WO2008050603A1 - Dispositif d'affichage à cristaux liquides en mode ips et procédé de fabrication dudit dispositif - Google Patents

Dispositif d'affichage à cristaux liquides en mode ips et procédé de fabrication dudit dispositif Download PDF

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Publication number
WO2008050603A1
WO2008050603A1 PCT/JP2007/069669 JP2007069669W WO2008050603A1 WO 2008050603 A1 WO2008050603 A1 WO 2008050603A1 JP 2007069669 W JP2007069669 W JP 2007069669W WO 2008050603 A1 WO2008050603 A1 WO 2008050603A1
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WIPO (PCT)
Prior art keywords
acid
liquid crystal
polarizing plate
film
crystal display
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PCT/JP2007/069669
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English (en)
Japanese (ja)
Inventor
Takashi Murakami
Shigeki Oka
Original Assignee
Konica Minolta Opto, Inc.
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Publication date
Application filed by Konica Minolta Opto, Inc. filed Critical Konica Minolta Opto, Inc.
Priority to KR1020097008058A priority Critical patent/KR101431292B1/ko
Priority to JP2008540937A priority patent/JPWO2008050603A1/ja
Publication of WO2008050603A1 publication Critical patent/WO2008050603A1/fr

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Classifications

    • 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
    • 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
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/0236—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element
    • G02B5/0242—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element by means of dispersed particles
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0273—Diffusing elements; Afocal elements characterized by the use
    • G02B5/0278—Diffusing elements; Afocal elements characterized by the use used in transmission
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G02F1/133634—Birefringent elements, e.g. for optical compensation the refractive index Nz perpendicular to the element surface being different from in-plane refractive indices Nx and Ny, e.g. biaxial or with normal optical axis
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1343—Electrodes
    • G02F1/134309—Electrodes characterised by their geometrical arrangement
    • G02F1/134363—Electrodes characterised by their geometrical arrangement for applying an electric field parallel to the substrate, i.e. in-plane switching [IPS]

