WO2007119560A1 - 偏光板, 液晶表示装置, および, 保護フィルム - Google Patents
偏光板, 液晶表示装置, および, 保護フィルム Download PDFInfo
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- WO2007119560A1 WO2007119560A1 PCT/JP2007/056631 JP2007056631W WO2007119560A1 WO 2007119560 A1 WO2007119560 A1 WO 2007119560A1 JP 2007056631 W JP2007056631 W JP 2007056631W WO 2007119560 A1 WO2007119560 A1 WO 2007119560A1
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- Prior art keywords
- polarizing plate
- film
- protective film
- layer
- liquid crystal
- Prior art date
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Classifications
-
- G02B1/105—
-
- 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
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/045—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means using resistive elements, e.g. a single continuous surface or two parallel surfaces put in contact
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/13338—Input devices, e.g. touch panels
Definitions
- the present invention uses a polarizing plate excellent in mechanical strength, capable of maintaining high visibility without dimensional change even in high temperature and high humidity environments, and a polarizing plate using the polarizing plate.
- the present invention relates to a liquid crystal display device.
- a polarizing plate used in a liquid crystal display device or the like is composed of at least a polarizer and two protective films arranged so as to face each other with the polarizer interposed therebetween.
- a polarizer constituting this polarizing plate a film in which iodine or a dichroic dye is adsorbed on a film formed by polybutanol by a solution casting method and stretched in a boric acid solution is usually used. It is.
- TAC film triacetyl cellulose film
- the protective film because of its excellent transparency.
- the TAC film has high moisture permeability! Therefore, in high temperature and high humidity environments, the dimensions may change due to moisture absorption and optical distortion may occur, so the reliability is not always sufficient. .
- a protective film a method using a film with low moisture permeability, such as an olefin-based film or a polyester-based film, has been proposed instead of a TAC film.
- a film with low moisture permeability such as an olefin-based film or a polyester-based film
- the protective film with extremely low moisture permeability is applied to the polarizer and the protective film, the moisture contained in the polarizer is insufficiently removed, and the moisture remains in the polarizer. There was a problem that the adhesion between the polarizer and the protective film was lowered by the moisture.
- Patent Document 1 Japanese Patent Laid-Open No. 2004-226799 proposes to use a laminated film composed of a polyester resin layer and a hydrophobic cellulose ester resin layer as a protective film.
- Patent Document 2 Japanese Patent Laid-Open No. 2002-331616 describes maleimide olefins.
- Film and Acrylonitrile 'Styrene Copolymer Strength A film formed by casting a resin composition using a casting method A laminate formed by applying a cellulose-based resin as an adhesive layer to a molded substrate is bonded to a polarizer as a polarizing plate protective film A polarizing plate is disclosed.
- Patent Document 3 Japanese Patent Laid-Open No. 2001-215331 discloses a polarizing plate in which a laminated film obtained by applying cellulose resin to the surface layer of a core layer made of a resin layer is attached to a polarizer. It is disclosed.
- the polarizing plate protective film used for the polarizing plate disclosed in each of the above patent documents is obtained by applying a coating solution in which cellulose esters are dissolved on a film having low moisture permeability. Since it is obtained by drying, a certain amount or more of residual solvent remains in the obtained film. For this reason, when the polarizing plate having these films is used in a high-temperature / high-humidity environment, the film shrinks when the residual solvent volatilizes, or the polarization of the polarizer to which the film is attached is polarized. Problems such as a decrease in the degree may occur. Therefore, the present situation is that a material having high optical performance and excellent strength even under a high temperature and high humidity environment is required.
- the present invention has been made in view of the above-described conventional problems, and the problem is that the mechanical strength is high and the scratch resistance is not deteriorated even at high temperatures and high humidity.
- Polarizing plate with less visibility hindrance such as color unevenness due to change; such polarizing plate can be used on the surface of the surface, surface hardness, scratch resistance, transparency, low thermal expansion, weather resistance, UV transmission prevention effect It is intended to provide a protective film capable of improving characteristics such as fruit and moldability; and a liquid crystal display device using the polarizing plate.
- a protective film used for the polarizing plate a film composed of a plurality of layers containing thermoplastic resin is used.
- the polarizer force of this protective film It was found that the above-mentioned problems can be solved by making the most distant layer of acrylic resin and making the protective layer arranged on the liquid crystal cell side specific. It was.
- the first protective film of the two protective films includes a plurality of layers containing thermoplastic resin.
- thermoplastic resin constituting the layer at the most distant position is an acryloyl resin
- the polarizing plate characterized in that the photoelastic coefficient of the second protective film of the two protective films is ⁇ 20 ⁇ 10 to 20 ⁇ 10 ⁇ 13 cm 2 Zdyn.
- the first protective film of the two protective films includes a plurality of layers containing thermoplastic resin.
- thermoplastic resin constituting the layer at the most distant position is an acryloyl resin
- the polarizing plate, wherein the second protective film of the two protective films is an optical compensation film having biaxiality.
- the first protective film of the two protective films includes a plurality of layers containing thermoplastic resin.
- the polarizer force of the plurality of layers The thermoplasticity constituting the most distant layer
- the rosin is an acryloline rosin
- the second protective film force of the two protective films Ratio of the retardation value Re (550) measured at a wavelength of 550 nm to the letter value Re (450) measured at a wavelength of 450 nm Re (450) / Re
- a polarizing plate characterized by being an optical compensation film having (550) of 1.007 or less.
- the first protective film includes an intermediate layer and surface layers provided on both sides of the intermediate layer,
- At least the intermediate layer of the intermediate layer and the surface layer contains an ultraviolet absorber
- the polarizing plate according to any one of [1] to [3], wherein the UV absorber concentration of the intermediate layer is higher than that of the other layers.
- the water vapor permeability of at least one of the two protective films is 10 gZ24 h′m 2 or more and less than 200 gZday′m 2 , according to any one of [1] to [3] Polarizing plate.
- the surface of the first protective film or the second protective film on the side opposite to the polarizer is substantially flat with a linear recess or a linear protrusion.
- the second protective film is a film having birefringence.
- the second protective film is a film in which the absolute value of the in-plane direction lettering (Re) and the absolute value of the thickness direction lettering (Rth) are both 3 (nm) or less.
- At least one of the incident side polarizing plate and the outgoing side polarizing plate is the polarizing plate according to [1] or [2], and the second protective film faces the liquid crystal cell.
- a liquid crystal display device characterized by being arranged as described above.
- a reflective liquid crystal display device including a reflector, a liquid crystal cell, and an output-side polarizing plate in this order,
- the output side polarizing plate is the polarizing plate according to [15], and the 1Z4 wavelength plate of the polarizing plate is located closer to the liquid crystal cell than the polarizer of the polarizing plate. Crystal display device.
- a transflective liquid crystal display device including an incident side polarizing plate, a transflective liquid crystal cell, and an output side polarizing plate in this order,
- At least one of the incident side polarizing plate and the outgoing side polarizing plate is the polarizing plate according to [15], and the 1Z4 wavelength plate of the polarizing plate is closer to the liquid crystal cell than the polarizer of the polarizing plate.
- a transflective liquid crystal display device characterized by being located in
- a touch panel provided on the surface of the display device
- a first transparent substrate provided on the front surface side, and a second transparent substrate disposed opposite to the first transparent substrate with a space therebetween,
- the first transparent substrate includes the polarizing plate according to [15] on the surface side thereof, and the 1Z4 wavelength plate of the polarizing plate is positioned on the second substrate side with respect to the polarizer of the polarizing plate.
- a special touch panel is provided.
- thermoplastic resin 1 An intermediate layer containing thermoplastic resin 1 and a thermoplastic laminated on one surface of the intermediate layer A surface layer 2 containing the conductive resin 2, and a surface layer 3 containing the thermoplastic resin 3 laminated on the other surface of the intermediate layer,
- Either one or both of the surface layer 2 and the surface layer 3 is composed of an acrylic resin having a glass transition temperature (Tg) of 100 ° C or higher,
- the intermediate layer contains an ultraviolet absorber
- any one or more of the intermediate layer, the surface layer 2 and the surface layer 3 contains elastic particles! /.
- At least the surface layer located on the side opposite to the side facing the object to be protected is composed of acrylic resin having a glass transition temperature (Tg) of 100 ° C or higher.
- the polarizing plate of the present invention can exhibit the following effects:
- the polarizing plate of the present invention can be suitably used for flat panel displays such as touch panels and liquid crystal display devices, particularly display devices having a large screen of 40 inches or more.
- the protective film for a display device of the present invention scratch resistance, appearance, transparency, and low thermal expansion can be greatly improved while maintaining conventional characteristics such as an ultraviolet transmission preventing effect.
- FIG. 1 is a cross-sectional view schematically showing a liquid crystal display device having a polarizing plate of the present invention.
- FIG. 2 is a cross-sectional view schematically showing a touch panel having the polarizing plate of the present invention.
- FIG. 3 is a plan view for explaining the positions of measurement points in the measurement of the light leakage degree of a polarizing plate in an example of the present invention.
- the polarizing plate according to the present invention is a polarizing plate including a polarizer and two protective films arranged so as to face each other with the polarizer interposed therebetween.
- the first protective film of the protective film includes a plurality of layers containing a thermoplastic resin, and the thermoplastic film constituting the layer farthest from the polarizer cover among the plurality of layers.
- the fat is acryl resin, and the second protective film of the two protective films has specific characteristics described later.
- the polarizer constituting the polarizing plate of the present invention the attaryl resin and other thermoplastic resin constituting the first protective film, and additional constituent elements constituting the first protective film.
- the optical functional layer and the second protective film will be described sequentially.
- the polarizer used in the present invention is a known polarizer used in a liquid crystal display device or the like.
- iodine or dichroic dye is adsorbed on a polyvinyl alcohol film and then uniaxially stretched in a boric acid bath, or iodine or dichroic dye is adsorbed and stretched on a polybulualcohol film.
- iodine or dichroic dye is adsorbed and stretched on a polybulualcohol film.
- iodine or dichroic dye is adsorbed and stretched on a polybulualcohol film.
- Other examples include a polarizer having a function of separating polarized light into reflected light and transmitted light, such as a grid polarizer, a multilayer polarizer, and a cholesteric liquid crystal polarizer. Of these, polarizers
- the degree of polarization of the polarizer used in the present invention is not particularly limited, but is preferably 98% or more, and more preferably 99% or more.
- the average thickness of the polarizer is preferably 5 to 80 ⁇ m.
- the first protective film includes a plurality of layers including a thermoplastic resin.
- Each of the plurality of layers is preferably composed mainly of thermoplastic resin.
- heat means that the content of the thermoplastic resin in the layer is usually 50% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more.
- the thermoplastic resin constituting the first protective film includes, in addition to acrylic resin, polycarbonate resin, polyethersulfone resin, polyethylene terephthalate resin, polyimide resin, polymethylmetatalylate, for example.
- resins that can be used include resin, polysulfone resin, polyarylate resin, polyethylene resin, polystyrene resin, polychlorinated cellulose resin, cellulose diacetate, cellulose triacetate, and alicyclic olefin polymers.
- alicyclic olefin polymer As the alicyclic olefin polymer, cyclic olefin random random copolymers described in JP-A No. 05-310845 and US Pat. No. 517 9171, JP-A No. 05-9 7978 A hydrogenated polymer described in US Pat. No. 5,202,388, a thermoplastic dicyclopentagen ring-opening polymer described in JP-A-11-124429 (WO99Z20676), and Examples thereof include hydrogenated products.
- the molecular weight of the thermoplastic resin used is gel 'permeation' chromatography (hereinafter referred to as “GPC”) using cyclohexane (toluene if the resin does not dissolve) as a solvent.
- the weight average molecular weight (Mw) in terms of polyisoprene measured in (5) is usually 5,00-100,000, preferably ⁇ is 8,000-80,000, more preferably ⁇ is 10, 00 0-50 , 000.
- the molecular weight distribution (weight average molecular weight (Mw) Z number average molecular weight (Mn)) of the thermoplastic resin is not particularly limited, but is usually 1.0 to 10.0, preferably 1.0 to 4.0, More preferably, it is in the range of 1.2 to 3.5.
- Thermoplastic resin has a resin component having a molecular weight of 2,000 or less (that is, an oligomer component) of 5% by weight or less, preferably 3% by weight or less, more preferably 2% by weight or less. . If the amount of the oligomer component is large, when manufacturing a laminate, fine irregularities may occur in the intermediate layer and the surface layer, and unevenness in thickness may occur in each layer, resulting in poor surface accuracy. There is.
- a polymerization catalyst or a hydrogenation catalyst In order to reduce the amount of the oligomer component, it is necessary to select a polymerization catalyst or a hydrogenation catalyst; a reaction condition such as a polymerization reaction or a hydrogenation reaction; and a step of pelletizing resin as a molding material. Temperature conditions; The component amount of the oligomer can be measured by a gel “permeation” chromatograph using cyclohexane (toluene when the polymer resin is not dissolved).
- the thermoplastic resin constituting the layer farthest from the polarizer among the plurality of layers constituting the first protective film is an acrylic resin.
- the glass transition temperature (Tg) of acrylic resin is usually 100 ° C or higher, preferably 100 to 170, more preferably 100 to 140 ° C.
- This acrylic resin is a copolymer resin mainly composed of (meth) acrylic acid ester, and it can be either a homopolymer or a copolymer that can only have (meth) acrylic acid ester. Meta) It may be a copolymer of an acrylate ester and a monomer copolymerizable therewith. In addition, one type of acrylic resin may be used alone, or two or more types may be used in combination.
- the layer “consisting of acrylic resin” refers to a layer other than acrylic resin, such as an ultraviolet absorber, other compounding agents, and elastic fine particles, which will be described later, in addition to a layer having only the power of acrylic resin. It also includes a layer that further includes material.
- the content of acrylic resin in the layer composed of acrylic resin is preferably 70% by weight or more, and more preferably 70 to 95% by weight.
- polymethylmethallate resin is more preferable even though polymetatalylate resin is preferred.
- (meth) acrylic acid means acrylic acid and Z or methacrylic acid.
- (meth) acrylic acid ester means acrylic acid ester and Z or methacrylic acid ester.
- the (meth) acrylic acid ester used as the main component of the acrylic resin is preferably a (meth) acrylic acid, a C 1-15 alkanol and a cycloalkanol carbonate-derived structure. . More preferably, the alkanolca having 1 to 8 carbon atoms is also derived. When the number of carbon atoms is too large, the elongation at break of the resulting brittle film becomes too large.
