KR101916710B1 - Decoration film and methods producing for the film's surface layer - Google Patents

Abstract

The present invention relates to a decoration film having excellent hardness, antifouling property, stain resistance and the like without a hard coating layer and a method for producing the surface layer, and more particularly to a decoration film having a surface layer composed of polymethyl methacrylate, fluororesin and nano silica on a support layer and a color- A decorative film formed by extrusion at one time, and a method for producing the surface layer.

Description

TECHNICAL FIELD [0001] The present invention relates to a decorative film and a method of manufacturing the same. [0002] DECORATION FILM AND METHODS PRODUCING FOR THE FILM'S SURFACE LAYER [

The present invention relates to a decorative film and a method for producing the surface layer. More particularly, the present invention relates to a decoration film having excellent surface scratch resistance and antifouling properties, The present invention relates to a decoration film having a surface layer which is easily covered with a product of the present invention.

Generally, transparent plastic polymers are widely used in the fields of sheet paper, decoration films, optical devices, lenses, and display devices. However, it is disadvantageous in that the surface hardness is low, durability against abrasion and stain resistance are low. Also, transparency may be deteriorated by inducing scattering of light due to the phenomenon of Kim Se-lim.

Recently, a hard coating method has been proposed for solving these drawbacks, and various hard coating materials have been developed. In particular, organic materials containing inorganic particles are being applied to various coating industries by using a sol-gel process.

Organic-inorganic composites having excellent mechanical strength and thermal stability of inorganic nanomaterials have been widely used as the hard coating method is actively researched, and flexibility and excellent processability of organic polymers are maintained.

In the decorative film industry in recent years, a decorating film having a surface layer hard-coated on the upper side of the support layer, the color imparting layer on the upper and lower sides of the support layer and the upper color imparting layer is generally used. Acrylic hard coating composition is used for the hard coating layer.

However, in the case of such a hard coating method, a separate hard coating process must be added to form a layer, which is a major cause of an increase in manufacturing cost and a prolonged manufacturing process time, and an environmental problem may be caused due to progression to a wet process have.

In the case of a conventional hard coating decorated film, there is no problem in coating the 2D shape, but when the 3D shape is coated by vacuum forming, a crack is generated in the hard hard coating layer. Therefore, in the case of the decoration film for the 3D shape, the entire amount is imported in Japan, and it is divided according to the shape, and the management cost according to the binary is additionally generated.

However, in addition to the hard coating method, methods for improving antifouling property, durability and hardness have not been studied.

The present invention aims at solving all of the above problems.

It is another object of the present invention to provide a decorative film and a method for producing the surface layer thereof which are laminated at one time by coextrusion without additionally adding a hard coating process.

Another object of the present invention is to provide a decorative film having excellent optical characteristics, hardness and antifouling property and a method for producing the surface layer thereof.

Another object of the present invention is to provide a decoration film in which no cracks are generated when covering a 3D shape, and a method of manufacturing the surface layer thereof.

In order to accomplish the objects of the present invention as described above and achieve the characteristic effects of the present invention described below, the characteristic structure of the present invention is as follows.

According to an aspect of the present invention, A color imparting layer formed on upper and lower portions of the support layer; And a surface layer composed of polymethyl methacrylate, a fluorine resin, and a silica nanoparticle composite formed on the upper color imparting layer, and a method for producing the surface layer.

According to one aspect of the present invention, there is provided a decoration film characterized by that the fluorine-based resin is polyvinylidene difluoride and a method for producing the surface layer thereof.

According to one aspect of the present invention, the support layer may include at least one member selected from the group consisting of polyvinyl chloride, polyethylene terephthalate, polypropylene and acrylonitrile butadiene styrene, and the upper and lower color imparting layers A decorating film which can include at least one selected from the group consisting of glycol-modified polyethylene terephthalate, polybutylene terephthalate and poly (cyclohexylene dimethylene terephthalate) glycol, and a method for producing the surface layer thereof.

The present invention provides a decorative film which is co-extruded together with a base layer and a hue imparting layer, not a separate coating process, by forming a surface layer composed of polymethyl methacrylate, a fluorine resin and a nanosilica composite, The manufacturing cost and the process time can be saved.

Further, the present invention has an effect of preventing cracks from occurring when covering a 3D shape by forming a surface layer composed of polymethylmethacrylate, a fluorine resin, and a nanosilica composite.

