-based resin may include one selected from the group consisting of thermoplastic polyolefin (TPO), polyolefin elastomer (POE), and combinations thereof. The thermoplastic polyolefin (TPO) has no elasticity, and the polyolefin elastomer (POE) has rubber-like elasticity.

The thermoplastic polyolefin (TPO) may be a polyethylene-based thermoplastic polyolefin (TPO). The mixed resin composition may include a polyethylene-based thermoplastic polyolefin as a second resin and may be crosslinked and cured by irradiating electron beam energy. Thus, the uneven pattern can be supported and retained to provide excellent average depth retention.

For example, the polyethylene-based thermoplastic polyolefin (TPO) may be selected from the group consisting of polyethylene (PE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE) . ≪ / RTI >

In addition, the polyolefin elastomer (POE) may include one selected from the group consisting of an ethylene -? - olefin copolymer, a propylene -? - olefin copolymer, and a combination thereof. Here, the? -Olefin may include one selected from the group consisting of 1-butene, 1-hexene, 1-octene, and combinations thereof.

In addition, the thermoplastic olefin-based resin may not contain polypropylene. The base layer includes a second resin including a thermoplastic olefin resin, and can be crosslinked and cured by irradiation of electron beam energy. Thus, the curing density of the base layer increases, and the performance of supporting and holding the uneven pattern can be greatly improved. On the other hand, among the thermoplastic olefin resins, polypropylene is not cured even when irradiated with electron beam energy. Specifically, when the thermoplastic olefin-based resin is irradiated with electron beam energy, the crosslinking and curing reaction can proceed by the dehydrogenation process. On the other hand, polypropylene can not undergo crosslinking and curing reactions even when irradiated with electron beam energy. Therefore, when the thermoplastic olefin-based resin contains polypropylene, cross-linking and hardening do not occur even when electron beam energy is applied to the substrate layer containing the polypropylene, so that the irregular pattern can not be supported and maintained, Can be remarkably deteriorated.

The third resin includes a styrene-butadiene-styrene (SBS) copolymer or a derivative thereof. The styrene-butadiene-styrene (SBS) copolymer is a block copolymer made of a styrene-butadiene-styrene block unit, which is prepared through polymerization reaction from a mono-component including styrene and butadiene.

The derivative of the styrene-butadiene-styrene (SBS) copolymer may include styrene-ethylene-butadiene-styrene (SEBS), styrene-butylene-butadiene-styrene (SBBS), or both. The SEBS is a block copolymer prepared through a polymerization reaction from a monomer component containing styrene, butadiene and ethylene, and the SBBS is a block copolymer prepared through polymerization reaction from a monomer component containing styrene, butadiene and butylene .

In one embodiment, the third resin may comprise styrene-ethylene-butadiene-styrene (SEBS), styrene-butylene-butadiene-styrene (SBBS), or both.

Since the third resin includes the SBS copolymer or a derivative thereof, the phase structure of the mixed resin composition can be easily adjusted to a desired level, as compared with the case where another kind of resin is used, The resin and the second resin can be mixed more uniformly.

The third resin may include a compound in which a reactive group is graft-polymerized on the main chain of the SBS copolymer or derivative thereof. The reactive group may include an epoxy group, a maleic-anhydride group, or both.

The mixed resin composition may include about 10 parts by weight to about 30 parts by weight of the second resin relative to 100 parts by weight of the first resin, specifically about 20 parts by weight to about 30 parts by weight . By using the second resin at a content ratio in the above-described range with respect to the first resin, it is possible to realize excellent electron beam crosslinking performance, and as a result, the durability of the base layer can be improved.

Specifically, when the content of the second resin is less than the above range, the cured density of the substrate layer containing the second resin is low, so that the concavo-convex pattern included in the decorative film can not be maintained. If the content of the second resin exceeds the above range, the content of the first resin may be inadequate and the heat resistance may be deteriorated. Accordingly, it is preferable that the concave- It may not be easy.

