Patent Application
20240255676
The present disclosure relates to an optical film containing a polymer resin having excellent restoring force after folding, and a display device including the same.
Recently, the use of an optical film instead of glass as a cover window of a display device has been considered with the goal of reducing the thickness and weight of the display device and increasing the flexibility thereof. In order for the optical film to be usable as a cover window of a display device, the optical film needs to have excellent optical and mechanical properties as well as superior restoring force after being folded.
Therefore, it is necessary to develop a film that exhibits excellent optical properties as well as superior mechanical properties, such as insolubility, chemical resistance, heat resistance, radiation resistance, low-temperature characteristics and restoring force after folding.
Among optical films, polyimide (PI)-based resins have excellent insolubility, chemical resistance, heat resistance, radiation resistance and low-temperature characteristics, and are used as automobile materials, aviation materials, spacecraft materials, insulating coatings, insulating films, protective films, and the like.
Recently, polyamide-imide-based resins having amide repeating units added to polyimide-based resins have been developed, and films prepared using polyamide-imide-based resins have superior optical properties and excellent mechanical properties such as excellent insolubility, chemical resistance, heat resistance, radiation resistance, and low-temperature characteristics as well as restoring force after folding.
Amide repeating units may be prepared through polymerization of a diamine-based compound and a dicarbonyl-based compound. However, for example, 2,2′-bis(trifluoromethyl)benzidine (TFDB), when used as the diamine, causes a problem in which, during polymerization of TFDB with the dicarbonyl-based compound, the dicarbonyl-based compound is gelled due to the rigid structure of TFDB, so the polymerization reaction is insufficient.
Therefore, there is a need to develop a polyamide-imide-based resin having a high degree of polymerization even when a dicarbonyl-based compound is added.
It is an aspect of the present disclosure to provide an optical film that contains a polymer resin having excellent restoring force after folding.
It is another aspect of the present disclosure to provide an optical film that exhibits excellent optical properties as well as mechanical properties.
In accordance with the present disclosure, the above and other objects can be accomplished by the provision of an optical film containing a polymer resin and having a yellowness index of 3.0 or less and a parameter of restoring force after folding, calculated using the following Equation 1, of 1.5 GPa or less:
The elastic strain index (E′) calculated using Equation 2 may be 5.5 or more.
The polymer resin may include an imide repeating unit and an amide repeating unit.
The amide repeating unit may be present in an amount of 80% or more of a total number of the imide repeating unit and the amide repeating unit.
The imide repeating unit may include a first repeating unit and a second repeating unit.
The amide repeating unit may include a third repeating unit and a fourth repeating unit.
The first repeating unit may be an imide repeating unit formed by polymerization of a first diamine-based compound and a first dianhydride-based compound, and the second repeating unit may be an imide repeating unit formed by polymerization of a second diamine-based compound and a second dianhydride-based compound.
The third repeating unit may be an amide repeating unit formed by polymerization of the first diamine-based compound and a first dicarbonyl-based compound, and the fourth repeating unit may be an amide repeating unit formed by polymerization of a second diamine-based compound and a second dicarbonyl-based compound.
The first diamine-based compound may be 2,2′-bis(trifluoromethyl)benzidine (TFDB).
The second diamine-based compound may include at least one functional group selected from the group consisting of sulfonyl, carbonyl, methylene, propylene, and halogens.
The second diamine-based compound may include at least one selected from the group consisting of bis(3-aminophenyl) sulfone (3DDS), bis(4-aminophenyl) sulfone (4DDS), 2,2-bis(3-aminophenyl) hexafluoropropane (3,3′-6F), 2,2-bis(4-aminophenyl) hexafluoropropane (4,4′-6F), 4,4′-methylenedianiline (MDA), 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, and tetrachloride benzidine (CIBZ).
A molar ratio of the polymerized first diamine-based compound and the polymerized second diamine-based compound may be 95:5 to 50:50.
The polymer resin may have a weight average molecular weight (Mw) of 200,000 to 500,000.
In accordance with another aspect of the present disclosure, there is provided a display device including a display panel, and the optical film according to the present disclosure disposed on the display panel.
An embodiment of the present disclosure provides an optical film containing a polymer resin having excellent restoring force after folding.
The optical film according to another embodiment of the present disclosure exhibits excellent optical and mechanical properties and thus is capable of effectively protecting the display surface of a display device when used as a cover window of the display device.
Hereinafter, embodiments of the present disclosure will be described in detail with reference to the accompanying drawings. However, the following embodiments are illustratively provided merely for clear understanding of the present disclosure, and do not limit the scope of the present disclosure.
The shapes, sizes, ratios, angles, and numbers disclosed in the drawings for describing embodiments of the present disclosure are merely examples, and the present disclosure is not limited to the illustrated details. Like reference numerals refer to like elements throughout the present specification. In the following description, when a detailed description of relevant known functions or configurations is determined to unnecessarily obscure important points of the present disclosure, the detailed description will be omitted.
In the case in which the term such as “comprise”, “have”, or “include” is used in the present specification, another part may also be present, unless “only” is used. Terms in a singular form may include the plural meanings, unless noted to the contrary. Also, in construing an element, the element is to be construed as including an error range even if there is no explicit description thereof.
In describing a positional relationship, for example, when the positional relationship is described as “on”, “above”, “below”, or “next”, the case of no contact therebetween may be included, unless “just” or “directly” is used.
