KR20170024809A - Retardation film and liquid crystal display comprising the same - Google Patents
Retardation film and liquid crystal display comprising the same Download PDFInfo
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- KR20170024809A KR20170024809A KR1020150120313A KR20150120313A KR20170024809A KR 20170024809 A KR20170024809 A KR 20170024809A KR 1020150120313 A KR1020150120313 A KR 1020150120313A KR 20150120313 A KR20150120313 A KR 20150120313A KR 20170024809 A KR20170024809 A KR 20170024809A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C09D7/007—
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- C09D7/1216—
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/32—Holograms used as optical elements
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
Abstract
Description
The present invention relates to a coating liquid composition, a coating layer formed using the coating liquid composition, a retardation film including the coating layer, and a liquid crystal display including the same. More particularly, the present invention relates to a retardation film that can be applied to an IPS mode liquid crystal display device as a retardation film, and a liquid crystal display device including the retardation film.
The liquid crystal display is spreading as an optical display device because it has lower power consumption, smaller volume, lighter weight and easier to carry than a cathode ray tube display. In general, a liquid crystal display has a basic structure in which a polarizing plate is provided on both sides of a liquid crystal cell, and the orientation of the liquid crystal cell is changed according to whether an electric field of the driving circuit is applied or not and the characteristics of light transmitted through the polarizing plate are changed, Visualization is done. At this time, the path of light and the birefringence change depending on the incident angle of the incident light because the liquid crystal is an anisotropic material having two different refractive indices.
Due to such characteristics, the liquid crystal display has a disadvantage that the contrast ratio, which is a measure of how clearly the image looks depending on the viewing angle, is changed and a gray scale inversion phenomenon occurs, . In order to overcome such disadvantages, an optical compensation film for developing an optical retardation generated in a liquid crystal cell is used for a liquid crystal display device.
Various liquid crystal modes have been developed to secure a clear image quality and a wide viewing angle in a liquid crystal display. Typical examples thereof include a double domain TN (twisted nematic), an axially symmetric aligned microcell (ASM), an optically compensated blend ), VA (vertical alignmnt), MVA (multidomain VA), SE (surrounding electrode), PVA (patterned VA), IPS (in-plane switching) and FFS (fringe-field switching) modes. Each of these modes has a unique liquid crystal arrangement and has inherent optical anisotropy.
Therefore, in order to manifest the phase difference due to the optical anisotropy of these liquid crystal modes, an optically anisotropic phase difference film corresponding to each mode is required. In particular, since the liquid crystal having a positive dielectric anisotropy is horizontally aligned in the IPS mode, the optical anisotropy in the non-driven state is not greater than the other modes, which is advantageous in that an excellent viewing angle can be secured even by using the isotropic protective film alone . In this case, however, compensation for the absorption axis of the polarizer at the high inclination angle is not performed at all, so that the contrast may be deteriorated due to the viewing angle and color modulation may occur. Therefore, in order to secure a perfect viewing angle, the IPS mode liquid crystal display should also use an appropriate retardation film do.
The structure in which the retardation film for IPS mode is composed of two or more layers of layers is practically presented. In order to realize a multilayer film, a method of laminating each different film using an adhesive is proposed. Alternatively, a process of coating a liquid crystal or a material exhibiting a phase difference after a stretched film is prepared through a separate stretching process is separately performed.
However, when the adhesive layer is laminated using the pressure-sensitive adhesive as described above, it is difficult to reduce the thickness of the film, and if the optical axes of the two films to be laminated are not precisely arranged, the desired retardation characteristics are not exhibited. When a step of coating a liquid crystal after the stretched film is formed through a stretching process is separately performed, various steps such as a separate alignment step are performed, which complicates the manufacturing process and increases manufacturing cost.
In addition, when organic materials are coated with a material exhibiting a retardation, curl may occur, or substrate phase erosion due to an organic solvent may cause a phase difference of the base film to change.
Therefore, there is a demand for a phase difference film and a manufacturing method thereof which are excellent in the viewing angle improving effect when applied to an IPS mode liquid crystal display device, can be manufactured in a thin shape, and can be manufactured by a simple process.
The present invention is to provide a coating liquid composition, a coating layer formed using the coating liquid composition, a retardation film including the coating layer, and a liquid crystal display device including the retardation film.
The present invention provides a coating liquid composition comprising a layered inorganic material, a water-dispersible urethane-based resin, a titanium-based chelate compound and a solvent, wherein the water-dispersible urethane-based resin comprises an aliphatic unit.
In another embodiment of the present invention, the titanium chelate compound is 0.1 to 20 parts by weight based on 100 parts by weight of the water-dispersible urethane resin.
In one aspect of the present invention, the layered inorganic material may include one or more selected from the group consisting of smectite series.
Specifically, the layered inorganic material may include one or more selected from the group consisting of hectorite, montmorillonite, and bentonite.
In another aspect, the layered inorganic material has an average diameter of 10 nm to 30 nm and a thickness of more than 0 nm and 2 nm or less.
In one embodiment of the present invention, the layered inorganic material is in the form of a plate-like disk.
In another embodiment of the present specification, the layered inorganic material is represented by the following
[Structural formula 1]
Na + 0.7 [(Si 8 Mg 5.5 Li 0.3) O 20 (OH) 4] -0.7
In one embodiment of the present invention, the solid content of the coating liquid composition is 5 wt% to 15 wt%, and the solvent content is 85 wt% to 95 wt%.
In one embodiment of the present invention, the viscosity of the coating liquid composition is 10 cP to 500 cP.
In one embodiment of the present invention, the viscosity change amount of the coating liquid composition is less than 500 cP.
In one embodiment, the viscosity change measured after storage for one week at 20 占 폚 of the coating liquid composition is less than 500 cP.