- (meth) acrylic acid esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, and alkyl.
- these (meth) acrylic acid esters may have an arbitrary substituent such as a hydroxyl group or a halogen atom.
- substituents include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-methacrylic acid 2 —Hydroxypropyl, 4-hydroxybutyl methacrylate, 3 chloro-2-hydroxypropyl methacrylate, and the like.
- the content of the (meth) acrylic acid ester is 50 wt% or more, preferably 85 wt% or more, more preferably 90 wt% or more.
- (Meth) acrylic acid esters may be used alone or in combination of two or more.
- the molecular weight of acrylic resin is not particularly limited, but is usually 50,000 to 500,000 in weight average molecular weight. When the molecular weight is within this range, a homogeneous film can be easily produced by the casting method.
- the monomer copolymerizable with (meth) acrylic acid ester is not particularly limited, but ⁇ , ⁇
- (meth) acrylic acid alkanol ester and cycloalkanol ester ⁇ , ⁇ ethylenically unsaturated carboxylic acid ester monomer, alkaryl aromatic monomer, conjugated gene Examples include monomers, non-conjugated diene monomers, vinyl cyanide monomers, unsaturated carboxylic acid amide monomers, carboxylic acid unsaturated alcohol esters, and olefin monomers.
- the a, ⁇ ethylenically unsaturated carboxylic acid monomer may be any of a monocarboxylic acid, a polyvalent carboxylic acid, a partial ester of a polyvalent carboxylic acid, and a polyvalent carboxylic acid anhydride.
- Acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itako Examples include acid, monoethyl maleate, mono n-butyl fumarate, maleic anhydride, and itaconic anhydride.
- ⁇ , ⁇ -ethylenically unsaturated carboxylic acid ester monomers other than (meth) acrylic acid ester alkanol esters and cyclic force diol esters include glycidyl methacrylate, dimethyl fumarate, ethyl fumarate, and maleic acid. Examples include dimethyl, jetyl maleate, and dimethyl itaconate.
- alkaryl aromatic monomer include styrene, a-methylstyrene, methyl ⁇ -methylstyrene, butyltoluene, and dibutenebenzene.
- conjugation monomers include 1,3 butadiene, 2-methyl-1,3 butadiene, 1,3 pentagene, 2,3 dimethyl-1,3 butadiene, 2 chloro 1,3 butadiene, and cyclohexane.
- pentagen etc. can be mentioned.
- non-conjugated diene monomer include 1,4 monohexagen, dicyclopentagen, ethylidene norbornene and the like.
- cyanated butyl monomer examples include acrylonitrile, meta-tallow-tolyl, ⁇ -chloroacrylonitrile, ⁇ - ethylacrylonitrile and the like.
- Specific examples of a, j8-ethylenically unsaturated carboxylic acid amide monomer include acrylic amide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N, N dimethyl acrylamide and the like. Can do.
- Specific examples of the carboxylic acid unsaturated alcohol ester monomer include butyl acetate.
- Specific examples of the olefin monomer include ethylene, propylene, butene, pentene and the like.
- the content of the unit based on the monomer capable of copolymerizing with the (meth) acrylic acid ester is 50% by weight or less, preferably 15% by weight or less. Preferably it is 10 weight% or less.
- the monomer copolymerizable with (meth) acrylic acid ester one type may be used alone, or two or more types may be used in combination.
- the monomer copolymerizable with (meth) acrylic acid ester styrene is preferable among alkenyl aromatic monomers.
- acrylic resin used in the present invention preference is given to the acrylic resin used in the present invention.
- U. Specific examples include methyl methacrylate. Z methyl acrylate Z butyl acrylate Z styrene copolymer, methyl methacrylate Z methyl acrylate copolymer, methyl methacrylate Z styrene Z butyl acrylate copolymer, and the like.
- the acrylic resin used in the present invention preferably has an elongation at break in the range of 10 to 180%, more preferably in the range of 50 to 170%.
- the brittle film has good dregs.
- the elongation at break of the mixture is preferably in the above range.
- the thickness of the surface layer made of the above-mentioned acrylic resin is preferably 10 m or more, more preferably 20 to 60 / ⁇ ⁇ .
- the first protective film can be sufficiently provided with surface pencil hardness and flexibility.
- the first protective film is also composed of a plurality of thermoplastic resin layers.
- the first protective film further includes an intermediate layer and an intermediate layer.
- Each of the intermediate layer and at least one of the surface layers contains an ultraviolet absorber, and the layer containing the ultraviolet absorber,
- the layer having the highest ultraviolet absorber concentration is preferably the intermediate layer.
- the intermediate layer may be a single layer or a multilayer. Further, the ultraviolet absorber may be contained only in the intermediate layer.
- the surface layer may contain an ultraviolet absorber.
- the content in that case is 0.1 to 5% by weight of the total amount of the acrylic resin constituting the surface layer. Is appropriate. More specifically, this content is determined in consideration of the content of the ultraviolet absorber in the intermediate layer so as to ensure the necessary ultraviolet transmission preventing performance as the entire protective film. If the lower limit value is not reached, the ultraviolet absorption effect cannot be obtained, and if the upper limit value is exceeded, the ultraviolet absorber may ooze out of the protective film.
- the ultraviolet absorber used in the present invention is not particularly limited !, but is an oxybenzophenone compound, a benzotriazole compound, a salicylic acid ester compound, a benzophenone ultraviolet absorber, a benzotriazole
- Known materials such as ultraviolet absorbers, acrylonitrile ultraviolet absorbers, triazine compounds, nickel complex compounds and inorganic powders can be used.
- 2,2′-methylenebis (4- (1, 1, 3, 3-tetramethylbutyl) 1-6- (2H benzotriazole 2-yl) phenol) is particularly preferred.
- a method of containing the ultraviolet absorber a method of previously blending an ultraviolet absorber into a thermoplastic resin; a method using a master batch of thermoplastic resin containing a high concentration of an ultraviolet absorber; Examples include a method of supplying the molten resin directly to the molten resin at the time of melt extrusion molding, and a deviation method may be adopted.
- the content of the ultraviolet absorber contained in the thermoplastic resin layer is preferably 0.5 to 5% by weight per 100% by weight of the resin. Further, it is desirable that the variation in the concentration of the UV absorber in the intermediate layer is within ⁇ 0.1% over the entire surface.
- the content of the ultraviolet absorber is 0.5 to 5% by weight, the ultraviolet rays can be effectively blocked without deteriorating the color tone of the polarizing plate, and the degree of polarization during long-term use can be reduced. Decline can be prevented.
- the content of the UV absorber in the intermediate layer is more preferably 1.0 to 5% by weight.
- the content of the ultraviolet absorber in the thermoplastic resin layer is less than 0.5% by weight, the light transmittance at wavelengths of 370 ⁇ m and 380nm increases, and when such a protective film is used, The polarization degree of the child is lowered. On the other hand, if the UV absorber content exceeds 5% by weight, the light transmittance on the short wavelength side becomes small, and the yellow color of the laminate becomes too strong.
- the concentration of the UV absorber in the thermoplastic ⁇ layer constituting the first protective film is ⁇ 0. 1 wt 0/0 within the entire surface. This is because, by suppressing the variation in density within this range, the color tone unevenness of the initial film disappears.In addition, deterioration due to ultraviolet rays after long-term use occurs uniformly, resulting in color tone unevenness when mounted on a liquid crystal display device. Power is also.
- the concentration of UV absorber in the intermediate layer When variability exceeds ⁇ 0. 1 wt 0/0 on the entire surface, unevenness of color tone can be clearly visible, the color tone bad. In addition, after long-term use, the deterioration due to ultraviolet rays becomes non-uniform and the color tone becomes worse.
- the ultraviolet transmittance of the laminate is measured with a spectrophotometer.
- the thickness of the laminate is measured with a contact-type thickness meter.
- the cross section of the measurement part is observed with an optical microscope, the ratio of the thickness of the surface layer to the intermediate layer is determined, and the thickness of the intermediate layer is determined.
- the concentration of the UV absorber is calculated from the following formula (1) from the UV transmittance and thickness.
- C is the concentration (% by weight) of the UV absorber
- T is the light transmittance (%)
- K is the extinction coefficient (one)
- L is the thickness m of the laminate.
- Means for setting the dispersion of the concentration of the ultraviolet absorber in the thermoplastic resin layer to ⁇ 0.1% by weight over the entire surface are as follows: (1) The dried thermoplastic resin and the ultraviolet absorber And are mixed. Next, the mixture is put into a hopper connected to an extruder, supplied to a single screw extruder and melt extruded; (2) A thermoplastic resin is put into a hopper with a dryer. In addition, a UV absorber is added from another input Loka. A method of supplying the thermoplastic resin and the ultraviolet absorbent to a twin-screw extruder while measuring them with a feeder and melt-extruding them.
- the thickness of the intermediate layer excluding the outermost surface layer of the plurality of thermoplastic resin layers is preferably 10 to 40 ⁇ m. If the thickness of the intermediate layer is less than 10 ⁇ m, the interface between the layers may be roughened, and the surface state such as flatness and smoothness may be deteriorated. On the other hand, if the thickness of the intermediate layer exceeds 40 m, it will be biased when used as a polarizing plate protective film. The entire light plate becomes thick, making practical use difficult. As will be described later, the first protective film is usually used after various optical functional layers are laminated on the surface on the viewing side. Further, the total thickness of the protective film formed by laminating various optical functional layers is preferably 200 / zm or less. The reason is that the entire polarizing plate is not unnecessarily thickened as described above.
- the variation in the thickness of the intermediate layer is within ⁇ 1 m over the entire surface.
- This variation in the thickness of the intermediate layer is within ⁇ 1 m across the entire surface, which reduces the variation in color tone.
- the color change after long-term use is uniform, there will be no uneven color after long-term use.
- the thickness of the intermediate layer is determined by measuring the total thickness using a commercially available contact-type thickness meter, cutting the thickness measurement portion and observing the cross section with an optical microscope. The thickness ratio is obtained, and the thickness of the intermediate layer is calculated from the ratio. The above operation is performed at regular intervals in the horizontal and vertical directions of the laminate.
- the variation in the thickness of the intermediate layer is as follows: the arithmetic average value of the measured values measured above is defined as the reference thickness Tave, the maximum value of the measured thickness T is Tmax, and the minimum value is Tmin. Calculated from the formula
- Thickness variation (m) Tave—Tmin and Tmax—Tave, whichever is greater.
- the position force closest to the polarizer is also counted and the second eye (i is The refractive index at a wavelength ⁇ in the range of 380 nm to 780 nm in the thermoplastic resin layer (integer of l to k ⁇ l) is ⁇ ( ⁇ ), and the wavelength adjacent to this layer is in the wavelength ⁇ of 380 nm to 780 nm.
- Refractive index is ⁇
- n ( ⁇ ) is the average value of the main refractive index at the wavelength.
- is i + l i i + l
- any of the plurality of thermoplastic resin layers may contain a compounding agent other than the ultraviolet absorber.
- compounding agents are not particularly limited, but organic fine particles; stabilizers such as antioxidants, heat stabilizers and near infrared absorbers; resin modifiers such as lubricants and plasticizers; dyes and pigments, etc. Coloring agents; antistatic agents and the like. These compounding agents can be used alone or in combination of two or more, and the compounding amount is appropriately selected within a range not impairing the object of the present invention.
- Examples of the lubricant include inorganic particles such as silicon dioxide, titanium dioxide, magnesium oxide, calcium carbonate, magnesium carbonate, barium sulfate, and strontium sulfate, as well as polymethyl acrylate, polymethyl methacrylate, poly Organic particles such as acrylonitrile, polystyrene, cellulose acetate, and cellulose acetate propionate. As particles constituting the lubricant, organic particles are preferred, and particles made of polymethylmethalate are particularly preferred.
- any of the plurality of thermoplastic resin layers can contain elastic particles that also have rubbery elastic force as the lubricant or for other purposes.
- any one or more of these layers preferably contain elastic fine particles.
- acrylic resin as the thermoplastic resin and to include the elastic particles in order to improve impact resistance and flexibility.
- Examples of the material for the rubber-like elastic body include acrylate-based rubber-like polymers, rubber-like polymers containing butadiene as a main component, and ethylene-vinyl acetate copolymers.
- Acrylic ester rubbery polymers include those containing butyl acrylate and 2-ethylhexyl acrylate as the main component. Of these, acrylate polymers based on butyl acrylate and rubbery polymers based on butadiene are preferred.
- the elastic particles may be a layered product of two types of polymers.
- Typical examples thereof include a grafted rubber elastic portion containing alkyl acrylate such as butyl acrylate and styrene, and methyl
- the elastic particles include a core-shell structure in which a hard resin layer having a copolymer power of talylate and Z or methyl metatalylate and alkyl acrylate is formed.
- the number average particle diameter of the elastic particles in a state dispersed in the thermoplastic resin is usually 2. O / zm or less, preferably 0.1 to 1.0 111, more preferably. It is 0.1 to 0.5 m.
- the “number average particle diameter” is preferably the diameter of the secondary particles when the primary particles form larger secondary particles by aggregation.
- the protective film for polarizing plate has a high haze and a low light transmittance. Not suitable for display screens. Moreover, when the number average particle size becomes too small, flexibility tends to decrease.
- the refractive index ⁇ ( ⁇ ) of the elastic particles at a wavelength of 380 to 780 nm is
- the relationship of the formula (3) is satisfied between the refractive index ⁇ ( ⁇ ) at a wavelength of 380 nm to 780 nm of the thermoplastic resin serving as a trick.
- I the average value of the main refractive index at wavelength ⁇ .
- the protective film preferably has a photoelastic coefficient whose absolute value is preferably 30 X 10-13 cm 2 Zdyn or less (that is, 20 X 10-13 cm 2 Zdyn ⁇ 20 X 10 " 13 cm 2 / d yn), more preferably 10 X 10-13 cm 2 / dyn or less, and even more preferably 5 X 10-13 cm 2 Zdyn or less. If it is larger, it is not preferable for protecting the polarizer, because it tends to develop a phase difference due to the contraction stress of the polarizer and may deteriorate the optical properties of the polarizing plate.
- Re (Re d X (n— n), where n and n are the in-plane principal refractive index of the protective film; d is the average thickness of the protective film) is small.