Definitions

  • IPS type liquid crystal display device and method for manufacturing IPS type liquid crystal display device
  • the present invention relates to an IPS liquid crystal display device and a method for manufacturing an IPS liquid crystal display device.
  • a liquid crystal display device having an in-plane switching (IPS) type liquid crystal cell has approximately 45 liquid crystal molecules aligned in a substantially horizontal direction when no electric field is applied. Rotate the light to control light transmission (white display) ⁇ shielding (black display) (Patent Document 1).
  • IPS in-plane switching
  • a liquid crystal display device equipped with an IPS liquid crystal glass cell displays a screen from an oblique direction at angles of 45 degrees (azimuth angles of 45 degrees, 135 degrees, 225 degrees, and 315 degrees) with respect to the absorption axis of the polarizing plate.
  • angles of 45 degrees azimuth angles of 45 degrees, 135 degrees, 225 degrees, and 315 degrees
  • the contrast ratio decreases, and if the phenomenon that the display color varies depending on the viewing angle (also known as power shift!), There is a problem!
  • Non-Patent Document 1 a retardation film is not used, and a cellulose ester film having substantially zero Ro and Rt is present between both polarizers and the liquid crystal glass cell sandwiching the liquid crystal glass cell. It proposes a method to improve it by using it for both polarizing plate protective films.
  • This phenomenon is a result of the use of a stronger adhesive as a result of an increase in screen size. As a result, it was applied to a polarizing plate protective film located between the glass cell and the polarizer. It was found that the stress at the time was concentrated and the retardation of the polarizing plate protective film changed with time.
  • Patent Document 1 Patent No. 2982869
  • Non-Patent Literature l Hajime Nakayama et al. (FUJI PHOTO FILM Co., Lt d) IDW / AD '05 pl 317-1320
  • the present invention has been made to solve such a problem, and an object of the present invention is to provide an IPS liquid crystal display device with improved color shift over time and a method for manufacturing the IPS liquid crystal display device. It is to be.
  • the present inventors have found that the above object can be achieved by the following polarizing plate, liquid crystal display device, and liquid crystal display device manufacturing method. It came to complete.
  • An IPS liquid crystal display device comprising: an IPS liquid crystal glass cell; and two polarizing plates attached to both surfaces of the IPS liquid crystal glass cell via an adhesive layer,
  • At least one of the two polarizing plates comprises a polarizer and two polarizing plate protective films bonded to both sides of the polarizer,
  • the refractive index in the slow axis direction in the film plane is nx
  • the refractive index in the direction perpendicular to the slow axis is ny
  • the refractive index in the film thickness direction is nz
  • d is the film thickness (nm). Represent each.
  • the polarizing plate protective film force comprising the cellulose ester is a cellulose ester film containing a compound having negative orientation birefringence, described in (3) IPS liquid crystal display device.
  • At least one of the two polarizing plates comprises a polarizer and two polarizing plate protective films bonded to both sides of the polarizer,
  • ST stiffness
  • Rt is -5 ⁇ Rt ⁇ 5 nm
  • the film thickness is 20 to 60 am.
  • the refractive index in the slow axis direction in the film plane is nx
  • the refractive index in the direction perpendicular to the slow axis is ny
  • the refractive index in the film thickness direction is nz
  • d is the film thickness (nm). Represent each.
  • the color shift with time due to the step of sticking the polarizing plate can be improved. What has not become a problem in the previous process has become a new issue in the area where the screen size of the liquid crystal display device is increased and the retardation Ro and Rt of the polarizing plate protective film are essentially zero. Because it is the use of, we believe that slight changes have become apparent.
  • FIG. 1 is a schematic view of a liquid crystal display device according to a preferred embodiment of the present invention.
  • Non-electrode-side polarizing plate protective film 4 Non-electrode side cell glass substrate
  • Electrode side cell glass substrate (An electrode is formed on the substrate! /)
  • Electrode side polarizing plate (polarizing plate of the present invention)
  • At least one of the two polarizing plates used in the liquid crystal display device of the present invention is characterized in that the stiffness (ST) at 23 ° C. and 55% RH is in the range of 20 to 80 (g). It is.
  • the stiffness is an average value of the absorption axis direction and the transmission axis direction of the polarizing plate.
  • the range of 30 to 80 g is more preferable.
  • the range of 35 to 80 g is particularly preferable.
  • the stiffness of the present invention can be adjusted by adjusting the film thickness of the polarizing plate protective film and the polarizer, and may further be adjusted by the kind and amount of the specific compound to be contained in the polarizing plate protective film. .
  • Specific compounds include compounds having negative orientation birefringence. Negative orientation The type and amount of the compound having birefringence are determined in relation to the retardation.
  • the total film thickness of the polarizing plate is 80 to 150 ⁇ m, preferably 80-140.
  • the total film thickness of the polarizing plate includes the thickness of the polarizer, the polarizing plate protective film bonded to both sides of the polarizer, and the pressure-sensitive adhesive for bonding the polarizer and the polarizing plate protective film. .
  • the polarizing plate protective film on the side sandwiched between the liquid crystal glass cell and the polarizer of the present invention has Ro of 0 to 5 nm, Rt of -5 to 5 nm, and preferably Ro force of 2 to 2 nm.
  • Ro and Rt As a means for setting Ro and Rt to desired values, it can be preferably adjusted by adding a compound having negative orientation birefringence to the cellulose ester, and the film thickness of the cellulose ester film can be further reduced. 20 to 60 m is preferable.
  • the polarizing plate having the film thickness and retardation (hereinafter referred to as the polarizing plate of the present invention) is preferably disposed on the electrode side of the liquid crystal glass cell.
  • the polarizing plate protective film at this position is preferably uniform as a film. For example, even if a plurality of films are stacked or a coating layer is provided to have the same Ro and Rt, In the case of a single film, the performance improvement effect is greater.
  • Examples of the cellulose ester forming the polarizing plate protective film used in the present invention include triacetinoresenorelose (TAC), dicetinoresenorelose (DAC), senorelose acetate propionate (CAP), senorelose acetate butyrate.
  • TAC triacetinoresenorelose
  • DAC dicetinoresenorelose
  • CAP senorelose acetate propionate
  • CAB senorelose esters such as cenololose acetate tophthalate, cenololose acetate trimellitate, and cenololose nitrate.
  • the cellulose used as a raw material for the cellulose ester used in the present invention is not particularly limited. There are cotton linters, wood pulp, kenaf, etc. In addition, the cellulose ester obtained from these strengths is preferably used in an amount of 50% by mass or more of cotton linters that can be mixed and used at any ratio.
  • Cellulose esters have a number average molecular weight (Mn) of 30000-200000, preferably 50000-200000.
  • the cellulose ester used in the present invention preferably has an Mw / Mn ratio of 1 to 5, more preferably 1 to 3, and particularly preferably 1.4 to 2.3.
  • the average molecular weight and molecular weight distribution of cellulose ester can be measured using high performance liquid chromatography, the number average molecular weight (Mn) and the mass average molecular weight (Mw) are calculated using this, and the ratio is calculated. Can do.
  • a particularly preferred cellulose ester has an acyl group having 2 to 4 carbon atoms as a substituent, the substitution degree of the acetyl group is Xac, and the substitution degree of the propionyl group or butyryl group is Ypb. It is a cellulose ester that simultaneously satisfies (I) and (II).
  • V or a compound having such negative orientation birefringence is contained in the present invention is determined in relation to Ro, Rt, and stiffness.
  • the compound having negative orientation birefringence of the present invention means a material exhibiting negative birefringence in the stretching direction of the film in the cellulose ester film, and is an acrylic polymer, polyester, Examples include compounds having a furanose structure or a bilanose structure, sulfone compounds, and the like.
  • Whether or not the film has negative orientation birefringence can be determined by measuring the birefringence of the film in a system not added with the compound with a birefringence meter and comparing the difference. And force S.
  • acrylic polymers, polyesters, and compounds having a furanose structure or a biranose structure that can be used in the present invention will be described.
  • the cellulose ester film of the present invention preferably contains an acrylic polymer having negative orientation birefringence in the stretching direction and having a weight average molecular weight of 500 or more and 30000 or less.
  • the acrylic polymer has an aromatic ring as a side chain.
  • An acrylic polymer having a cyclohexyl group in the side chain is preferable.
  • the compatibility between the cellulose ester and the polymer can be improved.
  • an acrylic polymer, an acrylic polymer having an aromatic ring in the side chain, or an acrylic polymer having a cyclohexyl group in the side chain preferably has a weight average molecular weight of 500 or more. If it is 10000 or less, in addition to the above, the cellulose ester film after film formation has excellent performance as a protective film for polarizing plate with excellent transparency and extremely low moisture permeability.
  • the polymer has a weight average molecular weight of 500 or more and 30000 or less, it is considered to be between the oligomer and the low molecular weight polymer.
  • a method using a peroxide polymerization initiator such as cumene peroxide or t-butyl hydroperoxide, or a method using a polymerization initiator in a larger amount than usual polymerization is used.