In one embodiment of the present disclosure, the solvent comprises water.
In another embodiment, the solvent further comprises one or more solvents selected from the group consisting of alcohols and ketones.
In one embodiment of the present invention, the content of water is 50 wt% to 100 wt% with respect to the total weight of the solvent, and the content of one or more solvents selected from the group consisting of alcohols and ketones is 0 By weight to 50% by weight.
In another embodiment, the layered inorganic material is dispersed in the water.
In one embodiment of the present invention, the elongation percentage of the water-dispersible urethane-based resin is 50% or more.
In another aspect of the present disclosure, there is provided a coating layer formed using the above-described coating liquid composition.
In one embodiment, the coating layer is a -C-plate.
In yet one embodiment, the thickness retardation value of the film measured at a wavelength of 550nm which is represented by the following formula (1) of the coating layer (R th) is -400 nm to 0 nm.
(1): R th = (nz - ny) x d
In the formula (1)
n y is the refractive index in the vertical direction in the n x direction in the plane direction of the coating layer,
n x is a refractive index in a direction in which the surface direction refractive index of the coating layer becomes maximum,
n z means the refractive index in the thickness direction,
d means the thickness of the coating layer.
In one embodiment of the present invention, the thickness of the coating layer is preferably in the range of more than 0 to 20 占 퐉.
The present specification also provides a retardation film comprising the above-mentioned coating layer.
The disclosure also relates to a substrate film comprising a negative birefringent material; And a coating layer provided on at least one surface of the base film, wherein the coating layer satisfies the following formulas (2) to (4).
(2): 50 nm? R in ? 300 nm
Equation (3): 10 nm ≤ R th ≤ 300 nm
Equation (4): 0.1? Nz <1
In the above formulas (2) to (4)
R in is the retardation value in the plane direction of the film measured at a wavelength of 550 nm,
R th is the thickness direction retardation value of the film measured at a wavelength of 550 nm,
Nz is the ratio (R th / R in) of the thickness retardation value on a plane direction retardation value measured at a wavelength of 550nm.
In one aspect of the present invention, the base film comprises an acrylic resin; Styrene type resin; And a copolymer comprising an acrylic monomer and a styrene monomer.
In another aspect of the disclosure, the substrate film is a + B plate.
In another aspect of the present invention, the thickness of the base film is preferably 80 占 퐉 or less.
In one embodiment of the present invention, the base film and the coating layer are provided in contact with each other.
The present specification provides a polarizing plate comprising the above-described retardation film.
The present specification also provides a polarizing plate comprising the above-described composite retardation film.
Finally, the present invention provides an IPS mode liquid crystal display including the above-mentioned polarizing plate.
The retardation film according to one embodiment of the present disclosure has a retardation property suitable for use as an IPS mode retardation film, and thus has an excellent viewing angle improving effect when applied to an IPS mode retardation film.
Further, the retardation film according to one embodiment of the present invention is economical in terms of time and / or cost of manufacture since it does not require a separate pressure-sensitive adhesive layer.
In addition, the phase difference film according to one embodiment of the present invention does not require a separate alignment process, and therefore, the manufacturing method is very simple as compared with the conventional method of coating liquid crystal and phase contrast material.
Further, since the retardation film according to one embodiment of the present invention does not require a step of laminating using a pressure-sensitive adhesive, there is no decrease in optical characteristics or deviation of retardation axes due to the presence of the pressure-sensitive adhesive layer.
In addition, the retardation film according to one embodiment of the present invention has an advantage that occurrence of defects such as curl is minimized.
Finally, the coating liquid composition according to one embodiment of the present disclosure can include a titanium chelate-based compound to reduce the viscosity of the coating liquid composition, and can provide a stable coating liquid composition. Therefore, the coating liquid composition according to one embodiment of the present invention is excellent in coatability, and is economical in terms of time and / or cost in the production.
1 is a view illustrating an IPS mode liquid crystal display according to an embodiment of the present invention.
Fig. 2 is a graph showing changes in viscosity of the coating liquid composition according to Comparative Example 1 and Examples 1 to 4 with time. Fig.
FIG. 3 is a graph showing changes in viscosity of the coating liquid composition according to Comparative Example 2 and Examples 5 to 7 with time. FIG.
Hereinafter, the present specification will be described in more detail.
First, terms used in this specification are defined.
(1) When a member is referred to herein as being "on " another member, it includes not only a member in contact with another member but also another member between the two members.
(2) Whenever a part is referred to as "including " an element in this specification, it is to be understood that it may include other elements as well, without departing from the other elements unless specifically stated otherwise.
(3) In the present specification, n x is the refractive index in the direction in which the refractive index in the plane direction is the maximum (that is, in the slow axis direction), and n y is the refractive index in the direction perpendicular to the slow axis in the plane direction And n z means the refractive index in the thickness direction.
In addition, n x , n y , and n z mean values measured at a wavelength of 550 nm. On the other hand, the n x, n y, n z can be measured by a method known well-known in the art and, for example, the mean refractive index by using a prism coupler devices (SAIRON TECHNOLOGY社SPA-3DR) measuring, measuring a birefringence aekso scan (Axoscan) of Axomatrics社, we can calculate the n x, n y, n z, respectively.
(4) In the present specification, R in denotes a plane retardation value measured with light having a wavelength of 550 nm, and the retardation value R in = (n x - n y ) x d. Here, n x and n y are the same as described above, and d means the thickness of the optical film. On the other hand, in the R it can be measured by a known method known in the art and, for example, can be measured using the equipment of Axoscan Axomatrics社.
