WO2016126101A1 - Film d'acétate de cellulose - Google Patents

Film d'acétate de cellulose Download PDF

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Publication number
WO2016126101A1
WO2016126101A1 PCT/KR2016/001184 KR2016001184W WO2016126101A1 WO 2016126101 A1 WO2016126101 A1 WO 2016126101A1 KR 2016001184 W KR2016001184 W KR 2016001184W WO 2016126101 A1 WO2016126101 A1 WO 2016126101A1
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WIPO (PCT)
Prior art keywords
alkyl
cellulose acetate
alkenyl
cycloalkyl
acetate film
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PCT/KR2016/001184
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English (en)
Korean (ko)
Inventor
김명래
곽효신
박민상
임민정
장태석
조용균
Original Assignee
에스케이이노베이션 주식회사
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Publication of WO2016126101A1 publication Critical patent/WO2016126101A1/fr

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    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/12—Cellulose acetate
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers

Definitions

  • the present invention relates to a cellulose acetate film used for optical compensation, and more particularly, to a cellulose acetate film which can significantly reduce durability and change in retardation value due to harsh environment.
  • Cellulose acetate films are used in various photographic or optical materials because of their high strength and flame retardancy. Cellulose acetate films have lower optical anisotropy compared to other polymer films, providing a relatively low retardation. Therefore, it is used in polarizing plates and the like.
  • VA Vertical Alignment
  • transparent electrodes are formed on the upper and lower plates.
  • the polarizing plate is attached to the outer side of the upper and lower plates so that the initial alignment direction is vertical when the electric field is not applied. Therefore, the polarizing plate is completely dark.
  • the liquid crystal directors are rearranged properly to transmit the light. do.
  • the optical compensation film of the liquid crystal display of the VA mode requires high optical anisotropy, that is, high retardation.
  • the cellulose acetate film may be included in a polarizing plate or the like and applied to a display device.
  • the cellulose acetate film may be exposed to various harsh conditions such as high temperature and high humidity in manufacturing, transportation, use, etc., and such harsh conditions may affect the film, resulting in a change in retardation value, resulting in a film having excellent durability. Development is also required.
  • Korean Patent Publication No. 2014-91902 discloses a cellulose ester film for retardation and viewing angle compensation.
  • the present invention aims to provide a cellulose acetate film with markedly improved durability.
  • An object of the present invention is to provide a cellulose acetate film having a high retardation value in the thickness direction.
  • Another object of the present invention is to provide an optical compensation sheet, a polarizing plate, and a liquid crystal display device using the cellulose acetate film.
  • a cellulose acetate film comprising at least one durability improver selected from compounds of formula
  • Z is selected from NAR 2 or CR 11 R 12 , wherein R 11 and Each R 12 is independently hydrogen or (C 1 -C 10) alkyl,
  • A is selected from -CO-, -CS-, -COO-, -COS-, -NHCO-, -NHCS-, -CR 3 R 4- , -POR 5- , -SO-, -SO 2- , R 3 and R 4 are each independently hydrogen, (C 1 -C 10) alkyl, (C 6 -C 20) aryl, (C 3 -C 20) cycloalkyl, (C 2 -C 7) alkenyl and 5- to 7-membered heterocyclo It is selected from the group consisting of alkyl, R 5 is selected from hydrogen, (C1-C10) alkyloxy, (C6-C20) aryloxy, -NH-R 6 , wherein R 6 is hydrogen, (C1-C10) alkyl , (C2-C7) alkenyl and (C2-C4) alkynyl,
  • R 1 is hydrogen, (C1-C10) alkyl, (C6-C20) aryl, (C3-C20) cycloalkyl, (C2-C7) alkenyl, (C1-C10) alkoxy, 5- or 7-membered heterocyclo Alkyl, (C4-C20) heteroaryl, and
  • R 2 is selected from the group consisting of hydrogen, (C 1 -C 10) alkyl, (C 3 -C 20) cycloalkyl, (C 2 -C 7) alkenyl, (C 1 -C 10) alkoxy and 5- to 7-membered heterocycloalkyl; ,
  • the R 1 alkyl, aryl, cycloalkyl, alkenyl, alkoxy, heterocycloalkyl and heteroaryl, the R 2 alkyl, cycloalkyl, alkenyl, alkoxy and heterocycloalkyl are independently of each other (C1-C10) alkoxy, ( C1-C7) alkyl, halogen, nitro, cyano, hydroxy, amino, (C6-C20) aryl, (C2-C7) alkenyl, (C3-C20) cycloalkyl and 5- to 7-membered heterocycloalkyl
  • One or more selected from the group consisting of may be further substituted,
  • R 1 and R 2 may be linked to (C3-C20) alkylene or (C3-C20) alkenylene to form a fused ring).