  • a method using a chain transfer agent such as a mercapto compound or carbon tetrachloride
  • a method using a polymerization terminator such as benzoquinone dinitrobenzene in addition to the polymerization initiator
  • Examples include a method of bulk polymerization using a compound having one thiol group and a secondary hydroxyl group as described in Japanese Patent No. 128911 or 2000-344823, or a polymerization catalyst in which the compound and an organometallic compound are used in combination.
  • the force preferably used in the present invention is particularly preferable.
  • Examples of ethylenically unsaturated monomer units constituting a polymer obtained by polymerizing an ethylenically unsaturated monomer include: butyl esters such as butyl acetate, butyl propionate, butyl butyrate, valerate, and bivaleric acid.
  • Acrylic esters include methyl acrylate, ethyl acrylate, propyl acrylate (in 1), butyl acrylate (n-is-t 1), and pentyl acrylate.
  • the polymer composed of the above-mentioned monomers may be a copolymer or a homopolymer, and is preferably a vinylolestenore homopolymer, a vinylolestenole copolymer, or a copolymer of vinylolestenole and acrylic acid or methacrylic acid ester.
  • an acrylic polymer does not have a monomer unit having an aromatic ring or a cyclohexyl group! /, A homopolymer or copolymer of acrylic acid or alkyl methacrylate ester. Point to.
  • An acrylic polymer having an aromatic ring in the side chain is an acrylic polymer that always contains an acrylic acid or methacrylic acid ester monomer unit having an aromatic ring.
  • An acrylic polymer having a cyclohexyl group in the side chain is an acrylic polymer containing an acrylic acid or methacrylic acid ester monomer unit having a cyclohexyleno group.
  • Examples of the acrylate monomer having no aromatic ring and cyclohexyl group include methyl acrylate, ethyl acrylate, propyl acrylate (i ⁇ ), and butyl acrylate ( ⁇ -is-t ), Pentyl acrylate (n—is), hexyl acrylate (n—i 1), heptyl acrylate (ni 1), octyl acrylate (n—i—), nonyl acrylate (n—i) 1), Myristinolic Atalinoleate (n-i 1), Acrylic Acid (2-Ethylhexyl), Acrylic Acid (E-Strength Prolatatone), Acrylic Acid (2-Hydroxyethyl), Acrylic Acid (2 Hydroxypropyl) , Acrylic acid (3-hydroxypropyl), acrylic acid (4-hydroxybutyl), acrylic acid (2-hydroxybutyl), acrylic acid (2-methoxyethyl), acrylic acid (2-ethoxyethyl)
  • the acrylic polymer is a homopolymer or copolymer of the above monomers. It is preferable that the acrylic acid methyl ester monomer unit has 30% by mass or more, and the methyl methacrylate methyl ester monomer unit has 40% by mass. I prefer to have more! /. In particular, a homopolymer of methyl acrylate or methyl methacrylate is preferred.
  • acrylic acid or methacrylic acid ester monomers having an aromatic ring examples include phenyl acrylate, phenyl methacrylate, acrylic acid (2 or 4 phenyl), and methacrylic acid (2 or 4 phenyl).
  • the aromatic ring in the acrylic polymer having in the side chain, acrylic acid or main methacrylic acid ester monomer unit having an aromatic ring has a 20-40 mass 0/0, and acrylic acid or methacrylic acid methyl ester It is preferable to have 50 to 80% by weight of monomer units! /.
  • the polymer preferably has 2 to 20% by mass of a hydroxyl group-containing acrylic acid or methacrylic acid ester monomer unit.
  • Examples of the acrylate monomer having a cyclohexyl group include cyclohexyl acrylate, cyclohexyl methacrylate, acrylic acid (4-methylcyclohexyl), methacrylic acid (4-methylcyclohexyl), and acrylic acid.
  • Force S, cyclohexyl acrylate, and cyclohexyl methacrylate can be preferably used, such as (4-ethyl cyclohexyl) and methacrylic acid (4-ethyl cyclohexyl).
  • acrylic polymer having a cyclohexyl group in the side chain, having and 50-8 0% by mass has 20-40 mass 0/0 ⁇ acrylic acid or methacrylic acid ester monomer unit having a cyclohexyl group It is preferable. Further, in the polymer, or acrylic acid having a hydroxyl group preferably has a methacrylic acid ester monomer unit 2-20 mass 0/0.
  • acrylic acid or methacrylic acid ester monomers having these hydroxyl groups they are constituent units of copolymers that are not homopolymers.
  • the acrylic acid or methacrylic acid ester monomer unit having a hydroxyl group is contained in an amount of 2 to 20% by mass in the acrylic polymer! /.
  • a polymer having a hydroxyl group in the side chain can also be preferably used.
  • the monomer unit having a hydroxyl group the same force as the above-mentioned monomer, acrylic acid or methacrylic acid ester is preferred.
  • acrylic acid ester or methacrylic acid ester monomer unit having a hydroxyl group in the polymer is preferably contained in the polymer in an amount of 2 to 20% by mass, more preferably 2 to 10% by mass.
  • a polymer containing 2 to 20% by mass of the above-mentioned monomer unit having a hydroxyl group has excellent compatibility with cellulose ester, retention, and dimensional stability, and low moisture permeability. It is particularly excellent in adhesiveness with a polarizer as a polarizing plate protective film that is strong and has an effect of improving the durability of the polarizing plate.
  • the method for allowing a hydroxyl group to have at least one terminal of the main chain of the acrylic polymer is not particularly limited as long as it has a hydroxyl group at the terminal of the main chain, but azobis (2-hydroxyethyl)
  • a compound having one thiol group and a secondary hydroxyl group as disclosed in JP-A-2000-128911 or JP-T 2000-344823, or a compound thereof.
  • the polymer produced by the method related to the description in this publication is commercially available as Act Flow Series manufactured by Soken Chemical Co., Ltd. and can be used preferably.
  • the polymer having a hydroxyl group at the terminal and / or the polymer having a hydroxyl group in a side chain has an effect of significantly improving the compatibility and transparency of the polymer.
  • a polymer using styrenes as the ethylenically unsaturated monomer exhibiting negative orientation birefringence with respect to the stretching direction is preferred in order to exhibit negative refraction.
  • styrenes include styrene, methyl styrene, dimethyl styrene, trimethylol styrene, ethynole styrene, isopropino styrene, chloromethylol styrene, methoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, vinyl benzoic acid.
  • the force including methyl ester is not limited to these.
  • the birefringence For the purpose of controlling the birefringence, it may be copolymerized with the exemplified monomers listed as the unsaturated ethylenic monomer, and may be used by compatibilizing with cellulose ester using two or more of the above polymers. Also good.
  • the cellulose ester film according to the present invention includes an ethylenically unsaturated monomer Xa having no aromatic ring and a hydrophilic group in the molecule and ethylene having a hydrophilic group and no aromatic ring in the molecule. Obtained by polymerizing polymer X having a weight average molecular weight of 5,000 to 30,000, and more preferably ethylenically unsaturated monomer Ya having no aromatic ring.
  • the polymer Y preferably has a weight average molecular weight of 500 or more and 3000 or less.
  • the polymer X of the present invention comprises an ethylenically unsaturated monomer Xa having no aromatic ring and a hydrophilic group in the molecule and an ethylenically unsaturated monomer Xb having no aromatic ring and having a hydrophilic group in the molecule.
  • Xa is an acrylic or methallyl monomer having no aromatic ring and a hydrophilic group in the molecule
  • Xb is an acryl or methallyl monomer having no aromatic ring and having a hydrophilic group in the molecule.
  • the polymer X of the present invention is represented by the following general formula (1). [0062] General formula (1)
  • R4 represents —CH 2 —C H or —C H.
  • c represents a monomer unit polymerizable to Xa Xb.
  • Monomers as monomer units constituting the polymer X of the present invention are listed below, but are not limited thereto.
  • the hydrophilic group in X is a group having a hydroxyl group or an ethylene oxide chain.
  • the ethylenically unsaturated monomer Xa having no aromatic ring and no hydrophilic group in the molecule includes, for example, methyl acrylate, ethyl acrylate, propyl acrylate (in), butynole acrylate (n-is-t 1), pentyl acrylate (nis), hexyl acrylate (ni 1), heptyl acrylate (n-i 1), octyl acrylate (ni 1), nonyl acrylate (n-i 1), attalinoleic acid Myristinole (n-i 1), acrylic acid (2-ethylhexyl), acrylic acid ( ⁇ -strength prolatathone), acrylic acid (2-ethoxyethyl), etc., or the above acrylic acid ester replaced with methacrylic acid ester Can be mentioned.
  • Ethylenically unsaturated monomer Xb having no aromatic ring in the molecule and having a hydrophilic group is preferably acrylic acid or methacrylic acid ester as a monomer unit having a hydroxyl group.
  • acrylic acid 2-hydroxyethyl
  • acrylic acid (4-hydroxybutyl) acrylic acid (2-hydroxybutyl)
  • acrylic acid (2-hydroxybutyl) or these acrylic acids with methacrylic acid
  • acrylic acid (2-hydroxyethyl), methacrylic acid (2-hydroxyethyl), acrylic acid (2-hydroxypropyl), acrylic acid (3-hydroxypropyl) are used. is there.
  • Xc is not particularly limited as long as it is an ethylenically unsaturated monomer other than Xa and Xb and is copolymerizable, but preferably has no aromatic ring.
  • the molar composition ratio m: n of Xa, Xb and Xc is preferably in the range of 99:;! To 65:35, and more preferably in the range of 95: 5 to 75:25.
  • P of Xc is 0-10.
  • Xc may be a plurality of monomer units.
  • the molecular weight of the polymer X has a weight average molecular weight of 5000 or more and 30000 or less, and more preferably ⁇ 8000 or more and 25000 or less.
  • the cellulose ester film has advantages such as little dimensional change under high temperature and high humidity and less curling as a polarizing plate protective film.
  • the weight average molecular weight is within 30000, the compatibility with cellulose ester is further improved, and bleeding out under high temperature and high humidity and further haze generation immediately after film formation are suppressed.
  • the weight average molecular weight of the polymer X of the present invention can be adjusted by a known molecular weight adjusting method.
  • a molecular weight adjusting method include a method of adding a chain transfer agent such as carbon tetrachloride, lauryl mercaptan, octyl thioglycolate, and the like.
  • the polymerization temperature is usually from room temperature to 130 ° C, preferably from 50 ° C to 100 ° C. This temperature or the polymerization reaction time can be adjusted.
  • the weight average molecular weight can be measured by the following method.
