KR102426430B1 - Coextruded film and display cover window including the same - Google Patents

Abstract

The present invention relates to a coextrusion film that has high transparency, excellent surface properties, and low shrinkage, which can be used for a display cover window, comprising a polycarbonate resin layer and an acrylic resin layer, and after heat treatment at 150° C. for 1 hour It is characterized in that the shrinkage in the extrusion direction is 0 to 3.0%, and the shrinkage in the width direction is 0 to 1.0%.

Description

COEXTRUDED FILM AND DISPLAY COVER WINDOW INCLUDING THE SAME

The present invention relates to a coextruded film having high transparency, excellent surface properties, and low shrinkage, which can be used for display cover windows.

There are various types and sizes of displays ranging from small displays such as mobile phones to LCD or PDP TVs, or outdoor billboards (PID, DID). In particular, since the LCD or PDP panel of the display is a key component, it must be protected from external impact or harsh conditions. Accordingly, most displays have a front panel. In addition, as the display itself becomes slimmer and larger, the importance of the front panel becomes greater.

Conventionally, glass was used as such an optical transparent film. However, glass has good transparency but lacks impact resistance due to the nature of the glass, so it is easily damaged by impact and has a limit in thinning it, and there is a limit in reducing the weight due to the large weight per unit volume. Therefore, recently, polymers with good impact resistance and light weight, such as polycarbonate (PC), polyimide (PI), polyethersulfone (PES), and polyarylate ( Thermoplastic polymers such as polyarylate, PAR), polyethylene naphthalate (poly(ethylene naphthalate), PEN), polyethylene terephthalate (poly(ethylene terephthalate), PET), cycloolefin copolymer, acrylic resin epoxy resin, Transparent films manufactured using polymers cured with curable resins such as unsaturated polyesters are gradually replacing glass.

However, it is also necessary to reinforce the mechanical properties of the optically transparent film formed of the above-mentioned polymers. As a method for reinforcing mechanical properties without almost degrading the optical properties of the transparent film, a method of improving physical properties by laminating different types of transparent films has recently emerged. This is a method of supplementing the insufficient physical properties of an optical transparent film formed of a single type of polymer by laminating films formed of a different type of polymer. For example, polymethyl methacrylate has excellent chemical resistance and surface hardness, but is brittle and has poor thermal properties. In addition, polycarbonate has excellent thermal properties, but has poor chemical resistance and surface hardness than polymethyl methacrylate. On the other hand, polyether sulfone has very excellent heat resistance characteristics, and has characteristics of excellent high temperature stability.

As a method of manufacturing a multilayer transparent film for optical use by laminating different types of transparent films, a co-extrusion method, a thermal lamination method, and a film adhesion method using an adhesive are used.

In the coextrusion method, the thermal properties of the film to be laminated should be considered. That is, since the melting temperature of the polymer constituting each film is different, it is difficult to control the process temperature during processing, and it is necessary to control the optimal process temperature that can solve various problems such as deformation of the co-extruded film or interfacial adhesion. In addition, if the melting temperature difference of the polymer constituting each film is too large, there is a limit to using the coextrusion method.

In order to overcome the limitations in manufacturing a film using such a co-extrusion method, the present invention intends to develop a co-extrusion film that has high transparency, excellent surface properties, and low shrinkage, which can be used for display cover windows.

An object of the present invention is to provide a co-extruded film that can be used for a display cover window due to high transparency, excellent surface properties, and low shrinkage in order to solve the problems of the prior art.

A co-extrusion film according to an embodiment of the present invention includes a polycarbonate resin layer; and an acrylic resin layer, and after heat treatment at 150° C. for 1 hour, the shrinkage in the extrusion direction may be 0 to 3.0%, and the shrinkage in the width direction may be 0 to 1.0%.

Here, when the thickness of the co-extrusion film is 500 ~ 1,000㎛, the ratio (S1/S2) of the shrinkage ratio (S1) in the extrusion direction to the shrinkage ratio (S2) in the width direction may be 1.0 ~ 2.5.

In addition, when the thickness of the co-extrusion film is 300㎛ or less, the ratio (S1'/S2') of the shrinkage ratio (S1') in the extrusion direction and the shrinkage ratio (S2') in the width direction may be 2.0 to 4.5.

In addition, the co-extrusion film may further include a hard coating layer disposed on the acrylic resin layer.

In addition, the present invention also provides a display cover window manufactured by in-mold labeling molding the co-extrusion film as described above.