  • the compound of Formula 1 is a cellulose acetate film selected from the following compounds:
  • the cellulose acetate film is a cellulose acetate film, wherein Re ( ⁇ ) and Rth ( ⁇ ) satisfy the following formula (I), (II) and (III):
  • Re ((lambda)) is in-plane retardation value (nm) in wavelength (lambda) nm
  • Rth ((lambda)) is retardation value (nm) of a film thickness direction in wavelength (lambda) nm.
  • the cellulose acetate film is 60 °C, 90% relative humidity conditions of Re and Rth change rate before and after 500 hours left within 10%, cellulose acetate film.
  • Cellulose acetate composition comprising 1 to 15 parts by weight of at least one durability improving agent selected from compounds represented by the following formula (1) based on 100 parts by weight of cellulose acetate:
  • Z is selected from NAR 2 or CR 11 R 12 , wherein R 11 and Each R 12 is independently hydrogen or (C 1 -C 10) alkyl,
  • A is selected from -CO-, -CS-, -COO-, -COS-, -NHCO-, -NHCS-, -CR 3 R 4- , -POR 5- , -SO-, -SO 2- , R 3 and R 4 are each independently hydrogen, (C 1 -C 10) alkyl, (C 6 -C 20) aryl, (C 3 -C 20) cycloalkyl, (C 2 -C 7) alkenyl and 5- to 7-membered heterocyclo It is selected from the group consisting of alkyl, R 5 is selected from hydrogen, (C1-C10) alkyloxy, (C6-C20) aryloxy, -NH-R 6 , wherein R 6 is hydrogen, (C1-C10) alkyl , (C2-C7) alkenyl and (C2-C4) alkynyl,
  • R 1 is hydrogen, (C1-C10) alkyl, (C6-C20) aryl, (C3-C20) cycloalkyl, (C2-C7) alkenyl, (C1-C10) alkoxy, 5- or 7-membered heterocyclo Alkyl, (C4-C20) heteroaryl, and
  • R 2 is selected from the group consisting of hydrogen, (C 1 -C 10) alkyl, (C 3 -C 20) cycloalkyl, (C 2 -C 7) alkenyl, (C 1 -C 10) alkoxy and 5- to 7-membered heterocycloalkyl; ,
  • the R 1 alkyl, aryl, cycloalkyl, alkenyl, alkoxy, heterocycloalkyl and heteroaryl, the R 2 alkyl, cycloalkyl, alkenyl, alkoxy and heterocycloalkyl are independently of each other (C1-C10) alkoxy, ( C1-C7) alkyl, halogen, nitro, cyano, hydroxy, amino, (C6-C20) aryl, (C2-C7) alkenyl, (C3-C20) cycloalkyl and 5- to 7-membered heterocycloalkyl
  • One or more selected from the group consisting of may be further substituted,
  • R 1 and R 2 may be linked to (C3-C20) alkylene or (C3-C20) alkenylene to form a fused ring).
  • optical compensation sheet comprising the cellulose acetate film of any one of the above 1 to 5.
  • Above polarizing plate comprising the cellulose acetate film of any one of 1 to 5.
  • the image display device comprising the cellulose acetate film of any one of the above 1 to 5.
  • the cellulose acetate film of this invention is excellent in durability. Accordingly, even when exposed to high temperature, high humidity for a long time, the amount of change in the phase difference value is very small.
  • the cellulose acetate film of this invention has a very high retardation value of the thickness direction. Accordingly, the present invention can be particularly preferably applied to a VA mode liquid crystal display device, thereby improving viewing angle and contrast.