  • the weight average molecular weight Mw was measured using gel permeation chromatography.
  • the polymer ⁇ of the present invention is a polymer having a weight average molecular weight of 500 or more and 3000 or less obtained by polymerizing an ethylenically unsaturated monomer Ya having no aromatic ring.
  • a weight average molecular weight of 500 or more is preferable because the residual monomer of the polymer decreases. Moreover, it is preferable to set it to 3 000 or less in order to maintain the retardation value Rt reduction performance.
  • Ya is preferably an acrylic or methacrylic monomer having no aromatic ring.
  • the polymer Y of the present invention is represented by the following general formula (2).
  • R6 represents an alkyl group or cycloalkyl group having 1 to 12 carbon atoms.
  • Yb represents a monomer unit copolymerizable with Ya.
  • Yb is not particularly limited as long as it is an ethylenically unsaturated monomer copolymerizable with Ya.
  • Y b may be plural.
  • k + q 100, q is preferably 0-30.
  • Ethylenically unsaturated monomer Ya is an acrylate ester such as methyl acrylate, ethyl acrylate, propyl acrylate (in), butyl acrylate (nis-t), pentyl acrylate (n-is), Hexyl acrylate (n-i 1), heptyl acrylate (ni 1), octyl acrylate (n-i 1), nonyl acrylate (n-i 1), myristinolic acrylate (ni-), acrylic Cyclohexyl acid, Acrylic acid (2-ethylhexyl), Acrylic acid ( epsilon -force prolatatone), Acrylic acid (2-hydroxyethyl), Acrylic acid (2-hydroxypropyl), Acrylic acid (3-hydroxypropyl) , Acrylic acid (4-hydroxybutyl), acrylic acid (2-
  • Yb is not particularly limited as long as it is an ethylenically unsaturated monomer copolymerizable with Ya.
  • the bull ester include, but are not limited to, butyrate acetate, butyrate propionate, butyrate butyrate, butyrate vale, and butyrate bullate.
  • Caproic acid bull, strong purine bull, lauric acid bull, myristic acid bull, palmitate bull, stearate bull, cyclohexane carbonate bull, octyl acid bull, methacrylate bull, crotonate bull, sorbic acid bull, cinnamon Acid bur is preferred.
  • Yb may be plural.
  • cumene peroxide is a method using a peroxide polymerization initiator such as t-butyl hydroperoxide, a method using a polymerization initiator in a larger amount than normal polymerization, a polymerization initiator.
  • the ends of the polymer X and the polymer Y have a hydroxyl group and a thioether resulting from the polymerization catalyst and the chain transfer agent.
  • This terminal residue can adjust the compatibility of the polymers X and ⁇ with the cellulose ester.
  • the hydroxyl values of the polymers X and X are preferably 30 to 150 [mgKOH / g]! / ⁇ .
  • This measurement conforms to JIS K 0070 (1992).
  • This hydroxyl value is defined as the number of mg of potassium hydroxide required to neutralize acetic acid bound to a hydroxyl group when sample lg is acetylated.
  • sample Xg (about lg) is precisely weighed in a flask, and 20 ml of acetylating reagent (20 ml of acetic anhydride added to pyridine to make 400 ml) is accurately added. Attach an air condenser to the mouth of the flask and heat in a glycerin bath at 95 ° C or 100 ° C.
  • Hydroxyl value ⁇ (B— C) X f X 28. 05 / X ⁇ + D (where B is the amount of 0.5 mol / L potassium hydroxide ethanol solution used in the blank test (ml)) , C is the amount of 0.5 mol / L potassium hydroxide ethanol solution used for titration (ml), f is the factor of 0.5 mol / L potassium hydroxide ethanol solution, D is the acid value, and 28. 05 Represents 1/2 of potassium hydroxide lmol 56.11)
  • All of the above-mentioned X polymer polymers Y have excellent compatibility with cellulose esters, excellent productivity without evaporation and volatilization, good retention as a protective film for polarizing plates, low moisture permeability, and excellent dimensional stability. ing.
  • a preferable range of the formula (i) is 10 to 25% by mass.
  • the total amount of the polymer X and the polymer Y is 5% by mass or more, the polymer X and the polymer Y sufficiently act to reduce the retardation value Rt. If the total amount is 35% by mass or less, the adhesion with the polarizer PVA is good.
  • Polymer X and polymer Y have the power to directly add and dissolve as a material constituting the dope liquid described later, or the power to pre-dissolve in the organic solvent that dissolves the cellulose ester and then add to the dope liquid. Monkey.
  • the cellulose ester film of the present invention preferably contains the following polyester.
  • the cellulose ester film of the present invention preferably contains a polyester represented by the following general formula (3) or (4).
  • B1 represents a monocarboxylic acid component
  • B2 represents a monoalcohol component
  • G represents a divalent alcohol component
  • A represents a dibasic acid component. Represents that it was synthesized.
  • Bl, B2, G, and A are all characterized by containing no aromatic ring.
  • m and n represent the number of repetitions.
  • the monocarboxylic acid represented by B1 is not particularly limited, and known aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, and the like can be used.
  • Examples of preferable monocarboxylic acids include the following forces S, Akira is not limited to this.
  • aliphatic monocarboxylic acid a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used. It is particularly preferred that the number of carbons is more preferably 1 to 20; When acetic acid is contained, the compatibility with the cellulose ester increases, so that it is also preferable to use a mixture of acetic acid and other monocarboxylic acids.
  • aliphatic monocarboxylic acids formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, strong prillic acid, pelargonic acid, strong purine acid, 2-ethyl hexanecarboxylic Acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, Examples thereof include saturated fatty acids such as rataceric acid, unsaturated fatty acids such as undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, and ar
  • the monoalcohol component represented by B2 is not particularly limited, and it is possible to use known alcohols.
  • an aliphatic saturated alcohol or aliphatic unsaturated alcohol having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used. More preferably, the carbon number is! ⁇ 20, particularly preferably the carbon number is! ⁇ 12.
  • Examples of the divalent alcohol component represented by G can include the following. Power The present invention is not limited to these.
  • Examples include pentanediol, 1,6-hexanediol, 1,5-pentyleneglycol, diethylene glycol, triethylene glycol, tetraethylene dallicol, etc.
  • the dibasic acid (dicarboxylic acid) component represented by A includes an aliphatic dibasic acid and an alicyclic diacid salt.
  • an aliphatic dibasic acid malonic acid, succinic acid, dartaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid are preferred.
  • An acid or the like, in particular, an aliphatic dicarboxylic acid having 4 to 12 carbon atoms or at least one selected from these is used. In other words, use a combination of two or more dibasic acids! / ,.
  • m and n represent the number of repetitions, and preferably 1 or more and 170 or less.
  • G represents a divalent alcohol having 2 to 12 carbon atoms, and A represents 2 to 12 carbon atoms) B2, G, and A do not contain an aromatic ring, n represents the number of repetitions.
  • B1 represents a monocarboxylic acid component
  • B2 Represents a monoalcohol component
  • G represents a divalent alcohol component having 2 to 12 carbon atoms
  • A represents a dibasic acid component having 2 to 12 carbon atoms, and represents that they were synthesized.
  • Bl, G, and A do not contain an aromatic ring.
  • m and n represent the number of repetitions.
  • Bl and B2 have the same meanings as Bl and B2 in the general formula (3) or (4).
  • G and A are an alcohol component or a dibasic acid component having 2 to 12 carbon atoms among G and A in the general formula (3) or (4).
  • the weight average molecular weight of the polyester is preferably 20000 or less, more preferably 10,000 or less.
  • polyesters having a weight average molecular weight of 500 to 10,000 are preferably used because of their good compatibility with cellulose esters.
  • Polycondensation of polyester is carried out by a conventional method.
  • a direct reaction of the above dibasic acid and dallicol the above dibasic acid or an alkyl ester thereof, for example, a polyesterification reaction or transesterification reaction between a methyl ester of a dibasic acid and a glycol.
  • It can be easily synthesized by either the hot melt condensation method or the dehydrohalogenation reaction of acid chlorides and glycols of these acids, but V and polyesters with a relatively large weight average molecular weight are directly reacted. I like it!
  • Polyester having a high distribution on the low molecular weight side has very good compatibility with the cellulose ester, and after forming the film, it is possible to obtain a cellulose ester film having a low moisture permeability and a high transparency.
  • a conventional method can be used as the molecular weight adjustment method without any particular limitation. For example, force depending on the polymerization conditions The method of blocking the molecular ends with a monovalent acid or monovalent alcohol can be controlled by the amount of these monovalent compounds added.
  • a monovalent acid is preferable from the viewpoint of polymer stability.
  • acetic acid, propionic acid, butyric acid, etc. can be mentioned.
  • the weight average molecular weight can also be adjusted by measuring the timing of stopping the reaction according to the amount of water distilled off during the reaction.
  • it can be adjusted by biasing the number of moles of glycol or dibasic acid to be charged, or can be adjusted by controlling the reaction temperature.
  • the polyester according to the present invention preferably contains 1 to 40% by mass of the cellulose ester.
  • S The polyester represented by the general formula (5) or (6) should contain 2 to 30% by mass. Is preferred! It is particularly preferable to contain 5 to 15% by mass! /.
  • the cellulose ester film of the present invention has at least one furanose structure or bilanose structure, and is a compound obtained by esterifying all or a part of OH groups in a compound in which 1 to 12 of the furanose structure or bilanose structure is bonded. It is characterized by including
  • Examples of preferable "compounds having at least one furanose structure or bilanose structure and having 1 to 12 of the furanose structure or bilanose structure” include, for example, the following strengths: S, The present invention is not limited to these.