(5) In the present specification, R th means a retardation value in the thickness direction measured with light having a wavelength of 550 nm, and the thickness direction retardation value R th = (n z - n y ) x d. In this case, n y and n z are the same as described above, and d represents the thickness of the optical film. On the other hand, the R th can be determined by well-known methods known in the art and, for example, can be measured using the equipment of Axoscan Axomatrics社.
6 that in the present specification means the ratio Nz of the retardation value in the thickness direction to the retardation value in the plane direction is obtained by Nz = R th / R in.
7, the negative birefringence material is then stretched (after alignment), the optical axis in a direction perpendicular to the stretching direction in this specification means the substance expressing (plane direction refractive index is the maximum refractive index of the direction in which the n x), and Refers to a material that exhibits a refractive index distribution of n z > n x = n y when coated (only before stretching). Definition: A birefringent material is a material that expresses an optical axis in a direction parallel to a stretching direction after stretching (after orientation). When a coating is performed only (before stretching), a refractive index distribution of n x = n y > n z is expressed Of the substance.
(8) In the present specification, the thickness means an average width between one surface of a member and a surface facing the surface.
(9) In the present specification, the + B plate means a film having a refractive index distribution of n z ≥ n x > n y or n x > n z > n y . Nx , ny, and nz are the same as described above.
(10) In the present specification, the -C plate means a film having a refractive index distribution of n x = n y > n z . Nx , ny, and nz are the same as described above.
Hereinafter, preferred embodiments of the present invention will be described. However, the embodiments of the present invention can be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below. Furthermore, embodiments of the present disclosure are provided to more fully describe the present disclosure to those skilled in the art.
≪ Coating liquid composition &
The present invention provides a coating liquid composition comprising a layered inorganic material, a water-dispersible urethane-based resin, a titanium-based chelate compound and a solvent, wherein the water-dispersible urethane-based resin comprises an aliphatic unit.
When a coating layer is formed using a coating liquid composition containing a layered inorganic material as in the embodiment of the present invention, the occurrence of curl is minimized, and a desired retardation film can be realized even with a thin layer thickness. In addition, in the case of a coating liquid composition containing a layered inorganic material as in the embodiment of the present specification, excellent phase retardation and viscosity of the coating layer formed using the coating liquid composition can be expected.
In addition, the coating liquid composition according to one embodiment of the present disclosure can improve the adhesion of the layered inorganic material as well as the water-dispersed urethane-based resin to the other member and prevent the layer from being broken.
In addition, in one embodiment of the present invention, a titanium chelate compound is further contained in the coating liquid composition to prevent an increase in viscosity with time, and the viscosity of the coating liquid composition can be reduced. In this case, there is an excellent effect in terms of stability of the coating liquid composition.
In another embodiment of the present invention, the titanium chelate compound is 0.1 to 20 parts by weight based on 100 parts by weight of the water-dispersible urethane resin. When the titanium chelate compound is contained within the above range, the effect of viscosity stability can be exhibited, and the viscosity can be prevented from being too low to prevent the hardening of the coating composition with time.
Therefore, the coating liquid composition according to one embodiment of the present invention has an effect of facilitating coating while exhibiting the effect of viscosity stability.
In the present specification, the layered inorganic material may include one or more selected from the group consisting of smectite series.
According to one embodiment of the present invention, the layered inorganic material may be one or more selected from the group consisting of hectorite, montmorillonite, and bentonite. However, the present invention is not limited thereto and may be selected from the group consisting of a compound having a crystal structure similar to these.
In one embodiment of the present invention, the average diameter of the layered inorganic material is 10 nm to 30 nm, and the thickness is more than 0 nm and 2 nm or less. In one embodiment, the layered inorganic material has an average diameter of 15 nm to 25 nm.
In another embodiment, the thickness is 0.5 nm to 1 nm.
In the present specification, the layered inorganic material may be in the form of a disk-shaped disk. The average diameter may mean the average diameter of the cross section of the plate, and the thickness may mean the distance between the lower surface and the upper surface of the layered inorganic material. The above average diameter and thickness can be measured by a method used in the art.
In one embodiment of the present specification, the layered inorganic material is represented by the following
[Structural formula 1]
Na + 0.7 [(Si 8 Mg 5.5 Li 0.3) O 20 (OH) 4] -0.7
In one embodiment of the present invention, the layered inorganic material has a structure represented by the
In one embodiment of the present invention, the layered inorganic material may be dispersed in water. That is, the layered inorganic material according to one embodiment of the present invention may be selected from one or more of water-dispersible layered inorganic materials.
In this case, erosion of the other member can be prevented, and deformation of the expression of the retardation value can be prevented, as compared with the case of including the layered inorganic substance dispersed in the organic solvent.
In this specification, the coating liquid composition includes an aqueous dispersion urethane-based resin. According to one embodiment of the present invention, the water-dispersed urethane-based resin contained in the coating layer can prevent cracking due to the layered inorganic material and improve adhesion between the other member and the coating layer.
In the present specification, the "water-dispersed urethane-based resin" means a urethane-based resin that may exist in a state dispersed in water.
As described above, when the water-dispersible urethane-based resin is used, environmental pollution due to the release of harmful solvents can be prevented, and the stability of the particles in the aqueous dispersion phase is excellent. In addition, when a water-dispersible resin is used, it is possible to prevent the phase difference of the substrate film from changing due to substrate erosion due to an organic solvent.
In the present specification, the titanium-based chelate compound may have a structure in which an organic group is directly bonded to a titanium atom, or an organic group is bonded to a titanium atom through an oxygen atom or a nitrogen atom, and the coordination by coordination of the chelate compound is at least ≪ / RTI >
In the present specification, the structure in which the organic group is bonded may mean a covalent bond with a titanium atom, or may be a coordinate bond.
The titanium-based chelate compound according to one embodiment of the present invention can be represented by the following formula (1).
