WO2020105810A1 - Film à différence de phase d'ester de cellulose - Google Patents

Film à différence de phase d'ester de cellulose

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Publication number
WO2020105810A1
WO2020105810A1 PCT/KR2019/003128 KR2019003128W WO2020105810A1 WO 2020105810 A1 WO2020105810 A1 WO 2020105810A1 KR 2019003128 W KR2019003128 W KR 2019003128W WO 2020105810 A1 WO2020105810 A1 WO 2020105810A1
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WO
WIPO (PCT)
Prior art keywords
cellulose ester
dope
film
norbornene
retardation film
Prior art date
Application number
PCT/KR2019/003128
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English (en)
Korean (ko)
Inventor
서창원
Original Assignee
효성화학 주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020180142553A external-priority patent/KR102134148B1/ko
Priority claimed from KR1020180142554A external-priority patent/KR102156198B1/ko
Application filed by 효성화학 주식회사 filed Critical 효성화학 주식회사
Priority to CN201980075751.0A priority Critical patent/CN113056370B/zh
Priority to JP2021527092A priority patent/JP7157248B2/ja
Publication of WO2020105810A1 publication Critical patent/WO2020105810A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/14—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose characterised by containing special compounding ingredients
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/20—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

Definitions

  • the present invention relates to a cellulose ester phase difference film having + C plate optical properties, and more specifically, a phase difference film and phase difference uniformity produced by solvent casting a dope containing a cellulose ester and a specific additive are improved, and triacetyl cellulose It relates to a retardation film capable of producing an excellent quality polarizing plate with high compatibility with (TAC).
  • the display has been developed with a liquid crystal display device and an OLED center. Accordingly, the protective film of the polarizing plate has been increasingly in demand for thinner and higher performance furnaces. Since a liquid crystal display device displays a display by polarization control by liquid crystal, a polarizing plate is necessary, and a stretched PVA film containing iodine is usually used as the polarizing plate. Since this polarizing plate is vulnerable, a polarizing plate protective film is used as a thing to protect it. In general, a triacetyl cellulose film is widely used for the polarizing plate protective film. Apart from these polarizing plate protective films, a retardation film is also used to control the retardation of polarization. The retardation film used in such a liquid crystal display device is used in combination with a polarizing plate to solve problems such as color compensation and wide viewing angle, and the retardation film used in OLED devices has an anti-reflection function.
  • the polarizing plate protective film is most preferably in the case of considering the manufacturing process of the polarizing plate using a film made of cellulose acetate in order to protect the polarizing plate made of PVA containing moisture and to protect the polarizing plate.
  • a retardation film materials other than cellulose acetate have been used to express optical performance. That is, conventionally, as a material for the retardation film, there are, for example, polycarbonate, polysulfone, polyethersulfone, amorphous polyolefin, and the like. These polymer films have a characteristic that the longer the wavelength, the smaller the retardation, and it is difficult to impart ideal retardation characteristics to all wavelengths in the visible region.
  • the retardation in the wavelength ( ⁇ ) incident on the retardation film is ⁇ It is desirable to be.
  • a retardation film for example, using a retardation film having a phase difference of ⁇ and only one polarizing plate, can implement an anti-reflection function in an OLED image display device.
  • it must have a specific birefringence (or phase difference) depending on the type of liquid crystal used.
  • a retardation film showing + C behavior is applied.
  • the compensation and optical films are typically quantified in terms of the birefringence relative to the refractive index (n).
  • nx, ny and nz refractive indices of interest
  • MD machine direction
  • TD transverse direction
  • thickness direction thickness direction
  • birefringence the difference between any two refractive indices will increase. This difference is referred to as "birefringence.” Since there are many combinations of material directions to choose from, there are different values of the corresponding birefringence. The most common are two birefringences, namely the plane birefringence ( ⁇ e) defined by Equation 1a below and the thickness birefringence ( ⁇ th) defined by Equation 1b below.
  • the plane birefringence ( ⁇ e) is a measure of the relative orientation in the plane between MD and TD, and is unitless. Conversely, ⁇ th provides a measure of thickness direction orientation relative to the average planar orientation.
  • optical retardation (R) is simply multiplied by the birefringence and thickness (d) of the target film, as in the following equations 2a and 2b.
  • phase difference is a direct measure of the relative phase shift between two orthogonal light waves and is typically reported in nanometers (nm). Note that the definition of Rth is defined differently according to some descriptors, especially for ⁇ signs.
  • birefringence / phase difference behavior of a material varies. For example, most materials, when stretched, will exhibit a higher refractive index along the stretching direction and a lower refractive index perpendicular to the stretching direction. This is because the refractive index at the molecular level is typically higher along the axis of the polymer chain and lower perpendicular to the chain. Such materials are commonly referred to as "positive birefringence" and represent most standard polymers, including all commercial cellulose esters.