  • the force S mentioned, particularly those having both a furanose structure and a bilanose structure are preferred.
  • An example is sucrose.
  • the monocarboxylic acid to be used is not particularly limited, and a known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid or the like can be used.
  • One type of carboxylic acid may be used, or a mixture of two or more types may be used.
  • Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, strength prillic acid, pelargonic acid, strength puric acid, 2-ethyl hexanecarboxylic acid, Undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, araquinic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, Examples thereof include saturated fatty acids such as lacteric acid, unsaturated fatty acids such as undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic
  • Examples of preferable alicyclic monocarboxylic acid include cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, and derivatives thereof.
  • aromatic monocarboxylic acids include those in which an alkyl group or an alkoxy group is introduced into the benzene ring of benzoic acid such as benzoic acid or toluic acid, kaycin acid, benzylic acid, biphenylcarboxylic acid, An aromatic monocarboxylic acid having two or more benzene rings such as naphthalenecarboxylic acid and tetralincarboxylic acid, or a derivative thereof can be mentioned, and benzoic acid is particularly preferable.
  • R 1 represents an alkyl group or an aryl group
  • R 2 and R 3 each independently represent a hydrogen atom, an alkyl group, or an aryl group. Also, It is particularly preferable that the total number of carbon atoms of R 2 and R 3 is 10 or more.
  • R 4 and R 5 each independently represents an alkyl group or an aryl group. Further, the total number of carbon atoms of R 4 and R 5 is 10 or more, and each of the alkyl group and aryl group may have a substituent. As the substituent, a fluorine atom, alkyl group, aryleno group, alkoxy group, sulfone group and sulfonamido group are preferred, and an alkyl group, aryleno group, alkoxy group, sulfone group and sulfonamido group are particularly preferred.
  • the alkyl group may be linear, branched or cyclic, and preferably has 1 to 25 carbon atoms, more preferably 6 to 25 carbon atoms.
  • aryl group those having 6
  • the polarizing plate of the present invention is preferably disposed on the electrode side of the liquid crystal glass cell, but the polarizing plate disposed between the non-electrode-side polarizing plate and the polarizing plate and between the liquid crystal cell and the polarizer.
  • the polarizing plate protective film preferably has Ro of 0 to 5 nm and Rt of 30 to 80 nm.
  • the polarizing plate protective film has a thickness of 30 to 80 ⁇ m, and the total thickness of the polarizing plate is preferably 80 to 180 ⁇ m.
  • the polarizing plate protective film used for the polarizing plate disposed on the non-electrode side of the present invention is usually A normal polarizing plate protective film comprising the cellulose ester can be used. It is not always necessary to newly coat a retardation layer and combine a retardation film. Normally used, 30 ⁇ ; 100 ⁇ m polarizing plate protective film can be used as it is! / ⁇ . Moreover, it is also possible to use the polarizing plate protective film used for the electrode side as it is.
  • the polarizing plate protective film used in the present invention has a photoelastic modulus C (590 nm (m 2 / N)) of 1.
  • the total Ro of both the electrode side and non-electrode side polarizing plate protective films is 0 to;! Onm Is more preferably 0 to 5 nm.
  • the total Rt is preferably 0 to 85 nm, more preferably 10 to 60 nm.
  • the thickness of the polarizing plate protective film on the electrode side is preferably 20 to 60 m, and the thickness of the polarizing plate protective film on the non-electrode side is preferably 30 to 100.
  • the total force S of the polarizing plate thickness S should be 80 to 260 m, more preferably 50 to 200 mm 111. is there.
  • the cellulose ester film used in the present invention may contain an additive that can be added to a normal cellulose ester film.
  • additives examples include plasticizers, ultraviolet absorbers, and fine particles.
  • the plasticizer that can be used in the present invention is not particularly limited, but is preferably a polyvalent carboxylic ester plasticizer, glycolate plasticizer, phthalate ester plasticizer, or fatty acid ester plasticizer. And a polyhydric alcohol ester plasticizer, a polyester plasticizer, an acrylic plasticizer, and the like. Of these, when two or more plasticizers are used, at least one of them is preferably a polyhydric alcohol ester plasticizer.
  • a polyhydric alcohol ester plasticizer is a plasticizer comprising an ester of a divalent or higher aliphatic polyhydric alcohol and a monocarboxylic acid, and has an aromatic ring or a cycloalkyl ring in the molecule. It is preferable to have. Preferably it is a 2-20 valent aliphatic polyhydric alcohol ester
  • the ultraviolet absorber that can be used in the present invention is intended to improve durability by absorbing ultraviolet rays of 400 nm or less, and particularly has a transmittance of 10% or less at a wavelength of 370 nm. More preferably, it is 5% or less, more preferably 2% or less.
  • the ultraviolet absorber used in the present invention is not particularly limited! /, For example, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds Examples include compounds, nickel complex compounds, inorganic powders, and the like. It is good also as a polymer type ultraviolet absorber.
  • the fine particles used in the present invention include, as examples of inorganic compounds, silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, Mention may be made of hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. As the fine particles, those containing silicon are preferred in view of low turbidity, and silicon dioxide is particularly preferred.
  • the average primary particle diameter of the fine particles is preferably 5 to 50 nm, more preferably 7 to 20 nm. These are preferably contained mainly as secondary aggregates having a particle size of 0.05 to 0.3 m.
  • the content of these fine particles in the cellulose ester film is preferably from 0.05 to 1% by mass, particularly preferably from 0.;! To 0.5% by mass. In the case of a cellulose ester film having a multi-layer structure formed by a co-casting method, it is preferable that the added amount of fine particles is contained on the surface.
  • the fine particles of silicon dioxide are, for example, Aerozinole R972, R972V, R974, R812, 200, 200V, 300, R202, 0X50, TT600 (above Enomoto Aerosil Co., Ltd.) It is sold on the market and can be used.
  • the fine particles of zirconium oxide are commercially available under the trade names of Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) and can be used.
  • Examples of the polymer include silicone resin, fluororesin, and acrylic resin. Silicone resins are preferred, especially those having a three-dimensional network structure (e.g., Suzunonore 103, 105, 108, 120, 145, 3120 and 240 (and above) It is commercially available under the trade name of Toshiba Silicone Co., Ltd. and can be used.
  • Aerosil 200V and Aerosil R972V are particularly preferably used because they have a large effect of reducing the friction coefficient while keeping the turbidity of the cellulose ester film low.
  • Rt and Ro are represented by the formulas (i) and (ii) at a wavelength of 590 nm at 23 ° C. and 55% RH.
  • Rt ⁇ (nx + ny) / 2— nz ⁇ X d (where the refractive index in the film slow axis direction is nx, the refractive index in the direction perpendicular to the slow axis is ny, and the film (The refractive index in the thickness direction is nz and d is the film thickness (nm).)
  • the birefringence and retardation values of the film are not limited to the force that can be measured using an automatic birefringence measuring device (trade name KOBRA-21ADH manufactured by Oji Scientific Instruments).
  • the cellulose ester film according to the present invention is preferably a cellulose ester film produced by a solution casting method or a melt casting method!
  • the cellulose ester film of the present invention is prepared by dissolving a cellulose ester, a compound having negative orientation birefringence, and an additive in a solvent to prepare a dope, and an endless metal that moves the dope indefinitely.
  • the concentration of cellulose ester in the dope is high, which is preferable because the drying load after casting on the metal support can be reduced. However, if the concentration of cellulose ester is too high, the load during filtration increases. , Filtration accuracy deteriorates.
  • the concentration that achieves both of these is preferably 10 to 35% by mass, more preferably 15 to 25% by mass. %.
  • Solvents used in the dope may be used alone or in combination of two or more. However, it is preferable in terms of production efficiency to use a mixture of good and poor solvents of cellulose ester. Good Solvents are more preferred, and cellulose ester is preferred for solubility of cellulose esters!
  • the preferable range of the mixing ratio of the good solvent and the poor solvent is 70 to 98% by mass for the good solvent and 2 to 30% by mass for the poor solvent.
  • a good solvent and a poor solvent are defined as a good solvent, a solvent that swells alone, or a substance that does not dissolve!
  • the good solvent and the poor solvent change depending on the average degree of acetylation (degree of substitution of acetyl group) of cellulose ester.
  • degree of substitution of acetyl group degree of substitution of acetyl group 2.
  • Cellulose acetate propionate is a good solvent
  • cellulose acetate ester acetylation degree 2.8
  • the good solvent used in the present invention is not particularly limited, and examples thereof include organic halogen compounds such as methylene chloride, dioxolanes, acetone, methyl acetate, and methyl acetate acetate. Particularly preferred is methylene chloride or methyl acetate.
  • the poor solvent used in the present invention is not particularly limited, but for example, methanol, ethanol, n-butanol, cyclohexane, cyclohexanone and the like are preferably used. Further, the dope preferably contains water in an amount of 0.0;! To 2% by mass. The solvent used for dissolving the cellulose ester is used by collecting the solvent removed from the film by drying in the film-forming process and reusing it.