[Chemical Formula 1]
In the general formula (1),
In the present specification, the organic group may mean a functional group containing at least a carbon atom, and examples thereof include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. The organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic.
The organic group may form a cyclic structure, may form a cyclic structure, and may form a bond including a heteroatom unless the effect of the invention is impaired.
Specifically, a bond containing a hetero atom such as an oxygen atom, a nitrogen atom, or a silicon atom. Specific examples thereof include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond (-N═C (-A) -: A represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinyl bond, an azo bond, and the like.
The cyclic structure may be an aromatic ring, an aliphatic ring, or the like, and may be monocyclic or polycyclic.
In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 50. Specific examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl and heptyl.
In the present specification, the alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, Butenyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, (Diphenyl-1-yl) vinyl-1-yl, stilbenyl, stilenyl, and the like.
In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and in particular, cyclopentyl group, cyclohexyl group, and the like, but is not limited thereto.
In one embodiment, the solid content of the coating liquid composition is 5 wt% to 15 wt%, and the solvent content is 85 wt% to 95 wt%.
In one embodiment of the present invention, the content of the layered inorganic material, the water-dispersible urethane resin, and the titanium chelate compound is 5 wt% to 15 wt% and the content of the solvent is 85 wt% 95% by weight.
As used herein, the term solids refers to solutes or solids excluding the solvent in the total mass of the solution. The solid content in the coating liquid composition in the present specification may mean a layered inorganic material, an aqueous dispersion urethane resin, and a titanium chelate-based compound.
In one embodiment of the present invention, the solid content may include only a layered inorganic material, an aqueous dispersion-based urethane resin, and a titanium-based chelate compound.
In another embodiment, the solid content may further include one or two additives selected from the group consisting of the layered inorganic material, the water-dispersible urethane resin, the titanium chelate compound, and further the sodium pyrophosphate-based and oxazoline-based polymer . By further including the additive, the viscosity stability of the coating liquid composition can be provided.
In this specification, the sodium pyrophosphate system may be TetraSodium Pyrophosphate (TSP).
In the present specification, the oxazoline-based polymer is not limited as long as it contains an oxazoline group in the main chain of the polymer and may further include additional monomers. As the oxazoline-based polymer, a commercially available polymer can be used. Examples of the oxazoline-based polymer include Epocross series (for example, Epocross WS700, Japan Catalysts).
In one embodiment of the present invention, the content of the additive is 0 to 20 parts by weight based on the total amount of the water-dispersible urethane-based resin. In another embodiment, the content of the additive is more preferably 0.1 to 20 parts by weight based on the total amount of the water-dispersible urethane-based resin.
In this specification, when the content of the solid content in the coating liquid composition is more than 15% by weight, the inorganic material is not well dispersed and the viscosity is too high, so that uniform coating is difficult to cause unevenness of phase difference and / have. If the content of the solid content is less than 5% by weight, the viscosity may be low, causing a problem of flowing during coating, lowering the drying efficiency, and reducing the area of the coating layer to be obtained relative to the amount of the coating solution.
Therefore, as in one embodiment of the present invention, the content of the layered inorganic material, the water-dispersible urethane-based resin, and the titanium-based chelate compound in the above range is preferable in view of process and retardation characteristics.
In one embodiment, the solvent comprises water.
In another embodiment, the solvent is selected from the group consisting of alcohols such as ethanol and methanol; And ketones such as acetone, methyl ethyl ketone (MEK), and the like.
In one embodiment of the present invention, the content of water may be 85 wt% to 96 wt% based on the total weight of the coating liquid composition.
In one embodiment of the present invention, the content of water is 50 wt% to 100 wt% with respect to the total weight of the solvent, and the content of one or more solvents selected from the group consisting of alcohols and ketones is 0 By weight to 50% by weight.
In one embodiment of the present invention, the content of one or more solvents selected from the group consisting of alcohols and ketones is preferably 0 wt% to 20 wt% based on the total amount of the water.
When the content of water in the total content of the solvent is 50% by weight or more as in the embodiment of the present specification, erosion of the substrate due to the use of the organic solvent is prevented and deformation of the retardation due to erosion of the substrate can be prevented . In addition, it is possible to minimize the occurrence of curling of the coating layer formed by using the coating liquid composition, thereby effectively increasing the viewing angle compensation effect, improving the durability, and preventing defects occurring during the lapping process with other members. In the above-mentioned aspect, the content of water in the total solvent is preferably 70% by weight or more, more preferably 80% by weight.
In another embodiment of the present invention, the water content of the coating liquid composition is 75 wt% to 96 wt%, and the content of one or more solvents selected from the group consisting of alcohols and ketones is 0 By weight to 10% by weight.
The water-dispersible urethane-based resin contained in the coating liquid composition according to one embodiment of the present specification includes an aliphatic unit. In this case, it is possible to form a coating layer excellent in toughness. More preferably, in one embodiment of the present invention, the water-dispersible urethane-based resin includes only aliphatic units. That is, it does not contain an aromatic unit.
In the present specification, the "aliphatic unit" may mean a structure that does not include an aromatic structure such as benzene as a structural unit. When the aromatic structure is not included, it is not limited to a straight chain, a branched chain, or a ring, but may be composed of only hydrocarbon, but may contain a heteroatom unless the effect of the invention is impaired.
Saturated aliphatic units such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, cyclopentyl and cyclohexyl; Unsaturated aliphatic units such as vinyl, 1-propenyl, isopropenyl, cyclohexenyl, and the like. In the above-mentioned examples, a carbon atom may be substituted with a hetero atom such as S, O, have.
As used herein, the urethane-based resin is a structure having a urethane bond in a molecule, and may be produced by a method known in the art, for example, by reacting a diisocyanate (-NCO) with a polyol, .