In addition, the mixed resin composition may include about 5 to about 20 parts by weight of the third resin, for example, about 5 to about 15 parts by weight, based on 100 parts by weight of the first resin. The third resin is used in a content ratio in the above-described range with respect to the first resin so that the first resin and the second resin can be uniformly mixed, and the base layer realizes improved supporting performance.

The base layer includes a cured product of the mixed resin composition, and the cured product may be an electron beam cured product. That is, the mixed resin composition can be cured through electron beam irradiation. Since the base layer is made of an electron beam hardened material, the hardened density is increased and the performance of supporting the uneven pattern can be greatly improved, compared with the case where the base layer is made of an optical hardened material or a thermally hardened material. In addition, the average depth retention ratio of the concavo-convex pattern can be improved. At this time, the mixed resin composition can be cured by irradiation with an electron beam energy having an absorbed dose of 50 kGy to 200 kGy at an irradiation intensity of an acceleration voltage of 500 KeV to 1000 keV. The mixed resin composition can be cured to a proper crosslinking density when it is cured using such electron beam energy while containing the first resin, the second resin and the third resin in the above-mentioned content ratio.

When the substrate layer contains only one of the first resin, the second resin and the third resin, not the mixed resin composition, even when the electron beam energy is irradiated, a sufficient curing density is not formed and the support performance can not be realized , The concavo-convex pattern included in the film can not be supported and held, and the surface texture may be deteriorated.

The base layer includes the mixed resin composition and is cured by electron beam energy irradiation to realize excellent support performance for the hard coat layer and the print layer so that the rough pattern can be maintained without damage even in a severe environment, And it is possible to realize excellent moldability based on high elongation.

The decorative film may have an average depth retention ratio of about 70% to about 95% of the concavo-convex pattern according to the following formula (1).

[Formula 1]

Mean depth retention (%) = mean post-molding depth / average pre-molding depth X 100

The average depth after molding is a value obtained by measuring the average depth of the concavo-convex pattern included in the decorative film after allowing the decorative film to stand at a temperature of 200 ° C for 10 minutes, Means a value obtained by measuring the average depth of the concave-convex pattern included in the decorative film. The average depth of the concavo-convex pattern is determined by a first irregular pattern A1 on the hard coating layer 30, a second irregular pattern A2 on the interface between the hard coating layer 30 and the print layer 20, Means an average value of the average depths of the third relief patterns A3 at the interface between the print layer 20 and the base layer 10

In a decorative film having a concavo-convex pattern, in particular, a film having a deep embossed pattern such as a deep emboss is liable to be collapsed because the depth or the like is not maintained when the film is placed in a harsh environment such as high temperature and vacuum. Accordingly, when a decorative film having a concave-convex pattern is applied to an injection molded article, there is a problem that the decorative property is deteriorated due to the lack of surface texture during processing in a harsh environment such as high temperature and vacuum.

On the other hand, the decorative film can maintain the average depth retention ratio of the concave-convex pattern at a high level even in a severe environment such as high temperature and vacuum as described above, thereby improving the surface texture and maintaining the decorative property.

Specifically, the decorative film includes the above-described laminated structure and material, and can be cured through electron beam energy irradiation, thereby increasing the curing density and supporting and holding the concave-convex pattern.

Referring to FIG. 1, the decorative film 100 includes a printing layer 20 on the base layer 10. The printing layer 20 may be formed of a layer including patterns, characters, and the like required depending on the use of the decorative film 100, and the manufacturing method thereof is not particularly limited.

In one embodiment, the printing layer 20 comprises a binder resin comprising an acrylic resin or a vinyl resin; And urethane-based inks.

In addition, the decorative film 100 includes a hard coating layer 30 on the printing layer 20. When the decorative film 100 is applied to an end use, the hard coating layer 30 is the layer closest to the exterior and serves to realize the surface texture and surface durability of the decorative film.

In one embodiment, the hard coat layer 30 may comprise a thermoset material of a composition for forming a hard coat layer comprising an acrylic resin having a weight average molecular weight (Mw) of about 30,000 to about 200,000. The hard coating layer 30 is a layer which is a direct object of the uneven pattern forming process in the process of manufacturing the decorative film 100. The hard coating layer 30 contains an acrylic resin having a weight average molecular weight in the above- The formation process of the concave / convex pattern can be facilitated, and excellent durability can be realized.