- the in-plane retardation Re is preferably 50 nm or less, more preferably 10 nm or less, and more preferably 5 nm or less at a wavelength of 550 nm.
- the in-plane slow axis of the entire protective film is taken as the transmission axis of the polarizer. Or it must match the absorption axis, and it must match!
- the in-plane retardation Re and the thickness direction retardation Rth of the protective film can be measured using a commercially available automatic birefringence meter.
- a method for obtaining the laminated film (also referred to as a base film) constituting the protective film includes a coextrusion T-die method, a coextrusion inflation method, a coextrusion lamination method, and the like.
- Known methods such as a co-extrusion molding method, a film lamination molding method such as dry lamination, and a coating molding method in which the film constituting the intermediate layer is coated with the resin solution constituting the surface layer. Can be used as appropriate.
- a molding method by coextrusion is preferable from the viewpoint of production efficiency and the fact that volatile components such as a solvent do not remain in the film.
- the coextrusion T-die method is preferable. Further, the coextrusion T-die method includes a feed block method and a multi-hold method. A multi-hold method is more preferable in that variation in the thickness of the intermediate layer can be reduced.
- the melting temperature of the thermoplastic resin in the extruder having the T-die is the glass transition temperature (T g )
- T g The temperature is preferably 80 to 180 ° C higher than the glass transition temperature, more preferably 100 to 150 ° C higher than the glass transition temperature. If the melting temperature in the extruder is excessively low, the fluidity of the thermoplastic resin may be insufficient. Conversely, if the melting temperature is excessively high, the resin may be deteriorated.
- a polymer filter having an opening of 20 ⁇ m or less is provided in the extruder; 2) Rotate the gear pump at 5rpm or higher; (3) Place an enclosure around the die; (4) Set the air gap to 200mm or less; (5) Edge casting when casting the film on the cooling roll. (6) Use a twin screw extruder or a single flight extruder with a double flight type screw as the extruder. Unless even one of the above (1) to (6) is implemented, it is difficult to make the thickness variation of the intermediate layer within ⁇ 1 m.
- the extrusion temperature may be appropriately selected according to the thermoplastic resin used. Inside the extruder The temperature of the oil inlet is Tg ⁇ (Tg + 100) ° C, the extruder outlet is (Tg + 50) ⁇ (Tg + 170) ° C, and the die temperature is (Tg + 50) ° C ⁇ (Tg + 170 ) ° C is preferred. Where Tg is the glass transition temperature of the extruded resin.
- the melt extrusion method is used as a method for obtaining the laminated film (base film)
- the sheet-shaped molten resin extruded from the opening of the die is brought into close contact with the cooling drum.
- the method for bringing the molten resin into close contact with the cooling drum is not particularly limited, and examples thereof include an air knife method, a vacuum box method, and an electrostatic contact method.
- the number of cooling drums is not particularly limited, but is usually two or more. Further, examples of the arrangement method of the cooling drum include, but are not particularly limited to, a linear type, a Z type, and an L type. Also, there is no particular restriction on how the molten resin extruded through the die is forced through the cooling drum.
- the degree of adhesion of the extruded sheet-like thermoplastic resin to the cooling drum varies depending on the temperature of the cooling drum. Increasing the temperature of the cooling drum improves adhesion 1S If the temperature is increased too much, the sheet-shaped thermoplastic resin does not peel off the cooling drum force and may cause a problem that the drum sticks to the drum. Therefore, the cooling drum temperature, and preferably a glass transition temperature of the thermoplastic ⁇ extruding also die force and Tg (° C), (Tg + 30) ° C or less, more preferably 8 - 5) in ⁇ 8 -45 ). By doing so, it is possible to prevent defects such as scratches if slipping.
- the first method for producing a protective film in the present invention it is important to reduce the content of residual solvent.
- (1) residual thermoplastic resin itself (2) Preliminarily dry the thermoplastic resin used before forming the film; and the like.
- the preliminary drying is performed with a hot air dryer or the like, for example, in the form of pellets.
- the drying temperature is preferably 100 ° C or more, and the drying time is preferably 2 hours or more.
- Adhesives include acrylic adhesives, urethane adhesives, polyester adhesives, polybutyl alcohol adhesives, and polyolefin adhesives.
- acrylic adhesives such as ethylene-based adhesives, ethylene- (meth) acrylic acid methyl copolymers, and ethylene- (meth) acrylic acid ethyl copolymers.
- the flexibility of the laminated base film can be improved. Good cutting characteristics when punched to dimensions suitable for the product.
- this adhesive layer when this adhesive layer is commercialized as a protective film, it acts as a stress buffer layer that relieves stress generated when an external force is applied to the product, so that the protective properties as a protective film can be further improved. .
- the average thickness of the adhesive layer is usually 0.01 to 30 ⁇ m, preferably 0.1 to 15 ⁇ m.
- This adhesive layer is a layer having a tensile fracture strength of 40 MPa or less according to JIS K 7113.
- the surface of the base film constituting the first protective film in the present invention that is, the surface of the surface layer composed of attalyl resin (the surface opposite to the polarizer in the case of a polarizing plate) It is preferable that the irregularly formed linear concave portions and linear convex portions are not substantially formed, and the surface thereof is a flat surface.
- substantially not formed means that even if linear recesses or linear protrusions are formed, the depth is less than 50 nm or the width is greater than 500 nm, the linear recess, and the height is less than 50 nm or the width. Is a linear protrusion larger than 500 nm.
- it is a linear concave portion having a depth of less than 30 nm or a width of 700 nm, and a linear convex portion having a height force of less than S30 nm or a width of greater than 700 nm.
- the depth of the linear concave portion, the height of the linear convex portion, and the width thereof can be obtained by the following method.
- Light is applied to the base film, the transmitted light is projected onto the screen, and the lighted or dark stripes of light appearing on the screen. It is a part with a high height.
- the surface of the cut film piece is observed using a three-dimensional surface structure analysis microscope (viewing area 5 mm x 7 mm), converted to a three-dimensional image, and a cross-sectional profile in the MD direction is obtained from this three-dimensional image.
- the cross-sectional profile is obtained at lmm intervals in the field of view.
- An average line is drawn on this cross-sectional profile, and the length from the average line to the bottom of the concave portion is the depth of the concave portion, or the length from the average line to the top of the convex portion is the convex portion height.
- the distance between the intersection of the average line and the profile is the width.
- the maximum value is obtained from the measured values of the concave portion depth and the convex portion height, and the width of the concave portion or convex portion showing the maximum value is obtained.
- the maximum values of the concave depth and the convex height obtained from the above, the width of the concave portion and the width of the convex portion showing the maximum values, the depth of the linear concave portion of the film, the height of the linear convex portion. And their width.
- one surface layer of the base film constituting the first protective film is one surface layer of the base film constituting the first protective film
- the protective film may be completed by providing an optical functional layer on (the layer farthest from the polarizer; the surface opposite to the polarizer).
- optical functional layer examples include a hard coat layer, an antireflection layer, an antifouling layer, a gas barrier layer, a transparent antistatic layer, a primer layer, an electromagnetic wave shielding layer, and an undercoat layer.
- a hard coat layer an antireflection layer, an antifouling layer, a gas barrier layer, a transparent antistatic layer, a primer layer, an electromagnetic wave shielding layer, and an undercoat layer.
- an optical functional layer include a hard coat layer, an antireflection layer, an antifouling layer, a gas barrier layer, a transparent antistatic layer, a primer layer, an electromagnetic wave shielding layer, and an undercoat layer.
- the hard coat layer is preferably formed of a heat or photo-curing material having a hardness of "1H" or higher in a pencil hardness test (test plate is a glass plate) shown in JIS K5600-5-4. .
- test plate is a glass plate
- the first protective film provided with such a hard coat layer has a pencil hardness of 11 or more.
- the pencil strength of the surface can be adjusted to 4H or more.
- the hard coat layer materials include organic hard coat materials such as organic silicone, melamine, epoxy, acrylic, and urethane acrylate; and inorganic hard coat materials such as nickel carbonate ; Among these, from the viewpoint of good adhesive force and excellent productivity, it is preferable to use urethane acrylate and polyfunctional acrylate hard coat materials.
- This hard coat layer has a refractive index n 1S and a refractive index n of a low refractive index layer laminated thereon.
- the hard coat protective film having such a hard coat layer laminated thereon preferably conforms to JIS K7105 and has a haze value of 1.0% or less in a haze meter.
- this hard coat layer if desired, for the purpose of adjusting the refractive index, improving the flexural modulus, stabilizing the volumetric shrinkage, improving heat resistance, antistatic properties, antiglare properties, etc.
- Various fillers may be included.
- various additives such as an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, a leveling agent, and an antifoaming agent can be blended.
- an oxide doped with titanium oxide, zirconium oxide, zinc oxide, tin oxide, cerium oxide, antimony pentoxide, or tin is used.
- examples include indium (ITO), antimony-doped tin oxide (ATO), aluminum-doped acid zinc (AZO), and fluorine-doped acid oxide tin (FTO). From the standpoint of maintaining transparency, antimony pentoxide, ITO, ATO, and FTO are preferred.
- the filler preferably has a refractive index of 1.6 or more.
- the primary particle size of these fillers is usually Inm or more and lOOnm or less, preferably Inm or more and 30 nm or less.
- an antireflection layer is preferably further laminated on the hard coat layer.
- the antireflection layer is a layer for preventing the transfer of external light.
- a hard coat protective film with such an antireflection layer has a reflectance power of 2.0% or less at an incident angle of 5 ° and 430 to 700 nm, and a reflectance at 550 nm of 1.0% or less. It is preferable that The thickness of the antireflection layer is preferably from 0.01 ⁇ m to l ⁇ m, more preferably from 0.02 / ⁇ ⁇ to 0.5 / zm.
- an antireflection layer examples include those obtained by laminating a low refractive index layer having a refractive index smaller than that of the hard coat layer, preferably a refractive index of 1.30 to L45, an inorganic compound layer. And the like, which are obtained by repeatedly laminating a low refractive index layer and a high refractive index layer made of an inorganic compound.
- the material for forming the low refractive index layer is not particularly limited as long as it has a refractive index lower than that of the base material or the hard coat layer.
- a resin material such as an ultraviolet curable acrylic resin is used.
- examples thereof include a hybrid material in which inorganic fine particles such as colloidal silica are dispersed in a resin, a resin, and a sol-gel material using a metal alkoxide such as tetraethoxysilane.
- the material for forming the low refractive index material exemplified above may be a polymerized polymer, or may be a monomer or oligomer serving as a precursor. Each material preferably contains a compound containing a fluorine group in order to impart antifouling properties to the surface.
- sol-gel materials containing fluorine groups include fluoroalkylalkoxysilanes.
- fluoroalkylalkoxysilane for example, general formula (4): CF (CF) nCH CH Si (OR) (wherein R represents an alkyl group having 1 to 5 carbon atoms)
- N represents an integer of 0 to 12).
- the low refractive index layer is preferably a cured product of a thermosetting fluorine-containing compound or an ionizing radiation-curable fluorine compound.
- the dynamic friction coefficient of the cured product is preferably 0.03 to 0.15, and the contact angle with water is preferably 90 to 120 degrees.
- curable fluorine-containing high molecular weight compounds include fluoroalkyl group-containing silane compounds (for example, (heptadecafluor 1,1,2,2-tetradecyl) triethoxysilane) and other fluorine-containing copolymers having a crosslinkable functional group. Coalescence is mentioned.
- This fluorine-containing polymer is obtained by copolymerizing a fluorine-containing monomer and a monomer having a crosslinkable functional group, or by copolymerizing a fluorine-containing monomer and a monomer having a functional group, and then It can be obtained by adding a compound having a crosslinkable functional group to the group.
- fluorine-containing monomer unit examples include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoroolefin, perfluoroethylene, 2, 2-dimethinole 1, 3- dioxol, etc.), (meth) acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (Osaka Organic Chemical) or M-2020 (Daikin)) , Complete Such as fully or partially fluorinated vinyl ethers.
- fluoroolefins for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoroolefin, perfluoroethylene, 2, 2-dimethinole 1, 3- dioxol, etc.
- (meth) acrylate monomer having a crosslinkable functional group such as glycidyl metatalylate, a carboxyl group or hydroxyl group.
- (Meth) acrylate monomer for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, etc. having a group, an amino group, a sulfonic acid group and the like.
- the composition used for the formation of the low refractive index layer includes a sol in which fine particles of silica, alumina, titer, zircoure, magnesium fluoride and the like are dispersed in an alcohol solvent in order to impart scratch resistance. May be added. From the viewpoint of antireflection, the lower the refractive index of the fine particles, the better. It is preferable to use silica-based hollow fine particles, which may be fine particles having voids.
- the average particle size of the hollow fine particles is not particularly limited, but is preferably in the range of 5 to 2, OOOnm, more preferably 20: LOOnm.
- the average particle diameter is a number average particle diameter by observation with a transmission electron microscope.
- the method for forming the low refractive index layer is not particularly limited, but the wet coating method is preferred because it is a simpler method than the vacuum deposition method or the like.
- Examples of the method for forming the low refractive index layer by coating include a dip coating method, an air knife coating method, a powerful ten coating method, a roller coating method, a wire bar coating method, and a gravure coating method.
- the thickness of the low refractive index layer is not particularly limited, but is about 0.05 to 0.3 / z m, particularly 0.1 to 0.
- the low refractive index In the first protective film, in order to enhance the antifouling property of the low refractive index layer, the low refractive index An antifouling layer may be further provided on the rate layer (observation side).
- the antifouling layer is a layer that can impart water repellency, oil repellency, sweat resistance, antifouling properties, etc. to the surface of the protective film.
- a fluorine-containing organic compound As a material used for forming the antifouling layer, a fluorine-containing organic compound is suitable. Examples of the fluorine-containing organic compound include fluorocarbon, perfluorosilane, and a polymer compound thereof.
- a physical vapor deposition method such as vapor deposition or sputtering, a chemical vapor deposition method such as CVD, or a wet coating method can be used depending on the material to be formed.
- the average thickness of the antifouling layer is preferably 1 to 50 nm, more preferably 3 to 35 nm.
- the surface of the substrate film can be subjected to a hydrophilic treatment.
- the hydrophilic treatment means is not particularly limited, and for example, a surface treatment method such as corona discharge treatment, sputtering treatment, low-pressure UV irradiation, plasma treatment, etc. can be suitably employed.