The co-extrusion film according to the present invention has a low shrinkage rate, so that no shrinkage occurs in the post-processing process, so there is an advantage of less deformation. In addition, the co-extrusion film according to the present invention is suitable for use as a display cover window because of its excellent hardness, and it has little thermal deformation during the post-processing, so it can be suitably used in fields requiring post-processing, thin displays, and the like.

Since the present invention can have various changes and can have various forms, specific embodiments will be described in detail in the text. However, this is not intended to limit the present invention to the specific disclosed form, it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention.

In the present application, terms such as “comprise” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, but one or more other features It is to be understood that it does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof. Also, when a part of a layer, film, region, plate, etc. is said to be “on” another part, this includes not only cases where it is “directly on” another part, but also cases where another part is in between. Conversely, when a part of a layer, film, region, plate, etc. is said to be “under” another part, this includes not only cases where it is “directly under” another part, but also cases where there is another part in between. In addition, in the present application, “on” may include the case of being disposed not only on the upper part but also on the lower part.

Hereinafter, embodiments of the present invention will be described in more detail.

The present invention relates to a coextruded film having high transparency, excellent surface properties, and low shrinkage, which can be used for display cover windows.

The coextrusion film according to an embodiment includes a polycarbonate resin layer and an acrylic resin layer.

The polycarbonate resin constituting the polycarbonate resin layer has transparency and is a material excellent in heat resistance, strength and flexural modulus. In addition, the polycarbonate resin is composed of carbonic ester (-O-(C=O)-O-) in which the bonds between the monomer units are easily processed and thermoformable.

There are mainly two methods for the production of such polycarbonate resin: a solvent method using phosgene and a melting method. First, the solvent method is a method of synthesizing BPA (bisphenol A) by dissolving phosgene in the aqueous layer and phosgene in the organic solvent layer, and then reacting at the interface in the presence of an acid binder and solvent. As the acid binder, there are a method of using pyridine and a method of using an aqueous alkali solution. In addition, the melting method is a reaction of polymerizing polycarbonate by separating phenol as a by-product in a high vacuum in a transesterification reaction by a bulk polymer of bisphenol A and diphenyl carbonate.

The polycarbonate resin used in the present invention may be a high heat-resistant polycarbonate having a melt index (MI) in the range of 5 to 15 g/10 min.

On the other hand, since the polycarbonate resin has a disadvantage of low hardness, in order to improve this, in the present invention, an acrylic resin layer having excellent surface hardness is formed on the polycarbonate resin layer to provide a multi-layered coextrusion film.

The acrylic resin constituting the acrylic resin layer may be a methacrylic resin. The methacrylic resin may be a methyl methacrylate homopolymer containing 100% by weight of methyl methacrylate units, or a copolymer of methyl methacrylate and at least one monomer copolymerizable therewith.

In addition, the polycarbonate resin layer and the acrylic resin layer may include, for example, at least one additive selected from a light stabilizer, an ultraviolet absorber, an antioxidant, a mold release agent, a flame retardant, an antistatic agent, and the like.

The coextrusion film of the present invention is manufactured by laminating and integrating a polycarbonate resin layer and an acrylic resin layer by coextrusion molding. Specifically, the co-extrusion film comprises the steps of melting a polycarbonate resin and an acrylic resin with an extruder, respectively; coextrusion of the molten resin from the die; and cooling with a cooling roll.

First, in the melting step, flowability is imparted to the polycarbonate resin and the acrylic resin through heat and pressure using separate extruders. Here, the polycarbonate resin may use a main extruder, and the acrylic resin may use a sub-extruder. The temperature of the extruder is not particularly limited as long as it is a temperature that can impart flowability to the resin, but the temperature of the main extruder is 230 to 260° C., and the temperature of the sub-extruder is preferably 220 to 240° C.

Thereafter, the molten resin is subjected to a screen changer. The screen changer filters internal and external foreign substances and unmelted substances contained in the molten resin and protects the rear end of the machine.

After passing through the screen changer, the molten resin passes through a T-die that creates a film shape. At this time, the molten polycarbonate resin and the acrylic resin are extruded from the T-die to be laminated and integrated. The temperature of the T-die is preferably 280 ~ 300 ℃. If the temperature of the T-die is too low, stretching orientation occurs due to the drawing of the cooling roll, resulting in increased birefringence. If the temperature is too high, extremely fine cooling wrinkles are generated on the cooling roll, resulting in non-uniformity of optical birefringence.