2 schematically shows a cross section of a decorative film 100 'according to another embodiment of the present invention. Referring to FIG. 2, the decorative film 100 'may further include a carrier film 40 on one side of the base layer 10. In addition, the carrier film 40 includes an adhesive layer 41 and a protective film 42.

The carrier film 40 protects the decorative film 100 'during distribution. When the decorative film 100 'is to be adhered to a predetermined molded article, the protective film 42 is removed from the carrier film 40, and then processed to be attached to the molded article through the adhesive layer 41 can do.

The adhesive layer 41 may include one selected from the group consisting of acrylic adhesive, silicone adhesive, epoxy adhesive, urethane adhesive, polyamide adhesive, ethylene-vinyl acetate (EVA) adhesive, and combinations thereof.

The protective film 42 may be a polyethylene terephthalate (PET) film, a polycarbonate (PC) film, or the like.

In the decorative film 100, 100 ', the base layer 10 may have a thickness of about 100 μm to about 500 μm. The base layer is a cured product of the mixed resin composition. Concretely, when the thickness of the base layer is less than the above range, the support performance and workability are poor, and it may be difficult to use the laminate in an injection product. When the thickness of the base layer is more than the above range, the degree of curing due to ultraviolet curing is not sufficient and uniform curing is not formed over the entire base layer, so that the problem that the irregular patterns can not be supported and maintained have. The thickness of the print layer 20 may be about 1 탆 to about 5 탆, and the hard coat layer 30 may have a thickness of about 5 탆 to about 20 탆. The thickness of each layer satisfies the above range so that the uneven pattern can be formed over the entire laminated structure of the base layer 10, the print layer 20 and the hard coat layer 30, and the base layer 10 The performance of supporting the print layer 20 and the hard coat layer 30 can be excellently realized.

In another embodiment of the present invention, there is provided a method of making the decorative film.

Specifically, the method for producing the decorative film includes a first resin including an acrylonitrile-butadiene-styrene (ABS) copolymer, a second resin including a thermoplastic olefin resin, and a styrene-butadiene-styrene (SBS) Preparing a substrate layer from a mixed resin composition comprising a third resin comprising a covalent bond or a derivative thereof; Preparing a printing layer and a hard coat layer on the base layer; Heating and pressing the hard coat layer side to form a concave-convex pattern; And irradiating the electron beam energy.

Through the method of manufacturing the decorative film, in one embodiment, a decorative film as shown in Fig. 1 can be produced.

That is, referring to FIG. 1, the decorative film 100 manufactured through the method of manufacturing the decorative film sequentially includes the hard coating layer 30, the printing layer 20, and the substrate layer 10, The print layer 20 is directly under the hard coat layer 30 and the base layer 10 is in contact with the print layer 20 immediately below the print layer 20.

 The decorative film 100 produced by the method of manufacturing the decorative film includes a concave-convex pattern A and the concave-convex pattern A is formed on the hard coating layer 30, the printing layer 20, May be formed throughout the layer (10).

More specifically, the uneven pattern A has a first uneven pattern A1 on the hard coat layer 30, a second uneven pattern A2 on the interface between the hard coat layer 30 and the print layer 20, And a third uneven pattern A3 at the interface between the print layer 20 and the base layer 10. [ At this time, the surface of the hard coat layer 30 refers to one surface opposite to the print layer 20 side.

Further, the first irregular pattern A1, the second irregular pattern A2, and the third irregular pattern A3 may be mutually compliant. That is, as shown in Fig. 1, the recessed portions and the convex portions of the first uneven pattern A1, the second uneven pattern A2, and the third uneven pattern A3 are present at positions corresponding to each other , The average depth and the average spacing may be the same or similar to an error range of 占 1 占 퐉.

The ranges of the average depth h and the average spacing d of the first relief pattern A1, the second relief pattern A2 and the third relief pattern A3 are as described above.