Spatially relative terms, such as “below”, “beneath”, “lower”, “above”, and “upper”, may be used herein to describe the relationship between a device or element and another device or element, as shown in the figures. It will be understood that spatially relative terms are intended to encompass different orientations of a device during the use or operation of the device, in addition to the orientation depicted in the figures. For example, if a device in one of the figures is turned upside down, elements described as “below” or “beneath” other elements would then be positioned “above” the other elements. The exemplary term “below” or “beneath” can, therefore, encompass the meanings of both “below” and “above”. In the same manner, the exemplary term “above” or “upper” can encompass the meanings of both “above” and “below”.
In describing temporal relationships, for example, when a temporal order is described using “after”, “subsequent”, “next”, or “before”, the case of a non-continuous relationship may be included, unless “just” or “directly” is used.
It will be understood that, although the terms “first”, “second”, etc. may be used herein to describe various elements, these elements are not limited by these terms. These terms are only used to distinguish one element from another. Therefore, a first element could be termed a second element within the technical idea of the present disclosure.
It should be understood that the term “at least one” includes all combinations related with one or more items. For example, “at least one among a first element, a second element, and a third element” may include all combinations of two or more elements selected from among the first, second, and third elements, as well as each of the first, second, and third elements.
Features of various embodiments of the present disclosure may be partially or completely coupled to or combined with each other, and may be variously interoperated with each other and driven technically. The embodiments of the present disclosure may be carried out independently from each other, or may be carried out together in an interrelated manner.
An embodiment of the present disclosure provides an optical film. The optical film according to the embodiment of the present disclosure contains a polymer resin.
The polymer resin may be contained in the film in any one of various shapes and forms, for example, as a solid powder, in the state of being dissolved in a solution, or as a matrix solidified after having been dissolved in a solution. Any resin may be considered as the same as the polymer resin of the present disclosure, regardless of the shape and form thereof, as long as it is a resin containing the same repeating unit as in the present disclosure. In general, the polymer resin may exist in the film in the form of a matrix, obtained by applying a polymer resin solution and drying the same to form a solid.
According to an embodiment of the present disclosure, an optical film has a parameter of restoring force after folding, calculated using the following Equation 1, of 1.5 GPa or less:
The modulus of the optical film may be measured under the following conditions using a universal testing machine (e.g., from Instron Corp.) in accordance with the ASTM D882 standard.
The Poisson's ratio of the optical film is the ratio of a lateral strain to an axial strain of a specimen to which an axial load is applied, and may be measured using a non-contact (video extensometer) method in accordance with the ASTM E-132 standard. Specifically, the Poisson's ratio can be measured under the following conditions using a universal testing machine (e.g., an Instron 3367 from Instron Corp.).
The parameter of restoring force after folding of the present disclosure will be described in more detail with reference to the drawings.
When the parameter of restoring force after folding of the optical film is 1.5 GPa or less, the resistance generated when folded decreases and thus excellent restoring force after folding can be achieved, and no folding traces may be formed. As the radius of curvature (R) decreases, the occurrence of folding traces increases. When the parameter of restoring force after folding is 1.5 GPa or less, restoring force after folding is excellent, and thus no folding traces occur. In particular, the radius of curvature (R) in the parameter of restoring force after folding is 0.5 mm. When the parameter of restoring force after folding is 1.5 GPa or less, the radius of curvature (R) is 0.5 mm, no folding traces are formed and excellent restoring force after folding can be achieved.
Specifically, when the optical film is folded, a mechanical change in the film may occur. As used herein, the term “folding traces”, for example, refers to a phenomenon e film is bent, has an uneven wrinkled surface, or, in the case of a transparent film, develops white turbidity. Also, in addition to the occurrence of wrinkles or turbidity, before and after folding, a change in length of the optical film, as well as changes in the mechanical and optical properties of the optical film, such as a change in light transmittance, may occur.
When the optical film is folded, stress is applied to the film. At this time, compressive stress is applied along the folding direction to the inner surface (hereinafter referred to as the “inner diameter”) of the fold of the optical film, and tensile stress is applied to the outer surface thereof (hereinafter referred to as the “outer diameter”), which is the surface opposite thereto. Accordingly, compressive strain occurs in the inner diameter of the optical film, and tensile strain occurs in the outer diameter of the optical film.
Specifically, as shown in
Compressive stress and tensile stress are proportional to the magnitude of the length change. The length change of the outer diameter is +Π(d/2), and the length change of the inner diameter is −Π(d/2). Therefore, the stress applied to the inner diameter is proportional to d/2R (=[Π(d/2)]/ΠR), and the stress applied to the outer diameter is proportional to d/2R. As the stress applied to the outer and inner diameters decreases, the restoring force after folding of the optical film improves. Therefore, a lower value of d/2R of the optical film is advantageous for folding. Specifically, when d/2R is 0.08 or less, the optical film exhibits excellent restoring force after folding and thus leaves no folding traces, and when d/2R exceeds 0.08, excessive pressure is applied during folding folding traces may be left after folding.
In addition, the parameter of restoring force after folding of the optical film is proportional to the elastic strain index (E′). As the elastic strain index (E′) increases, the restoring force after folding of the optical film improves, and as the elastic strain index (E′) decreases, the restoring force after folding of the optical film deteriorates.
According to an embodiment of the present disclosure, the optical film may have an elastic strain index (E′), calculated using Equation 2, of 5.5 GPa or more. The restoring force after folding of the optical film can be improved by controlling the thickness and radius of curvature of the optical film, as well as the modulus and Poisson's ratio thereof. As the modulus and Poisson's ratio of the optical film increase, the resistance to strain (deformation) of the optical film during folding increases. For example, even if the thickness of the optical film increases, when the modulus of the optical film increases, restoring force after folding improves. On the other hand, even if the thickness of the optical film decreases, when the modulus of the optical film also decreases, restoring force after folding deteriorates, so the optical film is unsuitable for use as a cover window of a flexible display device. Further, if the Poisson's ratio of the optical film increases, restoring force after folding improves, and conversely, when the Poisson's ratio of the optical film decreases, restoring force after folding deteriorates.