- the first protective film is subjected to mechanical treatment by etching, sand blasting, embossing roll, etc. on the surface for the purpose of strengthening adhesion with the optical functional layer and imparting anti-glare property in addition to the hydrophilic treatment.
- An uneven portion may be formed by applying.
- grooved part is the substantially regular uneven
- a treatment for improving the adhesion such as a thin layer coating treatment of a cellulose-based material or a polyester-based material can be performed.
- the total number of the thermoplastic resin layers constituting the first protective film is preferably 7 or less, more preferably 5 or less. When the number of layers is larger than this, it may be difficult to control the surface shape and thickness of each layer.
- the moisture permeability of the first protective film is preferably 10 gZm 2 '24h or more and 200 gZm 2 ' 24h or less.
- the moisture permeability is less than 10gZm 2 '24h, in the process of bonding the protective film and the polarizer, the moisture contained in the polarizer is insufficiently removed, and the polarizer and protective film in a high temperature / high humidity environment There is a possibility that the adhesiveness of the material will be lowered.
- moisture permeability exceeds 200 gZm 2 '24h, the degree of moisture absorption and exhaustion due to temperature changes increases, the dimensional accuracy of the film decreases, and the optical properties of the polarizing plate deteriorate.
- a suitable range of moisture permeability that can be achieved can be realized by selecting the type and thickness of the resin. [0107] This moisture permeability can be measured by the cup method described in JIS Z 0208 under the test conditions of leaving for 24 hours in an environment of 40 ° C and 92% RH.
- the second protective film constituting the polarizing plate of the present invention will be described.
- the second protective film consists of (i) a force whose photoelastic coefficient is 20 X 10-13 cm 2 / dyn or less, (ii) biaxiality, or (iii) letter data measured at a wavelength of 550 nm.
- the ratio Re (450) / Re (550) of the threshold value Re (550) and the letter value Re (450) measured at a wavelength of 450 nm is 1.007 or less.
- the second protective film may be the same as or different from the first protective film.
- the second protective film has one or more, preferably two or more of the above requirements (i) to (iii). Specifically, for example, a film having the requirements (i) and (ii), a film having the requirements (i) and (iii), a film having the requirements (ii) and (iii), or the requirements ( It can be set as the film which has i)-(iii). Further, it is more preferable that the first protective film also has one or more of the requirements (i) to (iii).
- more preferable range of the photoelastic coefficient is a 10 X 10- 13 cm 2 / d yn less, more preferably, equal to or less than 5 X 10- 13 cm 2 / dyn .
- the photoelastic coefficient is larger than the above numerical value, the protective film is likely to develop a retardation due to the shrinkage stress of the polarizer to which the protective film is attached, which may deteriorate the optical performance of the polarizing plate.
- a layer made of a resin having a positive photoelastic coefficient and a negative light For example, a method of laminating a layer made of a resin having an elastic modulus can be cited, and in order to set a retardation value in the in-plane direction, the slow axis of each layer constituting the first protective film is set to a retardation in the in-plane direction. There is a method of setting so that the values are offset.
- the second protective film may be configured in a configuration different from the multi-layer configuration of the first protective film.
- the constituent material is not particularly limited, and a conventionally known material can be used, but a material excellent in transparency, mechanical strength, thermal stability and the like is preferable.
- Transparency is less than 3 ⁇ 40% light transmittance power in the visible region of 400-700nm at lmm thickness The above is more preferable, more preferably 85% or more, and still more preferably 90% or more.
- Specific materials include polycarbonate resin, polyethersulfone resin, polyethylene terephthalate resin, polyimide resin, polymethylmethacrylate resin, polysulfone resin, polyarylate resin, polyethylene resin.
- thermoplastic resin such as polyvinyl chloride resin, dicetinolecene mouth, triacetyl cellulose (TAC), and alicyclic olefin polymer (COP).
- thermosetting resins such as acrylic, urethane, acrylic urethane, epoxy, and silicone, or ultraviolet curable resins are also included.
- the alicyclic olefin polymer is a cyclic olefin random random copolymer described in JP-A No. 05-310845, or a hydrogenated weight described in JP-A No. 05-97978.
- the thermoplastic resin includes colorants such as pigments and dyes, optical brighteners, dispersants, thermal stabilizers, light stabilizers, ultraviolet absorbers, antistatic agents, antioxidants, lubricants, solvents, and the like. It may be a combination of these ingredients.
- polymethylmetatalate resin alicyclic polyolefin polymer, and cellulose ester are preferred because of their excellent transparency.
- the method of forming the second protective film is not limited.
- the materials exemplified above can be obtained by forming into a film using a known molding method.
- a film having birefringence can be used for the purpose of, for example, widening the viewing angle.
- a film having birefringence has optical compensation functions such as color compensation and viewing angle compensation, and has an effect of improving the visibility of a liquid crystal display device.
- the birefringence is controlled in the width direction and the longitudinal direction.
- a film having a uniaxial property, a film having a biaxial property, or a laminate thereof can be used, and is appropriately selected according to the mode of the liquid crystal cell to be used. Having uniaxiality means that the refractive index in the slow axis direction in the film plane is n, the refractive index in the direction perpendicular to the slow axis in the plane is n, and in the thickness direction.
- the film having a refractive index means that all the refractive indexes in the three directions are different, and includes a film in which n>n> n and n ⁇ xyzxn ⁇ n.
- Biaxial films must meet the requirements (ii) yz
- the film can be used as the second protective film used in the polarizing plate of the present invention.
- the retardation Re in the in-plane direction and the retardation Rth in the thickness direction of the birefringent film are the mode of the liquid crystal cell used and the cell side of the other polarizing plate facing each other across the cell. It is adjusted as appropriate according to the Re and Rth of the protective film.
- the in-plane retardation Re and the thickness direction letter Rth are n and n as the main refractive index in the plane of the film, and n as the refractive index in the thickness direction of the film.
- Re (n ⁇ n) Xd
- the ratio of the retardation value Re (550) measured at a wavelength of 550 nm of the second protective film to the letter value Re (450) measured at a wavelength of 450 nm Re ( 450) If ZRe (550) is 1.007 or less, the requirement (iii) is satisfied. Therefore, even if the requirements (i) and (ii) are not satisfied, the second polarizing plate used in the polarizing plate of the present invention is used. It can be used as a protective film.
- Examples of the film having birefringence include a film obtained by stretching a film containing a thermoplastic resin, a film obtained by forming an optically anisotropic layer on an unstretched thermoplastic resin film, and a thermoplastic film. After an optically anisotropic layer is formed on a film containing fat, a stretched film or the like can be used.
- the stretched film may be in the form of a single layer or in the form of a plurality of layers.
- the thermoplastic resin preferably has excellent transparency, mechanical strength, thermal stability, and the like. Transparency is preferably 85% or more, more preferably 90%, more preferably 80% or more of the light transmittance in the visible region of 400 to 700 nm when the resin is made into a 1 mm thick film. That's it.
- the thermoplastic resin can be selected from the examples of the thermoplastic resin given as the material of the second protective film. Of these, alicyclic olefin polymers and cellulose esters are preferred because of their excellent transparency and low birefringence.
- the cellulose ester those having a substitution degree of the acyl group of 2.5 to 2.9 determined according to ASTM D-817-96 can be preferably used.
- the acyl group include a acetyl group, a propiol group, and a butyryl group.
- a mixture of cellulose esters having different substituents such as cellulose acetate propionate can be preferably used.
- the acetyl group and the propiol group are substituted with the substitution degree of the acetyl group as A and propio- Cellulose esters containing the following formulas (5) and (6) are preferred when the substitution degree of the alkyl group is B:
- a letter raising agent can be added to the thermoplastic resin.
- a letter-decreasing agent is a compound that, when added to a thermoplastic resin, raises the letter-decision compared to when it is not added.
- a retardation increasing agent it is preferable to use it in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of cellulose acetate. It is more preferable to use in the range of 0.5 to 5 parts by mass, and it is more preferable to use in the range of 0.5 to 2 parts by mass.
- Two or more types of letter decision raising agents may be used in combination. It is preferable that the letter decision increasing agent has a maximum absorption in a wavelength region of 250 to 400 nm. It is preferred that the letter descent enhancer has a substantial absorption in the visible region.
- the “aromatic ring” includes an aromatic hetero ring in addition to an aromatic hydrocarbon ring.
- the aromatic hydrocarbon ring is particularly preferably a 6-membered ring (that is, a benzene ring).
- Aromatic heterocycles are generally unsaturated heterocycles.
- the aromatic heterocycle is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring.
- Aromatic heterocycles are generally the most Has multiple double bonds.
- the heteroatom is particularly preferably a nitrogen atom, preferably a nitrogen atom, an oxygen atom or a sulfur atom.
- aromatic heterocycles include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, triazole ring, pyran ring, pyran ring.
- Aromatic rings include benzene ring, furan ring, thiophene ring, pyrrole ring, oxazole ring, thiazole ring, imidazole ring, triazole ring, pyridine ring, pyrimidine ring, pyrazine ring and 1, 3, 5-triazine ring. Is preferred.
- the number of aromatic rings possessed by the above-mentioned letter-decreasing agent is preferably 2-20, more preferably 2-12, and even more preferably 2-8. 2 to 6 is most preferable.
- the bond relationship between two aromatic rings can be categorized as (a) forming a condensed ring, (b) connecting directly with a single bond, and (c) connecting via a linking group (for aromatic rings). Spiro bonds cannot be formed.)
- the connection relationship may be a deviation of (a) to (c).
- a uniaxial stretching method such as a uniaxial stretching method using a tenter or the like
- the biaxial stretching method in which the guide rail is stretched in the lateral direction according to the spread angle of the guide rail, or the longitudinal direction using the difference in peripheral speed between the rolls, and then holding the clips at both ends and using the tenter Biaxial stretching method such as sequential biaxial stretching method that stretches in the direction
- Tenter stretching machine that can add feed force, pulling force or take-up force at different speeds in the lateral or longitudinal direction, or lateral or longitudinal direction
- Tenter stretching machine with the same moving distance and fixed stretching angle ⁇ , or different moving distance, by adding a right or left feed force, pulling force or pulling force The method of extending diagonally with the use of:
- the stretching temperature is usually Tg to Tg + 20 °, where Tg is the glass transition temperature of the resin having the lowest glass transition temperature among the materials forming the second protective film, particularly the resin. Can be done in the range of C.
- the draw ratio is usually adjusted within a range of 1.1 to 3.0 times in order to obtain desired optical characteristics.
- optically anisotropic layer can be formed by using a polymer compound or a liquid crystalline compound. Can be used. These may be used alone or in combination.
- polyamide polyimide
- polyester polyetherketone
- polyetherketone polyetherketone
- Specific examples include compounds described in JP-T-8-511812 (International Publication No. W094Z24 191), 2000-511296 (International Publication No. WO97 / 44704), and the like.
- the liquid crystalline compound may be a rod-like liquid crystal or a discotic liquid crystal. These are high-molecular liquid crystals, low-molecular liquid crystals, or low-molecular liquid crystals that are cross-linked to exhibit liquid crystallinity. This includes lost items.
- Preferable examples of the rod-like liquid crystal include those described in JP-A 2000-304932.
- Preferred examples of the discotic liquid crystal include those described in JP-A-8-50206.
- the optically anisotropic layer is generally an alignment formed on a thermoplastic resin film by dissolving a discotic compound and another compound (eg, plasticizer, surfactant, polymer, etc.) in a solvent. It can be obtained by coating on a film, drying, then heating to the discotic nematic phase formation temperature, and then cooling while maintaining the orientation state (discotic nematic phase).
- a discotic compound e.g, plasticizer, surfactant, polymer, etc.
- the optically anisotropic layer is formed by applying a solution obtained by dissolving a discotic compound and another compound (for example, a polymerizable monomer, a photopolymerization initiator) in a solvent onto the alignment film, drying, and then discotic It can be obtained by heating to the nematic phase formation temperature, polymerizing by irradiation with UV light, etc., and further cooling.
- the alignment state can be appropriately adjusted according to the mode of the liquid crystal to be used. For example, when the liquid crystal cell is in the horizontal alignment mode (IPS), the liquid crystal cell in which it is preferable that the liquid crystal cell is substantially vertically aligned on the substrate is in the bend alignment mode (OCB) or the twist alignment mode (TN). In this case, it is preferable that the optical axis is in a hybrid orientation in the film thickness direction.
- the thickness of the optically anisotropic layer is preferably 0.1 to 10 ⁇ m, more preferably 0.5 to 5 ⁇ m, and 0.7 to 5 m. Most preferably it is. However, depending on the mode of the liquid crystal cell, it may be thick (3 to 10 / zm) in order to obtain high optical anisotropy.
- the method for producing the second protective film including the optically anisotropic layer is not particularly limited. For example, the polymer compound and Z or a liquid crystalline compound are applied to a film containing a thermoplastic resin. To produce a coated film, which is further stretched or shrunk to produce a coated film. Can build.
- a film having the above-mentioned birefringence can be separately laminated on a protective film on the cell side.
- the cell-side protective film is optically isotropic.
- both of the retardations Re and Rth preferably have an absolute value of 3 nm or less.
- One aspect of the liquid crystal display device of the present invention is a liquid crystal display device having a light source, an incident side polarizing plate, a liquid crystal cell, and an output side polarizing plate in this order.
- the output side polarizing plate is the polarizing plate.
- the polarizing plate is used as an output side polarizing plate. With such a configuration, a liquid crystal display device with excellent display quality can be provided.
- a preferred liquid crystal display device of the present invention is one in which the polarizing plate is provided on the observation side of the liquid crystal panel.
- a liquid crystal display device is usually provided with two polarizing plates sandwiching a liquid crystal panel.
- the viewing side of the liquid crystal panel is the side on which the viewer can view the displayed image. Since the polarizing plate of the present invention, particularly the polarizing plate in which the protective film for polarizing plate is laminated on the observation side, has excellent visibility, it is preferably disposed on the observation side of the liquid crystal panel.
- the liquid crystal display device of the present invention comprises at least one polarizing plate of the present invention and at least a liquid crystal panel.
- the liquid crystal panel is not particularly limited as long as it is used in a liquid crystal display device.