Further, the decoration film of the present invention is a transparent thermoplastic film even when hard coating process is not included, and has an excellent optical characteristic, antifouling property and hardness.

In addition, since the hard coating process is omitted, the present invention has the effect of preventing the problem of environmental pollution that has already existed.

1 is a schematic cross-sectional view of a decoration film according to the present invention.
2 is a schematic view of a twin extruder for extruding polymethyl methacrylate, a fluorine resin and a nano silica compounding constituting the surface layer according to the present invention.
FIG. 3 is a schematic drawing of a screw portion of a twin extruder for extruding polymethyl methacrylate, fluororesin and nano silica compounding constituting the surface layer according to the present invention.

The following description of the invention refers to the accompanying drawings, which illustrate, by way of example, specific embodiments in which the invention may be practiced. These embodiments are described in sufficient detail to enable those skilled in the art to practice the invention. It should be understood that the various embodiments of the present invention are different, but need not be mutually exclusive. For example, certain features, structures, and characteristics described herein may be implemented in other embodiments without departing from the spirit and scope of the invention in connection with one embodiment. It should also be understood that the position or arrangement of individual components within each disclosed embodiment may be varied without departing from the spirit and scope of the present invention. The following detailed description is, therefore, not to be taken in a limiting sense, and the scope of the present invention is to be limited only by the appended claims, along with the full scope of equivalents to which such claims are entitled, if properly explained. In the drawings, like reference numerals refer to the same or similar functions throughout the several views.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings, so that those skilled in the art can easily carry out the present invention.

A decoration film according to an embodiment of the present invention may include a support layer, a color imparting layer, and a surface layer.

First, the support layer of the present invention is characterized by being at least one selected from polyvinyl chloride (PVC), polyethylene terephthalate (PET), polypropylene (PP), acrylonitrile butadiene styrene (ABS) Amorphous polyethylene terephthalate.

Since amorphous polyethylene terephthalate has high transparency and is environment-friendly, it has been attracting attention as a substitute for thermoplastic resins such as PVC and PS.

The thickness of the above-described support layer may be 50 to 250 占 퐉, and preferably 150 to 200 占 퐉, but is not limited thereto. When the supporting layer is less than 50 탆, the mechanical properties such as hardness, progress and hardness are poor. When the supporting layer is more than 250 탆, the decoration film is thick and is not good in appearance and is difficult to be applied to real life.

In addition, the upper and lower portions of the support layer of the present invention may each include a color imparting layer, and the color imparting layer may include glycol-modified polyethylene terephthalate (PETG), polybutylene terephthalate (PBT), and glycol- Silane dimethylene terephthalate) (PCTG), and is preferably glycol-modified polyethylene terephthalate.

The thickness of the above-mentioned color imparting layer may be independently 10 to 60 mu m, preferably 30 mu m, but is not limited thereto.

The glycol-modified polyethylene terephthalate is environmentally friendly because it does not generate chlorine gas when it is incinerated or a fire and does not contain harmful substances such as environmental hormones, and improves processability, moldability, printing property and impact resistance and prevents deformation due to shrinkage . In addition, polyethylene terephthalate, which does not cause thermal crystallization even when heat is applied, can always maintain transparency.

The glycol-modified polyethylene terephthalate may be an amorphous resin obtained by copolymerizing an acid component containing terephthalic acid as a main component and a diol component containing 5 to 80 mol% of ethylene glycol and 10 to 40 mol% of cyclohexane dimethanol.

However, the film made of only the support layer and the color imparting layer has a disadvantage that scratches and cracks easily occur on the surface, contamination due to external stimuli can easily occur, and the film is easily discolored due to exposure to light for a long time. I do not.

Therefore, the present invention can include a polymethylmethacrylate resin layer as a surface layer on the upper color imparting layer, and more specifically, it can include polymethyl methacrylate, a fluorine resin, and a nanosilica composite.

The surface layer of the present invention may be 5 to 100 mu m, preferably 20 mu m.

Polymethyl methacrylate is a polymer obtained by polymerizing methyl methacrylate, and is a representative methacrylic resin. Among plastic materials, it has outstanding transparency and light resistance, and has good balance of mechanical strength and formability.

 The fluorine-based resin may preferably include polyvinylidene fluoride represented by the following formula (1), which may be a vinylidene fluoride homopolymer or a copolymer containing vinylidene fluoride.