  • the negative birefringent polymer exhibits a higher refractive index perpendicular to the stretching direction (with respect to the parallel direction) and consequently has a negative intrinsic birefringence.
  • Certain styrenes and acrylics are known to have negative birefringent behavior due to their relatively bulky side groups.
  • the zero birefringence is a special case, and does not exhibit a birefringence during stretching, so it represents a material having a zero intrinsic birefringence.
  • These materials are ideal for optical applications because they can be molded, stretched or otherwise stressed without exhibiting any optical retardation or distortion during processing. Such materials are also extremely rare.
  • the type of compensation film that can be produced is limited by the birefringence properties (ie, positive or negative) of the polymer.
  • a film having a refractive index having a relational expression of Equation 3a below is referred to as a “+ A” plate.
  • the x direction of the film has a high refractive index, and the y and thickness directions have approximately the same (and lower than nx) size.
  • Films of this type are also referred to as positive uniaxial crystal structures with optical axes along the x-direction. Such films are easily produced by, for example, uniaxially stretching a positive birefringent material using a film drafter.
  • the refractive index of the x-axis is lower than those of the other directions (they are approximately the same).
  • the most common method of making the -A plate is to stretch the negative birefringent polymer, or alternatively coat the surface with a negative birefringent liquid crystal polymer so that the molecules are aligned in the desired direction.
  • C plates which can also be "+ C” or "-C".
  • the difference between the C plate and the A plate is that, as in the following equations 4a and 4b, in the case of the C plate, a unique refractive index (or optical axis) exists in the thickness direction, not in the plane of the film.
  • nz> ny nx ("+ C" plate)
  • the C plate can be produced by biaxial stretching when the relative stretching in the x and y directions remains constant.
  • the C plate can be made by compression molding. Compression or equibiaxial stretching of an initially isotropic positive intrinsic birefringent material will provide a -C plate because an effective orientation direction is present in the plane of the film.
  • the + C plate can be made by compressing or isoaxially stretching an initial isotropic film made of a negative intrinsic birefringent material. In the case of biaxial stretching, if the orientation level in the MD and TD directions remains the same, then the material is no longer a true C plate, only a biaxial film with only two optical axes.
  • a third, more common option for making C plates is to use the stress that is formed during solution casting of the film. Tensile stress is created in the plane of the film due to the strain imposed by the casting belt (which is also equiaxed in nature). This tends to orient the chains in the plane of the film, providing -C and + C films respectively for positive and negative intrinsic birefringent materials. It is clear that solvent cast cellulose esters generally only produce -C plates, since most of the cellulose ester films used in displays are solvent cast and all of them are essentially birefringent. These films can also be uniaxially stretched to produce + A plates (assuming the phase difference is very low during initial casting), but the ability to make + C or -A plates using cellulose esters is extremely limited.
  • films based on retardation caused by negative birefringence such as + C film
  • the uniformity was lowered.
  • Commercial films that also exhibit + C plate behavior are made using a nematic liquid crystal coating and subsequently using a polymerization process.
  • these coating processes and liquid crystal materials are very expensive and require additional processing steps to coat the film to achieve the desired properties.
  • the present invention has been devised to solve the problems of the prior art as described above, and is produced by solvent casting a dope containing one or more acetyls and a cellulose ester resin having an acetyl substitution degree of 0.5 to 2.9, and a specific additive.
  • a cellulose ester phase difference film is prepared.
  • a first dope layer solvent-cast a first dope comprising a cellulose ester resin substituted with acetic acid and propionic acid or butyl acid and a phase difference controlling agent having a specific structure;
  • a second dope layer solvent-cast a second dope containing a cellulose ester resin is a first dope layer solvent-cast a first dope comprising a cellulose ester resin substituted with acetic acid and propionic acid or butyl acid and a phase difference controlling agent having a specific structure.
  • R1, R2 are each independently hydrogen, one or more of C1 ⁇ C20 alkyl, alcohol, acid, ester, aromatic hydrocarbons
  • the content of the phase difference control agent is 0.1 to 35% by weight of 100% by weight of the retardation film, the structure is characterized in that one selected from the following formulas 2 to 5.
  • the thickness of the retardation film according to the present invention is 25 to 80 ⁇ m
  • the plane direction retardation value (Ro) is 0 to 30 nm
  • the thickness retardation value (Rth) is ⁇ 10 to ⁇ 105 nm.
  • the retardation film is characterized in that more than one layer or two layers.
  • 1 or 2 or more selected from R1 to R3 in Formula 6 is selected from the group consisting of acetic acid, propionic acid and butyric acid.
  • the thickness of the first dope layer provides a cellulose ester multilayer retardation film, characterized in that 10 to 90% of the total thickness of the entire film.
  • R1 to R3 are each independently a hydrogen atom or a hydrocarbon having 1 to 15 carbon atoms, and n is 1 or more
  • the content of the phase difference controlling agent is 0.01 to 10% by weight, preferably 0.03 to 9.94% by weight, based on the total weight of the first dope, 0.1% to 35% based on 100% by weight of the multi-layer retardation film, and the following Chemical Formula 1 It is characterized by the same structure.