The melt from the T-die is cooled by going through a chill roll and filmed to the desired thickness. In this case, the cooling rolls may be first to third cooling rolls arranged in a horizontal direction. In addition, as the first cooling roll, it is preferable to use a shaft roll made of metal and an elastic roll in which a thin metal film is coated on an outer circumferential surface of the shaft roll. When an elastic roll is used as the first cooling roll, the contact with the molten resin in the first cooling roll is made close to the surface forming due to the surface of the elastic roll, which is effective in reducing foreign matter.

On the other hand, the temperature of the first to third cooling rolls is preferably a temperature below the glass transition temperature (Tg) of the resin. Specifically, the temperature of the first cooling roll may be 100 to 130°C, the temperature of the second cooling roll may be 100 to 130°C, and the temperature of the third cooling roll may be 130 to 150°C. At this time, if the temperature of the cooling roll is too high, the film adheres to the roll shape and becomes a source of poor appearance, and if the temperature of the cooling roll is too low, a problem of fine cooling wrinkles occurs. In addition, the speed of the first to third cooling rolls may be appropriately adjusted in consideration of the desired thickness of the film, and the film coming out of the T-die is supplied loosely to the roll so that the film is drawn on the first and second cooling rolls. It is important not to let it happen.

The thickness of the coextrusion film prepared as described above may be 1,000 μm or less, preferably 500 μm or less, and more preferably 300 μm or less. In addition, the thickness ratio of the polycarbonate resin layer and the acrylic resin layer is preferably 9:1 to 7:3.

In addition, after the coextrusion film of the present invention is heat-treated at 150 ℃ for 1 hour, it is preferable that the shrinkage in the extrusion direction is 0 to 3.0%, and the shrinkage in the width direction is 0 to 1.0%. As described above, the co-extrusion film according to the present invention has a low thermal shrinkage rate, and thus no shrinkage occurs in the post-processing process, and thus there is an advantage of less deformation.

On the other hand, after heat treatment, when the shrinkage in the extrusion direction exceeds 3.0% or the shrinkage in the width direction exceeds 1.0%, thermal deformation such as shrinkage occurs a lot in the post-processing process, resulting in a difficult processing problem. When the heat treatment condition exceeds 150° C., the condition exceeds the glass transition temperature (Tg) of the polycarbonate resin and the acrylic resin, and wrinkles or curling occurs, which makes precise measurement difficult.

When the coextrusion film according to the present invention has a thickness of 500 to 1,000 μm, after heat treatment at 150° C. for 1 hour, the ratio (S1/ S2) may be 1.0 to 2.5. In addition, when the thickness of the co-extrusion film is 300 μm or less, after heat treatment at 150° C. for 1 hour, the ratio (S1'/S2') of the shrinkage ratio in the extrusion direction (S1') and the shrinkage ratio in the width direction (S2') is It can be 2.0-4.5. When the above ranges are satisfied, there is an advantage in that there is little deformation in the post-processing process, and for this reason, it can be suitably used in fields requiring post-processing, thin displays, and the like.

By disposing the hard coating layer on the acrylic resin layer of the prepared co-extrusion film, it is possible to improve the hardness, thereby advantageously applied as a display cover window.

The hard coating layer may be formed by applying a hard coating solution on the acrylic resin layer of the coextrusion film, and performing heat or UV curing. At this time, the hard coating solution is preferably an acrylic hard coating solution, and more specifically, a (meth)acrylate monomer, a (meth)acrylate oligomer having an epoxy group and a weight average molecular weight of 500 to 10,000, and a curable coating solution containing silica particles. have.

The (meth)acrylate monomer controls the viscosity and curing density of the curable coating solution and performs a function of improving the adhesion of the coating layer. The (meth)acrylate monomer may be a monofunctional or polyfunctional monomer. It may also exist in ethoxylated or propoxylated form. As (meth)acrylate monomer, 2(2-ethoxyethoxy)ethyl acrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, caprolactone acrylate, dicyclopentadienyl methacrylic Late, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, 1,3-butylene glycol diacrylate, 1,4-tandiol dimethacrylate, diethylene glycol diacrylate, ethoxylated bisphenol A Diacrylate, ethoxylated bisphenol A dimethacrylate, ethylene glycol dimethacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, propoxylated glyceryl triacrylate, propoxy Trimethylolpropane triacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, etc. alone or a mixture of two or more thereof can be used by

The (meth)acrylate oligomer having an epoxy group and having a weight average molecular weight of 500 to 10,000 is an oligomer having a (meth)acrylate group and an epoxy group, and contributes to a good adhesion of the hard coating layer to the acrylic resin layer.