The method for producing the decorative film includes a step of producing a base layer from a mixed resin composition comprising the first resin, the second resin and the third resin.

In the mixed resin composition, the details of the first resin, the second resin and the third resin are all as described above.

Specifically, the mixed resin composition is prepared by compounding the first resin, the second resin, and the third resin without simple blending. Specifically, the first resin, the second resin and the third resin exist in a solid state at room temperature. As a method of mixing these materials, it is simple blending that they are put into a solvent or the like and mixed. Alternatively, in the manufacturing method according to an embodiment of the present invention, the mixed resin composition is prepared by using a compounding method in which the resins in a solid state are melted and mixed at a temperature above the melting point. The first resin, the second resin and the third resin may be evenly mixed by the compounding method.

The mixed resin composition, which is melted and melted at a temperature equal to or higher than the melting point, is solidified again into a solid state, pelletized, and then extruded from a T-die or the like to form a base layer.

The method for producing the decorative film includes a step of producing a printing layer and a hard coating layer on the base layer, wherein the printing layer and the hard coating layer are each formed using a composition for forming a printing layer and a composition for forming a hard coating layer.

Specifically, the step of preparing the printing layer and the hard coating layer on the base layer may include the steps of: preparing a transfer film in which the hard coating layer and the printing layer are sequentially formed on a release film; And a step of laminating the print layer of the transfer film so as to be in contact with the base layer, and then thermally transferring the print layer and the hard coat layer on the base layer.

At this time, the transfer film is formed by applying the hard coat layer composition on the release film and drying the hard coat layer to form a hard coat layer, and forming a print layer on the hard coat layer using the composition for forming a print layer.

In one embodiment, the composition for forming a hard coating layer may include an acrylic resin having a weight average molecular weight (Mw) of about 30,000 to about 200,000. In this case, the composition for forming a hard coat layer secures an appropriate viscosity and is applied without defects, and an advantage advantageous in formation of a concavo-convex pattern and shape retention can be secured.

The composition for forming a hard coat layer may be a thermosetting composition. In the case of the composition for forming a hard coat layer, when the concave-convex pattern is formed, it becomes a direct object of processing. When the composition for forming a hard coat layer is composed of a thermosetting composition, A process advantage can be obtained.

In one embodiment, the printing layer forming composition comprises a binder resin comprising an acrylic resin or a vinyl resin; And urethane-based inks . A specific method for forming the print layer using the composition for forming a print layer is not particularly limited, and for example, a comma coating method, a microgravure coating method, a slot die coating method, and the like can be used, .

The method for manufacturing the decorative film includes heating and pressing the hard coating layer side to form a concave / convex pattern. In this step, the first concave-convex pattern A1 is formed on the surface of the hard coat layer by heating and pressing the hard coating layer side, and the second concave-convex pattern A2 and the third convex pattern A3 May be formed.

Specifically, the temperature of the environment in which the step of pressing the hard coating layer side is performed may be about 400 ° C. to about 500 ° C., and the thermal energy received by the hard coating layer may be a thermal energy corresponding to about 190 ° C. to about 200 ° C. . By performing the process at such a temperature condition, the hard coating layer can be hardened to an appropriate hardness, and concavo-convex patterns having a desired average depth and average interval can be formed over the hard coating layer, the print layer, and the substrate layer.

The method of manufacturing the decorative film includes irradiating electron beam energy. The step of irradiating the electron beam energy may be performed separately after the step of heating and pressing the hard coat layer to form a concavo-convex pattern, so that the substrate layer can realize excellent support performance and strength, Patterns can be prevented from being broken or damaged even in harsh environments.

Specifically, the electron beam energy can be irradiated with an irradiation intensity of an acceleration voltage of 500 KeV to 1000 keV and an absorbed dose of 50 kGy to 200 kGy. As described above, the mixed resin composition includes the first resin, the second resin and the third resin, and when the electron beam energy of the above conditions is irradiated by controlling the specific kind and the content ratio thereof, As a base layer.