According to an embodiment of the present disclosure, the optical film may have a yellowness index (Y. I.) of 3.0 or less. The yellowness index may be measured in accordance with E313 the ASTM standard using a spectrophotometer (CM-3700D, KONICA MINOLTA).
According to an embodiment of the present disclosure, the optical film may contain a polymer resin.
The optical film can be imparted with a parameter of restoring force after folding of 1.5 GPa or less by controlling the components and content of the repeating units of the polymer resin. In addition, the parameter of restoring force after folding can be reduced and restoring force after folding can be improved by increasing the degree of polymerization of the polymer resin.
The polymer resin may include at least one of an imide repeating unit and an amide repeating unit. For example, the polymer resin may include either an imide repeating unit or an amide repeating unit, and may include both an imide repeating unit and an amide repeating unit. The polymer resin may include at least one of a polyimide-based resin, a polyamide-based resin, and a polyamide-imide-based resin.
In the present disclosure, the imide repeating unit of the polymer resin may be prepared from monomer components including a diamine-based compound and a dianhydride-based compound. The diamine-based compound and the dianhydride-based compound may be polymerized to form amic acid, and the amic acid may be imidized again to form an imide repeating unit. In addition, the amide repeating unit may be prepared by polymerization of monomer components including a diamine-based compound and a dicarbonyl-based compound. The specific structures of the imide repeating unit and the amide repeating unit may vary depending on the monomers used for polymerization.
However, the polymer resin according to an embodiment of the present disclosure is not limited thereto. The polymer resin according to an embodiment of the present disclosure may be prepared from monomer components further including other compounds, in addition to the diamine-based compound, the dianhydride-based compound, and the dicarbonyl-based compound. Therefore, the polymer resin according to an embodiment of the present disclosure may further include other repeating units, in addition to the imide repeating unit and the amide repeating unit.
The optical film according to an embodiment of the present disclosure may contain at least one of a polyimide-based resin, a polyamide-based resin, and a polyamide-imide-based resin.
According to an embodiment of the present disclosure, the optical film may be any one of a polyimide-based film, a polyamide-based film, and a polyamide-imide-based film, but the embodiments of the present disclosure are not limited thereto. Any film having light transmittance may be used as the optical film according to an embodiment of the present disclosure.
In an embodiment of the present disclosure, the polymer resin may include the amide repeating units in an amount which corresponds to 80% or more of the total number of imide repeating units and amide repeating units. Preferably, the polymer resin may include the amide repeating units in an amount which corresponds to 95% or more of the total number of imide repeating units and amide repeating units, more preferably 98% or more thereof.
When the polymer resin includes the amide repeating units in an amount which corresponds to 80% or more of the total number of imide repeating units and amide repeating units, the optical properties of the film produced from the polymer resin can be maintained while the mechanical properties thereof can be improved; in particular, restoring force after folding can be greatly improved. That is, it is possible to produce an optical film which includes a greater amount of amide repeating units than imide repeating units, it is colorless and transparent and has excellent insolubility, chemical resistance, heat resistance, radiation resistance, low-temperature characteristics, restoring force after folding, and the like.
When a large amount of dicarbonyl-based compound is added in order to form a large number of amide repeating units, there is a problem in that the degree of polymerization of the resin decreases because the dicarbonyl-based compound is gelled and thus the polymerization reaction is insufficiently performed.
In the present disclosure, gelation of the dicarbonyl-based compound can be prevented or inhibited by performing polymerization using two or more different types of diamine-based compounds.
According to an embodiment of the present disclosure, the imide repeating unit may include a first repeating unit and a second repeating unit.
The imide repeating unit is formed by polymerization of a diamine-based compound and a dianhydride-based compound, the first repeating unit is an imide repeating unit obtained by polymerization of a first diamine-based compound and a first dianhydride-based compound, and the second repeating unit is an imide repeating unit obtained by polymerization of a second diamine-based compound and a second dianhydride-based compound. The polymer resin of the present disclosure includes repeating units derived from at least two types of diamine-based compounds, including the first diamine-based compound and the second diamine-based compound.
Specifically, according to an embodiment of the present disclosure, the first diamine-based compound is 2,2′-bis(trifluoromethyl)benzidine (TFDB). According to an embodiment of the present disclosure, the second diamine-based compound includes an aromatic diamine-based compound other than TFDB. The imide repeating unit and the amide repeating unit of the present disclosure may be derived from TFDB and an aromatic diamine-based compound other than TFDB.
Since the 2,2′-bis(trifluoromethyl)benzidine (TFDB) has a specific linear and rigid structure, a film that includes repeating units derived from TFDB can be imparted with greatly improved mechanical properties, such as insolubility, chemical resistance, heat resistance, radiation resistance, and low-temperature characteristics.
However, polymerization between TFDB and a dicarbonyl-based compound is accelerated due to the rigid structure of 2,2′-bis(trifluoromethyl)benzidine (TFDB). Such rapid polymerization may allow only a part of the dicarbonyl-based compound to react with the diamine-based compound, and the remainder of the dicarbonyl-based compound may be gelled rather than being polymerized. The gelation of the dicarbonyl-based compound may reduce the degree of polymerization of the resin and deteriorate the optical properties of the film. Therefore, it is difficult to prepare a polymer resin including a large amount of amide repeating units merely through addition of 2,2′-bis(trifluoromethyl)benzidine (TFDB). According to the present disclosure, the second diamine-based compound can prevent gelation of the dicarbonyl-based compound and improve the polymerization degree of the polymer.