The silica particles may have an average particle diameter of 100 nm or less, or 40 to 90 nm, or 50 to 80 nm.

Moreover, it is preferable that the curable coating liquid further contains the silicon alkoxide which has a (meth)acrylate group. In the present specification, (meth)acrylate means acrylate or methacrylate. Examples of the silicon alkoxide for the (meth)acrylate group include (3-acryloxypropyl)dimethylmethoxysilane, (3-acryloxypropyl)methyldimethoxysilane, (3-acryloxypropyl)trimethoxysilane, (meth) Acryloxymethyl) dimethylethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, (3-methacryl Oxypropyl) triethoxysilane, (3-methacryloxypropyl) trimethoxysilane, etc. can be used individually or in mixture of 2 or more types, respectively.

The thickness of the hard coating layer may be 0.5 to 10 μm, or 1 to 5 μm. When the thickness of the hard coating layer satisfies this range, physical properties and flexibility can be secured at the same time.

As described above, the co-extrusion film with the hard coating layer has high transparency, excellent surface properties, and low shrinkage, so that it can be easily applied to the display cover window.

In order to apply the coextrusion film with the hard coating layer of the present invention to the display cover window, in-mold labeling molding, thermal bending, or thermoforming depending on the display size, molding size, and molding shape ) may be required. In order to prevent cracking of the hard coating layer in this molding process, the hard coating layer may be cured in 2-step according to the molding depth (deep draw ratio). In 2-step curing, pre-curing is performed during the hard coating process first, and post-curing can be performed after molding.

Hereinafter, the present invention will be described in detail through examples. However, the following examples only illustrate the present invention, and the present invention is not limited by the following examples.

[Examples 1 to 3]

PC/PMMA co-extrusion films were prepared using the co-extrusion process conditions described in Table 1 and Table 2, respectively. At this time, the polycarbonate resin was put into the main extruder (90 pie), and the polymethyl methacrylate resin was put into the sub extruder (45 pie). In addition, as the polycarbonate resin used, Teijin PC having an MI level of 9 g/10 min was used, and as the polymethyl methacrylate resin, Lotte MCC VH grade having an MI level of 2 g/10 min was used. When each of the coextrusion films of Examples 1 to 3 were prepared, the extruder temperature and the roll temperature were the same controlled under the conditions described in Table 1 below, and the roll speed was adjusted under the conditions described in Table 2 below.

Extruder Classification main serve Extruder temperature (℃) extruder 245 230 screen changer 270 225 adapter 270 225 melt pump 270 225 die 290 245 Roll temperature (℃) first roll 115 2nd roll 115 3rd roll 140

Example 1 Example 2 Example 3 roll speed
(m/min) first roll 5.742 12.625 15.25 2nd roll 5.83 12.5 15.1 3rd roll 5.835 12.5 15.1

[Comparative Examples 1 and 2]

A single-layer polycarbonate film was used as Comparative Example 1, and a single-layer polymethyl methacrylate film was used as Comparative Example 2.

[Experimental Example 1]

The physical properties of the coextruded films prepared in Examples 1 to 3 and the films according to Comparative Examples were measured in the following manner, and the results are shown in Tables 2 and 3 below.

1) Heat shrinkage: Sections 1 and 2 (100mm) in the MD (Machine Direction) and TD (Transverse Direction) directions for each film were identified, and this length was set as the length before heat treatment (T1). Then, each film was heat-treated under high-temperature conditions (150° C., 60 minutes), and the identification length (T2) after heat treatment was measured. Thermal shrinkage was calculated as (T1-T2)/T1 X 100.

2) Total light transmittance: 　 When light passes through the film, the ratio of the transmitted (straight, scattered) light through the film using an integrating sphere is shown.

3) Haze: The film was evaluated for haze using a total light transmittance meter according to ASTM D1003 standard, and was evaluated with a measuring device NDH5000 and equivalent equipment.

4) Birefringence: It was measured by multiplying the thickness of the difference in refractive index in directions orthogonal to each other of the film. R = (n||-n⊥) x d(thickness in nm) In this case, the equipment was measured with an equipment conforming to Axoscan MMSP (FSVM).