  • the present invention includes at least one durability improving agent selected from the compound of Formula 1, so that even when exposed to high temperature and humidity conditions for a long time, the amount of change in the phase difference is small, and the phase difference value is high, so that the viewing angle and
  • the present invention relates to a cellulose acetate film and a method for producing the same that can improve contrast.
  • the cellulose acetate film of the present invention comprises at least one durability improving agent selected from compounds of the formula:
  • Z is selected from NAR 2 or CR 11 R 12 , wherein R 11 and Each R 12 is independently hydrogen or (C 1 -C 10) alkyl,
  • A is selected from -CO-, -CS-, -COO-, -COS-, -NHCO-, -NHCS-, -CR 3 R 4- , -POR 5- , -SO-, -SO 2- , R 3 and R 4 are each independently hydrogen, (C 1 -C 10) alkyl, (C 6 -C 20) aryl, (C 3 -C 20) cycloalkyl, (C 2 -C 7) alkenyl and 5- to 7-membered heterocyclo It is selected from the group consisting of alkyl, R 5 is selected from hydrogen, (C1-C10) alkyloxy, (C6-C20) aryloxy, -NH-R 6 , wherein R 6 is hydrogen, (C1-C10) alkyl , (C2-C7) alkenyl and (C2-C4) alkynyl,
  • R 1 is hydrogen, (C1-C10) alkyl, (C6-C20) aryl, (C3-C20) cycloalkyl, (C2-C7) alkenyl, (C1-C10) alkoxy, 5- or 7-membered heterocyclo Alkyl, (C4-C20) heteroaryl, and
  • R 2 is selected from the group consisting of hydrogen, (C 1 -C 10) alkyl, (C 3 -C 20) cycloalkyl, (C 2 -C 7) alkenyl, (C 1 -C 10) alkoxy and 5- to 7-membered heterocycloalkyl; ,
  • the R 1 alkyl, aryl, cycloalkyl, alkenyl, alkoxy, heterocycloalkyl and heteroaryl, the R 2 alkyl, cycloalkyl, alkenyl, alkoxy and heterocycloalkyl are independently of each other (C1-C10) alkoxy, ( C1-C7) alkyl, halogen, nitro, cyano, hydroxy, amino, (C6-C20) aryl, (C2-C7) alkenyl, (C3-C20) cycloalkyl and 5- to 7-membered heterocycloalkyl
  • One or more selected from the group consisting of may be further substituted,
  • R 1 and R 2 may be linked to (C3-C20) alkylene or (C3-C20) alkenylene to form a fused ring).
  • the cellulose acetate film of the present invention has significantly improved durability by including the compound of formula (1). Thereby, even if it is exposed to high temperature, high humidity conditions for a long time, the amount of change of phase difference value is small. For example, the amount of change in Re and Rth before and after 500 hours at 60 ° C. and 90% relative humidity may be 10% or less.
  • the compound of Formula 1 significantly improves the phase difference.
  • the cellulose acetate film of the present invention includes the compound of Formula 1, whereby Re ( ⁇ ) and Rth ( ⁇ ) after stretching 5 to 100% by length in the width direction are represented by the following formulas (I), (II) and Satisfies (III):
  • Re ((lambda)) is in-plane retardation value (nm) in wavelength (lambda) nm
  • Rth ((lambda)) is retardation value (nm) of a film thickness direction in wavelength (lambda) nm.
  • the cellulose acetate film of the present invention exhibits the above improved retardation range to improve viewing angle and contrast. Accordingly, the cellulose acetate film of the present invention can be particularly preferably used in the liquid crystal display device for VA mode.
  • the cellulose acetate film has a density of about 1.2 to 1.35 (g / cm 3 ), although its density is not limited.
  • Cellulose acetate is an ester of cellulose and acetic acid, in which all or part of the hydrogen atoms of the hydroxyl groups in the second, third and sixth positions of the glucose units constituting cellulose are substituted with acetyl groups.