That is, while the base layer realizes excellent support performance for the print layer and the hard coat layer thereon, the first irregular pattern, the second irregular pattern, and the third irregular pattern can be formed at high temperature and / Even in a harsh environment such as a vacuum, the shape can be maintained well.

Further, through the irradiation of the electron beam energy, the printed layer and the hard coat layer itself can be provided with physical properties such that the concavo-convex patterns formed thereon do not collapse in a harsh environment and are maintained well.

Hereinafter, specific embodiments of the present invention will be described. However, the embodiments described below are only intended to illustrate or explain the present invention, and thus the present invention should not be limited thereto.

<Production Example>

Production Example 1

25 parts by weight of polyethylene (PE, LG Chem, SP310) and 100 parts by weight of styrene-ethylene-butadiene-styrene (SEBS) were added to 100 parts by weight of an acrylonitrile-butadiene-styrene (ABS) copolymer containing 30% by mol of a structural unit derived from butadiene. , Asahi Kasei Co., Ltd., H1043) were compounded to prepare a first mixed resin composition.

Production Example 2

Except that 10 parts by weight of a styrene-butylene-butadiene-styrene (SBBS, Asahi Kasei Corporation, P2000) copolymer was used in place of the styrene-ethylene-butadiene-styrene (SEBS) copolymer To prepare a second mixed resin composition.

Production Example 3

A third mixed resin composition was prepared in the same manner as in Preparation Example 1, except that 25 parts by weight of a thermoplastic polyolefin elastomer (TPE, LG Chem, 1192A) was used instead of polyethylene (PE).

Production Example 4

Except that 10 parts by weight of a compound (maleic anhydride group) grafted onto the main chain of SEBS (manufactured by Asahi Kasei Corporation) instead of the styrene-butadiene-styrene (SEBS) copolymer was used To prepare a fourth mixed resin composition.

Production Example 5

A fifth mixed resin composition containing no polyethylene (PE) and styrene-ethylene-butadiene-styrene (SEBS) copolymer was prepared from the first mixed resin composition of Production Example 1.

Production Example 6

A sixth mixed resin composition containing no styrene-ethylene-butadiene-styrene (SEBS) copolymer was prepared from the first mixed resin composition of Production Example 1.

Production Example 7

A seventh mixed resin composition not containing polyethylene (PE) was produced from the first mixed resin composition of Production Example 1.

Production Example 8: Preparation of composition for forming printing layer

Gravure printing ink: binder ink: MEK = 2: 2: 1 at a weight ratio of 1: 1 to prepare a print layer forming composition.

Production Example 9: Preparation of composition for forming hard coat layer

A monomer component obtained by mixing 70 parts by weight of methyl methacrylate (MMA), 10 parts by weight of butyl methacrylate (BMA), 5 parts by weight of hexylethyl methacrylate (HEMA) and 14 parts by weight of isobonyl methacrylate (IBOMA) And 1 part by weight of a heat initiator 2,2'-azo-bisisobutyronitrile (AIBN) were mixed and reacted under a nitrogen atmosphere at 60 ° C for 12 hours to prepare a random copolymer. At this time, 50 parts by weight of methyl ethyl ketone (MEK) and 50 parts by weight of ethyl acetate (EAc) were used as a polymerization solvent to obtain a polymer having a final solid content of 30% by weight and a weight average molecular weight of 100,000. The solid content was diluted to 25% by weight with methyl isobutyl ketone (MIBK), and 2 parts by weight of a curing agent (TKA-100 by Asahi Kasei Co., Ltd.) was blended to prepare a hard coat layer composition.