The above-mentioned polyvinylidene fluoride has excellent compatibility with polymethyl methacrylate, maintains transparency upon blending, has excellent chemical resistance, relative ease of processing, high strength, elongation, rigidity and abrasion resistance, and has a high crystalline melting point It is resistant to continuous use at a high temperature of 130 degrees Celsius, has excellent mold resistance, and has a very smooth surface, which makes it suitable for forming a surface layer of a decoration film. In addition, polyvinylidene difluoride can lower the water absorption rate, minimizing warpage and dimensional change due to moisture absorption, and has good releasability, thereby improving the co-extrusion processability by reducing the sticking of the film to the roll during coextrusion .

However, it is difficult to ensure sufficient co-extrusion processability when only polymethyl methacrylate and polyvinylidene fluoride are mixed. This is a result of the fact that sufficient improvement of the thermal properties is not achieved, and it is also insufficient to meet the hardness enough to exhibit sufficient hardness even without a separate hard coating layer.

Thus, nanosilica particles can be added to the polymethylmethacrylate and polyvinylidene fluoride composite to form a composite.

When the nanosilica is dispersed, the individual particle size should be 60 nm or less, preferably 30 nm or less, in order to ensure transparency in the visible light region. In addition, nanosilica can be used in various shapes such as spherical shape and tube shape.

In addition, other additives may include antioxidants, lubricants, slip agents, diluents, and the like.

Antioxidants are quinones, amines, phenols, etc. that directly participate in the oxidation reaction to prevent oxidation, and indirect antioxidants that inactivate the metal that catalyzes the oxidation reaction. Phenyl-β-naphthylamine is generally used for synthetic rubbers, and aromatic amines, hydroquinone and the like are used. In natural rubber, amino acids in the latex are natural antioxidants. Vitamin E, sesamol, vitamin C, quercetin and the like are contained as a natural antioxidant. This may be included to prevent yellowing that may occur during processing.

Further, the lubricant is added for facilitating the processing by making the flowability of the thermoplastic resin good when the thermoplastic resin is heated, and for easily removing the molded product from the mold (removing the mold). Rubber and plastics have softening agents and plasticizers mainly for improving plasticity in processing. Molding agents are used for the purpose of improving mold removal. Lubricants have two functions. Generally, higher fatty acids or their salts are used, and in the case of vinyl chloride resin, about 0.5% of stearic acid is added to the resin. If the added amount is large, compatibility with the resin is poor, and the resin may come out from the surface after molding.

In the present invention, the lubricant may be added in an amount of 0.05 to 5 parts by weight based on the weight of the entire film composition.

Further, a slipping agent may be further added to the surface of the present invention in order to make the surface smoother, and the slipping agent may be selected from silicon acrylate and polyester modified silicone But are not limited thereto.

The decoration film of the present invention may further include an antibacterial coating layer and a glossy coating layer. By forming an antibacterial coating layer, it is possible to minimize the propagation of bacteria transferred from the outside, thereby preventing the bacteria, which are harmful to human body, , And the gloss coating layer is able to express a better gloss on the surface, thereby improving the aesthetic value.

The surface layer of the decoration film according to the present invention is prepared by independently preparing polymethyl methacrylate, fluororesin and nanosilica compositions, drying each prepared composition independently, mixing the dried compositions with a mixer Then putting it into a subsequent extruder, processing the extruded compounding into chips, and drying it.

When the nanosilica is added to the constituent components of the surface layer described above, there may arise a problem that the surface becomes uneven due to the lowering of the dispersibility of the nanosilica.

In order to solve this problem, a twin extruder is used to extrude the surface layer compounding of the present invention, and process conditions for improving the dispersibility are designed.

In one embodiment, a dispersive mixing section is provided immediately after the plasticizing section in the extruder to perform dispersion mixing, and a distributive mixing section is installed just before the screw tip to perform distribution mixing, So that the nanosilica can be uniformly dispersed on the surface layer.

This is because the viscosity of the resin is low when the temperature is low, and when the temperature is high, the viscosity of the resin is low. The temperature distribution of the resin gradually increases from the plasticizing part to the highest rising point at the end of the screw. The dispersion mixing is carried out with a high viscosity of the fluid, the better the mixing. . Since the high viscosity condition is immediately after the plasticizing portion, a mixing mixer is installed and mixing is performed. A mixing mixer is installed around the screw tip having a high temperature and a low viscosity condition to allow mixing to proceed.