- TN Transmission Nematic
- STN Super Twisted Nematic
- HAN Hybrid Alignment Nematic
- IPS In Plane Switching
- VA Vertical Alimentation
- LCD Examples include liquid crystal panel, MVA (Multiple Vertical Alignment type liquid crystal panel, OCB (Optical Compensated Bend) type liquid crystal panel.
- FIG. 1 A preferred specific example of the liquid crystal display device of the present invention is shown in FIG.
- the apparatus shown in FIG. 1 is a liquid crystal display device having a light source 10, an incident side polarizing plate 11, a liquid crystal cell 12, and an outgoing side polarizing plate 13 in this order.
- both the incident side polarizing plate 11 and the outgoing side polarizing plate 13 are obtained from the polarizer 2, the first protective film 3, and the second protective film (also referred to as an optical compensation film in this specification) 4. It has a configured polarizing plate.
- the exit side polarizing plate 13 further has an optical functional layer 5 on the exit surface side of the polarizing plate.
- a reflective liquid crystal display device comprising a reflector, a liquid crystal cell, and an output side polarizing plate in this order, the output side polarizing plate of the present invention.
- the thing which is a polarizing plate is mentioned.
- the second protective film in the polarizing plate of the present invention satisfies the requirement (iii) and the optical compensation film is a 1Z4 wavelength plate, it functions as a circularly polarizing plate.
- the 1Z4 wavelength plate of this circularly polarizing plate is preferably positioned closer to the liquid crystal cell than the polarizer of this polarizing plate.
- a transflective liquid crystal display device including an incident side polarizing plate, a transflective liquid crystal cell, and an output side polarizing plate in this order.
- the polarizing plate of the present invention is at least one of the incident side polarizing plate and the outgoing side polarizing plate.
- the second protective film in the polarizing plate of the present invention satisfies the requirement (iii) and the optical compensation film is a 1Z4 wavelength plate functions as a circularly polarizing plate.
- the 1Z4 wavelength plate of this circularly polarizing plate is preferably positioned closer to the liquid crystal cell than the polarizer of this polarizing plate.
- the touch panel of the present invention is a touch panel provided on the surface of the display device, and a first transparent substrate provided on the front surface side and a second transparent substrate disposed opposite to the first transparent substrate. A transparent substrate. And the said 1st transparent substrate is equipped with the polarizing plate of the said this invention in the said surface side.
- the polarizing plate when the second protective film satisfies the requirement (iii) and the optical compensation film is a 1Z4 wavelength plate, it functions as a circularly polarizing plate.
- the 1Z4 wavelength plate of this circularly polarizing plate is located closer to the second substrate than the polarizer of this polarizing plate.
- the touch panel 28 shown in FIG. 2 includes an upper electrode 23 as a first transparent substrate and a lower electrode 26 as a second transparent substrate.
- the upper electrode 23 and the lower electrode 26 are opposed to each other with a space therebetween through a dot spacer 27.
- the upper electrode 23 has a polarizing plate and a hard coat composed of a polarizer 2, a first protective film 3, and a second protective film (optical compensation film) 4 on the surface side (the upper side in FIG. 2). It has a layer 21 and a transparent conductive film 22.
- the lower electrode 26 includes a glass plate 24 and a transparent conductive film 25.
- the surface side force when the user touches the touch panel 28, the upper electrode 23 is squeezed and the transparent conductive films 22 and 25 are in contact with each other. It can be detected that the user touches the touch panel.
- the touch panel shown in FIG. 2 can be obtained, for example, as follows.
- a hard coat layer 21 is formed on the surface having the optical compensation film (optical isomer) 4 of the polarizing plate of the present invention, and then a transparent conductive film 22 is formed to obtain an upper electrode 23.
- a transparent conductive film 25 is formed on one surface of the glass plate 24 to obtain a lower electrode 26.
- a dot spacer 27 is formed on the surface of the glass plate 24 having the transparent conductive film 25 and bonded so that the transparent conductive films 22 and 25 of the upper electrode 23 and the lower electrode 26 face each other to obtain a touch panel 28.
- the protective film of the present invention is a protective film that can be particularly preferably used as the first protective film in the polarizing plate of the present invention.
- the protective film of the present invention includes an intermediate layer containing the thermoplastic resin 1, a surface layer 2 including the thermoplastic resin 2 laminated on one surface of the intermediate layer, and the other layer of the intermediate layer. And surface layer 3 including thermoplastic resin 3 laminated on the surface.
- One or both of the surface layer 2 and the surface layer 3 are made of an acrylic resin having a glass transition temperature (Tg) of 100 ° C. or higher.
- At least the surface layer located on the opposite side to the side facing the protection target (the polarizer in the polarizing plate of the present invention) has a glass transition temperature (Tg). Consists of acrylic resin at 100 ° C or higher.
- the intermediate layer includes an ultraviolet absorber, and any one or more of the intermediate layer, the surface layer 2, and the surface layer 3 include elastic particles. .
- the surface layer 2 and the surface layer 3 includes elastic particles.
- thermoplastic resin 1-3 constituting the protective film of the present invention specifically, those listed as materials for the intermediate layer and the surface layer constituting the first protective film can be used. .
- the polarizing plate includes a polarizer (P), an exit-side protective film (first protective film (A)) attached to the exit side of the polarizer (P), and a polarizer ( Hard coat that is laminated on the viewing-side surface of the incident-side protective film (second protective film (B)) and output-side protective film (first protective film (A)) that is attached to the incident side of P) Layer (H), low refractive index (antireflection) layer laminated on the outer surface of the hard coat layer (H) (constructed from one person.
- Example 1-1 As will be described in detail later, in Example 1-1, as the first protective film, a polymethyl methacrylate (PMMA) resin layer and a low-hardness polymethyl metatalate (R-PMMA) resin layer A laminated film (A1) having a three-layer force of a tarrylate (PMMA) resin layer was used. Further, a second protective film (B1) described later was used as the second protective film.
- PMMA polymethyl methacrylate
- R-PMMA low-hardness polymethyl metatalate
- Example 1-2 the laminated film (A1) was used as the first protective film, and the second protective film (B2) described later was used as the second protective film.
- Example 1-3 the laminated film (A1) was used as the first protective film, and the laminated film (A1) was also used as the second protective film.
- Example 1-4 the laminated film (A1) was used as the first protective film, and the second protective film (B3) described later was used as the second protective film.
- Example 1-5 polymethyl methacrylate (PMM A) resin layer one cellulose acetate petrate (CAB) resin layer one polymethyl methacrylate (PMMA) )
- a laminated film (A3) consisting of three layers of the resin layer was used, and a laminated film (A1) was used as the second protective film.
- Example 1-6 polymethylmetatalylate (PMM A) resin layer monoaliphatic olefin polymer (COP) layer one polymethyl metatalylate ( A laminated film (A2) composed of three layers of PMMA) resin layer was used, and a laminated film (A1) was used as the second protective film.
- PMM A polymethylmetatalylate
- COP resin layer monoaliphatic olefin polymer
- a laminated film (A2) composed of three layers of PMMA) resin layer was used, and a laminated film (A1) was used as the second protective film.
- Example 1-7 as the first protective film, polymethyl metatalylate (R-P MMA2) resin layer polymethyl metatalylate (PMMA2) layer polymethyl metatalylate (R- PMMA2) Second protective film using laminated film (A6) consisting of three layers of resin layer The laminated film (Al) described later was used.
- Comparative Example 1-1 the laminated film (A1) was used as the first protective film, and the second protective film (B4) described later was used as the second protective film.
- a single-layer PMMA resin film (A4) was used as the first protective film, and a second protective film (B1) described later was used as the second protective film.
- a single-layer TAC resin film (A5) was used as the first protective film, and a second protective film (B1) described later was used as the second protective film.
- the polarizer (P), the hard coat layer (H) forming material, the low refractive index layer (L) explain production examples of the forming material, CAB, first protective film, and second protective film.
- a polybulal alcohol film with a refractive index of 1.545 at a wavelength of 380 nm and a refractive index of 1.521 at a wavelength of 780 nm and a thickness of 75 m is uniaxially stretched 2.5 times, and 0.2 g of iodine and potassium iodide are stretched uniaxially.
- the sample was immersed in an aqueous solution containing 60 gZL at 30 ° C. for 240 seconds, and then immersed in an aqueous solution containing 70 gZL of hydrofluoric acid and 30 gZL of potassium iodide, and simultaneously uniaxially stretched 6.0 times and held for 5 minutes. Finally, it was dried at room temperature for 24 hours to obtain a polarizer (P) having an average thickness of 30 m and a polarization degree of 99. 95%.
- P polarizer
- a hard coat layer (H) forming material was prepared by mixing at a ratio of 50% by weight of the total solid content of the composition.
- hollow silica isopropanol dispersion sol (manufactured by Catalytic Chemical Industry Co., Ltd., solid content: 20% by weight, average primary particle size: about 35 nm, outer shell thickness: about 8 nm) is added to this dissolved matter with respect to the fluorine-containing monomer solid content 30% by weight of hollow silica solids, 3% by weight of dipentaerythritol hexaatalylate (manufactured by Shin-Etsu Chemical Co., Ltd.) based on the above solids, photoradical generator Irgacure 184 (Ciba Specialty Chemicals) 5% by weight was added to the solid content to prepare a material for forming a low refractive index layer (L).
- Irgacure 184 Ciba Specialty Chemicals
- Cellulose acetate butyrate as acetylyl acyl cellulose, a polymer compound having a hydrophilic group (substitution degree of acetyl group: 1.0, substitution degree of butyryl group: 1.7, weight average molecular weight: 15 . 50,000; manufactured by Eastman Chemical Company CAB - 381 - 20) and 91 weight 0/0, diglycerol tetra caprylate 9 wt% plasticizers kneaded at 190 ° C using a twin-ethanone strike ruder, Cutting to about 5 mm yielded cellulose acetate butyrate.
- Polymethylmethacrylate resin (glass transition temperature 110 ° C, tensile elastic modulus 3.3 GPa, in the table and hereinafter referred to as PMMA) without elastic particles, a leaf disk-shaped polymer filter with 10 m aperture was introduced into the double-flight type single-screw extruder, and the molten resin was supplied to one of the multi-hold dies having a die slip surface roughness Ra of 0.1 ⁇ m at an extruder outlet temperature of 260 ° C.
- polymethylmetatalylate resin containing elastic particles with a number average particle size of 0.4 ⁇ m glass transition temperature 100 ° C, tensile modulus 2.8 GPa, in table and below
- an ultraviolet absorber (LA31; manufactured by Asahi Denka Kogyo Co., Ltd., trade name) were mixed so that the concentration of the ultraviolet absorber was 5% by weight to obtain a mixture 1.
- the above mixture 1 is charged into a double flight type single screw extruder equipped with a 10 m mesh disk with a leaf disk shape, and the molten resin is melted at an extruder outlet temperature of 260 ° C and the surface roughness Ra of the die slip is 0. Supplied to the other end of a multi-hold die that is 1 ⁇ m.
- a polymethylmethacrylate resin elastic particles that do not contain molten elastic particles
- Each of the polymethylmetatalate resin containing the children was discharged from the multi-hold die at 260 ° C, cast on a cooling roll adjusted to 130 ° C, and then adjusted to 50 ° C. Pass through a chill roll and consist of three layers: PMMA resin layer (20 ⁇ m) —R—PMMA resin layer (40 ⁇ m) —PMMA resin layer (20 ⁇ m), width 600 mm, thickness 80 A ⁇ m protective film (A1) was obtained by coextrusion.
- the PMMA resin layer had a refractive index of 1.512 at a wavelength of 380 nm and a refractive index of 1.488 at a wavelength of 780 nm.
- the R-PMMA resin layer had a refractive index of 1.507 at a wavelength of 380 nm and a refractive power of 489 at a wavelength of 780 nm.
- the water vapor permeability of the obtained protective film (A1) was 51.0 gZm 2 '24h. Further, the depth of the linear concave portion or the height of the convex portion on the surface of the protective film (A1) was 20 nm or less and the width was in the range of 800 nm or more. Further, Re of the obtained protective film (A1) was 0.4 nm and Rth—2.6 nm.
- the above mixture 2 was introduced into a second double-flight type single-screw extruder equipped with a leaf disk-shaped polymer filter with an opening of 10 ⁇ m, and molten resin was melted at an extruder outlet temperature of 260 ° C. Then, the multi-hold die was supplied to one of the second hold dies that had a die slip surface roughness Ra of 0.1 ⁇ m.
- each of polymethylmethacrylate resin, cellulose acetate butyrate, and ethylene / vinyl acetate copolymer as an adhesive containing no elastic particles in a molten state was discharged from a multi-hold die at 260 ° C. Cooling low temperature adjusted to 130 ° C PMMA resin layer (20 ⁇ m) —adhesive layer (4 ⁇ m) —CAB resin layer (32 ⁇ m) —adhesion Layer (4 ⁇ m) — PMM
- the PMMA resin layer had a refractive index of 1.512 at a wavelength of 380 nm and a refractive index of 1.488 at a wavelength of 780 nm.
- the refractive index at 780 nm was
- the obtained first protective film (A2) had a moisture permeability of 84. Og / m 2 '24h. Further, the depth of the linear concave portion or the height of the convex portion on the surface of the protective layer 2 was 20 nm or less and the width was in the range of 800 nm or more.
- One protective film (A3) was obtained by coextrusion molding.
- the PMMA resin layer had a refractive index of 1.512 at a wavelength of 380 nm and a refractive index of 1.488 at a wavelength of 780 nm.
- the COP resin layer has a refractive index of 1.55 at a wavelength of 380 nm.
- the obtained first protective film (A3) had a moisture permeability of 1. Og / m 2 '24h.
- the depth of the linear concave portion or the height of the convex portion on the surface of the first protective film (A3) is 2
- this raw film 1 is oven temperature (preheating temperature, stretching temperature, heat setting temperature) 136 ° C, film feed speed lmZ min, chuck movement accuracy within ⁇ 1%
- the film was subjected to simultaneous biaxial stretching at a longitudinal stretching ratio of 1.41 times and a lateral stretching ratio of 1.41 times to obtain a second protective film (B1).
- corona discharge treatment was performed on both sides of the second protective film (B1) using a high-frequency transmitter (manufactured by Kasuga Electric Co., Ltd., high-frequency power supply AGI-024, output 0.8 KW), and the surface tension was 0.
- a second protective film (B1) of 055 NZm was obtained.