&Lt; Examples and Comparative Examples &

Example 1

The first mixed resin composition of Production Example 1 was pelletized and extruded to prepare a base layer having a thickness of 200 mu m. Subsequently, a hard coat layer having a thickness of 15 탆 was prepared by applying the composition for forming a hard coat layer of the above Production Example 9 on a polyethylene terephthalate (PET) release film and drying the same. Using the composition for forming a print layer Gravure printing was carried out to prepare a 2 탆 printed layer. Subsequently, the print layer and the hard coat layer were transferred to the base layer by a thermal transfer method after the print layer was laminated on the base layer. Next, a heat treatment is performed in an environment of 500 ° C so that the temperature at which the composition for forming a hard coat layer is received is about 190 ° C to about 200 ° C, and then a pressure is applied to the hard coat layer side to form a first relief pattern, A second uneven pattern was formed on the interface between the hard coat layer and the print layer, and a third uneven pattern was formed on the interface between the print layer and the base layer. At this time, each of the layers had a concave-convex pattern with an average depth of 100 mu m and an average interval of 500 mu m. Each of the concavo-convex patterns was formed so as to conform to each other. Subsequently, electron beam energy of an absorbed dose of 100 KGy was irradiated at an irradiation intensity of an acceleration voltage of 500 kev to 1000 kev and electron beam cured to produce a decorative film.

Example 2

A decorative film was prepared in the same manner as in Example 1, except that the base layer was prepared by extruding the second mixed resin composition of Production Example 2.

Example 3

A decorative film was prepared in the same manner as in Example 1, except that the base layer was prepared by extruding the third mixed resin composition of Production Example 3.

Example 4

A decorative film was prepared in the same manner as in Example 1, except that the base layer was prepared by extruding the fourth mixed resin composition of Production Example 4.

Comparative Example 1

A decorative film was prepared in the same manner as in Example 1 except that the base layer was prepared by extruding the fifth mixed resin composition of Production Example 5. [

Comparative Example 2

A decorative film was prepared in the same manner as in Example 1 except that the base layer was prepared by extruding the sixth mixed resin composition of Production Example 6. [

Comparative Example 3

A decorative film was prepared in the same manner as in Example 1 except that the base layer was prepared by extruding the seventh mixed resin composition of Production Example 7. [

Comparative Example 4

In Example 1, a decorative film was produced in the same manner as in Example 1, except that a polyvinyl chloride (PVC) film was used as the base layer with the same thickness and no electron beam curing was performed.

<Evaluation>

For each of the decorative films of Examples 1-4 and Comparative Examples 1-4, the average depth of the concavo-convex pattern at room temperature was measured. At this time, it was confirmed that the average depth of the concavo-convex pattern at the room temperature was about 100 mu m. Then, each of the decorative films was allowed to stand in an oven at a temperature of 200 DEG C for 10 minutes, and the average depth of the concavo-convex pattern was measured. Then, the average depth maintenance ratio (%) according to the following formula 1 was derived. In this case, the average depth of the concave-convex pattern means an average value of the average depths of the first convex pattern, the second convex pattern and the third convex pattern.

 The results are shown in Table 1 below.

[Formula 1]

Mean depth retention (%) = mean post-molding depth / average pre-molding depth X 100

Average Depth Retention Rate [%] Example 1 90 Example 2 90 Example 3 80 Example 4 80 Comparative Example 1 30 Comparative Example 2 50 Comparative Example 3 30 Comparative Example 4 20

Referring to the results of Table 1, the decorative film according to Examples 1 to 4 according to an embodiment of the present invention is characterized in that the base layer is made of a mixed resin composition of a first resin, a second resin and a third resin Comparative Examples 1 to 3, in which a base layer was formed using a composition that did not contain any of the first resin, the second resin and the third resin, and a base layer of a conventional polyvinyl chloride (PVC) It can be confirmed that the decorative film of Comparative Example 4 is superior in depth retention performance under a harsh environment at a high temperature.

Specifically, the decorative film according to one embodiment of the present invention shows an average depth retention ratio (%) of 80% or more, for example, about 90% or more according to the formula 1, .

That is, the decorative film produced by the method of manufacturing a decorative film according to an embodiment of the present invention can be applied to various shapes of injection molding materials, and it can be applied to injection molding products even if it is processed under harsh environments such as high temperature and vacuum, And can exhibit excellent moldability based on high elongation.