According to an embodiment of the present disclosure, the second diamine-based compound includes an aromatic diamine-based compound.
In an embodiment of the present disclosure, the term “aromatic diamine-based compound” refers to a diamine-based compound in which an amino group is directly bonded to an aromatic ring, and may include an aliphatic group or other substituents as part of the structure thereof. The aromatic ring may be a single ring, a fused ring including a single ring linked thereto directly via a heteroatom, or a condensed ring. Examples of the aromatic ring may include, but are not limited to, a benzene ring, a biphenyl ring, a naphthalene ring, an anthracene ring, and a fluorene ring.
According to an embodiment of the present disclosure, the second diamine-based compound may be represented by the following Formula 1:
An optical film produced using a diamine-based compound in which a hydrogen atom is substituted with a fluorine-substituted hydrocarbon group can be imparted with excellent light transmittance and excellent workability.
A1 in Formula 1 may, for example, include a structure represented by any one of the following formulas.
In the above formulas, * represents a bonding position. In the above formulas, X may be any one of a single bond, O, S, SO2, CO, CH2, C(CH3)2, and C(CF3)2. Although the bonding position of X on each ring is not particularly limited, the bonding position of X may be, for example, a meta or para position on each ring.
According to an embodiment of the present disclosure, the second diamine-based compound may include at least one functional group selected from the group consisting of sulfonyl, carbonyl, methylene, propylene, and halogens.
The sulfonyl, carbonyl, methylene, propylene, and halogen substituents function to control the movement of electrons in the compound. Accordingly, the second diamine-based compound includes at least one substituent of sulfonyl, carbonyl, methylene, propylene, and halogens, thereby controlling the ionization energy. As a result, the reactivity and reaction rate of the polymerization reaction with the dicarbonyl-based compound can be appropriately adjusted.
According to an embodiment of the present disclosure, the second diamine-based compound may include at least one selected from the group consisting of bis(3-aminophenyl) sulfone (3DDS), bis(4-aminophenyl) sulfone (4DDS), 2,2-bis(3-aminophenyl) hexafluoropropane (3,3′-6F), 2,2-bis(4-aminophenyl) hexafluoropropane (4,4′-6F), 4,4′-methylenedianiline (MDA), 3,3′-(dimethylamino)benzophenone (3,3′-CO), 4,4′-(dimethylamino)benzophenone (4,4′-CO), and tetrachloride benzidine (CIBZ).
According to an embodiment of the present disclosure, the first dianhydride-based compound and the second dianhydride-based compound may be each independently represented by the following Formula 2. The first dianhydride-based compound and the second dianhydride-based compound may be the same as or different from each other. The present disclosure is not limited with regard thereto.
In Formula 2, A2 represents a tetravalent organic group. For example, A2 may include a tetravalent organic group having 4 to 40 carbon atoms. A hydrogen atom in the organic group in Formula 2 may be substituted with a halogen element, a hydrocarbon group, or a hydrocarbon group substituted with a halogen element. Here, the hydrocarbon group or the hydrocarbon group substituted with a halogen element may have 1 to 8 carbon atoms.
A2 in Formula 2 may, for example, include a structure represented by any one of the following formulas.
In the above formulas, * represents a bonding position. In the above formulas, Z may independently be any one of a single bond, O, S, SO2, CO, (CH2)n, (C(CH3)2)n, and (C(CF3)2)n, and n may be an integer of 1 to 5. Although the bonding position of Z on each ring is not particularly limited, the bonding position of Z may be, for example, a meta or para position on each ring.
In an embodiment of the present disclosure, the first dianhydride-based compound and the second dianhydride-based compound may each independently include at least one selected from the group consisting of 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), biphenyl tetracarboxylic dianhydride (BPDA), naphthalene tetracarboxylic dianhydride (NTDA), diphenyl sulfone tetracarboxylic dianhydride (DSDA), 4-(2,5-oxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (TDA), pyromellitic dianhydride (PMDA), benzophenone tetracarboxylic dianhydride (BTDA), oxydiphthalic anhydride (ODPA), bis(carboxyphenyl) dimethyl silane dianhydride (SiDA), bis(dicarboxyphenoxy) diphenyl sulfide dianhydride (BDSDA), sulfonyldiphthalic anhydride (SO2DPA), and isopropylidenediphenoxy bis(phthalic anhydride) (BPADA).
The optical film according to an embodiment of the present disclosure may include, for example, a plurality of dianhydride-based compounds.
An optical film produced using a dianhydride-based compound in which a hydrogen atom is substituted with a fluorine-substituted hydrocarbon group can exhibit excellent light transmittance and workability.
According to an embodiment of the present disclosure, the amide repeating unit may include a third repeating unit and a fourth repeating unit.
The amide repeating unit is formed by polymerization of a diamine-based compound and a dicarbonyl-based compound, the third repeating unit is an amide repeating unit obtained by polymerization of a first diamine-based compound and a first dicarbonyl-based compound, and the fourth repeating unit is an amide repeating unit obtained by polymerization of a second diamine-based compound and a second dicarbonyl-based compound.
According to an embodiment of the present disclosure, the first dicarbonyl-based compound and the second dicarbonyl-based compound may be each independently represented by the following Formula 3. The first dicarbonyl-based compound and the second dicarbonyl-based compound may be the same as or different from each other. The present disclosure is not limited with regard thereto.
In Formula 3, A3 represents a divalent organic group. For example, A3 may include a divalent organic group having 4 to 40 carbon atoms. A hydrogen atom in the organic group in Formula 3 may be substituted with a halogen element, a hydrocarbon group, or a hydrocarbon group substituted with fluorine. Here, the hydrocarbon group or the hydrocarbon group substituted with fluorine may have 1 to 8 carbon atoms. For example, the hydrogen in A3 may be substituted with —F, —CH3, —CF3, or the like.