  • a general method can be used as a method for dissolving the cellulose ester when preparing the dope described above. When combined with heating and pressurization, it can be heated above the boiling point at normal pressure. It is preferable to stir and dissolve while heating at a temperature in the range above the boiling point of the solvent at normal pressure and under pressure, in order to prevent the formation of massive undissolved materials called gels and macos. Further, a method in which a cellulose ester is mixed with a poor solvent and wetted or swollen, and then a good solvent is added and dissolved is also preferably used. In the present invention, two or more of these solvents can be mixed and used.
  • the pressurization may be performed by a method of injecting an inert gas such as nitrogen gas or a method of increasing the vapor pressure of the solvent by heating. Heating is preferably performed from the outside. For example, a jacket type is preferable because temperature control is easy.
  • the heating temperature with the addition of a solvent is preferably high! /, From the viewpoint of the solubility of the cellulose ester, but if the heating temperature is too high, the required pressure increases and the productivity deteriorates.
  • the preferred caloric temperature is 45-20. C and 60-10. 70 more preferred than C. C ⁇ ; C is more preferred.
  • the pressure is adjusted so that the solvent does not boil at the set temperature.
  • a cooling dissolution method is also preferably used, whereby the cellulose ester can be dissolved in a solvent such as methyl acetate.
  • the cellulose ester solution is filtered using a suitable filter medium such as filter paper.
  • the filter medium it is preferable that the absolute filtration accuracy is small in order to remove insoluble matters and the like, but there is a problem that the filter medium is likely to be clogged if the absolute filtration accuracy is too small. Therefore, a filter medium with an absolute filtration accuracy of 0.008 mm or less is preferred. A filter medium with a capacity of 0.001 to 0.008 mm is preferred, and a filter medium power of 0.003 to 0.006 mm is more preferred! /.
  • the ability to use ordinary filter media with no particular restrictions on the filter material The plastic filter media such as polypropylene and Teflon (registered trademark), and metal filter media such as stainless steel are used to drop the fibers. Etc. are preferred. It is preferable to remove and reduce impurities, particularly bright spot foreign matter, contained in the raw material cellulose ester by filtration.
  • the bright spot foreign matter is arranged in a crossed Nicols state between two polarizing plates, a roll-like cellulose ester is placed between them, light is applied from one polarizing plate side, and the other polarizing plate side is placed. It is a point (foreign matter) that light from the opposite side appears to leak when observed by force, and the number of bright spots having a diameter of 0.01 mm or more is preferably 200 / cm 2 or less. More preferably, it is 100 pieces / cm 2 or less, still more preferably 50 pieces / m 2 or less, and still more preferably 0 to 10 pieces / cm 2. Further, it is preferable that the number of bright spots of 0.01 mm or less is small.
  • the ability to filter the dope by a usual method The boiling point at normal pressure of the solvent is higher than the boiling point of the solvent, and the solvent does not boil under pressure!
  • the increase in the difference in filtration pressure before and after filtration (referred to as differential pressure) is preferably small.
  • a preferable temperature is 45 to 120 ° C, and 45 to 70 ° C is more preferable, and 45 to 55 ° C is still more preferable.
  • the filtration pressure is preferably small.
  • the filtration pressure is preferably 1.6 MPa or less. 1. It is preferably 2 MPa or less, more preferably 1. OMPa or less.
  • the metal support in the casting (casting) step preferably has a mirror-finished surface, and as the metal support, a stainless steel belt or a drum whose surface is polished with a porcelain is preferably used.
  • the cast width can be l ⁇ 4m.
  • the surface temperature of the metal support in the casting process is from 50 ° C to less than the boiling point of the solvent, and the high temperature force is preferable because the web can be dried quickly, but if it is too high, the web may foam. The flatness may deteriorate.
  • the preferred support temperature is 0 to 40 ° C, more preferably 5 to 30 ° C.
  • the web is gelled by cooling and peeled off from the drum in a state containing a large amount of residual solvent! /.
  • the method for controlling the temperature of the metal support is not particularly limited! /, But there are a method of blowing hot air or cold air, and a method of contacting hot water with the back side of the metal support.
  • the use of warm water is more efficient in transferring heat, so it is preferable to have a short time until the temperature of the metal support becomes constant.
  • warm air it may be higher than the target temperature!
  • the residual solvent amount when peeling the web from the metal support is preferably 10 to 150% by mass, more preferably 20 to 40% by mass. Or it is 60-130 mass%, Most preferably, it is 20-30 mass% or 70-; 120 mass%.
  • the amount of residual solvent is defined by the following formula.
  • Residual solvent amount (mass%) ⁇ (M-N) / N ⁇ X 100
  • M is the mass of the sample collected at any time during or after the production of the web or film
  • N is the mass after heating M at 115 ° C for 1 hour.
  • the web is peeled off from the metal support and further dried to make the residual solvent amount 1% by mass or less. 1% by mass or less, particularly preferably 0 to 0.01% by mass or less.
  • a roll drying method a method in which a plurality of rolls arranged above and below are alternately dried by passing through a web
  • a tenter method is used while drying the web.
  • the cellulose ester film of the present invention is produced, it is subjected to a hatching treatment, whereby the polarizing plate of the present invention can be prepared by bonding with the polarizer described below.
  • a polarizer which is the main component of a polarizing plate, is an element that passes only light with a plane of polarization in a certain direction, and a typical polarizing film that is currently known is a polybulal alcohol-based polarizing film.
  • polybutane alcohol film dyed with iodine and dichroic dye There are two types: polybutane alcohol film dyed with iodine and dichroic dye.
  • a polarizer having an ethylene-modified polybutyl alcohol and having a film thickness of 5 to 20 Hm it is particularly preferable to use a polarizer having an ethylene-modified polybutyl alcohol and having a film thickness of 5 to 20 Hm.
  • the polarizer is formed from an ethylene-modified polybutyl alcohol having an ethylene unit content of 1 to 4 mol%, a polymerization degree of 2000 to 4000, and a saponification degree of 99.0 to 99.99 mol%. It is preferably made from an ethylene-modified polybutyl alcohol film having a hot water cutting temperature of 66 to 73 ° C.
  • the ethylene-modified PVA film may be dyed, uniaxially stretched, fixed, dried, and further subjected to heat treatment as necessary.
  • the ethylene-modified PVA film may be dyed, uniaxially stretched, fixed, dried, and further subjected to heat treatment as necessary.
  • staining, uniaxial stretching, and a fixing process There is no restriction
  • a wet stretching method or a dry heat stretching method can be used.
  • Hot water such as a boric acid aqueous solution (in a solution containing the dye or in a fixed treatment bath described later! /), Or after water absorption. It can be performed in air using a Tylene-modified PVA film.
  • the stretching temperature is not particularly limited, but is preferably 30 to 90 ° C when stretching an ethylene-modified PVA film in warm water (wet stretching), and 50 to 180 ° C when performing dry heat stretching. Is preferred.
  • the stretching ratio of uniaxial stretching is preferably 4 times or more from the viewpoint of the polarizing performance of the polarizing film, and most preferably 5 times or more.
  • the upper limit of the stretching ratio is not particularly limited, but it is preferably 8 times or less because uniform stretching is easily obtained.
  • the thickness of the stretched polarizer is preferably 2 to 25 ⁇ m, more preferably 5 to 20 ⁇ m, and particularly preferably 5 to 15 ⁇ m.
  • the polarizer obtained as described above is usually used as a polarizing plate by laminating the polarizing plate protective film of the present invention on both sides thereof.
  • PVA adhesive is preferably used among the forces that can include PVA adhesives and urethane adhesives.
  • the polarizing plate protective film is hatched with an alkaline solution before being bonded to the polarizer.
  • the polarizing plate used in the present invention is used by being attached to a liquid crystal glass cell via an adhesive layer.
  • an adhesive layer is formed with an adhesive on the surface of the surface-modified polarizing plate.
  • the pressure-sensitive adhesive can use various pressure-sensitive adhesives such as rubber-based adhesives, acrylic-based adhesives, silicone-based adhesives, etc. Acrylic adhesives that are colorless and transparent and have good adhesion to liquid crystal cells. Generally used.
  • the base polymer preferably has a weight average molecular weight of about 300,000 to 2.5 million.
  • alkyl (meth) acrylates refers to alkyl acrylate and / or methacrylic acid. It refers to an acid alkyl, and the following (meth) has the same meaning.
  • alkenyl (meth) acrylates include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-methylhexyl (meth) acrylate, etc. And can be used alone or in combination.
  • (meth) acrylic acid, glycidyl (meth) acrylate, and (meth) acrylic acid 2-hydroxyschetil instead of a part of the alkyl (meth) acrylate.
  • N methylol (meth) acrylamide can be used in combination.
  • other copolymerizable monomers such as butyl acetate and styrene may be used in combination without impairing the adhesive properties of the acrylic polymer.
  • the acrylic polymer can be produced by various known methods.
  • a radical polymerization method such as a bulk polymerization method, a solution polymerization method or a suspension polymerization method can be appropriately selected.
  • the radical polymerization initiator various known azo and peroxide types can be used.
  • polar solvents such as ethyl acetate and toluene are generally used as the solvent for the acrylic polymer for which the solution polymerization method is preferred.
  • Examples of the base polymer of the rubber adhesive include natural rubber, isoprene rubber, styrene butadiene rubber, recycled rubber, polyisobutylene rubber, and styrene isoprene styrene rubber and styrene butadiene styrene rubber. Etc.
  • Examples of the base polymer of the silicone adhesive include dimethylpolysiloxane and diphenylpolysiloxane.