  • R1, R2 are each independently hydrogen, C1 ⁇ C20 alkyl, alcohol, acid, ester, aromatic hydrocarbons, one or more
  • phase difference control agent is characterized in that it is one selected from the following formulas 2 to 5.
  • the total thickness of the cellulose ester multilayer retardation film according to the present invention is 20 to 80 ⁇ m, the plane direction retardation value (Ro) is 0 to 30 nm, and the thickness retardation value (Rth) is ⁇ 5 to ⁇ 105 nm. .
  • the cellulose ester multilayer retardation film is characterized by having a structure of three or more layers, and specifically, a second dope layer is provided on both sides of the first dope layer to provide a second dope layer, a first dope layer, and It is an object to provide a cellulose ester multilayer retardation film characterized in that the second dope layer has a three-layer structure sequentially stacked.
  • the present invention having the above configuration, it is possible to manufacture a single-layer or multi-layer retardation film that is economical because it does not use a liquid crystal material that is an expensive material that has been conventionally used in commercial films showing + C plate behavior.
  • the present invention is a single-layer or multi-layer retardation film production
  • the dope of the present invention is superior in compatibility when mixed with Tri Acetate Cellulose (TAC) (no rise in haze), when applying the dope of the present invention, solvent
  • TAC Tri Acetate Cellulose
  • FIG. 1 is a view showing the structure of a cellulose ester multilayer retardation film according to an embodiment of the present invention.
  • the retardation film according to an embodiment of the present invention includes at least one acetyl and a cellulose ester resin having an acetyl substitution degree of 0.5 to 2.9; And it provides a cellulose ester phase difference film having a + C plate optical properties, characterized in that produced by solvent casting a dope containing ;;
  • R1, R2 are each independently hydrogen, one or more of C1 ⁇ C20 alkyl, alcohol, acid, ester, aromatic hydrocarbons
  • the thickness of the retardation film of the cellulose ester retardation film is 25 to 80 ⁇ m
  • the plane direction retardation value (Ro) is 0 to 30 nm, preferably 2.7 to 8.6 nm
  • the thickness direction retardation value (Rth) is ⁇ 10.
  • the retardation film according to the embodiment may have a multi-layer structure in which one or two or more layers are stacked.
  • one or two or more selected from R1 to R3 in the following Chemical Formula 6 is acetic acid, propionic acid, and butyric acid.
  • the thickness of the first dope layer provides a cellulose ester multilayer retardation film, characterized in that 10 to 90% of the total thickness of the entire film.
  • R1 to R3 are each independently a hydrogen atom or a hydrocarbon having 1 to 15 carbon atoms, and n is 1 or more.
  • the total thickness of the cellulose ester multilayer retardation film is 20 to 80 ⁇ m, preferably 40 to 80 ⁇ m, and the surface direction retardation value (Ro) is 0 to 30 nm, preferably 1.4 to 7.5 nm, and the thickness direction retardation
  • the value Rth is -5 to -105 nm, preferably -7 to -102 nm.
  • the first dope layer is made of a first dope in which 18 to 28 wt% of the first cellulose ester resin is dissolved in a solvent
  • the second dope layer is 10 to 20 wt% of the second cellulose ester resin in a solvent. It is preferably prepared as a dissolved second dope.
  • a monolayer cellulose ester phase difference film prepared by solvent casting a dope containing a cellulose ester resin and a phase difference control agent
  • a first dope containing a first cellulose ester resin and a phase difference control agent and a second dope containing a second cellulose ester resin are prepared by solvent casting and laminating, respectively, to produce a multilayer cellulose ester phase difference film. It is characterized by providing.
  • the commonly used cellulose ester is preferably a lower fatty acid ester of cellulose.
  • Lower fatty acids used in the production of lower fatty acid esters of cellulose refer to fatty acids having 6 or fewer carbon atoms.
  • Examples of lower fatty acid esters are fatty acid esters of mixed cellulose such as cellulose acetate, cellulose propionate, cellulose butyrate and cellulose acetate propionate or cellulose acetate butyrate.
  • cellulose triacetate (TAC) or cellulose acetate propionate (CAP) is particularly preferred.
  • the structure of the cellulose ester is generally represented by the following formula (6).
  • R1 to R3 are each independently a hydrogen atom or a hydrocarbon having 1 to 15 carbon atoms, and n is 1 or more
  • the cellulose ester resin used in the retardation film of the present invention contains at least one acetyl group, and it is preferable to use a cellulose ester having an acetyl substitution degree of 0.5 to 2.9.
  • the acetyl substitution degree is less than 0.5, a problem may occur in which the film is hazeed by an unsubstituted OH group, and when it exceeds 2.9, there is a problem in that solubility in a solvent is lowered and unsolvent is generated.