5) Pencil hardness: The presence or absence of scratches on the film surface was evaluated by the pencil hardness measurement method according to ASTM D3363-05 standard.

division before heat treatment
(T1, mm) after heat treatment
(T2, mm) T1-T2
(mm) shrinkage
(%) Average shrinkage (%) Example 1 MD 1 section 100 98.37 1.63 1.63 1.61 2nd section 100 98.4 1.6 1.6 TD 1 section 100 99.25 0.75 0.75 0.8 2nd section 100 99.15 0.85 0.85 Example 2 MD 1 section 100 98.25 1.75 1.75 1.87 2nd section 100 98.01 1.99 1.99 TD 1 section 100 99.3 0.7 0.7 0.65 2nd section 100 99.4 0.6 0.6 Example 3 MD 1 section 100 97.9 2.1 2.1 2.195 2nd section 100 97.71 2.29 2.29 TD 1 section 100 99.3 0.7 0.7 0.55 2nd section 100 99.6 0.4 0.4 Comparative Example 1 MD 1 section 100 97.76 2.24 2.24 2.24 TD 1 section 100 99.65 0.35 0.35 0.35 Comparative Example 2 MD 1 section 100 97.12 2.88 2.88 2.88 TD 1 section 100 99.71 0.29 0.29 0.29

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Thickness (㎛) 640 300 250 640 300 Total light transmittance (%) 90.8 91.1 91.2 90.5 91 Haze (%) 0.12 0.10 0.08 0.11 0.10 Birefringence (nm) 28 20 18 103 73 pencil hardness H F F H F

As can be seen from Table 3, the coextrusion films according to Examples 1 to 3 had a shrinkage rate of 0 to 3.0% in the extrusion direction after heat treatment at 150° C. for 1 hour, and a shrinkage rate in the width direction of 0 to 1.0%. that can be checked As described above, the co-extrusion film according to the present invention has a low thermal shrinkage rate and thus no shrinkage occurs in the post-processing process and thus has the advantage of less deformation, and thus can be suitably used in fields requiring post-processing, thin displays, and the like.

In addition, as can be seen in Table 4, it can be seen that the coextrusion films according to Examples 1 to 3 have high transmittance optical properties with a total light transmittance of 90% or more, and a haze is 0.2% or less, and the pencil hardness is F You can check what's wrong. In addition, the coextrusion film of the present invention has a birefringence of 30 nm or less, and even if a display to which the coextrusion film is applied is used while wearing polarized sunglasses, there is an advantage in that rainbow mura does not occur due to a change in birefringence.

On the other hand, in the case of Comparative Examples 1 and 2, as the shrinkage in the extrusion direction was significantly higher than in Examples, it was confirmed that the birefringence was high. In this case, there is a problem in that rainbow mura occurs due to the change in birefringence. In addition, in the case of the comparative example, since the ratio of the shrinkage ratio in the extrusion direction to the shrinkage ratio in the width direction is significantly higher than that of the Example, there is a problem that a lot of deformation occurs in the post-processing process, so it is difficult to apply to a display or the like.

Therefore, the co-extrusion film according to the present invention has a low shrinkage rate, so there is no shrinkage in the post-processing process, so there is little deformation, and it has high transparency and excellent surface properties, so it is suitable for use as a display cover window. Due to its low thermal deformation, it can be used for fields requiring post-processing and for thin displays.

Although the above has been described with reference to the preferred embodiment of the present invention, those skilled in the art or those having ordinary knowledge in the technical field will not depart from the spirit and technical scope of the present invention described in the claims to be described later. It will be understood that various modifications and variations of the present invention can be made without departing from the scope of the present invention.

Accordingly, the technical scope of the present invention should not be limited to the contents described in the detailed description of the specification, but should be defined by the claims.

Claims (5)

polycarbonate resin layer; and an acrylic resin layer,
In the coextrusion film having a shrinkage rate of 0 to 3.0% in the extrusion direction and 0 to 1.0% in the width direction after heat treatment at 150° C. for 1 hour,
When the thickness of the co-extrusion film is 250 ~ 300㎛, the ratio (S1'/S2') of the shrinkage ratio (S1') in the extrusion direction and the shrinkage ratio (S2') in the width direction is 2.5 to 4.5,
The total light transmittance of the co-extrusion film is 91.1 to 91.2%,
The haze of the coextrusion film is 0.08 to 0.10%,
The birefringence of the coextrusion film is 18-20 nm,
The pencil hardness of the co-extrusion film is F or more,
The coextrusion film further comprising a hard coating layer disposed on the acrylic resin layer. delete delete delete A display cover window manufactured by in-mold labeling molding the coextrusion film according to claim 1 .