- the obtained second protective film (B1) had an in-plane letter-deformation Re of 50 nm and a thickness-direction letter-deposition Rth of 130 nm at the center of the film width direction measured at a wavelength of 550 nm.
- the variation of Letter D Re is ⁇ 5 nm in the width direction and ⁇ 2 nm in the longitudinal direction.
- Polymethylmetatalate resin containing elastic particles with a number average particle size of 0.4 ⁇ m A second protective film (B3) having a thickness of 80 ⁇ m was obtained by extruding and molding a single layer with a modulus of 2.8 GPa).
- Polycarbonate resin (tensile elastic modulus 2. GPa) was subjected to single-layer extrusion molding to obtain a second protective film (B4) having a thickness of 80 / zm.
- the obtained latex was put into a 0.5% aluminum chloride aqueous solution to agglomerate the polymer, washed 5 times with warm water, and then dried to obtain multilayer acrylic rubber particles.
- ⁇ 12-2 Preparation of polymethylmethacrylate resin containing elastic particles> Polymethylmetatalylate resin “Delpet 80NH” (product name, manufactured by Asahi Kasei Chemicals Co., Ltd., methylmetatalylate Z-methyl acrylate copolymer) 80 parts by weight and the above-mentioned ⁇ 12-1> multilayer acrylic system After mixing 20 parts by weight of rubber particles, the mixture was melt kneaded at 260 ° C. using a twin screw extruder to obtain a methacrylic resin containing elastic particles (hereinafter “R-PMMA2”).
- R-PMMA2 methacrylic resin containing elastic particles
- the obtained R-PMMA2 had a glass transition temperature of 102 ° C and a tensile modulus of 2.5 GPa.
- Polymethylmetatalylate resin "Delpet 980N” product name, manufactured by Asahi Kasei Chemicals Co., Ltd., methylmetatalate Z styrene Z maleic anhydride copolymer, glass transition temperature 120 ° C, tensile modulus 3. 5GPa
- UV absorber product name "LA31", manufactured by Asahi Denka Kogyo Co., Ltd.
- PM MA2 concentration of the UV absorber
- R-PMMA2 obtained above was introduced into a double-flight single screw extruder equipped with a leaf-disk-shaped polymer filter with a mesh size of 10 ⁇ m, and melted at an extruder outlet temperature of 260 ° C.
- the resin was fed to the other of the multi-hold dies where the surface roughness Ra of the die slip was 0.1 ⁇ m.
- molten R-PMMA2 and PMMA2 were each discharged from a multi-holder hold at 260 ° C, cast onto a cooling roll adjusted to 130 ° C, and then adjusted to 50 ° C. And passed through a cooling roll, R—PMMA2 layer (10 ⁇ m) / PMMA2 layer (60 / ⁇ ⁇ ) ⁇ : ⁇ —PMMA2 layer (10 / zm) 3 layers, 600mm width, 80m thickness
- the first protective film (A6) was obtained by coextrusion molding.
- the PMMA2 resin layer had a refractive index of 1.540 at a wavelength of 380 nm and a refractive index of 1.510 at a wavelength of 780 nm. Further, the refractive index power of the R-PMMA2 resin layer was 516 at a wavelength of 380 nm, and S1. 488 at a wavelength of 780 nm.
- the obtained first protective film (A6) had a moisture permeability of 51 g / m 2 '24h.
- the depth of the linear recess or the height of the protrusion on the surface of the first protective film (A6) is 20 nm or less.
- the width was in the range of 800 nm or more.
- Re of the first protective film (A6) is 3 nm, Rth is - 6 nm, the photoelastic coefficient - 3. was 5 X 10- 13 cm 2 / dyn .
- a predetermined amount of the following materials were mixed, and the mixture was placed in a sealed container.
- the mixture was gradually heated while being slowly stirred, and was heated to 45 ° C over 60 minutes to be dissolved.
- the inside of the container was adjusted to 1.2 atm.
- This solution was filtered using Azumi filter paper No. 244 manufactured by Azumi Filter Paper Co., Ltd., and then left as it was to obtain a dope.
- Tinuvin 109 (Ciba 'Specialty Chemicals) 3 parts by mass
- the dope prepared as described above was cast from a die onto a stainless steel belt (both of casting supports!) At a dope temperature of 30 ° C. to form a web. Dry the web for 1 minute on a temperature-controlled stainless steel belt by contacting hot water of 25 ° C from the back of the stainless steel belt. After that, the back surface of the stainless steel belt was further contacted with cold water at 15 ° C. and held for 15 seconds, and then the web was peeled from the stainless steel belt. The amount of residual solvent in the web at the time of peeling was 100% by mass. Next, using a tenter, both ends of the peeled web were gripped by clips, and the film was stretched at a draw ratio of 1.15 by changing the clip interval in the width direction.
- This biaxial optical compensation film (B5) had an in-plane letter Re measured at a wavelength of 550 nm and an in-plane letter Re of 50 nm and a thickness direction letter Rth of 145 nm.
- Glutaraldehyde 0.5 parts by mass
- Liquid crystalline discotic compound 1. 8 parts by weight, ethylene glycol modified trimethylol propane acrylate, 0.2 part by weight, cellulose acetate butyrate 0.04 part by weight, light Polymerization initiator (IRGACURE-907, manufactured by Ciba Specialty Chemicals Co., Ltd., trade name) 0.06 parts by weight and sensitizer (Kacure 1 DETX, manufactured by Nippon Kayaku Co., Ltd., trade name) 0.02 parts by weight was dissolved in 3.43 parts by weight of methyl ethyl ketone to obtain a coating solution. This coating solution was applied to the alignment film using a # 3 wire bar, and the coating film was immersed in a thermostatic bath at 120 ° C.
- the coating film was irradiated with ultraviolet rays for 1 minute with a high-temperature mercury lamp (120 W Zcm) at 120 ° C.
- a biaxial optical compensation film (B7) having a layer containing a discotic quiz compound having a thickness of 1 m was obtained.
- the average tilt angle of the optical axis angle of this biaxial optical compensation film (B7) was 21 °, and the retardation in the thickness direction of the liquid crystal layer was 117 nm.
- Norbornene polymer layer used in Production Example 17 (saddle layer), styrene-maleic acid copolymer (manufactured by Nova Chemical Co., Ltd., trade name “Daylark D332”, glass transition temperature 130 ° C., oligomer component content consisting alcohol copolymer (manufactured by Mitsubishi Chemical Corporation, trade name "Modic AP A543", Vicat ⁇ I ⁇ 80 ° C) - 3 weight 0/0) consists of a layer (I layer), and the modified ethylene acetate-bi Adhesive layer (skin layer) force Layer II (30 ⁇ m) —Skin layer (6 ⁇ m) —Layer I (150 ⁇ m) —Layer III (6 m) —Skin layer (30 ⁇ m) A raw film 3 was obtained by coextrusion molding.
- the raw film 2 obtained in Production Example 16 is heated to the oven temperature (preheating temperature).
- (Stretching temperature, heat setting temperature) 140 ° C., stretching speed 6 mZ min, longitudinal stretching ratios 1.5 and 1.3 were stretched to obtain optical compensation films C1 and C2, respectively.
- Retardation values 1 ⁇ (550) at wavelengths 55011111 of the obtained optical compensation films 1 and 2 were 265 and 132.5 nm, respectively.
- the optical compensation film C2 is attached to one side of the optical compensation film C1 via an acrylic adhesive (manufactured by Sumitomo 3EM, DP-8005 clear).
- a laminated optical compensation film (B8) was obtained so as to be at an angle.
- the ratio of Re (550) of this optical compensation film (B8) to the letter value Re (450) at a wavelength of 450 nm was Re (45 0) / Re (550) «1.005.
- Optical compensation film C1 on one side another optical compensation film (Nippon Petroleum's product name NH film) is passed through an acrylic adhesive (Sumitomo 3EM, DP-8005 clear), and each slow axis intersects A laminated optical compensation film (B9) was obtained so that the angle was 59 °. ItRe (450) / Re (550) of Re (550) of this optical compensation film (B9) and a letter value Re (450) at a wavelength of 450 nm was 0.86.
- the original fabric film 3 was subjected to oblique stretching at a stretching temperature of 138 ° C, a stretching ratio of 1.5 times, a stretching speed of 115% Zmin, and tilted in the 13 ° direction with respect to the width direction. This was wound up in a roll over 3000 m to obtain an optical compensation film C5.
- the retardation Re (550) at a wavelength of 550 nm of the obtained optical compensation film C5 was measured, it was 137.2 nm.
- the optical compensation film C1 obtained in Production Example 18 was passed through an acrylic adhesive (DP-8005 clear, manufactured by Sumitomo 3EM Co., Ltd.).
- a laminated optical compensation film (B11) was obtained so that the angle was 59 °.
- the retardation values 1 ⁇ (550) of the obtained optical compensation films 7 and 8 at the wavelength 55011111 were 265 ⁇ m and 132.5 nm, respectively.
- the optical compensation film C8 is applied to one side of the optical compensation film C7 via an acrylic adhesive (DP-8005 clear, manufactured by Sumitomo 3EM). The crossing angle of each slow axis is 59.
- a laminated optical compensation film (B12) was obtained so as to be at an angle.
- a corona discharge treatment was performed on both sides of the first protective film (A1) using a high frequency transmitter (output 0.8 KW), and the surface tension was adjusted to 0.055 NZm.
- the hard coat layer (H) forming material was applied to one side of the first protective film (A1) using a die coater in an environment of a temperature of 25 ° C. and a humidity of 60% RH.
- the film was obtained by drying for 5 minutes in a drying oven at ° C.
- this coating was irradiated with ultraviolet rays (accumulated dose of 300 miZcm 2 ) to form a 6 ⁇ m thick hard coat layer (H), and a first protective film with a hard coat layer (A1-H) was obtained. It was.
- the refractive index of the hard coat layer (H) was 1.62, which exceeded the pencil hardness force on the hard coat layer (H) side.
- the low refractive index layer (L) is applied to the hard coat layer (H) side of the film (A1—H) using a wire bar coater in an environment of a temperature of 25 ° C. and a humidity of 60% RH.
- a low refractive index (antireflective) layer (L) (refractive index 1.37) with a thickness of lOOnm and a first protective film (A1-H-L) with a hard coat layer and a low refractive index layer. Obtained.
- a polyvinyl alcohol adhesive is applied to both sides of the polarizer (P), and one side of the second protective film (B1) is applied to one side of the polarizer (P) of the second protective film (B1). Bonding was performed so that the slow axis and the absorption axis of the polarizer were perpendicular. Then, the other side of the polarizer (P) is overlapped with the surface of the film (A1-H-L) where the antireflection layer (L) is not formed, and bonded by a roll-to-roll method. An observer side polarizing plate FP1 was obtained. [0212] (Production of backlight-side polarizing plate)
- a polyvinyl alcohol-based adhesive is applied to both sides of the other polarizer (P), and one side of the second protective film (B1) is applied to one side of the polarizer (P) of the second protective film (B1). Bonding was performed so that the slow axis and the absorption axis of the polarizer (P) were perpendicular. Then, the other surface of the polarizer (P) was overlapped with the one surface of the first protective film (A1), and was bonded by a roll-to-roll method to obtain a backlight side polarizing plate BP1.
- the viewer-side polarizing plate FP1 is bonded so that the protective film (A1) is on the output side, and the backlight-side polarized light is applied so that the first protective film (A1) is on the incident side on the other surface of the liquid crystal cell.
- the liquid crystal display device 1 was produced by laminating the plate BP1.
- Example 11 Except that the second protective film ( ⁇ 2) was used in place of the second protective film (B1), the observer side polarizing plate FP2 and the backlight side polarizing plate ⁇ 2 were set in the same manner as in Example 1-1. I got each one.
- the observer side polarizing plate FP2 is used instead of the observer side polarizing plate FP1
- the backlight side polarizing plate BP2 is used instead of the knocklight side polarizing plate BP1.
- a liquid crystal display device 2 was obtained.
- Example 11 Except for using the first protective film (A1) instead of the second protective film (B1), the observer-side polarizing plate FP3 and the backlight-side polarizing plate BP3 were placed in the same manner as in Example 1-1. I got each one.
- the observer side polarizing plate BP3 is used instead of the observer side polarizing plate FP1
- the backlight side polarizing plate BP3 is used instead of the knock side polarizing plate BP1.
- a liquid crystal display device 3 was obtained.
- Example 1-1 Except that the second protective film (B3) was used in place of the second protective film (B1), the observer side polarizing plate FP4 and the backlight side polarizing plate BP4 were respectively set in the same manner as in Example 1-1. It was possible.
- the observer-side polarizing plate FP1 instead, the liquid crystal display device 4 was obtained using the observer side polarizing plate BP4 and using the backlight side polarizing plate BP4 instead of the knock light side polarizing plate BP1.
- the first protective film (A2) was used instead of the first protective film (A1), and the second protective film (B1) was used instead of the first protective film (A1) used in Example 1-1 as the first protective film. Except for using the protective film (A1), an observer-side polarizing plate FP5 and a backlight-side polarizing plate BP5 were obtained in the same manner as in Example 1-1.
- the observer-side polarizing plate FP5 is used instead of the observer-side polarizing plate FP1
- the backlight-side polarizing plate BP5 is used instead of the knock-side polarizing plate BP1.
- a liquid crystal display device 5 was obtained.
- the first protective film (A3) was used instead of the first protective film (A1), and the second protective film (B1) was used instead of the first protective film (A1) used in Example 1-1 as the first protective film. Except that the protective film (A1) was used, an observer-side polarizing plate FP6 and a backlight-side polarizing plate BP6 were obtained in the same manner as in Example 1-1.
- the observer side polarizing plate FP6 is used instead of the observer side polarizing plate FP1
- the backlight side polarizing plate BP6 is used instead of the knock side polarizing plate BP1.
- a liquid crystal display device 6 was obtained.
- Example 1-1 Except for using the first protective film (A6) in place of the first protective film (A1), the observer side polarizing plate FP10 and the backlight side polarizing plate BP10 were respectively the same as in Example 1-1. Obtained.
- the observer side polarizing plate FP10 is used instead of the observer side polarizing plate FP1
- the backlight side polarizing plate BP10 is used instead of the knock side polarizing plate BP1.
- a liquid crystal display device 10 was obtained.
- Example 11 Except for using the second protective film (B4) in place of the second protective film (B1), the observer-side polarizing plate FP7 and the backlight-side polarizing plate BP7 were mounted in the same manner as in Example 1-1. I got each one.