  • the substitution degree of cellulose acetate is not restrict
  • the molecular weight range of the cellulose acetate is not limited, but the weight average molecular weight is preferably in the range of 200,000 to 350,000. Moreover, it is preferable that the molecular weight distribution degree Mw / Mn (Mw is a weight average molecular weight, Mn is a number average molecular weight) of cellulose acetate is 1.4-1.8, and it is more preferable that it is 1.5-1.7.
  • a cellulose acetate film by the solvent cast method using a cellulose acetate dope solution.
  • the solvent cast method casts a solution (dope) in which cellulose acetate is dissolved in a solvent on a support, and evaporates the solvent to form a film.
  • cellulose acetate particles as a raw material of the cellulose acetate dope solution.
  • grains used are 1-4 mm in average particle diameter.
  • the cellulose acetate particles have a shape as close as possible to the spherical shape, and the cellulose acetate particles are preferably dried into a dope solution after drying to have a water content of 2% by weight or less, more preferably 1% by weight or less.
  • cellulose acetate solution (dope) used for the solvent cast method various additives according to the use in each preparation process, for example, a plasticizer, an ultraviolet inhibitor, a deterioration inhibitor, a microparticle, a release agent, an infrared absorber, an optically anisotropic control agent, etc. Can be added. Specific kinds of such additives may be used without limitation as long as it is conventionally used in the art, the content is preferably used in a range that does not lower the physical properties of the film.
  • the timing of adding the additive is determined by the type of the additive.
  • the process of adding an additive at the end of dope preparation can also be performed.
  • the plasticizer may be used to improve the mechanical strength of the film, and may shorten the drying process time of the film when the plasticizer is used.
  • the plasticizer can be used without limitation as long as it is commonly used, and examples thereof include phosphate esters and carboxylic acid esters selected from phthalic acid esters or citric acid esters. Triphenyl phosphate (TPP), biphenyl diphenyl phosphate (BDP), tricresyl phosphate (TCP), etc. are mentioned as an example of phosphate ester.
  • phthalate esters examples include dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP), diphenyl phthalate (DPP), butyldecyl phthalate (BDP) and diethylhexyl phthalate. (DEHP) etc. are mentioned.
  • citric acid esters include o-acetyltriethyl citrate (OACTE) and o-acetyltributyl citrate (OACTB).
  • carboxylic acid esters examples include butyl oleate, methyl acetyl lysine oleate, dibutyl sebacate and various trimellitic acid esters. It is preferable to use a phthalate ester (DMP, DEP, DBP, DOP, DPP, BDP, DEHP) plasticizer.
  • DMP, DEP, DBP, DOP, DPP, BDP, DEHP phthalate ester
  • the content of the plasticizer is 2 to 20 parts by weight, more preferably 5 to 15 parts by weight based on 100 parts by weight of cellulose acetate.
  • the ultraviolet inhibitor may be a hydroxy benzophenone compound, a benzotriazole compound, a salicylic acid ester compound, a cyanoacrylate compound and the like.
  • the amount of the sunscreen is used in an amount of 0.1 to 3 parts by weight, more preferably 0.5 to 2 parts by weight, based on 100 parts by weight of cellulose acetate.
  • deterioration inhibitor for example, an antioxidant, a peroxide decomposing agent, a radical inhibitor, a metal deactivator, a deoxygenating agent, a light stabilizer (hindered amine, etc.) and the like can be used.
  • Particularly preferred deterioration inhibitors include butylated hydroxytoluene (BHT) and tribenzylamine (TBA).
  • BHT butylated hydroxytoluene
  • TAA tribenzylamine
  • the amount of the deterioration inhibitor is 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight based on 100 parts by weight of cellulose acetate.
  • the said fine particles are added in order to maintain the curl suppression, conveyance property, adhesion prevention in a roll form, or flaw resistance of a film favorably, and you may use any selected from an inorganic compound and an organic compound.
  • the inorganic compound include silicon-containing compounds, silicon dioxide, titanium oxide, zinc oxide, aluminum oxide, barium oxide, zirconium oxide, strontium oxide, antimony oxide, tin oxide, tin oxide / antimony, calcium carbonate, talc, Clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate and the like are preferred, and more preferably silicon-containing inorganic compounds, zirconium oxide and the like can be used.