  • the pressure-sensitive adhesive preferably contains a crosslinking agent.
  • the crosslinking agent include polyisocyanate compounds, polyamine compounds, melamine resins, urea resins, epoxy resins, metal chelate and the like.
  • the pressure-sensitive adhesive may include a tackifier, a plasticizer, a filler, an antioxidant, an ultraviolet absorber, a silane, and a pulling agent, as necessary, without departing from the scope of the present invention. Each can be used as appropriate.
  • the formation of the pressure-sensitive adhesive layer is not particularly limited, and a method of applying a pressure-sensitive adhesive (solution) to the surface of the modified polarizing plate and drying, and a polarized light modified by a release sheet provided with the pressure-sensitive adhesive layer For example, a method of transferring to the plate surface.
  • the thickness of the pressure-sensitive adhesive layer (dry film thickness) is preferably thinner in consideration of the retardation of the pressure-sensitive adhesive layer itself and from the viewpoint of dimensional stability. Prefer Good.
  • Examples of the constituent material of the release sheet include paper, polyethylene, polypropylene, and synthetic resin films such as polyethylene terephthalate.
  • the surface of the release sheet is subjected to release treatment such as silicone treatment, long-chain alkyl treatment, fluorine treatment, etc. as necessary to improve the peelability from the adhesive layer! ,.
  • an automatic sticking device is used for sticking to a liquid crystal glass cell.
  • a polarizing plate is attached to the glass cell using a roller while closely contacting the polarizing plate with the device to ensure flatness.
  • the polarizing plate also has a force, and the retardation of the polarizing plate protective film that causes a color shift over time is generated.
  • color shift can be suppressed regardless of the strength of the pressure-sensitive adhesive and the thickness of the pressure-sensitive adhesive layer.
  • the liquid crystal layer of the liquid crystal panel in the initial state is homogeneously aligned parallel to the substrate surface, and the director of the liquid crystal layer on the plane parallel to the substrate is parallel to the electrode wiring direction or no voltage when no voltage is applied.
  • the direction of the director of the liquid crystal layer changes as the voltage is applied! /
  • the direction of the director direction of the liquid crystal layer shifts to the direction perpendicular to the electrode wiring direction.
  • the liquid crystal layer when the voltage is applied rotates the azimuth angle of the polarization by 90 ° like a half-wave plate and transmits through the output-side deflection plate.
  • the axis and the azimuth angle of the polarized light coincide with each other to display white.
  • the IPS liquid crystal display device of the present invention is preferably used for a large-sized liquid crystal television.
  • the screen size it can be preferably used for 17 type or more, and more preferably 26 type or more and about 100 type.
  • the IPS liquid crystal display device includes an FFS (fringe field switching) mode and an FLC (ferroelectric liquid crystal) mode.
  • Methyl acrylate monomer was polymerized by the polymerization method described in Example 3 of 128911.
  • silica particles having an average particle diameter of 16 nm 20 parts by mass of silica particles having an average particle diameter of 16 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) and 80 parts by mass of methanol were mixed well for 30 minutes to obtain a silica particle dispersion.
  • This dispersion was put into a disperser together with the following composition, and further stirred for 30 minutes or more to dissolve each component to prepare a matting agent solution.
  • the dope composition A having the above formulation was put into a sealed container, heated to 70 ° C, and stirred to completely dissolve cellulose triacetate (TAC) to obtain a dope.
  • TAC cellulose triacetate
  • the time required for dissolution was 4 hours.
  • 6.5 parts by weight of the matting agent solution is mixed and The mixture was uniformly cast on a stainless steel band support at 22 ° C at a dope temperature of 35 ° C using a belt casting apparatus.
  • the temperature of the stainless steel band support was 20 ° C.
  • the dope was peeled from the stainless steel band support.
  • the residual solvent amount of the dope was 25% by mass.
  • the time required from casting the dope to stripping was 3 minutes. It is peeled off from the stainless steel band support with a tension of 10kg / m, stretched 2% in the width direction with a tenter at 140 ° C, and then transported by many rolls at 120 ° C and 135 ° C drying zones.
  • the cellulose triacetate film sample 1 having a film thickness of 40 ⁇ m was manufactured by finishing drying and applying a knurling process with a width of 10 mm and a height of 5 ⁇ m to both ends of the film.
  • the Finorem width was 1500 mm and the winding length was 1000 m.
  • the haze (measured with HM150, manufactured by Murakami Color Research Laboratory) was 3%, and the single transmittance (measured with spectrophotometer U-4100 with integrating sphere, manufactured by Hitachi, Ltd.) was 97%. It was.
  • the winding tension was an initial tension of 10 kg / m and a final winding tension of 8 kg / m.
  • Samples 2, 3, 4, 5, and 6 having a thickness of 20 mm 111, 30 mm 111, ⁇ ⁇ ⁇ 60 mm, and 80 mm were manufactured.
  • Samples 2 and 3 had a winding length of 1000 m.
  • Triacetyl cellulose (acetyl substitution degree 2.9) 2. 2 parts by mass
  • the above dope composition A is 95.6 parts by mass
  • the matting agent solution is 1.8 parts by mass
  • the additive solution is 6.7 parts by mass.
  • Samples 1 to 8 above were immersed in an alkali solution bath adjusted to 55 ° C with an aqueous solution of 1.5N sodium hydroxide for 2 minutes.
  • the convection speed of the alkaline solution was 50 m / min, and a partition plate was provided near the outlet of the alkaline solution tank, and the part was adjusted to 58 ° C.
  • the alkali-soaked film was washed with water, then immersed in 0.05 mol / L sulfuric acid aqueous solution for 30 seconds, and further washed with water. Then, draining with an air knife was repeated three times, followed by drying for 30 seconds in a drying room at 70 ° C. to prepare a polarizing plate protective film subjected to a hatching treatment.
  • Ethylene unit content 2.1 mol%, saponification degree 99.92 mol%, polymerization degree 3000
  • Ethylene-modified PVA 100 parts by mass impregnated with 10 parts by mass glycerin and 200 parts by mass water After defoaming, the film was melt-extruded from a T die to a metal roll to form a film.
  • the ethylene-modified PVA film obtained after drying and heat treatment had a thickness of 40 m, and the average hot water cutting temperature of the film was 70 ° C.
  • the ethylene-modified PVA film was immersed in water at 30 ° C for 60 seconds to pre-swell, and the boric acid concentration was 40g / liter, iodine concentration was 0.4g / liter, and potassium iodide concentration was 60g / liter. It was immersed in an aqueous solution of C for 2 minutes. Subsequently, it was uniaxially stretched 6 times in a 55 ° C aqueous solution with a boric acid concentration of 4%, and 30 ° C with a potassium iodide concentration of 60 g / liter, boric acid concentration of 40 g / liter, and zinc chloride concentration of 10 g / liter.
  • the obtained polarizer had an average thickness of 10 m, and the polarization performance was a transmittance of 43.0%, a polarization degree of 99.5%, and a dichroic ratio of 40.1.
  • Polybutyl alcohol film (made by Kuraray Co., Ltd., average degree of polymerization 2400, degree of hatching 99.9 mol%, length 800 m) with a thickness of 80 111 and a width of 3100 mm is immersed in pure water at 30 ° C for 60 seconds. And uniaxially stretched in the length direction (flow direction) to a draw ratio of 2.5.
  • the film was stretched in an aqueous solution having a boric acid concentration of 4 mass% and a potassium iodide concentration of 3 mass% at 60 ° C until the total stretching ratio was 6 times. Thereafter, the film was immersed in an aqueous solution at 25 ° C. with a potassium iodide concentration of 5 mass% for 30 seconds without stretching. Next, drying was performed at 40 ° C for 1 minute while maintaining the tension, and a polarizer having a thickness of 20 111 and a width of 1550 mm was obtained. The polarizer was manufactured continuously.
  • polarizers A and B and the sample film are run in the longitudinal direction, they are bonded to the side of the liquid crystal glass cell of the polarizer with a polybulal alcohol adhesive, and Konica Minolta KC4UY is on the opposite side of the cell side.
  • 4UY 8UY
  • 8UY Fuji Photo Film Co., Ltd.
  • Fujitac UZ—TAC40 H m hereinafter referred to as 4UZ
  • 80 m hereinafter referred to as 8UZ
  • Acrylic adhesive (butyl acrylate / metatalic acid / hydroxyethyl acrylate copolymer, molecular weight 2 million, 0.3% isocyanate-based crosslinking agent) is applied to the liquid crystal glass cell side surface of the polarizing plate.
  • the solution was applied and dried to prepare a polarizing plate having a pressure-sensitive adhesive layer having a thickness of 10.
  • the spectrophotometer for thin films was measured using “Instant multi-photometry system MCPD-2000” manufactured by Otsuka Electronics Co., Ltd.
  • the measurement was performed using an Anritsu digital micrometer “KC-351C type”.
  • the liquid crystal panel Take out the liquid crystal panel from the liquid crystal display device [Panasonic LCD TV VIERA TH-26LX60 manufactured by Matsushita Electric Industrial Co., Ltd.] including the IPS mode liquid crystal cell, and remove the polarizing plates placed above and below the liquid crystal cell. The glass surface (front and back) of the liquid crystal cell was washed. Subsequently, the polarizing plate having the pressure-sensitive adhesive layer of the present invention was applied to a liquid crystal glass cell using a polarizing plate sticking apparatus so that the slow axis of the polarizer was parallel to the long side of the liquid crystal cell (0 ⁇ 0.2 degrees). Stuck on the electrode side of Yes
  • the azimuth angle of 45 ° represents an azimuth rotated 45 ° counterclockwise when the long side of the panel is 0 °.
  • the polar angle of 60 ° is 60 ° when the vertical direction to the panel is 0 °.
  • the IPS liquid crystal display device of the present invention has an effect of improving the color shift by adjusting the stiffness.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Polarising Elements (AREA)