A3 in Formula 3 may, for example, include a structure represented by any one of the following formulas.
In the above formulas, * represents a bonding position. In the above formulas, Y may independently be any one of a single bond, O, S, SO2, CO, CH2, C(CH3)2 and C(CF3)2. Although the bonding position of Y on each ring is not particularly limited, the bonding position of Y may be, for example, a meta or para position on each ring.
According to an embodiment of the present disclosure, the first dicarbonyl-based compound and the second dicarbonyl-based compound may each independently include at least one selected from the group consisting of terephthaloyl chloride (TPC), isophthaloyl dichloride (IPC), biphenyl dicarbonyl chloride (BPDC), 4,4′-oxybisbenzoyl chloride (OBBC), and naphthalene dicarbonyl dichloride (NTDC).
In an embodiment of the present disclosure, the ratio of the number of first and third repeating units to the number of second and fourth repeating units is 95:5 to 50:50. Both the first repeating unit and the third repeating unit are repeating units formed by polymerization using the first diamine-based compound, and both the second repeating unit and the fourth repeating unit are repeating units formed by polymerization using the second diamine-based compound. Therefore, the molar ratio of the first diamine-based compound used for polymerization to the second diamine-based compound used for polymerization is 95:5 to 50:50.
When, with regard to the ratio of the number of first and third repeating units to the number of second and fourth repeating units, the fraction of the number of first and third repeating units increases above 95:5, the haze of the film may increase due to the increased ratio of the repeating units derived from TFDB and the dicarbonyl-based compound. On the other hand, when the fraction of the number of second and fourth repeating units increases above 50:50, the heat resistance and strength of the film may be deteriorated.
The polymer resin according to an embodiment of the present disclosure may include a first repeating unit represented by the following Formula 4 and a second repeating unit represented by the following Formula 5:
The polymer resin according to an embodiment of the present disclosure may include a third repeating unit represented by the following Formula 6 and a fourth repeating unit represented by the following Formula 7:
According to an embodiment of the present disclosure, the weight average molecular weight (Mw) of the polymer resin of the present disclosure may be 200,000 to 500,000.
The weight average molecular weight of the polymer resin can be measured under the following conditions using a GPC (Alliance e2695/2414 RID, Waters).
The gelation of the dicarbonyl-based compound due to the high reaction rate with a diamine-based compound, in particular TFDB, reduces the degree of polymerization of the polymer resin including a large number of amide repeating units. The weight average molecular weight is proportional to the polymerization degree. That is, as the polymerization degree decreases, the weight average molecular weight of the polymer resin also decreases.
When the weight average molecular weight of the polymer resin is less than 200,000, the degree of polymerization decreases, the number of end groups of the polymer chain increases, and the physical properties of the polymer resin are deteriorated. On the other hand, it is difficult to prepare a polymer resin having a weight average molecular weight of more than 500,000 during the process. The weight average molecular weight of the polymer resin is adjusted by controlling the polymerization viscosity during polymerization. A resin having a weight average molecular weight exceeding 500,000 is disadvantageous for processing because of the very high polymerization viscosity and consequent reduced flowability of the reaction which make it difficult to control and handle, and the necessity of a large amount of solvent in order to dissolve the polymer resin again.
According to an embodiment of the present disclosure, the optical film is light-transmissive. In addition, the optical film is flexible. For example, the optical film according to an embodiment of the present disclosure is bendable, foldable, or rollable. The optical film may have excellent mechanical and optical properties.
According to an embodiment of the present disclosure, the optical film may have a thickness sufficient for the optical film to protect the display panel. For example, the optical film may have a thickness of 10 to 100 μm.
According to an embodiment of the present disclosure, the optical film may have an average light transmittance in the visible light region, measured using a UV spectrophotometer, of 88% or more based on a thickness of 50 μm.
The average light transmittance of the optical film may be measured in a wavelength range of 360 to 740 nm using a spectrophotometer.
According to an embodiment of the present disclosure, the optical film may have a haze of 0.5% or less based on a thickness of 50 μm.
The haze of the optical film may be determined by cutting the produced optical film to a sample having a size of 50 mm×50 mm, performing measurement five times using a haze meter (model name: HM-150, produced by Murakami Color Research Laboratory) in accordance with the ASTM D1003 standard, and taking the average of the five values as the haze of the optical film.
Referring to
Referring to
The substrate 510 may be formed of glass or plastic. Specifically, the substrate 510 may be formed of plastic such as a polymer resin or an optical film. Although not shown, a buffer layer may be disposed on the substrate 510.
The thin film transistor TFT is disposed on the substrate 510. The thin film transistor TFT includes a semiconductor layer 520, a gate electrode 530 that is insulated from the semiconductor layer 520 and at least partially overlaps the semiconductor layer 520, a source electrode 541 connected to the semiconductor layer 520, and a drain electrode 542 that is spaced apart from the source electrode 541 and is connected to the semiconductor layer 520.
Referring to
A planarization layer 552 is disposed on the thin film transistor TFT to planarize the top of the thin film transistor TFT.
A first electrode 571 is disposed on the planarization layer 552. The first electrode 571 is connected to the thin film transistor TFT through a contact hole provided in the planarization layer 552.
A bank layer 580 is disposed on the planarization layer 552 in a part of the first electrode 571 to define pixel areas or light-emitting areas. For example, the bank layer 580 is disposed in the form of a matrix at the boundaries between a plurality of pixels to define the respective pixel regions.