  • a resin in which cellulose acetate is substituted for at least one of the three substituents (R1, R2 and R3) as the cellulose ester it is preferable to use a resin in which cellulose acetate is substituted for at least one of the three substituents (R1, R2 and R3) as the cellulose ester.
  • the present invention is characterized in that three substituents of the cellulose ester use cellulose acetate propionate (CAP) having at least one acetyl group and at least one propionyl group.
  • CAP cellulose acetate propionate
  • the first cellulose ester resin used in the cellulose ester multilayer retardation film according to another embodiment of the present invention is one or two or more of the three substituents of the cellulose ester is acetic acid (Acetic acid), propionic acid (Propionic acid) And it is preferable to use a resin substituted with one selected from the group consisting of butyric acid (butyric acid).
  • the second cellulose ester resin it is preferable to use a resin in which one or two or more selected from R1 to R3 of Formula 6 is substituted with a hydrocarbon having 5 to 15 carbon atoms.
  • acetic acid propionic acid
  • butyric acid that can be substituted for the cellulose ester resin
  • the molecular weight range of the cellulose ester resin is not limited, but the weight average molecular weight is preferably in the range of 150,000 to 220,000. By setting the molecular weight to a certain level or more, it is possible to effectively prevent the strength of the film from being lowered. In addition, by making the molecular weight below a certain level, the viscosity of the cellulose ester solution (dope) is maintained below a certain level, making it easy to produce a retardation film by a solvent casting method.
  • the degree of molecular weight distribution of the cellulose ester resin is in the range of 2.0 to 4.5, preferably 2.0 to 3.0.
  • Molecular weight distribution affects the viscosity of the dope and the mechanical properties of the film to be produced. If the molecular weight distribution value is less than 2.0, the mechanical properties (especially modulus) are lowered. In the case of discharging to the die, a processability problem arises as the pressure increases.
  • a phase difference film is produced by performing solvent casting of a dope containing a cellulose ester resin and a phase difference control agent having a specific structure.
  • phase difference control agent used in the present invention is characterized by having the structure of Formula 1 below.
  • R1, R2 are each independently hydrogen, one or more of C1 ⁇ C20 alkyl, alcohol, acid, ester, aromatic hydrocarbons
  • the 5-Norbonene-2,3-dicarboxylate is preferably a structure of the formula 2 to 5 as follows.
  • the content of the retardation control agent is 0.1 to 35% by weight, preferably 0.1 to 20% by weight, more preferably 0.1 to 10% in 100% by weight of the retardation film.
  • Weight percent is 0.1 to 35% by weight, preferably 0.1 to 20% by weight, more preferably 0.1 to 10% in 100% by weight of the retardation film.
  • the dope 0.01 to 10% by weight of 100% by weight of the dope, preferably 0.03 to 9.94% by weight, more preferably 0.03 to 5.7% by weight.
  • the content of the retardation control agent is less than 0.1% by weight of 100% by weight of the retardation film or less than 0.01% by weight of 100% by weight of dope, a high negative Rth value cannot be obtained, and thus there is a problem in improving the viewing angle, and the content in the film
  • the content exceeds 35% by weight, or the content in the dope exceeds 10% by weight evaporation of the phase difference controlling agent in the production of the film deepens, causing serious problems in process contamination.
  • the content of the retardation control agent is 0.1 to 35% by weight, preferably 0.1 to 20% by weight, more preferably 100% by weight of the multilayer retardation film. 0.1 to 10% by weight,
  • 0.01 to 10% by weight of 100% by weight of the first dope preferably 0.03 to 9.94% by weight, more preferably 0.03 to 5.7% by weight.
  • the content of the retardation control agent is less than 0.1% by weight in 100% by weight of the multilayer retardation film or less than 0.01% by weight in 100% by weight of the first dope, a high negative Rth value cannot be obtained, and thus there is a problem in improving the viewing angle.
  • the content in the multi-layer retardation film exceeds 35% by weight or the content in the first dope exceeds 10% by weight, evaporation of the retardation control agent during film production increases, resulting in serious problems in process contamination.
  • the cellulose ester retardation film or the cellulose ester multilayer retardation film according to the present invention may be prepared by solvent casting a dope (including first and second dope) containing the cellulose ester and a retardation control agent.
  • Solvent casting method is prepared by dissolving in a stirrer dope (first and second dope) using additives such as cellulose ester, phase difference control agent and plasticizer, UV absorber, mat agent and mixed solvents such as methylene chloride and methanol, It can be used by filtration using a filtration device.
  • an organic solvent is preferably used as a solvent for preparing the dope.
  • halogenated hydrocarbons include chlorinated hydrocarbons, methylene chloride, and chloroform, and methylene chloride is most preferred.
  • organic solvent other than halogenated hydrocarbons may be mixed and used.
  • Organic solvents other than halogenated hydrocarbons include esters, ketones, ethers, alcohols and hydrocarbons.