- the observer side polarizing plate FP7 is used instead of the observer side polarizing plate FP1
- the backlight side polarizing plate BP7 is used instead of the knock light side polarizing plate BP1.
- a liquid crystal display device 7 was obtained.
- Example 1-1 except that instead of the first protective film (A1), a single-layer extruded film made of polymethylmetatalylate resin having a thickness of 80 m was used as the first protective film (A4). Similarly, an observer-side polarizing plate FP8 and a backlight-side polarizing plate BP8 were obtained. Then, in the liquid crystal display device 1 of Example 1-1, the viewer side polarizing plate BP8 is used instead of the viewer side polarizing plate FP1, and the backlight side polarizing plate BP8 is used instead of the backlight side polarizing plate BP1. Thus, a liquid crystal display device 8 was obtained.
- the moisture permeability of the first protective film (A4) was 41 g / m 2 '24h.
- the first protective film (A1) a single-layer cast film with a thickness of 80 ⁇ m, which is triacetyl cellulose (TAC) force, is used as the first protective film ( ⁇ 5), and the thickness of the hard coat layer is 15 m.
- the observer side polarizing plate FP9 and the knock light side polarizing plate BP9 were respectively obtained in the same manner as in Example 1-1. Then, in the liquid crystal display device 1 of Example 1-1, the observer side polarizing plate BP9 is used instead of the observer side polarizing plate FP1, and the backlight side polarizing plate BP9 is used instead of the knock side polarizing plate BP1. As a result, a liquid crystal display device 9 was obtained.
- the tensile modulus of the film is determined by molding a single layer of thermoplastic resin, cutting out a 1cm x 25cm test piece, and using a tensile tester (Tensilon UTM-10T-PL, Toyo Baldwin) based on ASTM882. Measurement was performed under the condition of a tensile speed of 25 mmZmin. Repeat the same measurement 5 times, and use the arithmetic average value as the representative value of the tensile modulus.
- the film thickness was measured by embedding the film in epoxy resin, slicing it with a microtome [RUB-2100, manufactured by Daiwa Kogyo Co., Ltd.], observing the cross section with a scanning electron microscope. Determine.
- the depth of the linear concave portion, the height of the linear convex portion, and the width thereof were measured.
- the maximum value of the obtained concave depth and convex height, the width of the concave portion and the width of the convex portion showing the maximum value, the depth of the linear concave portion of the film, the height of the linear convex portion and those And evaluated according to the following criteria.
- VG Very Good: Depth of linear recess or height of protrusion is less than 20nm and width force is more than S800nm
- G ( Good): The depth of the linear recess or the height of the protrusion is 20 nm or more and 50 nm or less and the width is 500 nm or more and less than 800 nm.
- the measurement was carried out by a method according to the cup method described in JIS Z 0208 under the test conditions of leaving for 24 hours in an environment of 40 ° C. and 92% RH.
- the unit of moisture permeability is gZm 2 '24h.
- the measurement was carried out using a photoelastic constant measuring apparatus (PHEL-20A manufactured by Uniobuto) under the conditions of a temperature of 20 ° C ⁇ 2 ° C and a humidity of 60 ⁇ 5%.
- the unit is xlO— 13 cm 2 / dyn.
- Thermoplastic resin is formed as a single layer, using a prism coupler (Metricon, model 2010), temperature 20. . From the refractive index values at wavelengths of 633 nm, 407 nm, and 532 nm under the conditions of ⁇ 2 and humidity of 60 ⁇ 5%, the refractive index of 380 nm to 780 nm was calculated by the Caucy dispersion formula.
- the assembled liquid crystal display device is left in a thermostatic bath at 60 ° C and 90% humidity for 500 hours, and the state after the observer polarizing plate is left in black display is visually observed.
- the surface of the protective film for polarizing plate (the surface opposite to the surface to be bonded to the polarizer) is tilted at an angle of 45 degrees and a load of 500 g is applied from above. I pulled it about 5mm and checked the degree of scratching. This was done with pencils of different hardness, and the pencil hardness at which scratches began to be determined was determined.
- a polarizing plate was punched out into lcm ⁇ 5cm to obtain a test film.
- the obtained test film was wound around a steel rod having a diameter of 3 mm, and it was tested whether the wound film was broken at the bar. A total of 10 tests were conducted, and the flexibility was expressed by the following index according to the number of breaks.
- the first protective film was cut into a size of 10 cm ⁇ 10 cm, placed on a horizontal plate, and the curl state of the test piece was observed to evaluate the curl property according to the following criteria.
- the first protective film was punched with a cutting machine (TCM-500A, manufactured by Toko Co., Ltd.) using a circular blade with a diameter of 35 mm, and the punchability was evaluated according to the following criteria.
- the pencil hardness of the present invention was harder than that of the comparative example in terms of pencil hardness.
- the polarization plate of the present invention shows a performance improvement equal to or higher than that of the comparative example in terms of change in polarization degree, suppression of interference fringes, and flexibility.
- frame failure is excellent in each stage.
- the polarizing plate according to the present invention does not impair the visibility even at high temperature and high humidity with high mechanical strength. Moreover, since it is excellent in flexibility and scratch resistance, it does not cause poor appearance.
- the polarizing plate of the present invention is particularly suitable for display devices such as large-area liquid crystal display devices and touch panels.
- the liquid crystal display device of the present invention is provided with the polarizing plate of the present invention, so that the display surface has a high mechanical strength and maintains good visibility even at high temperature and high humidity. Can do.
- the first protective film in the present invention is simply “protective film” and the second protective film is “ They are referred to as “optical compensation film” or “biaxial optical compensation film”, respectively.
- the laminated film (A1) was used as a protective film, and the biaxial optical compensation film (B5) was used as an optical compensation film.
- the laminated film (A1) was used as the protective film, and the biaxial optical compensation film (B6) was used as the biaxial optical compensation film.
- the laminated film (A1) was used as a protective film
- the biaxial optical compensation film (B7) was used as a biaxial optical compensation film.
- Examples 2-5 as a protective film, polymethylmethallate (PMMA) resin layer-cellulose acetate butyrate (CAB) resin layer-polymethylmetatalylate (PMMA) resin A laminated film (A2) consisting of three layers was used, and the biaxial optical compensation film (B1) was used as a biaxial optical compensation film.
- PMMA polymethylmethallate
- CAB cellulose acetate butyrate
- PMMA polymethylmetatalylate
- a polymethylmetatalylate (PMMA) resin layer monoalicyclic olefin polymer (COP) layer one polymethylmetatalylate (PMMA) resin A laminated film (A3) consisting of three layers was used, and the biaxial optical compensation film (B1) was used as a biaxial optical compensation film.
- a laminated film (A7) consisting of a polycarbonate film (PC) -polymethyl methacrylate (PMMA) resin layer was used.
- the biaxial optical compensation film (B1) was used as the optical compensation film.
- a single-layer PMMA resin film (A4) was used as the protective film, and the biaxial optical compensation film (B1) was used as the biaxial optical compensation film.
- a single-layer TAC resin film (A5) was used as the protective film, and the biaxial optical compensation film (B1) was used as the biaxial optical compensation film.
- Example 2 Except for using the biaxial optical compensation film (B5) in place of the biaxial optical compensation film (B1), the observer side polarizing plate FP2-2 and the backlight side were the same as in Example 1-1. Polarizing plates BP2-2 were obtained.
- the observer side polarizing plate FP2-2 is used instead of the observer side polarizing plate FP1
- the backlight side polarizing plate BP1 is used instead of the backlight side polarizing plate BP2. 2 was used to obtain the liquid crystal display device 2-2 [0255] (Example 2-3)
- An observer side polarizing plate FP2-3 was obtained in the same manner as in Example 1-1 except that the biaxial optical compensation film (B6) was used in place of the biaxial optical compensation film (B1). Specifically, a polybutyl alcohol adhesive is applied to both sides of the polarizer (P), and one side of the polarizer (P) is subjected to a keny treatment of a triacetyl cellulose film. The phase axis and the polarizer (P) were bonded so that the absorption axis was perpendicular.
- a bonded observer side polarizing plate FP2-3 is obtained by a roll-to-roll method. It was. Further, in the same manner as Example 1-1 and the observer-side polarizing plate FP2-3 except that the biaxial optical compensation film (B6) was used in place of the biaxial optical compensation film (B1), the knocklight was used. Side polarizing plate BP2-3 was obtained
- liquid crystal cell with an in-plane switching mode shown as IPS in the table
- IPS in-plane switching mode
- the viewer-side polarizing plate BP2-3 is placed so that the slow axis of the biaxial optical compensation film B6 is parallel to the rubbing direction of the liquid crystal cell and the discotic liquid crystal coating surface Affixed so that the side was the liquid crystal cell side.
- the knock light side polarizing plate BP2-3 was adhered in a cross-col arrangement to obtain a liquid crystal display device 2-3.
- the polarizer (P) was bonded with a polybutyl alcohol adhesive so that one surface of the protective film with the antireflection layer was not in contact with the surface where the antireflection layer was not formed. Further, the surface on the triacetyl cellulose film side of the biaxial optical compensation film (B7) is in contact with the other surface of the polarizer (P), and the absorption axis of the polarizer (P) is in contact with the biaxial optical compensation film.
- the rubbing direction of (B7) was 45 °, and it was bonded with a polybulu alcohol-based adhesive. In this way, an observer side polarizing plate FP2-4 was obtained. Instead of the protective film with antireflection layer, the same as FP2-4 on the viewer side, except that a protective film without antireflection layer was used. In this manner, a knock light side polarizing plate BP2-4 was obtained.
- a liquid crystal cell of the type (denoted as OCB in the table) was obtained.
- the observer-side polarizing plate FP2-4 is placed on one side of the bend-oriented liquid crystal cell so that the liquid crystal layer faces the cell, and the liquid crystal layer faces the cell on the other side of the liquid crystal cell.
- the backlight side polarizing plate ⁇ 2-4 was arranged.
- the observer-side polarizing plate FP2-4 and the backlight-side polarizing plate ⁇ 2-4 are in a cross-cor relationship with each other, and the rubbing direction of the glass substrate and the biaxial optical compensation film ⁇
- the liquid crystal display devices 2-4 were obtained by arranging them so that they were opposite to each other and parallel.
- Example 1-1 Except that the protective film ( ⁇ 2) was used in place of the protective film (A1), the observer side polarizing plate FP2-5 and the backlight side polarizing plate ⁇ 2-5 were each used in the same manner as in Example 1-1. Obtained.
- the observer side polarizing plate FP2-5 was used instead of the observer side polarizing plate FP1
- the backlight side polarizing plate BP2 was used instead of the knock side polarizing plate BP1.
- —5 was used to obtain a liquid crystal display device 2-5.
- Example 1-1 Except that the protective film (A3) was used in place of the protective film (A1), the observer side polarizing plate FP2-6 and the backlight side polarizing plate BP2-6 were respectively used in the same manner as in Example 1-1. Obtained.
- the observer side polarizing plate FP2-6 was used instead of the observer side polarizing plate FP1
- the backlight side polarizing plate BP2 was used instead of the knock side polarizing plate BP1.
- —6 was used to obtain liquid crystal display device 2-6.
- a protective film (A7) having a two-layer structure in which a polycarbonate resin (PC) 10 ⁇ m layer and a polymethylmetatalate resin (PMMA) 60 ⁇ m layer were laminated was obtained.
- the moisture permeability of the protective film (A7) was 40 g'm 2 'day— 1 .
- Refraction of PMMA resin layer at 380nm wavelength The refractive index was 1.512 and the refractive index at a wavelength of 780 nm was 1.488.
- the refractive index of the PC resin layer at a wavelength of 380 nm was 1.608 and the refractive index power was 556 at a wavelength of 780 nm.
- a protective film with an antireflection layer was obtained in the same manner as in Example 1-1, except that the protective film (A7) was used in place of the protective film (A1). At this time, polymethylmetatalate resin was placed on the polarizer side.
- an observer-side polarizing plate FP2-7 and a backlight-side polarizing plate BP2-7 were obtained in the same manner as in Example 11. Then, instead of the observer-side polarizing plate FP1, the observer-side polarizing plate FP2-7 is used, and the backlight-side polarizing plate BP2-7 is used instead of the knock-side polarizing plate BP1, and the liquid crystal display device 2-7 is used. Obtained.
- the observer side polarizing plate BP2-8 was used instead of the observer side polarizing plate FP1
- the backlight side polarizing plate BP1 was used instead of the backlight side polarizing plate BP1.
- the liquid crystal display device 2-8 was obtained using —8.
- the moisture permeability of the protective film (A4) was 41 gZm 2 ′ 24h.
- the protective film (A1) a single-layer cast molded film with a thickness of 80 ⁇ m that also has triacetyl cellulose (TAC) force was used as the protective film (A5), and the thickness of the hard coat layer was changed to 15 ⁇ m.
- observer side polarizing plate FP2-9 and backlight side polarizing plate BP2-9 were obtained.
- the observer side polarizing plate FP2-9 was used instead of the observer side polarizing plate FP1, and the backlight side polarizing plate was used instead of the knock light side polarizing plate BP1.
- a liquid crystal display device 2-9 was obtained using BP2-9.
- Example 1 1 1 to 1 1 7 and Comparative Example 1 1 1 to 1 1 3
- Example 1 1 1 to 1 1 7 and Comparative Example 1 1 1 to 1 1 3
- the two test polarizing plates used in the polarization degree change of the polarizing plate face each other between the optical compensation films! Measurements were made and the measured values were substituted into the following formula to calculate the light leakage.
- Tx represents the light transmittance at the measurement point (X) , (1), (2), (3), (4), (6), (7), (8), and (9) were measured at a position 10 mm from the end. In (5), the diagonal intersection of the test polarizing plate was used as the measurement point.
- the entire display screen in which the produced liquid crystal display device was brightly displayed in a dark room was observed from the front and evaluated according to the following indicators.
- the polarizing plate of Comparative Example 2-2 was inferior in that punchability and flexibility were insufficient.
- the polarizing plates of Comparative Examples 2-3 were inferior in terms of generation of interference fringes, light leakage, curlability, punchability, and flexibility.
- the liquid crystal display device using the polarizing plate of Comparative Example 2-3 was insufficient in terms of contrast and color unevenness.