The urethane resin in the present specification may contain an urethane monomer of "-O- (C═O) -NH-R-HN- (C═O) -O-", and may further contain additional monomers . The R may be a divalent aliphatic unit.
In one aspect of the present specification, in the toughness aspect, it is preferable that R is an alicyclic structure or a straight-chain saturated aliphatic unit.
Specifically, the water-dispersible urethane-based resin according to one embodiment of the present specification may be a resin containing only the above-mentioned urethane monomer.
The water-dispersible urethane-based resin according to another embodiment may be a copolymer comprising the above-mentioned urethane monomer and further monomers.
The additional monomers include, but are not limited to monomers known in the art, monomers comprising a carbonate group (-O- (C = O) -O-); Ester "(ester "-( C = O) -O-"); And an ether group ("-O-"), may be used alone or in combination of two or more.
In one embodiment of the present invention, the water-dispersible urethane-based resin may be a resin including a copolymer comprising a urethane monomer and a carbonate monomer.
In one embodiment of the present invention, the water-dispersible urethane-based resin comprises an urethane monomer containing an aliphatic unit; Or an aliphatic unit and at least one monomer selected from the group consisting of a monomer containing a carbonate group, a monomer containing an ester group and a monomer containing an ether group.
In one embodiment of the present invention, the elongation percentage of the water-dispersible urethane-based resin is 50% or more. In this case, the coating layer formed using the coating liquid composition according to one embodiment of the present invention can be prevented from being broken, and durability can be improved. In addition, excellent effects can be expected in terms of toughness and adhesion to other members.
In this specification, the elongation means a rate at which the material is stretched during the material tensile test, and the elongation can be measured by a method known in the art.
According to one embodiment of the present invention, the coating liquid composition may include the layered inorganic material and the water-dispersible urethane-based binder resin in a weight ratio of 1: 0.6 to 1: 2.
When the weight ratio of the layered inorganic material and the water-dispersible urethane binder resin is within the above range, it is advantageous to prevent cracking of the layer, and the mechanical characteristics of the retardation film for IPS mode liquid crystal display can be improved.
In one embodiment of the present invention, the viscosity of the coating liquid composition is 10 cP to 500 cP. In this case, a coating layer having a uniform thickness can be obtained with ease of coating, and appearance defects and the like can be minimized.
In one embodiment of the present invention, the viscosity change amount of the coating liquid composition is less than 500 cP. In this case, the viscosity stability effect of the coating liquid composition can be exhibited.
In one embodiment, the viscosity change measured after storage for one week at 20 占 폚 of the coating liquid composition is less than 500 cP.
≪ Coating layer &
One embodiment of the present invention provides a coating layer formed using the above-described coating liquid composition. In this specification, the coating liquid composition is the same as described above.
In one embodiment of the present disclosure, the coating layer is a -C-plate. In this case, the coating layer can be introduced into the base film of the + B plate to manifest the optical characteristics required in the IPS mode liquid crystal display device phase retardation film, and a high viewing angle compensation performance can be provided.
In another embodiment, the coating layer may be formed by a method known in the art. For example, the layered inorganic material may be dispersed in water and then mixed and coated with an aqueous dispersed urethane-based binder resin and a titanium-based chelate compound , Followed by drying.
In this specification, the coating layer may be formed by a method known in the art. For example, a method of forming a coating layer directly on the base film may be used, or by using an adhesive or an adhesive after forming the coating layer However, the direct coating method is economical in terms of time and cost of the process, and is preferable from the viewpoint of phase difference manifestation.
On the other hand, the method of forming the coating layer directly on the base film is not particularly limited, and any method known in the art may be used. For example, a bar coating, a slot die coating, a spray coating, Coating, dip coating, micro gravure coater, comma coater and the like can be used.
In one embodiment, the thickness direction retardation value (R th ) of the coating film measured at a wavelength of 550 nm represented by the following formula (1) is -400 nm to 0 nm. In the case of the coating layer having the retardation value in the thickness direction, it can be very usefully used as a retardation film for an IPS mode liquid crystal display device together with a base film described later. In one embodiment of the present disclosure, that the one (R th) in the thickness direction retardation value of the film measured at a wavelength of 550nm of the coating of -120 nm to -100 nm is more preferred.
Equation (1): R th = ( nz- ny) × d
In the formula (1)
n y is the refractive index in the vertical direction in the n x direction in the plane direction of the coating layer,
n x is a refractive index in a direction in which the surface direction refractive index of the coating layer becomes maximum,
n z means the refractive index in the thickness direction,
d means the thickness of the coating layer.
According to another embodiment of the present invention, the thickness of the coating layer is more than 0 to 20 占 퐉. More preferably more than 0 and 15 mu m or less. When the thickness of the coating layer is in the above range, problems such as drying failure, curling of the film and the like can be minimized and the display can be thinned.
In one embodiment of the present invention, the coating layer produced using the coating liquid composition has a planar phase retardation value (R in / 占 퐉) of 1 占 퐉 or less.
In one embodiment of the present invention, the coating layer produced using the coating liquid composition has a thickness direction retardation value (R th / 탆) per 1 탆 of -5 탆 to -30 탆.
In this specification, the retardation value in the plane direction and the retardation value in the thickness direction can be measured by the above-described method.
< Phase difference Film and composite Phase difference Film>
The present invention provides a retardation film comprising the coating layer.
The present disclosure relates to a substrate film comprising a negative birefringent material; And the above-described coating layer provided on at least one surface of the base film, wherein the composite retardation film satisfies the above-mentioned formulas (2) to (4). In this case, it can be very usefully used as a retardation film for an IPS mode liquid crystal display.
In one embodiment of the present invention, the retardation film is for an IPS mode liquid crystal display.