  • ester methyl formate, ethyl formate, propyl formate, pentyl formate, methyl acylate, ethyl acylate, pentyl acetate, etc.
  • ketone acetone, methyl ethyl ketone, diethyl ketone, di Isobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, etc.
  • diisopropyl ether dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxane
  • ether Solan, tetrahydrofuran, anisole, phenitol, etc.
  • alcohol methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol , 2-methyl-2-butanol, cyclohexanol, 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol, and the like.
  • methylene chloride may be used as a main solvent
  • alcohol may be used as a solvent.
  • methylene chloride and alcohol may be used by mixing in a weight ratio of 80:20 to 95: 5.
  • the cellulose ester multilayer retardation film one or two or more of the three substituents of the cellulose ester resin is composed of acetic acid, propionic acid or butyric acid It characterized in that a first dope in which 18 to 28% by weight of the first cellulose ester resin substituted with one selected from the group is dissolved in a solvent is used, preferably 25% by weight is dissolved.
  • a second dope is used by dissolving 10 to 20% by weight of a second cellulose ester resin in which 5 to 15 carbon atoms of hydrocarbons are substituted in one or more of the three substituents of the cellulose ester, with respect to the solvent. Is preferably 15 to 18% by weight, more preferably 17% by weight.
  • the viscosity of each dope is low. It is difficult, and when the first cellulose ester resin is dissolved in a solvent in excess of 28% by weight, or when the second cellulose ester resin is dissolved in a solvent in excess of 20% by weight, solubility is lowered, thereby increasing the amount of undissolved products.
  • additives may be added to the production of the cellulose ester phase difference film and the cellulose ester multilayer phase difference film of the present invention, for example, UV blocking agents, plasticizers, deterioration inhibitors, fine particles, and optical property control agents.
  • additives according to the use in each preparation step in the dope containing cellulose ester used in the solvent casting method (including the first and second dope), for example, plasticizer, deterioration inhibitor, microparticles, release agent, ultraviolet light Additives such as stabilizers, UV blocking agents, UV absorbers, infrared absorbers, wavelength dispersion modifiers, and optical anisotropy modifiers can be added. Specific types of these additives can be used without limitation as long as they are commonly used in the field, and the content is preferably used in a range that does not degrade the physical properties of the film.
  • the timing of adding the additive may be determined according to the type of additive.
  • a process of adding an additive to the end of the dope (including the first and second dope) preparations may be performed.
  • the cellulose ester retardation film and the cellulose ester multilayer retardation film contain a plasticizer for improving mechanical strength, imparting good castability and water absorption, and reducing water permeability.
  • the plasticizer may be used without limitation as long as it is commonly used, and examples thereof include carboxylic acid esters selected from phosphate esters and phthalic acid esters or citric acid esters, and terminal asymmetric aromatic compounds and terminal symmetric aliphatic compounds may also be used. Do. It is also preferable to use a polyhydric alcohol ester plasticizer, a polyester plasticizer, and a polyhydric carboxylic acid plasticizer.
  • the polyester plasticizer is preferably an aliphatic polyester plasticizer and an aromatic polyester plasticizer, and preferably has a weight average molecular weight of 500 to 1500. More preferably, the weight average molecular weight is 550 to 650.
  • the plasticizer When the plasticizer is contained, its content is preferably 2% to 15% by weight compared to the dope in consideration of dimensional stability and processability. If the content of the plasticizer is too small, the effect of reducing the moisture permeability of the film is small, and a smooth cut surface cannot be obtained when slit processing or punching processing is performed, and there is a tendency that the generation of cutting debris increases. That is, the effect of containing a plasticizer cannot be sufficiently exhibited. Moreover, when there are too many, the plasticizer tends to bleed out from a resin film, and the physical properties of the film tend to deteriorate.
  • a benzotriazole-based UV blocking agent or a triazine-based UV blocking agent having high transparency and having an excellent effect of preventing deterioration of a polarizing plate or a liquid crystal element is preferable, and a benzotriazole-based UV blocking agent having a more suitable spectral absorption spectrum is particularly preferable.
  • the conventionally known benzotriazole-based UV blocking agent used particularly preferably in combination with the UV blocking agent according to the present invention may be bisized, for example, 6,6'-methylene bis (2- (2H-benzo [d ] [1,2,3] triazol-2-yl))-4- (2,4,4-trimethylpentan-2-yl) phenol, 6,6'- methylenebis (2- (2H-benzo [ d] [1,2,3] triazol-2-yl))-4- (2-hydroxyethyl) phenol and the like.
  • the UV blocking agent is preferably added in an amount of 0.1% to 20% by mass compared to the dope, and preferably 0.5% to 10% by mass, and also preferably 1% to 5% by mass. . These may use 2 or more types together.
  • the solvent casting method used for manufacturing the cellulose ester retardation film and the cellulose ester multilayer retardation film of the present invention has an advantage of producing a film having excellent physical properties such as optical properties, compared to other manufacturing methods.