The organic light-emitting layer 572 is disposed on the first electrode 571. The organic light-emitting layer 572 may also be disposed on the bank layer 580. The organic light-emitting layer 572 may include one light-emitting layer, or two light-emitting layers stacked in a vertical direction. Light having any one color among red, green, and blue may be emitted from the organic light-emitting layer 572, and white light may be emitted therefrom.
The second electrode 573 is disposed on the organic light-emitting layer 572.
The first electrode 571, the organic light-emitting layer 572, and the second electrode 573 may be stacked to constitute the organic light-emitting device 570.
Although not shown, when the organic light-emitting layer 572 emits white light, each pixel may include a color filter for filtering the white light emitted from the organic light-emitting layer 572 based on a particular wavelength. The color filter is formed in the light path.
A thin-film encapsulation layer 590 may be disposed on the second electrode 573. The thin-film encapsulation layer 590 may include at least one organic layer and at least one inorganic layer, and the at least one organic layer and the at least one inorganic layer may be alternately disposed.
The optical film 100 is disposed on the display panel 501 having the stack structure described above.
Hereinafter, a method of manufacturing an optical film according to another embodiment of the present disclosure will be described in brief.
The method of manufacturing an optical film according to an embodiment of the present disclosure includes preparing a polymer resin, dissolving the polymer resin in a solvent to prepare a polymer resin solution, and producing an optical film using the polymer resin solution.
The preparation of the polymer resin may be carried out by polymerizing monomers for forming the polymer resin.
According to another embodiment of the present disclosure, the polymer resin may be prepared from monomer components including a first diamine-based compound, a second diamine-based compound, a first dianhydride-based compound, a second dianhydride-based compound, a first dicarbonyl-based compound, and a second dicarbonyl-based compound. There is no limitation as to the order or method of addition of the monomers in the present disclosure. For example, first and second dianhydride-based compounds and first and second diamine-based compounds may be sequentially added to a solution in which the first and second diamine-based compounds are dissolved, and the resulting mixture may be subjected to polymerization. Alternatively, in order to avoid randomness, the first diamine-based compound, the first and second dianhydride-based compounds, the second diamine-based compound, and the first and second dicarbonyl-based compounds may be added in that order, or the second diamine-based compound, the first and second dianhydride-based compounds, the first diamine-based compound, and the first and second dicarbonyl-based compounds may be added in that order, followed by polymerization.
More specifically, the polymer resin may be prepared through polymerization and imidization of monomers including the first diamine-based compound, the second diamine-based compound, the first and second dianhydride-based compounds, and the first and second dicarbonyl-based compounds. The imide repeating unit may be prepared through polymerization and imidization of monomers including the first and second diamine-based compounds and the first and second dianhydride-based compounds. In addition, the amide repeating unit may be prepared through polymerization of monomers including the first and second diamine-based compounds and the first and second dicarbonyl-based compounds.
Accordingly, the polymer resin according to another embodiment of the present disclosure may have the imide repeating unit and the amide repeating unit.
The imide repeating unit and the amide repeating unit may be separately prepared and then copolymerized. Alternatively, an imide repeating unit may be prepared first, and then a dicarbonyl-based compound may be further added to prepare an amide repeating unit, or an amide repeating unit may be prepared first, and then a dianhydride-based compound may be further added to prepare an imide repeating unit. The polymer resin of the present disclosure is not limited as to the formation order of the repeating unit (the order in which the monomers are added).
According to another embodiment of the present disclosure, the first and second dicarbonyl-based compounds may be added in an amount of 80 mol % or more based on the total molar amount of the first and second dianhydride-based compounds and the first and second dicarbonyl-based compounds. Accordingly, the polymer resin of the present disclosure includes the amide repeating unit in an amount of 80% or more. Preferably, the first and second dicarbonyl-based compounds may be added in an amount of 95 mol % or more, more preferably in an amount of 98 mol % or more, based on the total molar amount of the first and second dianhydride-based compounds and the first and second dicarbonyl-based compounds.
According to another embodiment of the present disclosure, the first diamine-based compound is 2,2′-bis(trifluoromethyl) benzidine (TFDB).
According to another embodiment of the present disclosure, the second diamine-based compound includes an aromatic diamine-based compound. Hereinafter, an explanation of the above configuration is omitted in order to avoid duplicate description.
2,2′-bis(trifluoromethyl) benzidine (TFDB) may be used as the first diamine-based compound, aromatic diamine-based compounds of Formula 1 described above may be used as the second diamine-based compound, and the compounds of Formula 2 described above may be used as the first and second dianhydride-based compounds. The compounds of Formula 3 described above may be used as the first and second dicarbonyl-based compounds.
According to another embodiment of the present disclosure, the aromatic diamine-based compound of the second diamine-based compound may include at least one functional selected from the group consisting of sulfonyl, carbonyl, methylene, propylene, and halogens.
According to another embodiment of the present disclosure, the aromatic diamine-based compound of the second diamine-based compound may include at least one selected from the group consisting of bis(3-aminophenyl) sulfone (3DDS), bis(4-aminophenyl) sulfone (4DDS), 2,2-bis(3-aminophenyl) hexafluoropropane (3,3′-6F), 2,2-bis(4-aminophenyl) hexafluoropropane (4,4′-6F), 4,4′-methylenedianiline (MDA), 3,3′-(dimethylamino)benzophenone (3,3′-CO), 4,4′-(dimethylamino)benzophenone (4,4′-CO), and tetrachloride benzidine (CIBZ).
According to another embodiment of the present disclosure, the ratio of the amount of the first diamine-based compound that is added to the amount of the second diamine-based compound that is added may be 95:5 to 50:50.