Another embodiment that allows for good dispersion is to increase the shear rate and residence time by installing a mixer with a narrow gap from the extruder barrel and installing a kneading block, .

The mixing of the surface layer composition can also be divided into two.

Specifically, a method of dry blending polymethyl methacrylate, a fluorine resin and nano silica together using a mixer before introduction into an extruder, or a method of dry blending polymethyl methacrylate and a fluorine resin using a mixer before introduction, And a method of directly feeding to the extruder barrel through a side feeder of the extruder may be selected and used.

The surface layer in the present invention may have a tensile elongation of 30 to 150%, wherein the tensile elongation is measured according to ASTM D638, and can be expressed by the following formula (1) as the elongation rate of the material during the tensile test of the material.

ASTM is a standard name according to the American Society for Testing and Materials (ASTM), which is defined as 1) definition of a common term in the field, 2) sequence that is considered appropriate to achieve a given task, 3) And 5) to determine the range or limit of the characteristics of a product or material.

In the present invention, the light transmittance of the surface layer may be 88 to 95%, and the light transmittance may be a value indicating the degree of absorption of light by the material layer. The intensity of the transmitted light is divided by the intensity of the incident light, and the measured value according to ASTM D1003 is shown in the present invention.

The pencil hardness of the present invention may be 1 to 7 H, preferably 2 to 5 H. The pencil hardness is the value measured according to ASTM D3363.

In addition, the nail hardness of the present invention may have the result of scratching. In the case of nail hardness, there is no quantitative evaluation standard such as KS or ASTM, and a sensory test depending on whether a mark remains when a person scratches the film surface with a nail Lt; / RTI >

In addition, the stain resistance of the present invention can be carried out according to Korean Industrial Standard KS M3332, which can show a slight change in the results when the test is conducted using coffee.

The decorative film according to the present invention is characterized in that a hard coat layer which is usually laminated on a conventional decoration film is omitted and a surface layer composed of polymethyl methacrylate, fluororesin and nasosilicate is formed on the uppermost layer.

The hard coating layer has to be formed by a wet process, which must be carried out separately from the film forming process of the film. The present invention provides a surface layer which can be produced by a process of coextruding in an extruder together with a support layer and a color imparting layer and layering into a film at one time without adding any additional process. Therefore, since no additional process is required in the manufacturing process of the decoration film, the manufacturing time and the manufacturing cost can be saved so that the economical efficiency can be improved. Since the wet process is not used, There is no advantage.

Specifically, the manufacturing cost can be reduced by 30% in the manufacturing cost of the conventional decoration film containing the hard coating.

In addition, since the conventional hard coating layer is thermosetting on the surface, when the film is applied to the 3D shape product, cracks are generated and used only in the 2D coating, and the decoration film used in covering the 3D shape is entirely imported from Japan It was inevitable. As a result, the decoration film is changed according to the shape of the product, so that there is a problem that the management cost according to the binary is further added.

However, since the decorating film of the present invention includes a surface layer that is a thermoplastic transparent material, unlike a thermosetting hard coating layer, it can be coated well even when it is coated on a 3D shape without causing cracking.

Further, since the fluorine resin of the surface layer has excellent antifouling property, a decoration film using the fluorine resin can provide a decorative film having excellent antifouling property without the hard coating layer.

In addition, polymethyl methacrylate, fluorine resin, and nanosilica of a certain size all have transparency and excellent light transmittance.

Further, the addition of the nanosilica enables the decoration film of the present invention to have a very excellent hardness.

The decorative film of the present invention is used to peel the appearance of MDF furniture, a sink, a bathroom tile, a door for a building and the like, and also has a function of making the appearance more beautiful in addition to the features of the above-mentioned decoration film.

FIG. 1 is a cross-sectional view of a decoration film according to the present invention. In FIG. 1, a color imparting layer is formed on upper and lower sides of a supporting layer, and polymethyl methacrylate, fluororesin and nano silica A surface layer is formed.

FIG. 2 is a schematic view of a line outline of a twin extruder for extruding polymethylmethacrylate, fluorine resin and nano silica compounding in the surface layer of the present invention. In the case of nano silica, The mixture can then be subjected to dry mixing with a mixer or directly into an extruder barrel via a feeder on the side of the extruder.