  • dope (including the first and second dope) is first prepared by mixing various additives such as cellulose ester resin, UV absorber, mat agent, retardation control agent, and plasticizer in a mixed solvent containing methyl chloride as a main solvent. .
  • a cellulose ester phase difference film is prepared by solvent casting a dope comprising a cellulose ester resin having an acetyl substitution degree of 0.5 to 2.9 and a phase difference control agent having the structure of Formula 1 as described above. can do.
  • the dope dissolves 18 to 28% by weight of the cellulose ester resin in which acetic acid and propionic acid are substituted in one or more of the three substituents of the cellulose ester in a solvent, and preferably 25% by weight.
  • the retardation control agent preferably contains 0.01 to 10% by weight in the dope, preferably 0.03 to 9.94% by weight.
  • the viscosity is low, so it is difficult to properly form a film when discharging the dope from the T-Die.
  • the first dope containing the first cellulose ester resin is solvent cast to prepare a first dope layer
  • the second dope containing the second cellulose ester resin is solvent. Cast to produce a two-layer cellulose ester multilayer retardation film.
  • the first dope is 18 to 28% by weight of the first cellulose ester resin in which acetic acid, propionic acid or butyric acid is substituted in at least one of the three substituents of the cellulose ester in a solvent, preferably 25% by weight It is good to dissolve.
  • the second cellulose ester resin having 5 to 15 carbon atoms in one or more of the three substituents of the cellulose ester is dissolved in a solvent by 10 to 20% by weight, preferably 15 to 18% by weight , More preferably 17% by weight.
  • the cellulose ester sheet in which the dope (including the first and second dope) is flexibly formed on a support from a flexible die or a T-die is peeled off from the support when the solvent volatilizes to obtain self-support, and is conveyed in a stretching process.
  • the stretching process is generally performed in a temperature range of -50 ° C to Tg + 50 ° C, and the elongation is 100 to 150% in the width direction or the length direction.
  • the higher the elongation the more preferable the non-stretching because the retardation value due to the non-uniform stretching of the edges and the center is non-uniform.
  • the cellulose ester retardation film and the cellulose ester multilayer retardation film thus formed are dried inside a dryer of Tg or less, which can simultaneously obtain the heat setting effect of the dryer, thereby controlling the appearance of wrinkles and the like of the film, and dimensioning such as heat shrinkage and moist heat expansion rate. Stability can be increased.
  • the cellulose ester retardation film which is an embodiment of the present invention, may be manufactured in a single-layer structure using dope, and is also preferably manufactured in a structure of two or more layers. It is preferable that at least one layer may be included by solvent casting the dope.
  • the cellulose ester multilayer retardation film which is another embodiment of the present invention, is also preferably composed of three layers, as well as a multi-layer retardation film having a two-layer configuration using a first dope and a second dope. It is preferable if the first cellulose ester resin and the second cellulose ester resin include at least one layer in the multilayer retardation film, and the total film thickness is preferably 20 to 80 ⁇ m.
  • a three-layer cellulose ester multilayer retardation film is disclosed, and a first dope layer prepared by solvent casting a first dope as a core layer is located, Disclosed is a structure in which a second dope layer prepared by solvent casting a second dope as a skin layer on both surfaces of the first dope layer is located.
  • the cellulose ester retardation film according to an embodiment of the present invention preferably has a thickness of 25 ⁇ m to 80 ⁇ m. Particularly, when the thickness is less than 25 ⁇ m, physical properties are deteriorated, and when it is more than 80 ⁇ m, industrial applicability is poor.
  • the cellulose ester multilayer retardation film according to another embodiment of the present invention has a total thickness of 20 ⁇ m to 80 ⁇ m. If the thickness is less than 20 ⁇ m, the physical properties are inferior, and if it is greater than 80 ⁇ m, industrial applicability is poor.
  • the cellulose ester retardation film and the cellulose ester multilayer retardation film have a retardation satisfying + C Plate characteristics, although the optimum retardation value varies depending on the liquid crystal, Ro is 0 to 30 nm, and Rth is -5 to -105 nm, preferably Is preferably in the range of -7 to -102 nm.
  • Rth is -10 to -105 nm
  • Rth is preferably -5 to -105 nm, more preferably -7 to -102 nm.
  • the + C plate characteristic with improved diagonal visibility is exhibited.
  • Ro is 0 to 10 nm
  • Rth is -50 to -80 nm, which is the most diagonal. It is known to have good visibility.
  • the Ro and Rth are represented by the following equations (1) and (2) as the phase direction retardation value and the thickness direction retardation value, respectively.
  • Nx is the maximum refractive index in the plane of the film
  • Ny is the refractive index in the direction perpendicular to Nx in the film plane
  • Nz is the refractive index of the film in the thickness direction
  • the cellulose ester retardation film and the cellulose ester multilayer retardation film produced by the present invention are capable of producing a retardation film having the characteristics of + C plate according to the above formula.