In another embodiment of the present disclosure, the solvent for preparing the polymer resin solution may be, for example, a polar aprotic organic solvent such as N,N-dimethylacetamide (DMAC), N,N-dimethylformamide (DMF), 1-methyl-2-pyrrolidinone (NMP), m-cresol, tetrahydrofuran (THF), chloroform, methyl ethyl ketone (MEK), or a mixture thereof. However, the solvent according to an embodiment of the present disclosure is not limited thereto, and other solvents may be used.
Hereinafter, the present disclosure will be described in more detail with reference to exemplary examples. However, the following preparation examples and examples should not be construed as limiting the scope of the present disclosure.
313.34 g of N, N-dimethylacetamide (DMAc) was charged in a 500 mL reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller, and a cooler while nitrogen was passed through the reactor. Then, the temperature of the reactor was adjusted to 25° C., 24.02 g (0.075 mol) of TFDB as a first diamine-based compound was dissolved therein, 6.21 g (0.025 mol) of bis(3-aminophenyl) sulfone (3DDS) as a second diamine-based compound was further dissolved therein, and the resulting solution was maintained at 25° C. 0.89 g (0.002 mol) of 6FDA was added to the resulting diamine-based compound solution and thoroughly dissolved therein by stirring for 2 hours. The reactor temperature was lowered to 10° C., 19.90 g (0.098 mol) of terephthaloyl chloride (TPC) was added thereto, completely dissolved, and reacted for 1 hour, and then the temperature was elevated to 25° C. 0.35 g of pyridine and 0.45 g of acetic anhydride were added to the resulting reaction solution and stirred at 80° C. for 30 minutes, and excess methanol was then added dropwise to obtain a polyamide-imide powder. The powder was filtered under reduced pressure, dried, and dissolved again in DMAC to prepare a polymer resin solution having a solid concentration of 14 wt %.
The obtained polymer resin solution was cast. A casting substrate was used for casting. There is no particular limitation as to the type of the casting substrate. As the casting substrate, a glass substrate, a stainless steel (SUS) substrate, a Teflon substrate, or the like may be used. According to an embodiment of the present disclosure, an organic substrate may be used as the casting substrate.
Specifically, the obtained polymer resin solution was applied onto a glass substrate, cast, and dried with hot air at 80° C. for 20 minutes and at 120° C. for 20 minutes to produce a film. Then, the produced film was peeled off of the glass substrate and fixed to a frame with a pin.
The frame to which the film was fixed was placed in an oven, and then was dried with hot air at a constant temperature of 270° C. for 10 minutes. As a result, an optical film having a thickness of 50 μm was completed.
Optical films of Examples 2 to 14 were manufactured in the same manner as in Example 1, except that the addition amount of the first diamine-based compound, the type and addition amount of the second diamine-based compound, the addition amount of the dianhydride-based compound, and the type and addition amount of the dicarbonyl-based compound were changed.
Details of the addition amount of the first diamine-based compound, the type and addition amount of the second diamine-based compound, the addition amount of the dianhydride-based compound, and the type and addition amount of the dicarbonyl-based compound of Examples 1 to 14 are shown in Table 1 below.
The optical films of Comparative Examples 1 to 3 were manufactured in the same manner as in Example 1, except that the addition amount of the first diamine-based compound, whether the second diamine-based compound was added and the type and addition amount thereof, the addition amount of the dianhydride-based compound, and the type and addition amount of the dicarbonyl-based compound were changed.
Details of the addition amount of the first diamine-based compound, whether the second diamine-based compound was added and the type and addition amount thereof, the addition amount of the dianhydride-based compound, and the type and addition amount of the dicarbonyl-based compound of Comparative Examples 1 to 3 are shown in Table 1 below.
313.34 g of N, N-dimethylacetamide (DMAc) was charged in a 500 mL reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller, and a cooler while nitrogen was passed through the reactor. Then, the temperature of the reactor was adjusted to 25° C., 28.8207 g (0.090 mol) of TFDB as a first diamine-based compound was dissolved therein, 2.483 g (0.010 mol) of bis(4-aminophenyl) sulfone (4DDS) as a second diamine-based compound was further dissolved therein, and the resulting solution was maintained at 25° C. 5.8833 g (0.030 mol) of cyclobutane-1, 2, 3, 4-tetracarboxylic dianhydride (CBDA) and 2.2212 g (0.005 mol) of 6FDA was added to the resulting diamine-based compound solution and thoroughly dissolved therein by stirring for 2 hours. The reactor temperature was lowered to 10° C., 13.1989 g (0.065 mol) of terephthaloyl chloride (TPC) was added thereto, completely dissolved, and reacted for 1 hour, and then the temperature was elevated to 25° C. 0.35 g of pyridine and 0.45 g of acetic anhydride were added to the resulting reaction solution and stirred at 80° C. for 30 minutes, and excess methanol was added dropwise to obtain a polyamide-imide powder. The powder was filtered under reduced pressure, dried, and dissolved again in DMAc to prepare a polymer resin solution having a solid concentration of 14 wt %.
The obtained polymer resin solution was cast. A casting substrate was used for casting. There is no particular limitation as to the type of the casting substrate. As the casting substrate, a glass substrate, a stainless steel (SUS) substrate, a Teflon substrate, or the like may be used. According to an embodiment of the present disclosure, an organic substrate may be used as the casting substrate.
Specifically, the obtained polymer resin solution was applied onto a glass substrate, cast, and dried with hot air at 80° C. for 20 minutes and at 120° C. for 20 minutes to produce a film. Then, the produced film was peeled off of the glass substrate and fixed to a frame with a pin.