Further, in the present specification, the value of R in of the retardation film is more preferably 90 nm to 250 nm, and the value of R th of the retardation film is more preferably 30 nm to 100 nm.
It is also preferable that the retardation film has an Nz value of 0.2 to 0.9.
Conventionally, a polymer material such as a polyamide, a cyclic olefin-based polymer, a polycarbonate, a polyarylate, or an imide-based polymer has been used as a material of a layer provided on at least one surface of the base film. In this case, There was a problem in that a curl occurred. The occurrence of curl hinders efficient implementation of the viewing angle compensation effect, and may cause deterioration of the durability and the like of the liquid crystal display device including the curl. Further, it may cause defects such as wrinkles in the lapping process with other members.
Therefore, when a coating layer containing a layered inorganic material is included on at least one surface of a base film as in the embodiment of the present invention, the occurrence of curl is minimized and the desired phase difference can be realized even with a thin layer thickness have.
In addition, the retardation film according to one embodiment of the present invention can improve the adhesion to the base film and prevent the base film from being broken by including a layered inorganic material as well as an aqueous dispersion urethane resin in the coating layer.
In this specification, the coating layer of the retardation film is the same as described above.
- base film
In the present specification, "including a negative birefringent material" may be interpreted as "having a negative retardation property ". In other words, the base film containing the negative birefringent material may be a base film having negative retardation characteristics.
In one embodiment of the present invention, the base film comprises an acrylic resin; Styrene type resin; And copolymers comprising an acrylic monomer and a styrene monomer.
Specifically, in one embodiment of the present specification, the base film comprises an acrylic resin; A blend resin of an acrylic resin and a styrene resin; Or a copolymer comprising an acrylic monomer and a styrene monomer.
As used herein, the term "blend resin" means mixing two or more resins, and "copolymer" may mean one polymer formed by polymerizing two or more monomers.
In the present specification, the acrylic resin mainly contains an acrylate monomer and / or a methacrylate monomer, and includes not only a homopolymer resin composed of an acrylate monomer or a methacrylate monomer, but also an acrylate monomer and / Or a copolymer resin in which other monomers other than the methacrylate monomer are copolymerized.
Herein, the methacrylate monomer includes not only methacrylate but also methacrylate derivatives such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n -butyl methacrylate, t -butyl Methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, butoxymethyl methacrylate, or oligomers thereof, and the like. Of these, methyl methacrylate is more preferable, but is not limited thereto. These may be used alone or in combination.
In addition, the acrylate monomer includes not only an acrylate but also an acrylate derivative. Examples of the acrylate monomer include methyl acrylate, ethyl acrylate, propyl acrylate, n -butyl acrylate, t -butyl acrylate, cyclohexyl acrylate Methoxyethyl acrylate, ethoxyethyl acrylate, butoxymethyl acrylate, and oligomers thereof. Of these, methyl acrylate is more preferable, but is limited thereto. It is not. These may be used alone or in combination.
In the present specification, the styrene-based resin includes a styrene-based monomer, and examples thereof include, but are not limited to, styrene,? -Methylstyrene, and 4-methylstyrene.
The styrenic monomer is preferably prepared in a copolymerized form with an acrylic monomer, but alternatively, a separate styrenic copolymer may be blended with a polymer comprising the acrylic monomer. For example, the copolymer containing the acrylic monomer and the styrene monomer may be a styrene-maleic anhydride copolymer (SMA), a styrene-acrylonitrile copolymer (SAN), an a-methylstyrene-acrylonitrile copolymer ), But the present invention is not limited thereto.
On the other hand, in order to improve the heat resistance, the acrylic resin may include a lactone monomer, a maleic anhydride monomer, a maleimide monomer, or the like, other than the (meth) acrylic monomer. Examples of the maleic anhydride monomer include maleic anhydride, methyl maleic anhydride, ethyl maleic anhydride, propyl maleic anhydride, isopropyl maleic anhydride, cyclohexyl maleic anhydride and phenyl maleic anhydride. ; Examples of the maleimide-based monomer include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, But are not limited thereto. These may be used alone or in combination.
In another embodiment, in the case where a blend resin of an acrylic resin and a styrene resin is used as the base film, a high heat resistance of the acrylic resin and a high retardation of the styrene resin can be expected.
The glass transition temperature (Tg) of the base film is preferably 100 ° C to 160 ° C. When the glass transition temperature (Tg) is in the above range, it can have excellent durability. If the glass transition temperature is less than 100 ° C, the film is easily deformed under high temperature and high humidity conditions, There is a problem that this becomes uneven.
In one embodiment of the present invention, the base film has a retardation value (R in ) in the plane direction of the film measured at a wavelength of 550 nm of 95 nm to 120 nm.
In another embodiment, the thickness direction retardation value (R th ) of the base film measured at a wavelength of 550 nm is 150 nm to 160 nm.
The retardation value in the plane direction and the retardation value in the thickness direction can be calculated by the above-described method.
The base film may be a uniaxially stretched film in the width direction or a biaxially stretched film in the longitudinal direction (MD) and the transverse direction (TD).
The uniaxial or biaxial stretching may be performed by a method known in the art. For example, the stretching may be performed in a tenter equipped with a preheating portion, a stretching portion and a heat treatment portion. The term "preheating" refers to a process of softening the substrate film by heating in advance so that it can be satisfactorily stretched in a subsequent stretching process. The substrate film introduced into the preheating device is heated at a temperature lower than Tg, The stretching process is performed at a higher temperature. Thereafter, the stretched base film is subjected to heat treatment for the purpose of fixing the orientation of the film in the heat treatment section. At this time, the stretching magnification can be adjusted in the stretching portion according to the phase difference value to be acquired.
According to one embodiment of the present disclosure, the base film is a + B plate.