100, 100 ': decorative film
10: substrate layer
20: Printed layer
30: Hard coating layer
A: Uneven pattern
A1: 1st uneven pattern
A2: second uneven pattern
A3: Third uneven pattern
h: Average Depth
d: Average spacing

Claims (15)

A hard coat layer, a print layer and a substrate layer sequentially,
Including irregular patterns,
Wherein the base layer contains a cured product of the mixed resin composition,
In the mixed resin composition,
A first resin comprising an acrylonitrile-butadiene-styrene (ABS) copolymer;
A second resin comprising a thermoplastic olefin resin; And
And a third resin comprising a styrene-butadiene-styrene (SBS) copolymer or derivative thereof
Decorative film.
The method according to claim 1,
Wherein the thermoplastic olefin-based resin comprises one selected from the group consisting of thermoplastic polyolefin (TPO), polyolefin elastomer (POE), and combinations thereof
Decorative film.
The method according to claim 1,
The thermoplastic olefin-based resin is preferably a polypropylene-
Decorative film.
The method according to claim 1,
The concavo-
A first irregular pattern on the surface of the hard coat layer;
A second irregular pattern on an interface between the hard coat layer and the print layer; And
And a third uneven pattern on the interface between the print layer and the base layer
Decorative film.
5. The method of claim 4,
The first irregular pattern, the second irregular pattern, and the third irregular pattern each have an average depth of 10 mu m to 200 mu m and an average spacing of 50 mu m to 5 mm
Decorative film.
The method according to claim 1,
Wherein the mixed resin composition comprises 10 to 30 parts by weight of the second resin relative to 100 parts by weight of the first resin
Decorative film.
The method according to claim 1,
Wherein the mixed resin composition comprises 5 to 20 parts by weight of the third resin relative to 100 parts by weight of the first resin
Decorative film.
The method according to claim 1,
Wherein the acrylonitrile-butadiene-styrene (ABS) copolymer comprises 5 to 35 mol% of butadiene-derived constituent units
Decorative film.
The method according to claim 1,
Wherein the third resin comprises a compound in which a reactive group is graft-polymerized on the main chain of the styrene-butadiene-styrene (SBS) copolymer or derivative thereof,
The reactive group may be an epoxy group, a maleic-anhydride group, or both
Decorative film.
The method according to claim 1,
Wherein the decorative film has an average depth retention ratio of the concavo-convex pattern of 70% to 95%
Decorative film:

[Formula 1]
Mean depth retention (%) = mean post-molding depth / average pre-molding depth X 100

The average depth after molding is an average value of the measured values of the depth of the concavo-convex pattern included in the decorative film after the decorative film is allowed to stand at a temperature of 200 ° C for 10 minutes. Is an average value of the depth of the concave-convex pattern included in the decorative film.
The method according to claim 1,
Wherein the base layer has a thickness of 100 to 500 mu m
Decorative film.
A second resin comprising a thermoplastic olefin resin and a third resin comprising a styrene-butadiene-styrene (SBS) copolymer or a derivative thereof, wherein the first resin comprises an acrylonitrile-butadiene-styrene (ABS) Preparing a substrate layer from the mixed resin composition;
Preparing a printing layer and a hard coat layer on the base layer;
Heating and pressing the hard coat layer side to form a concave-convex pattern; And
Irradiating the electron beam energy
A method for manufacturing a decorative film.
13. The method of claim 12,
In the step of heating and pressing the hard coat layer side to form a concave / convex pattern,
The concavo-convex pattern is formed over the hard coat layer, the print layer, and the base layer
A method for manufacturing a decorative film.
13. The method of claim 12,
Wherein the step of preparing the print layer and the hard coat layer on the base layer comprises:
Preparing a transfer film on which the hard coat layer and the print layer are successively formed on a release film; And
Laminating the print layer of the transfer film so as to be in contact with the base layer, and then thermally transferring the print layer and the hard coat layer on the base layer
A method for manufacturing a decorative film.
13. The method of claim 12,
The step of irradiating the electron beam energy may include the step of irradiating the electron beam energy at an irradiation intensity of 500 keV to 1000 keV and an absorbed dose of 50 kGy to 200 kGy
A method for manufacturing a decorative film.

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