The frame to which the film was fixed was placed in an oven, and then was dried with hot air at a constant temperature of 270° C. for 10 minutes. As a result, an optical film having a thickness of 50 μm was completed.
Optical films of Comparative Examples 5 and 6 were manufactured in the same manner as in Example 1, except that the addition amount of the first diamine-based compound, the addition amount of the second diamine-based compound, the addition amount of the dianhydride-based compound, and the addition amount of the dicarbonyl-based compound were changed.
Details of the addition amount of the first diamine-based compound, the addition amount of the second diamine-based compound, the addition amount of the dianhydride-based compound, and the addition amount of the dicarbonyl-based compound of Comparative Examples 5 and 6 are shown in Table 1 below.
The following measurements were performed on the polymer resins and films produced in Examples 1 to 14 and Comparative Examples 1 to 6.
1) Weight average molecular weight of polymer resin: the weight average molecular weight of the polymer resin was measured under the following conditions using a GPC
(Alliance e2695/2414 RID, Waters).
2) Modulus: the modulus was measured under the following conditions using a universal testing machine (e.g., from Instron Corp.) in accordance with the ASTM D882 standard.
3) Poisson's ratio: the Poisson's ratio of the optical film was measured g a non-contact (video extensometer) method in accordance with the ASTM E-132 standard. Specifically, the Poisson's ratio was measured under the following conditions using a universal testing machine (e.g., Instron 3367 from Instron Corp.).
4) Elastic strain index (E′): the elastic strain index (E′) of the optical film was calculated using a non-contact (video extensometer) method in accordance with the following Equation 2:
5) Yellowness index (Y.I.): The yellowness index was measured using a spectrophotometer (CM-3700D, KONICA MINOLTA) in accordance with the ASTM E313 standard.
6) Parameter of restoring force after folding: the parameter of restoring force after folding of the optical film was calculated using the following Equation 1:
7) Light transmittance (%): an average optical transmittance at a wavelength of 360 to 740 nm was measured using a spectrophotometer (CM-3700D, KONICA MINOLTA).
8) Haze: haze was determined by cutting the produced optical film to a sample having a size of 50 mm×50 mm, performing measurement five times using a haze meter (model name: HM-150, produced by Murakami Color Research Laboratory) in accordance with the ASTM D1003 standard, and taking the average of the five values as the haze of the optical film.
9) Folding traces: a sample having a size of 100 mm×50 mm randomly obtained from the optical film was subjected to a bending test along a single bending axis. The bending test was performed by repeatedly bending a 100 mm×50 mm sample 200,000 times at a speed of 60 rpm at 25° C./50 RH % to a radius of curvature of 2.0 mm (diameter of 4.0 mm) using a bending test machine (YUASA, DLDM111LHA). Then, the occurrence of folding traces along the bending axis was analyzed.
At this time, an analysis method for sharpening the contrast (shading) of the folding traces may be required. For example, imaging may be performed by inspecting foreign material on the film. If possible, various inspection methods such as reflection, scattering, and transmission methods are used to detect defects or dents that are difficult to perceive using a CCD camera or the naked eye, in order to detect foreign matter having the same color as the material for the film. Preferred is the use of an inspection (i.e., determination) device rather than a measurement device.
Specifically, the inspection device includes three components, namely, an inspection device, a control unit (controller box: converts laser data received through the inspection device into image data) and a dedicated PC (imaging PC: a PC having installed thereon a dedicated application, which is connected to the control unit (controller box) and is capable of performing image processing). That is, the analysis/evaluation may be performed by setting measurement/evaluation conditions, converting laser data to image data, and conducting analysis using known software for analyzing the brightness, saturation, reflectivity, etc. of the image/photo, but is not limited thereto.
The measurement results are shown in Tables 2 and 3 below.
As can be seen from the results of measurement of Tables 2 and 3, Examples 1 to 14 of the present disclosure had a high weight average molecular weight and exhibited excellent yellowness index, light transmittance, and haze. In addition, all of Examples 1 to 14 of the present disclosure had a parameter of restoring force after folding of 1.5 GPa or less and an elastic strain index (E′) of 5.5 GPa or more, and left no folding traces (X) even after the bending test.
However, in Comparative Example 1, it was impossible to produce a film due to gelation of the dicarbonyl-based compound. In Comparative Example 2, the resin had a low weight average molecular weight, and visibility was poor due to the high yellowness index and haze. In Comparative Example 2, the parameter of restoring force after folding was 1.5 GPa or less, but the elastic strain index (E′) was less than 5.5 GPa, and thus slight folding traces (A) were left after the bending test. In Comparative Example 3, the parameter of restoring force after folding was 1.5 GPa or less, but the elastic strain index (E′) was less than 5.5 GPa, and slight folding traces were left after the bending test. In Comparative Example 4, yellowness index and haze were high, light transmittance was low, a parameter of restoring force after folding was higher than 1.5 GPa, and severe folding traces (O) were left after the bending test. In Comparative Example 5, yellowness index and haze were high and light transmittance was low, and thus visibility was low. In Comparative Example 5, the parameter of restoring force after folding was 1.5 GPa or less, but the elastic strain index (E′) was less than 5.5 GPa, and slight folding traces (Δ) were left after the bending test. In Comparative Example 6, the resin had a low weight average molecular weight, yellowness index and haze were high, and light transmittance was low, and thus visibility was poor. In Comparative Example 6, the parameter of restoring force after folding was 1.5 GPa or less, but the elastic strain index (E′) was less than 5.5 GPa, and slight folding traces (Δ) were left after the bending test.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2021-0092397 | Jul 2021 | KR | national |
| 10-2021-0186219 | Dec 2021 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2021/019823 | 12/24/2021 | WO |