  • the fine particles have an average primary particle diameter of 80 nm or less, preferably 5 to 80 nm, more preferably 5 to 60 nm, and particularly preferably 8 to 50 nm. If the average primary particle diameter exceeds 80 nm, the surface smoothness of the film is impaired.
  • the durability improving agent is used to improve the durability of the film and to increase the retardation value Rth in the film thickness direction, and is preferably a compound represented by the following formula (1).
  • Z is selected from NAR 2 or CR 11 R 12 , wherein R 11 and Each R 12 is independently hydrogen or (C 1 -C 10) alkyl,
  • A is selected from -CO-, -CS-, -COO-, -COS-, -NHCO-, -NHCS-, -CR 3 R 4- , -POR 5- , -SO-, -SO 2- , R 3 and R 4 are each independently hydrogen, (C 1 -C 10) alkyl, (C 6 -C 20) aryl, (C 3 -C 20) cycloalkyl, (C 2 -C 7) alkenyl and 5- to 7-membered heterocyclo It is selected from the group consisting of alkyl, R 5 is selected from hydrogen, (C1-C10) alkyloxy, (C6-C20) aryloxy, -NH-R 6 , wherein R 6 is hydrogen, (C1-C10) alkyl , (C2-C7) alkenyl and (C2-C4) alkynyl,
  • R 1 is hydrogen, (C1-C10) alkyl, (C6-C20) aryl, (C3-C20) cycloalkyl, (C2-C7) alkenyl, (C1-C10) alkoxy, 5- or 7-membered heterocyclo Alkyl, (C4-C20) heteroaryl, and
  • R 2 is selected from the group consisting of hydrogen, (C 1 -C 10) alkyl, (C 3 -C 20) cycloalkyl, (C 2 -C 7) alkenyl, (C 1 -C 10) alkoxy and 5- to 7-membered heterocycloalkyl; ,
  • the R 1 alkyl, aryl, cycloalkyl, alkenyl, alkoxy, heterocycloalkyl and heteroaryl, the R 2 alkyl, cycloalkyl, alkenyl, alkoxy and heterocycloalkyl are independently of each other (C1-C10) alkoxy, ( C1-C7) alkyl, halogen, nitro, cyano, hydroxy, amino, (C6-C20) aryl, (C2-C7) alkenyl, (C3-C20) cycloalkyl and 5- to 7-membered heterocycloalkyl
  • One or more selected from the group consisting of may be further substituted,
  • R 1 and R 2 may be linked to (C3-C20) alkylene or (C3-C20) alkenylene to form a fused ring).
  • aryl refers to an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, wherein each ring is a single or fused ring system containing 4 to 7, preferably 5 or 6 ring atoms, as appropriate. It includes. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, tolyl, and the like.
  • heterocycloalkyl refers to a cycloalkyl group containing 1 to 3 heteroatoms selected from N, O, S as aliphatic ring skeleton atoms and the remaining aliphatic ring skeleton atoms being carbon.
  • heteroaryl refers to an aryl group containing 1 to 3 heteroatoms selected from N, O, and S as an aromatic ring skeleton atom, and the remaining aromatic ring skeleton atoms are carbon, wherein the heteroaryl group is a ring
  • the heteroatoms in the group include divalent aryl groups that are oxidized or quaternized to form, for example, N-oxides or quaternary salts.
  • the durability improving agent of Chemical Formula 1 significantly improves the durability of the cellulose acetate film, so that even when exposed to high temperature and high humidity for a long time, the amount of change in the phase difference value is small, and the phase difference value can be improved. This is determined by the fact that the compound of formula 1 has a carbamate structure, and the heterocycloalkyl ring bonded to the carbamate is not substituted with an aryl group.
  • the compound of Formula 1 is not particularly limited, and for example, any one or more selected from compounds of Formulas 1-1 to 1-16 may be used. When the following compounds are used, the effect of improving durability and retardation can be maximized.
  • the content of the durability improving agent is not particularly limited, and may be included, for example, in an amount of 1 to 15 parts by weight based on 100 parts by weight of cellulose acetate. If the content is less than 1 part by weight, the effect of improving durability and retardation may be insignificant, and if it is more than 15 parts by weight, the durability improving agent may be bleed out.