  • the cellulose ester retardation film and the cellulose ester multilayer retardation film of the present invention can be applied to polarizing plates and liquid crystal displays.
  • the polarizing plate and the liquid crystal display device is characterized by comprising a retardation film.
  • the polarizing plate is a protective film is attached to both sides of the polarizer, at least one of the protective film is characterized in that the retardation film of the present invention.
  • the liquid crystal display device has a liquid crystal cell and two polarizing plates disposed on both sides of the liquid crystal cell, and is characterized in that the liquid crystal cell is in a vertical alignment mode.
  • the polarizing plate as described above may be manufactured according to a conventional method.
  • an aqueous solution of polyvinyl alcohol completely saponified on both sides of a polarizing film prepared by alkali saponifying the retardation film of the present invention immersing the resulting film in a polyvinyl alcohol (PVA) film in an iodine solution, and stretching the film.
  • PVA polyvinyl alcohol
  • Alkali saponification refers to a treatment in which a retardation film is immersed in a hot, strong alkaline solution to improve the wettability of the film to an aqueous adhesive and provide good adhesion to the film.
  • CAP Cellulose Acetate Propionate resin in which R1 to R3 are acetic acid and propionic acid in the following Chemical Formula 6 was used.
  • Cellulose Acetate Propionate (CAP) prepared in Step 1, 22.7% by weight, 5.7% by weight of a phase difference controlling agent having the structure of Formula 2 below, and a mixed solvent of methylene chloride and methanol in a ratio of 80:20 (71.6 Dope).
  • the dope prepared in step 2 was uniformly flexible to a stainless band support having a width of 800 mm using a belt casting device.
  • the solvent was evaporated on the stainless band support and peeled from the stainless band support. Subsequently, it was conveyed for 3 minutes in the Tenter section set at 150 ° C, and dried at 100 ° C in the Dryer to prepare a cellulose ester phase difference film having a film thickness of 40 ⁇ m.
  • a cellulose ester phase difference film was prepared by performing the same procedure as in Example 1, except that the film thickness was changed to 25 ⁇ m.
  • a cellulose ester retardation film was prepared by performing the same procedure as in Example 1, except that the film thickness was changed to 60 ⁇ m.
  • a cellulose ester retardation film was prepared by performing the same procedure as in Example 1, except that the film thickness was changed to 80 ⁇ m.
  • a cellulose ester retardation film was prepared by performing the same procedure as in Example 1, except that the content of the dope retardation control agent was changed to 0.03% by weight.
  • a cellulose ester retardation film was prepared by performing the same process as in Example 1, except that the content of the dope retardation control agent was changed to 2.84% by weight.
  • a cellulose ester retardation film was prepared by performing the same procedure as in Example 1, except that the content of the dope retardation control agent was changed to 9.94% by weight.
  • a cellulose ester phase difference film was prepared by performing the same process as in Example 1, except that a material having the structure of Formula 4 below was used as the phase difference control agent.
  • a cellulose ester phase difference film was prepared by performing the same procedure as in Example 1, except that no phase difference control agent was added.
  • Example 2 Example 3
  • Example 4 Example 5
  • Example 6 Example 7
  • Example 8 Comparative Example 1 Thickness ( ⁇ m) 40 25 60
  • Additive content (wt%) Dope Standard 5.7 5.7 5.7 5.7 0.03 2.84 9.94 5.7 0
  • Film standard 20 20 20 20 0.1 10 35 20 0
  • Phase difference (nm) Ro 4.3 2.7 6.5 8.6 2 2.4 4 8 5 Rth -50 -30 -75 -102 -10 -34 -71 -29 -8
  • the first cellulose ester resin and the second cellulose ester resin are prepared.
  • R1 to R3 in the following Chemical Formula 6 are used as a resin substituted with acetic acid and propionic acid
  • Cellulose Triacetate was used as the second cellulose ester resin.
  • R1 to R3 are each independently a hydrogen atom or a hydrocarbon having 1 to 15 carbon atoms, and n is 1 or more
  • the first dope was dissolved by dissolving 22.7% by weight of the first cellulose ester resin prepared in Step 1 and 5.7% by weight of a phase difference controlling agent having the structure of Formula 2 below in a mixed solvent of methylene chloride and methanol in a ratio of 80:20. It was prepared.
  • step 1 17% by weight of the second cellulose ester resin prepared in step 1 was dissolved in a mixed solvent of methylene chloride and methanol mixed at a ratio of 90:10, 8% of a polyester plasticizer having a weight average molecular weight of 550 to 650, and EVONIC A second dope was prepared by dissolving 450 ppm of R972 (made by Mat) of the company.
  • the first dope layer prepared in step 2 is prepared with a thickness of 36 ⁇ m, and a second dope prepared in step 2 is drawn on both sides of the first dope layer to a thickness of 2 ⁇ m, so that it is non-stretched and dried. Films were prepared through the process.