According to one embodiment of the present invention, the thickness of the base film is 80 mu m or less. Specifically, it may be 70 mu m or less or 60 mu m or less. More specifically, it may be more than 0 [mu] m but not more than 50 [mu] m. In one embodiment of the present invention, the thickness of the base film may be 30 占 퐉 to 40 占 퐉.
The phase difference film according to an exemplary embodiment of the present specification may be satisfied a relation of n x, total> n z, total> n y, total.
n x, total is the refractive index in the direction in which the refractive index in the plane direction of the entire retardation film becomes maximum (that is, in the slow axis direction)
n y, total is the refractive index of the entire retardation film in the direction perpendicular to the slow axis (i.e., the fast axis direction)
n z and total are refractive indices in the thickness direction of the entire retardation film.
In one embodiment of the present invention, the base film and the coating layer are provided in contact with each other. That is, in one embodiment of the present specification, the base film and the coating layer provide an integral complex phase difference film.
That is, the retardation film according to one embodiment of the present disclosure may not include additional members such as a primer layer, an adhesive layer, and a pressure-sensitive adhesive layer between the base film and the coating layer. This is because the water-dispersible urethane-based resin contained in the coating layer improves the adhesion as described above.
In this case, the influence due to external stress can be minimized owing to the additional member, and deterioration of the optical characteristics can be prevented. Further, the film can be made thinner easily, and the production process and cost are easy.
In another embodiment, it may further comprise an additional member between the base film and the coating layer.
In one embodiment of the present invention, the total thickness of the base film and the retardation film including the coating layer may be 20 탆 to 100 탆, but is not limited thereto. When the thickness of the polarizer is less than 20 탆, the retarder film does not firmly support the polarizer, and therefore, there is a high possibility that the polarizer shrinkage, the polarizer crack, curl and the like are likely to occur. When the thickness exceeds 100 탆, There is a problem in that defects are caused by drying failure of the ink.
On the other hand, in the production of the retardation film according to one embodiment of the present invention, if necessary, it may further include additives known in the art. Examples of the additive include, but are not limited to, a dispersant, a surface additive, a lubricant, a heat stabilizer, a UV absorber, a plasticizer and an antioxidant. ≪ / RTI >
An embodiment of the present disclosure also provides a method of manufacturing the above-described retardation film. Specifically, preparing a base film having negative retardation characteristics; And forming a coating layer comprising a layered inorganic material and an aqueous dispersion-based urethane resin on at least one surface of the base film.
The above-mentioned base film, the layered inorganic material contained in the coating layer, and the water-dispersed urethane-based resin are the same as described above.
One embodiment of the present disclosure also provides a polarizing plate comprising the above-described retardation film. At this time, the polarizing plate may have a component, a lamination sequence, and the like known in the art, except that the polarizing plate includes a retardation film according to one embodiment of the present disclosure. For example, a protective film or the like may further be included.
Specifically, it may be a polarizing plate comprising a retardation film according to one embodiment of the present invention on at least one side of a polyvinyl alcohol-based polarizer.
One embodiment of the present disclosure also provides an IPS mode liquid crystal display device including the above-mentioned polarizing plate.
The IPS mode liquid crystal display may include a liquid crystal cell and a first polarizing plate and a second polarizing plate disposed on both sides of the liquid crystal cell. The retardation film for the IPS mode liquid crystal display may include a liquid crystal cell, Or between the first polarizing plate and the second polarizing plate. That is, the retardation film may be provided between the first polarizer and the liquid crystal cell, between the second polarizer and the liquid crystal cell, or between the first polarizer and the liquid crystal cell, between the second polarizer and the liquid crystal cell One or two or more .
The first polarizing plate and the second polarizing plate may further include a protective film on one surface or both surfaces thereof. For example, the inner protective film may be a triacetate cellulose (TAC) film, a polynorbornene-based film produced by an acrylic film ring opening metathesis polymerization (ROMP) A ring opening metathesis polymerization followed by hydrogenation (HROMP) polymer film obtained by hydrogenating a ring-opening polymerized cyclic olefin polymer, a polyester film, or a polynorbornene-based film produced by addition polymerization. In addition, a protective film or the like made of a transparent polymer material may be used, but is not limited thereto.
Further, a surface coating layer may be further included on the protective film. The surface treatment layer may be a low reflection layer such as an anti-glare layer or an anti-reflection (AR) layer or a low reflection (LR) layer such as a hard layer, an anti-glare layer or a semi- Can be illustrated.
Hereinafter, the present invention will be described in more detail by way of examples. However, the following embodiments are intended to illustrate the present disclosure, and thus the scope of the present specification is not limited thereto.
≪ Comparative Example 1 &
A coating liquid composition prepared by mixing 4.0 wt% of laponite (BYK), which is a hectorite, and 4.8 wt% of R600 (DSM), an aqueous dispersion-based resin, in distilled water was coated on a base plate A coating layer of-C plate was coated on a FN-A film (Okura) using a bar coater and dried at 100 ° C for 5 minutes to prepare a retardation film.
≪ Example 1 >
A retardation film was prepared in the same manner as in Comparative Example 1, except that 1 part by weight of titanium chelate compound TC400 (manufactured by Matsumoto Chemical Co., Ltd.) was added to the coating liquid composition of Comparative Example 1.
≪ Example 2 >
A retardation film was prepared in the same manner as in Example 1 except that 3 parts by weight of TC400 was added to laponite in Example 1.
≪ Example 3 >
A retardation film was prepared in the same manner as in Example 1, except that 5 parts by weight of TC400 was added to laponite in Example 1.
<Example 4>
A retardation film was prepared in the same manner as in Example 1 except that TC400 was added in an amount of 7 parts by weight relative to laponite.