  • an optically anisotropic regulator, a wavelength dispersion regulator, etc. can be further added as needed.
  • Such additives can be used without limitation as long as they are conventionally used in the art.
  • the following cellulose acetate composition that is, a dope solution is prepared.
  • the cellulose acetate composition comprises a durability improving agent of the formula
  • Z is selected from NAR 2 or CR 11 R 12 , wherein R 11 and Each R 12 is independently hydrogen or (C 1 -C 10) alkyl,
  • A is selected from -CO-, -CS-, -COO-, -COS-, -NHCO-, -NHCS-, -CR 3 R 4- , -POR 5- , -SO-, -SO 2- , R 3 and R 4 are each independently hydrogen, (C 1 -C 10) alkyl, (C 6 -C 20) aryl, (C 3 -C 20) cycloalkyl, (C 2 -C 7) alkenyl and 5- to 7-membered heterocyclo It is selected from the group consisting of alkyl, R 5 is selected from hydrogen, (C1-C10) alkyloxy, (C6-C20) aryloxy, -NH-R 6 , wherein R 6 is hydrogen, (C1-C10) alkyl , (C2-C7) alkenyl and (C2-C4) alkynyl,
  • R 1 is hydrogen, (C1-C10) alkyl, (C6-C20) aryl, (C3-C20) cycloalkyl, (C2-C7) alkenyl, (C1-C10) alkoxy, 5- or 7-membered heterocyclo Alkyl, (C4-C20) heteroaryl, and
  • R 2 is selected from the group consisting of hydrogen, (C 1 -C 10) alkyl, (C 3 -C 20) cycloalkyl, (C 2 -C 7) alkenyl, (C 1 -C 10) alkoxy and 5- to 7-membered heterocycloalkyl; ,
  • the R 1 alkyl, aryl, cycloalkyl, alkenyl, alkoxy, heterocycloalkyl and heteroaryl, the R 2 alkyl, cycloalkyl, alkenyl, alkoxy and heterocycloalkyl are independently of each other (C1-C10) alkoxy, ( C1-C7) alkyl, halogen, nitro, cyano, hydroxy, amino, (C6-C20) aryl, (C2-C7) alkenyl, (C3-C20) cycloalkyl and 5- to 7-membered heterocycloalkyl
  • One or more selected from the group consisting of may be further substituted,
  • R 1 and R 2 may be linked to (C3-C20) alkylene or (C3-C20) alkenylene to form a fused ring).
  • the content of the durability improving agent is not particularly limited, and may be included, for example, in an amount of 1 to 15 parts by weight based on 100 parts by weight of cellulose acetate. If the content is less than 1 part by weight, the effect of improving durability and retardation may be insignificant, and if it is more than 15 parts by weight, the durability improving agent may be bleed out.
  • the solid concentration of the dope is, for example, 15 to 25% by weight, preferably 16 to 23% by weight. If the solid content concentration of the dope is less than 15% by weight, the fluidity is too high, it is difficult to form a film, when it exceeds 25% by weight it is difficult to be completely dissolved.
  • the content of cellulose acetate is, for example, 70% by weight or more, preferably 70 to 90% by weight, more preferably 80 to 85% by weight of the total solid content.
  • the cellulose acetate may be used by mixing two or more kinds of cellulose acetates having different degrees of substitution, polymerization degree or molecular weight distribution.
  • the solvent for preparing the cellulose acetate composition (dope) is preferably an organic solvent.
  • organic solvent halogenated hydrocarbons are preferably used, and halogenated hydrocarbons include chlorinated hydrocarbons, methylene chloride and chloroform, and methylene chloride is most preferably used.
  • organic solvents 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 acetate, ethyl acetate, pentyl acetate and the like can be used, and as ketone, acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone , Cyclopentanone, cyclohexanone, methylcyclohexanone and the like can be used, and ether is diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, tetra Hydrofuran, anisole, phentol, and the like can be used, and alcohols
  • methylene chloride may be used as the main solvent and alcohol may be used as the subsolvent.