  • the first and second dope were uniformly flexible on a stainless band support having a width of 800 mm using a belt casting device.
  • the solvent was evaporated on the stainless band support and peeled from the stainless band support. Subsequently, it was conveyed for 35 minutes in a drying section set at 110 ° C. and dried to prepare a three-layer retardation film of cellulose ester having a film thickness of 40 ⁇ m. At this time, the ratio of the thickness sum of the first dope layer and the second dope layer was 90:10.
  • a first dope layer is prepared with a thickness of 18 ⁇ m for the first dope, and a second dope is drawn to each 1 ⁇ m thickness on both sides of the first dope layer to obtain a film having a final thickness of 20 ⁇ m through a non-stretching and drying process.
  • a cellulose ester multilayer retardation film was prepared by performing the same procedure as in Example 9, except for preparing.
  • a first dope layer was prepared with a thickness of 72 ⁇ m as a first dope, and a second dope was drawn at a thickness of 4 ⁇ m on both sides of the first dope layer to obtain a film having a final thickness of 80 ⁇ m through a non-stretching and drying process.
  • a cellulose ester multilayer retardation film was prepared by performing the same procedure as in Example 9, except for preparing.
  • a cellulose ester multilayer retardation film was prepared by performing the same process as in Example 9, except that the content of the retardation control agent in the first dope was changed to 0.03% by weight.
  • a first dope layer was prepared with a thickness of 72 ⁇ m as a first dope, and a second dope was drawn at a thickness of 4 ⁇ m on both sides of the first dope layer to obtain a film having a final thickness of 80 ⁇ m through a non-stretching and drying process.
  • a cellulose ester multilayer retardation film was prepared by performing the same procedure as in Example 12, except for preparing.
  • a cellulose ester multilayer retardation film was prepared by performing the same process as in Example 9, except that the content of the retardation control agent in the first dope was changed to 2.84% by weight.
  • a first dope layer was prepared with a thickness of 72 ⁇ m as a first dope, and a second dope was drawn at a thickness of 4 ⁇ m on both sides of the first dope layer to obtain a film having a final thickness of 80 ⁇ m through a non-stretching and drying process.
  • a cellulose ester multilayer retardation film was prepared by performing the same procedure as in Example 14, except for preparing.
  • a cellulose ester multilayer retardation film was prepared by performing the same process as in Example 9, except that the content of the retardation control agent in the first dope was changed to 9.94% by weight.
  • a first dope layer was prepared with a thickness of 72 ⁇ m as a first dope, and a second dope was drawn at a thickness of 4 ⁇ m on both sides of the first dope layer to obtain a film having a final thickness of 80 ⁇ m through a non-stretching and drying process.
  • a cellulose ester multilayer retardation film was prepared by performing the same procedure as in Example 16, except for preparing.
  • the same process as in Example 9 was applied except that the cellulose resin in which R1 to R3 were all substituted with a naphthoyl group, and no phase difference control agent was added. By carrying out, a cellulose ester multilayer retardation film was prepared.
  • the first dope and the second dope of Examples and Comparative Examples were mixed at a ratio of 80:20, mixed for 15 hours, and then cast under a film at 22 ° C., 26% RH, and measured with a Haze meter.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polarising Elements (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Liquid Crystal (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

La présente invention concerne un film d'ester de cellulose ayant des propriétés optiques de plaque +C et, plus spécifiquement, tout d'abord, un film à différence de phase fabriqué par un procédé de coulée avec solvant utilisant un dopant comprenant un ester de cellulose et un additif spécifique. La présente invention concerne également un film à différence de phase d'ester de cellulose multicouche et, plus spécifiquement, un film à différence de phase qui a une uniformité de différence de phase améliorée et a une compatibilité élevée avec la triacétyl-cellulose (TAC), permettant ainsi la fabrication d'une plaque polarisante de haute qualité. Le film à différence de phase selon la présente invention présente les effets d'inhibition de détérioration de qualité, causée lorsqu'il est utilisé conjointement avec la triacétyl-cellulose (TAC), et d'amélioration de visibilité diagonale lorsqu'il est appliqué à des panneaux OLED et LCD.
PCT/KR2019/003128 2018-11-19 2019-03-19 Film à différence de phase d'ester de cellulose WO2020105810A1 (fr)

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JP2021527092A JP7157248B2 (ja) 2018-11-19 2019-03-19 セルロースエステル位相差フィルム

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KR1020180142553A KR102134148B1 (ko) 2018-11-19 2018-11-19 +c 플레이트 광학 특성을 갖는 셀룰로오스 에스테르 필름
KR10-2018-0142554 2018-11-19
KR1020180142554A KR102156198B1 (ko) 2018-11-19 2018-11-19 셀룰로오스 에스테르 다층 위상차 필름
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JP7157248B2 (ja) 2022-10-19
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