Fig. 3 is a diagram showing a screw portion of a twin extruder for extruding polymethyl methacrylate, a fluorine resin and a nano silica compounding in the surface layer of the constituent elements of the present invention. The feeding zone, the mixing zone and the vent zone were designed according to the position of the pressure zone close to the melting zone and the screw tip.

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.

Example

Example  One

Preparation of surface layer

Polyvinylidene difluoride (product name: Kynar PVDF), and nano silica (manufactured by Seikyou AT Co., Ltd.) were respectively dried and then dried, Mix using a mixer. This mixture is put into a twin extruder, processed and extruded, and then the extruded surface layer is dried. The dried surface layer was cut to a width of 8 cm and a thickness of 20 탆 to prepare a test piece.

Example  2

A specimen was prepared in the same manner as in Example 1, except that the content of polyvinylidene difluoride was adjusted to 0 to 100 wt% based on the weight of the entire surface layer. The prepared specimens were evaluated for transparency. The transparency was evaluated by NDH 2000 of Nippon Denshoku Co. The results are shown in Table 1 below.

Polyvinylidene difluoride
(weight%) Transmittance (%) 0 92 15 92.5 30 92.5 45 92.4 60 91.6 75 89.8 100 88

As shown in Table 1 above, it can be seen that the light transmittance is excellent with an overall light transmittance of 88% or more, and when the polyvinylidene difluoride is not added, the light transmittance is better when mixed in a certain amount, and when polyvinylidene difluoride In the case of the ridged single specimen, the transmittance was measured to be the lowest because of its crystallinity.

Example  3

decoration  Production of film

A surface layer was prepared in the same manner as in Example 1 except that nano silica was adjusted to 0 to 50 wt% based on the weight of the entire surface layer. This was co-extruded with amorphous polyethylene terephthalate (product of Toray Chemical Co.) and glycol-modified polyethylene terephthalate (product of inova) to form a stratified decorating film, which was 8 cm in length and 8 cm in length and 300 Mu m to prepare a specimen. At this time, the weight ratio of polymethyl methacrylate to polyvinylidene difluoride was fixed at 7: 3. The pencil hardness according to ASTM D3363 was measured using a pencil hardness meter for the prepared specimen and the measured values are shown in Table 2 below.

Nano silica content
(wt%) Pencil Hardness (H) 0 One 10 2 20 4 30 5 50 7

As shown in Table 2, it can be seen that pencil hardness increases as the content of nano silica increases. As a result, the decorating film of the present invention can have high hardness properties with only the surface layer that can be coextruded at one time without coating the hard coat layer.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood by those skilled in the art that various changes may be made and equivalents may be resorted to without departing from the scope of the appended claims.

Therefore, the spirit of the present invention should not be construed as being limited to the above-described embodiments, and all of the equivalents or equivalents of the claims, as well as the following claims, I will say.

100: Decoration film 200: Support layer
300: color imparting layer
400: a surface layer composed of polymethyl methacrylate, fluororesin, and nanosilica

Claims (9)

A support layer of 50 to 250 μm comprising at least one member selected from the group consisting of polyvinyl chloride, polyethylene terephthalate, polypropylene and acrylonitrile butadiene styrene;
Wherein the support layer has a thickness of 10 to 60 占 퐉 and at least one member selected from the group consisting of glycol-modified polyethylene terephthalate, polybutylene terephthalate and glycol-modified poly (cyclohexylene dimethylene terephthalate) Color imparting layer;
A surface layer composed of polymethylmethacrylate, a fluorine resin, and a silica nanoparticle composite of 60 nm or less formed on the upper color imparting layer, an antibacterial coating layer, and a glossy coating layer,
Wherein the surface layer further comprises an antioxidant, a lubricant and a slipping agent,
The antioxidant includes at least one selected from phenyl-β-naphthylamine, aromatic amine, hydroquinone, sesamol, and quercetin,
The lubricant is contained in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the total composition, the pencil hardness is 1 to 7H,
Wherein the slip agent comprises at least one selected from silicone acrylate and polyester-modified silicone,
Wherein the surface layer has a thickness of 5 to 100 占 퐉 and a light transmittance of 88 to 95%. delete delete The method according to claim 1,
Wherein the fluororesin is polyvinylidene difluoride. delete delete delete delete delete

Images