  • methylene chloride and alcohol may be mixed and used in a weight ratio of 80:20 to 95: 5.
  • the cellulose acetate composition can be prepared by normal temperature, high temperature or low temperature dissolution method.
  • the viscosity of the cellulose acetate composition is preferably 1 Pa.s to 400 Pa.s at 40 ° C, more preferably 10 Pa.s to 200 Pa.s.
  • Cellulose acetate films can be prepared according to conventional solvent casting methods. Specifically, for example, the prepared dope (cellulose acetate composition) is stored once in a reservoir, and defoaming the foam contained in the dope. The defoamed dope is sent to the press die through a pressurized metering gear pump that can quantitatively and precisely transfer the dope from the dope outlet to the press die, and the dope is placed on the metal support endlessly running from the slit of the press die. By casting uniformly, the less dry casting film is peeled from the metal support at the peeling point where the metal support is almost round.
  • both ends of the manufactured web are sandwiched by a clip and conveyed by a tenter while maintaining the width thereof, then conveyed by a roller of a drying apparatus, dried and wound to a predetermined length by a curling machine.
  • the elongation of the film is not particularly limited, and may be, for example, 5 to 100% by length in the width direction. If the draw ratio is less than 5%, the effect of retardation may be insignificant, and if the draw ratio is greater than 100%, the film may break during stretching. While maximizing the retardation synergistic effect, in terms of minimizing damage to the film may be preferably 5 to 30% by length.
  • the space temperature at the time of application coating of a solution
  • coating of a solution -50 degreeC-50 degreeC are preferable, -30 degreeC-40 degreeC are more preferable, -20 degreeC-30 degreeC are the most preferable.
  • the cellulose acetate solution applied at a low space temperature is instantaneously cooled on the support to improve gel strength, thereby obtaining a film in which much organic solvent remains. Therefore, the film can be peeled off from the support in a short time without evaporating the organic solvent from the cellulose acetate.
  • gas for cooling the space ordinary air, nitrogen, argon or helium may be used.
  • the relative humidity is preferably 0 to 70%, more preferably 0 to 50%.
  • coats a cellulose acetate solution -50-130 degreeC is preferable, -30 degreeC-25 degreeC are more preferable, -20 degreeC-15 degreeC are the most preferable.
  • the gas cooled to the casting part may be introduced.
  • a chiller may be placed in the casting to cool the space. In cooling, it is important to take care that water does not adhere to the casting part. When cooling with gas, it is preferable to dry the gas.
  • the cellulose acetate film can be surface-treated as needed.
  • Surface treatment is generally performed in order to improve the adhesiveness of a cellulose acetate film.
  • Surface treatment methods include glow discharge treatment, ultraviolet irradiation treatment, corona treatment, flame treatment and saponification treatment.
  • the thickness of the cellulose acetate film is preferably in the range of 20 ⁇ m to 140 ⁇ m, more preferably in the range of 40 ⁇ m to 100 ⁇ m.
  • the cellulose acetate film according to the present invention may be used in a polarizing plate, an optical compensation sheet and a liquid crystal display device, and may be used in one or two or more layers.
  • Re was measured by injecting light having a wavelength of 550 nm into the film normal direction with a birefringence measuring instrument (manufactured by Axoscan, Axometrics, Inc.).
  • Rth is obtained by measuring three refractive index components of the ellipsoid of the refractive index obtained by measuring the light axis of the Re plane as the inclination axis, and measuring 550 nm of light at 10 degrees intervals from 0 to 50 degrees with respect to the film normal direction. The value obtained from
  • n x Refractive index of the larger refractive index of the two refractive indices
  • n y Refractive index of the smaller refractive index of the two refractive indices
  • n z refractive index in the thickness direction
  • BDP Biphenyl diphenyl phosphate
  • the obtained dope After heating the obtained dope to 30 degreeC, it sent by gear pump, filtered with the filter paper of 0.01 mm of absolute filtration accuracy, and filtered by the cartridge filtration apparatus of 5 micrometers of absolute filtration accuracy.
  • the dope obtained through the filtration process was cast on the mirror stainless steel support through a casting die and peeled off.