- the polarizing plate of the present invention has a light leakage with less interference fringes than conventional polarizing plates, even when used at high temperatures and high humidity with high mechanical strength. It has good characteristics in curling property, punching property, flexibility, and the like, and a good optical compensation function.
- a polarizing plate excellent in durability under high temperature and high humidity can be suitably used for flat panel displays such as touch panels and liquid crystal display devices, particularly display devices having a large screen of 40 inches or more.
- the first protective film in the present invention is simply “protective film”, and the second protective film is simply They are called “optical compensation films”.
- Example 3-1 as a protective film, polymethylmethallate (PMMA) resin layer 1 low hardness polymethylmetatalylate (R—PMMA) resin layer 1 polymethylmetatalylate (PMMA) resin A laminated film (A1) consisting of three layers was used.
- the optical compensation film (B8) was used as the optical compensation film.
- Example 3-2 the laminated film (A1) was used as a protective film, and the optical compensation film (B9) was used as an optical compensation film.
- Example 3-3 the laminated film (A1) was used as a protective film, and the optical compensation film (B10) was used as an optical compensation film.
- the laminated film (A1) was used as a protective film, and the optical compensation film (B11) was used as an optical compensation film.
- Examples 3-5 as a protective film, polymethylmethalate (PMMA) resin layer-cellulose acetate butyrate (CAB) resin layer-one polymethylmetatalylate (PMMA) resin A laminated film (A2) having a three-layer force was used, and the optical compensation film (B8) was used as an optical compensation film.
- Examples 3-6 as the protective film, polymethylmetatalylate (PMMA) resin layer monoalicyclic olefin polymer (COP) layer one polymethylmetatalylate (PMMA) resin A laminated film (A3) having a three-layer force was used, and the optical compensation film (B8) was used as an optical compensation film.
- the laminated film (A1) was used as a protective film
- the optical compensation film (B10) was used as an optical compensation film.
- Comparative Example 3-1 a laminated film (A7) consisting of a polycarbonate film (PC) -polymethylmethacrylate (PMMA) resin layer was used as the protective film, and optical compensation was performed.
- the optical compensation film (B12) was used as the film.
- Comparative Example 3-2 a single-layer PMMA resin film (A4) was used as the protective film, and the optical compensation film (B8) was used as the optical compensation film.
- a single-layer TAC resin film (A5) was used as the protective film, and the optical compensation film (B8) was used as the optical compensation film.
- Both surfaces of the protective film (A1) were subjected to corona discharge treatment using a high frequency transmitter (output 0.8 KW), and the surface tension was adjusted to 0.055 NZm.
- the hard coat layer (H) forming material is applied to one side of the protective film (A1) using a die coater in an environment of a temperature of 25 ° C. and a humidity of 60% RH.
- the film was obtained by drying in a drying oven for 5 minutes.
- this coating was irradiated with ultraviolet rays (accumulated dose of 300 mjZcm 2 ) to form a hard coat layer ( ⁇ ) having a thickness of 6; ⁇ ⁇ .
- the refractive index of the hard coat layer ( ⁇ ) was 1.62, and the pencil hardness on the hard coat layer ( ⁇ ) side exceeded 4 ⁇ .
- the other surface of the polarizer (P) is overlapped with the surface of the protective film (A1), on which the antireflection layer (L) is laminated, on which the antireflection layer (L) is not formed.
- an observer side polarizing plate FP3-1 was obtained.
- An optical compensation film comprising a polyvinyl alcohol adhesive on both surfaces of another polarizer (P), the optical compensation film (B8) on one surface of the polarizer (P), and the optical compensation film (B8). Bonding was performed so that the crossing angle of the slow axis of C1 and the absorption axis of the polarizer (P) was 15 °, and the C1 side of (B8) of the optical compensation film was in contact with the polarizer P. Then, the other surface of the polarizer (P) was overlapped with one surface of the protective film (A1), and bonded by a roll-to-roll method to obtain a backlight side polarizing plate BP3-1.
- a TN mode transflective liquid crystal cell with a pretilt angle of 2 degrees on both interfaces of the substrate, a twist angle of 70 degrees to the left, an Andr force reflection display section of 230 nm, and a transmission display section of approximately 262 nm was used.
- the film thickness of the liquid crystal was 3.5 ⁇ ⁇ ⁇ in the reflective electrode region (reflective display portion) and 4. O / zm in the transparent electrode region (transparent display portion).
- observer-side polarizing plate FP3-1, the above liquid crystal cell, and backlight-side polarizing plate BP3-1 in this order, observer-side polarizing plate FP3-1, and backlight-side polarizing plate BP3-1 optical compensation film are laminated so that the surface where the layers are laminated faces the liquid crystal cell, and then the diffusion sheet, the light guide plate, and the backlight are arranged in this order so that they touch the protective film (A1) of the backlight side polarizing plate BP3-1. In this way, a liquid crystal display device 3-1 was produced.
- Example 3-1 Except that the optical compensation film (B9) was used instead of the optical compensation film (B8), the observer side polarizing plate FP3-2 and the backlight side polarizing plate BP3-2 were used in the same manner as in Example 3-1. I got each.
- the observer side Polarizer FP3-1 is used instead of the observer side polarizer FP3-2
- the backlight side polarizer BP3-2 is used instead of the knocker side polarizer BP3-1
- the liquid crystal display device 3-2 Obtained.
- the optical compensation film (B8) a polycarbonate film with Re (450) / Re (550) of 0.86 (trade name Pure Ace WR—W: written as PC in the table) manufactured by Teijin Ltd. is used as the optical compensation film ( B10), the observer side polarizer FP3-3 was used in the same manner as in Example 3-1, except that the crossing angle of the absorption axis of the polarizer and the slow axis of the polycarbonate film was 45 °. Got. Further, the surface of the protective film (A1) with the antireflection layer (A1) on which the antireflection layer is not formed is layered on the other surface of the polarizer (P), and bonded by the roll-to-roll method. Got 3.
- Example 3 except that the optical compensation film (B10) was used instead of the optical compensation film (B8), and the crossing angle of the absorption axis of the polarizer and the slow axis of the polycarbonate film was 45 °.
- Backlight side polarizing plate BP3-3 was obtained in the same manner as for -1 and observer side polarizing plate FP3-3.
- the observer side polarizing plate FP3-3 was used instead of the observer side polarizing plate FP3-1, and the knocklight side polarizing plate BP3-1 was used. Instead, a backlight side polarizing plate BP3-3 was used to obtain a liquid crystal display device 3-3.
- the observer side polarizing plate FP3-4 and the backlight side polarizing plate BP3-4 are the same as in Example 3-1. Respectively. Then, in the liquid crystal display device 3-1 of Example 3-1, the observer side polarizing plate FP3-4 was used instead of the observer side polarizing plate FP3-1, and instead of the knock light side polarizing plate BP3-1. A liquid crystal display device 3-4 was obtained using the backlight side polarizing plate BP3-4.
- Example 3-1 Except that the protective film (A2) was used instead of the protective film (A1), the observer side polarizing plate FP3-5 and the backlight side polarizing plate BP3-5 were respectively the same as in Example 3-1. Obtained. Then, in the liquid crystal display device 3-1 of Example 3-1, the observer side polarizing plate FP3-5 was used instead of the observer side polarizing plate FP3 1, and the backlight side instead of the knock light side polarizing plate BP3-1 was used. A liquid crystal display device 3-5 was obtained using the side polarizing plate BP3-5. [0307] (Example 3-6)
- Example 3-1 Except that the protective film (A3) was used in place of the protective film (Al), the observer side polarizing plate FP3-6 and the backlight side polarizing plate BP3-6 were each used in the same manner as in Example 3-1. Obtained. Then, in the liquid crystal display device 3-1 of Example 3-1, the observer side polarizing plate FP3-6 was used instead of the observer side polarizing plate FP3 1, and the backlight side instead of the knock light side polarizing plate BP3-1 was used. A liquid crystal display device 3-6 was obtained using the side polarizing plate BP3-6.
- a protective film (A7) having a two-layer structure in which a polycarbonate resin (PC) 10 ⁇ m layer and a polymethylmetatalate resin (PMMA) 60 ⁇ m layer were laminated was obtained.
- Moisture permeability of the protective film (A7) was 40g'm- 2 'day 1.
- the protective film (A7) is used, and the optical compensation film (B12) is used as the optical compensation film, and a protective film with an antireflection layer is formed in the same manner as in Example 3-1. Obtained.
- polymethyl methacrylate resin was placed on the polarizer side.
- an observer-side polarizing plate FP3-7 and a backlight-side polarizing plate BP3-7 were obtained in the same manner as in Example 3-1. Then, in place of the observer side polarizing plate FP3-1, the observer side polarizing plate FP3-7 is used, and in place of the knock side polarizing plate BP3-1, the backlight side polarizing plate BP3-7 is used. — Got 7.
- Example 3-1 In place of the protective film (A1), the same method as in Example 3-1, except that an 80 m thick monolayer extruded film made of polymethylmetatalylate resin was used as the protective film (A4).
- a polarizing plate FP3-8 and a backlight side polarizing plate BP3-8 were obtained.
- the observer side polarizing plate BP3-8 was used instead of the observer side polarizing plate FP3-1, and the knock light side polarizing plate BP3-1 was used.
- the backlight side polarizing plate BP3-8 a liquid crystal display device 3-8 was obtained.
- the moisture permeability of the protective film (A4) was 41 gZm 2 '24h.
- the protective film (A1) a 80 ⁇ m-thick single-layer cast film that also has triacetyl cellulose (TAC) force is used as the protective film (A5), and the thickness of the hard coat layer is Except for 15 ⁇ m, observer-side polarizing plate FP3-9 and backlight-side polarizing plate BP3-9 were obtained in the same manner as Example 3-1. Then, in the liquid crystal display device 3-1 of Example 3-1, the observer side polarizing plate FP3-9 was used instead of the observer side polarizing plate FP3-1, and the backlight side polarizing plate BP3-1 was used. Then, a liquid crystal display device 3-9 was obtained using the backlight side polarizing plate BP3-9.
- TAC triacetyl cellulose
- Example 1 1 ! ⁇ 1 1 7 and Comparative Example 1 1 1 3
- Example 1 1 ! ⁇ 1 1 7 and Comparative Example 1 1 1 -3
- Re (450) / Re (550) was obtained by obtaining the in-plane letter-deposition Re in the front direction at a wavelength of 550 nm and a wavelength of 450 nm, respectively.
- the in-plane letter decision Re in the front direction was measured using an automatic birefringence meter (manufactured by Oji Scientific Instruments, KOB RA-21).
- the polarizing plate of Comparative Example 3-1 was inferior in that the pencil hardness was reduced.
- the polarizing plate of Comparative Example 3-2 was inferior in that punchability and flexibility were insufficient.
- the polarizing plates of Comparative Examples 3-3 were inferior in terms of generation of interference fringes, light leakage (frame failure), curling properties, punching properties, and flexibility.
- the liquid crystal display device using the polarizing plate of Comparative Example 3-3 was insufficient in terms of insufficient contrast and uneven color.
- the thickness is 3 ⁇ m.
- a transparent conductive film 22 made of an ITO film having a thickness of 25 nm was formed by DC magnetron sputtering to obtain an upper electrode 23 of the touch panel.
- the surface resistivity on the transparent conductive film 22 side was measured in an environment of 25 ° C. and 20% RH by the 4-terminal method, and was 300 ⁇ .
- a transparent conductive film (ITO) 25 having a surface resistivity of 00 ⁇ / mouth was formed on one surface of the glass plate 24 by a DC magnetron sputtering method to obtain a lower electrode 26 of the touch panel.
- An lmm pitch dot spacer 27 is formed on the surface of the glass plate 24 having the transparent conductive film 25 and bonded so that the transparent conductive films 22 and 25 of the upper electrode 23 and the lower electrode 26 face each other.
- the touch panel 28 is arranged with the lower electrode 26 having the glass plate 24 facing the liquid crystal cell, and the touch panel is arranged.
- An attached liquid crystal display device was produced.
- the observer side polarizing plate FP3 8 obtained in Comparative Example 3-2 was used, and a transparent conductive film was formed on the surface having the optical compensation film (B8).
- the upper electrode of the touch panel was obtained in the same manner as Example 3-7.
- a liquid crystal display device with a touch panel was produced in the same manner as in Example 3-7, except that this upper electrode was used in place of the upper electrode 23 of Example 3-7.
- the polarizing plate of the present invention has a light leakage with less interference fringes than conventional polarizing plates, even when used at high temperatures and high humidity where mechanical strength is high. It has good characteristics in curling property, punching property, flexibility, and the like, and a good optical compensation function.
- a polarizing plate excellent in durability under high temperature and high humidity can be suitably used for flat panel displays such as touch panels and liquid crystal display devices, particularly display devices having a large screen of 40 inches or more.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Nonlinear Science (AREA)
- General Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
- Mathematical Physics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Human Computer Interaction (AREA)
- Polarising Elements (AREA)
- Liquid Crystal (AREA)
- Laminated Bodies (AREA)
Abstract
Description
Claims
Priority Applications (3)
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US12/295,278 US8139181B2 (en) | 2006-03-31 | 2007-03-28 | Polarization plate, liquid crystal display device and protective film |
CN2007800200932A CN101460306B (zh) | 2006-03-31 | 2007-03-28 | 偏振片、液晶显示装置以及保护膜 |
JP2008510875A JPWO2007119560A1 (ja) | 2006-03-31 | 2007-03-28 | 偏光板,液晶表示装置,および,保護フィルム |
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JP2006-100028 | 2006-03-31 | ||
JP2006100027 | 2006-03-31 | ||
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US (1) | US8139181B2 (ja) |
JP (3) | JPWO2007119560A1 (ja) |
KR (1) | KR20090003296A (ja) |
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Also Published As
Publication number | Publication date |
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TW200740605A (en) | 2007-11-01 |
US8139181B2 (en) | 2012-03-20 |
JP2012003281A (ja) | 2012-01-05 |
JP5692267B2 (ja) | 2015-04-01 |
CN101460306B (zh) | 2012-07-18 |
TWI386309B (zh) | 2013-02-21 |
JP2013140390A (ja) | 2013-07-18 |
JP5601297B2 (ja) | 2014-10-08 |
JPWO2007119560A1 (ja) | 2009-08-27 |
US20090257003A1 (en) | 2009-10-15 |
KR20090003296A (ko) | 2009-01-09 |
CN101460306A (zh) | 2009-06-17 |
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