Fig. 2 is a graph showing changes in viscosity of the coating liquid composition according to Comparative Example 1 and Examples 1 to 4 with time. Fig.
Experimental Example 1. Viscosity evaluation and Phase difference Expression measurement
Table 1 summarizes the thickness direction retardation values of the coating liquid compositions of Comparative Examples 1 and 1 to 4 according to the time and the thickness of the coating layer formed using the coating liquid composition.
≪ Comparative Example 2 &
A coating liquid composition prepared by mixing 4.0 wt% of laponite (BYK Co.) as hectorite and 4.8 wt% of SUPERFLEX 460S (DAIICHI KOGYO SEIYAKU) as an aqueous dispersion urethane resin in distilled water Was coated with a coating layer of a-C plate on a base plate FN-A film (Okura) as a + B plate using a bar coater and then dried at 100 ° C for 5 minutes to prepare a retardation film.
≪ Example 5 >
A retardation film was prepared in the same manner as in Comparative Example 2, except that 1 part by weight of titanium chelate compound TC400 (Matsumoto Chemical Co.) was added to the coating liquid composition of Comparative Example 2. [
≪ Example 6 >
A retardation film was prepared in the same manner as in Example 5 except that 3 parts by weight of TC400 was added to the laponite in Example 5.
≪ Example 7 >
A retardation film was prepared in the same manner as in Example 5 except that 5 parts by weight of TC400 was added to the laponite in Example 5.
FIG. 3 is a graph showing changes in viscosity of the coating liquid composition according to Comparative Example 2 and Examples 5 to 7 with time. FIG.
1 and 2, it can be confirmed that when the titanium-based chelate compound is included, the increase in viscosity is small even though the time passes.
Experimental Example 2. Viscosity evaluation and Phase difference Expression measurement
The thickness direction retardation values according to the viscosity of the coating liquid compositions of Comparative Examples 2 and 5 to 7 and the thickness of the coating layer formed using the coating liquid composition are summarized in Table 2 below.
In Table 1 and Table 2, the viscosity is a value measured by using BROOKFIELD LV DV-II + Pro, the viscosity of the coating liquid composition stored at 20 ° C, and the retardation developability was evaluated by the tacticity of the coating layer of -C plate formed using the coating liquid composition ( Rth / 占 퐉) per 1 占 퐉.
From the results of Table 1 and Table 2, it can be seen that the coating liquid composition according to one embodiment of the present invention maintains the retardation value required for the -C-plate and has excellent viscosity stability of the coating liquid composition.
801: Surface coating layer
701: Protective film
601: Polarizer
501: primer layer
401: base film
301: Coating layer
201: pressure-sensitive adhesive layer
101: IPS panel
Claims (27)
Wherein the water-dispersible urethane-based resin comprises an aliphatic unit.
Wherein the titanium chelate compound is 0.1 to 20 parts by weight based on 100 parts by weight of the water-dispersible urethane resin.
Wherein the layered inorganic material comprises at least one selected from the group consisting of smectite-based materials.
Wherein the layered inorganic material comprises one or more selected from the group consisting of hectorite, montmorillonite, and bentonite.
The average diameter of the layered inorganic material is 10 nm to 30 nm,
And the thickness is more than 0 nm but not more than 2 nm.
Wherein the layered inorganic material is in the form of a plate-like disk.
Wherein the layered inorganic material is represented by the following structural formula (1).
[Structural formula 1]
Na + 0.7 [(Si 8 Mg 5.5 Li 0.3) O 20 (OH) 4] -0.7
The solid content of the coating liquid composition with respect to the total weight of the coating liquid composition is 5 wt% to 15 wt%
Wherein the content of the solvent is 85 wt% to 95 wt%.
Wherein the viscosity of the coating liquid composition is 10 cP to 500 cP.
Wherein the viscosity change amount of the coating liquid composition is less than 500 cP.
Wherein the solvent comprises water.
Wherein the solvent further comprises one or more solvents selected from the group consisting of alcohols and ketones.
The content of the water relative to the total weight of the solvent is 50 wt% to 100 wt%
The content of one or more solvents selected from the group consisting of alcohols and ketones is 0 wt% to 50 wt%.
Wherein the layered inorganic material is dispersed in the water.
Wherein the water dispersed urethane resin has an elongation of 50% or more.
Wherein the coating layer is a -C-plate.
Wherein the thickness direction retardation value (R th ) of the film measured at a wavelength of 550 nm represented by the following formula (1) in the coating layer is -400 nm to 0 nm:
(1): R th = (nz - ny) x d
In the formula (1)
n y is the refractive index in the vertical direction in the n x direction in the plane direction of the coating layer,
n x is a refractive index in a direction in which the surface direction refractive index of the coating layer becomes maximum,
n z means the refractive index in the thickness direction,
d means the thickness of the coating layer.
Wherein the thickness of the coating layer is greater than 0 and 20 占 퐉 or less.
And a coating layer according to claim 16 provided on at least one side of the base film,
A composite retardation film satisfying the following formulas (2) to (4):
(2): 50 nm? R in ? 300 nm
Equation (3): 10 nm ≤ R th ≤ 300 nm
Equation (4): 0.1? Nz <1
In the above formulas (2) to (4)
R in is the retardation value in the plane direction of the film measured at a wavelength of 550 nm,
R th is the thickness direction retardation value of the film measured at a wavelength of 550 nm,
Nz is the ratio (R th / R in) of the thickness retardation value on a plane direction retardation value measured at a wavelength of 550nm.
The base film may be an acrylic resin; Styrene type resin; And a copolymer comprising an acrylic monomer and a styrene monomer.
Wherein the base film is a + B plate.
Wherein the base film has a thickness of 80 占 퐉 or less.
Wherein the base film and the coating layer are provided in contact with each other.
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