  • the amount of residual solvent at the time of peeling was adjusted to be 30 weight%.
  • the left and right ends of the film were removed by 150 mm.
  • the film from which the end was removed was dried through a drier, and both ends of the film from the drier were cut 3 cm, a knurling process having a height of 100 ⁇ m was further applied to a 10 mm portion from the end, and wound up in a roll shape.
  • the thickness of the produced film was 40 micrometers, and the obtained sample measured optical anisotropy by the method mentioned above.
  • BDP Biphenyl diphenyl phosphate
  • a cellulose acetate film was prepared by preparing dope in the same manner as in Example 1 except that the compound of Formula 1 was not included or the compound of Formula 2 was used.
  • the film was allowed to stand at 60 ° C. and 90% relative humidity for 500 hours to evaluate changes in Re and Rth before and after treatment.
  • Comparative Examples 1 to 4 confirmed that the amount of change in the phase difference after the high temperature and high humidity treatment was very large.

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  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Polarising Elements (AREA)

Abstract

La présente invention concerne un film d'acétate de cellulose, et plus spécifiquement un film d'acétate de cellulose et un procédé de production de celui-ci, le film d'acétate de cellulose ayant une excellente durabilité du fait qu'il comprend un ou plusieurs promoteur(s) de durabilité choisi(s) parmi les composés exprimés par la formule chimique 1, et présente ainsi une faible variation dans la valeur de différence de phase même en cas d'exposition à des conditions de température élevée et d'humidité élevée pendant une longue période de temps, et permet améliorer l'angle de vision et le contraste lorsqu'il est utilisé dans un appareil d'affichage car la valeur de différence de phase est élevée.
PCT/KR2016/001184 2015-02-03 2016-02-03 Film d'acétate de cellulose WO2016126101A1 (fr)

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KR1020150016460A KR20160095326A (ko) 2015-02-03 2015-02-03 셀룰로오스 아세테이트 필름

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116144080A (zh) * 2022-12-26 2023-05-23 乐凯光电材料有限公司 一种纤维素酯膜及其制备方法和应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20070121747A (ko) * 2005-04-18 2007-12-27 코니카 미놀타 옵토 인코포레이티드 셀룰로오스에스테르 필름 및 그의 제조 방법, 광학 필름,편광판 및 액정 표시 장치
JP2011075924A (ja) * 2009-09-30 2011-04-14 Fujifilm Corp 光学フィルム、位相差板、偏光板、ならびに液晶表示装置
JP2011207965A (ja) * 2010-03-29 2011-10-20 Fujifilm Corp セルロース系フィルム、偏光板、液晶表示装置、及び化合物
KR20120035285A (ko) * 2010-10-05 2012-04-16 에스케이이노베이션 주식회사 셀룰로오스아세테이트 필름
JP2013061465A (ja) * 2011-09-13 2013-04-04 Konica Minolta Advanced Layers Inc 光学フィルム、それを含む偏光板および液晶表示装置

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101472093B1 (ko) 2013-01-14 2014-12-15 주식회사 효성 위상차 및 시야각 보상을 위한 셀룰로오스 에스테르 필름

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20070121747A (ko) * 2005-04-18 2007-12-27 코니카 미놀타 옵토 인코포레이티드 셀룰로오스에스테르 필름 및 그의 제조 방법, 광학 필름,편광판 및 액정 표시 장치
JP2011075924A (ja) * 2009-09-30 2011-04-14 Fujifilm Corp 光学フィルム、位相差板、偏光板、ならびに液晶表示装置
JP2011207965A (ja) * 2010-03-29 2011-10-20 Fujifilm Corp セルロース系フィルム、偏光板、液晶表示装置、及び化合物
KR20120035285A (ko) * 2010-10-05 2012-04-16 에스케이이노베이션 주식회사 셀룰로오스아세테이트 필름
JP2013061465A (ja) * 2011-09-13 2013-04-04 Konica Minolta Advanced Layers Inc 光学フィルム、それを含む偏光板および液晶表示装置

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116144080A (zh) * 2022-12-26 2023-05-23 乐凯光电材料有限公司 一种纤维素酯膜及其制备方法和应用

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