Abstract

L'invention concerne un dispositif d'affichage à cristaux liquides en mode IPS présentant une distorsion chromatique améliorée avec le temps; et un procédé de fabrication du dispositif d'affichage à cristaux liquides en mode IPS. Le dispositif d'affichage à cristaux liquides en mode IPS est un dispositif ayant une cellule de verre à cristaux liquides en mode IPS et deux plaques de polarisation fixées au moyen d'une couche d'adhésif sur les deux surfaces principales de la cellule de verre à cristaux liquides en mode IPS. Ce dispositif est caractérisé en ce qu'au moins une des deux plaques de polarisation est une plaque de polarisation comprenant un polariseur et deux films de protection de plaque de polarisation fixés aux deux surfaces principales du polariseur, la plaque de polarisation ayant une épaisseur totale de 80 à 150 μm et une rigidité (ST), mesurée à 23°C et 55 % de HR, de 20 à 80 g, et en ce que parmi les deux films de protection de plaque de polarisation, le film de protection de plaque de polarisation sur le côté intercalé entre la cellule de verre à cristaux liquides en mode IPS et le polariseur présente Ro satisfaisant 0 ≤ Ro ≤ 5 nm, Rt satisfaisant -5 ≤ Rt ≤ 5 nm, et une épaisseur allant de 20 à 60 μm.
PCT/JP2007/069669 2006-10-24 2007-10-09 Dispositif d'affichage à cristaux liquides en mode ips et procédé de fabrication dudit dispositif WO2008050603A1 (fr)

Priority Applications (2)

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KR1020097008058A KR101431292B1 (ko) 2006-10-24 2007-10-09 Ｉｐｓ형 액정 표시 장치 및 ｉｐｓ형 액정 표시 장치의 제조 방법
JP2008540937A JPWO2008050603A1 (ja) 2006-10-24 2007-10-09 Ｉｐｓ型液晶表示装置及びｉｐｓ型液晶表示装置の製造方法

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JP2006-288445 2006-10-24

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010152334A (ja) * 2008-11-25 2010-07-08 Nitto Denko Corp 偏光板付ガラス板の製造方法、偏光板付ガラス板、偏光板付液晶セル
JP2014098911A (ja) * 2013-12-24 2014-05-29 Konica Minolta Inc 偏光板およびこれを用いた液晶表示装置
JP2017134413A (ja) * 2017-03-31 2017-08-03 日東電工株式会社 偏光フィルムおよびその製造方法、光学フィルムおよび画像表示装置
US9937689B2 (en) 2013-04-26 2018-04-10 Nitto Denko Corporation Polarizing film, method for manufacture thereof, optical film, and image display device
JP2018092187A (ja) * 2018-02-16 2018-06-14 日東電工株式会社 偏光フィルムおよびその製造方法、光学フィルムおよび画像表示装置
JP2018092186A (ja) * 2018-02-16 2018-06-14 日東電工株式会社 偏光フィルムおよびその製造方法、光学フィルムおよび画像表示装置
JP2019117381A (ja) * 2019-02-08 2019-07-18 日東電工株式会社 偏光フィルムおよびその製造方法、光学フィルムおよび画像表示装置

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005099476A (ja) * 2003-09-25 2005-04-14 Nitto Denko Corp 光学フィルムおよび画像表示装置
JP2006146138A (ja) * 2004-10-22 2006-06-08 Nitto Denko Corp 液晶パネルおよび液晶表示装置

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4142691B2 (ja) 2005-01-20 2008-09-03 富士フイルム株式会社 液晶表示装置
JP2006257143A (ja) 2005-03-15 2006-09-28 Fuji Photo Film Co Ltd セルロースアシレートフィルム、並びにそれを用いた偏光板及び液晶表示装置

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005099476A (ja) * 2003-09-25 2005-04-14 Nitto Denko Corp 光学フィルムおよび画像表示装置
JP2006146138A (ja) * 2004-10-22 2006-06-08 Nitto Denko Corp 液晶パネルおよび液晶表示装置

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010152334A (ja) * 2008-11-25 2010-07-08 Nitto Denko Corp 偏光板付ガラス板の製造方法、偏光板付ガラス板、偏光板付液晶セル
US9937689B2 (en) 2013-04-26 2018-04-10 Nitto Denko Corporation Polarizing film, method for manufacture thereof, optical film, and image display device
JP2014098911A (ja) * 2013-12-24 2014-05-29 Konica Minolta Inc 偏光板およびこれを用いた液晶表示装置
JP2017134413A (ja) * 2017-03-31 2017-08-03 日東電工株式会社 偏光フィルムおよびその製造方法、光学フィルムおよび画像表示装置
JP2018092187A (ja) * 2018-02-16 2018-06-14 日東電工株式会社 偏光フィルムおよびその製造方法、光学フィルムおよび画像表示装置
JP2018092186A (ja) * 2018-02-16 2018-06-14 日東電工株式会社 偏光フィルムおよびその製造方法、光学フィルムおよび画像表示装置
JP2019117381A (ja) * 2019-02-08 2019-07-18 日東電工株式会社 偏光フィルムおよびその製造方法、光学フィルムおよび画像表示装置

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