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CN109073929A - Liquid crystal display device - Google Patents

Liquid crystal display device Download PDF

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Publication number
CN109073929A
CN109073929A CN201780021586.1A CN201780021586A CN109073929A CN 109073929 A CN109073929 A CN 109073929A CN 201780021586 A CN201780021586 A CN 201780021586A CN 109073929 A CN109073929 A CN 109073929A
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CN
China
Prior art keywords
liquid crystal
film
crystal display
polarizer
display device
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Granted
Application number
CN201780021586.1A
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Chinese (zh)
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CN109073929B (en
Inventor
藤田敦史
村田浩
村田浩一
佐佐木靖
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Toyobo Co Ltd
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Toyobo Co Ltd
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Priority to CN202010291214.4A priority Critical patent/CN111443417B/en
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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • 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
    • 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
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • G02F1/133531—Polarisers characterised by the arrangement of polariser or analyser axes

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

Abstract

It provides: can highly control the liquid crystal display device of the curling of the laminated body formed by polarizer/liquid crystal cells/polarizer in liquid crystal display device.A kind of liquid crystal display device, it is with liquid crystal cells, it is pasted on the polarizer A in a face of liquid crystal cells, it is pasted on the polarizer B in another face of liquid crystal cells, it is characterized in that, aforementioned polarizer A is such as flowering structure: the light transmission axis direction of polarizing film is parallel with the longitudinal direction of liquid crystal display device, polyester film is laminated in at least single side of polarizing film, aforementioned polarizer B is such as flowering structure: the absorption axis direction of polarizing film is parallel with the longitudinal direction of liquid crystal display device, protective film is laminated in at least single side of polarizing film, the convergent force F of the longitudinal direction of the liquid crystal display device of aforementioned polyester filmfAnd the convergent force F of the longitudinal direction of the liquid crystal display device of polarizing film possessed by polarizer BpMeet 0.1≤F of formulaf/Fp≤2。

Description

Liquid crystal display device
Technical field
The present invention relates to liquid crystal display devices used in PC display, TV etc..
Background technique
In order to carry out the lightweight of liquid crystal display device, has the tendency that making glass substrate filming, have studied previous 0.7mm~0.5mm is hereinafter, the glass substrate etc. of 0.3mm in turn, it is believed that further filming carries out from now on.Liquid crystal display dress The glass substrate set has the effect of curling caused by the thermal behavior for inhibiting polarizer, therefore, with the thickness of glass substrate It reduces, curling inhibitory effect declines to a great extent, and is present in being formed in liquid crystal display device by polarizer/liquid crystal cells/polarizer Laminated body warpage the problem of obviously change.
All the time, the curling of a large amount of laminated body for inhibiting to be formed by polarizer/liquid crystal cells/polarizer is proposed Research, for example, proposing following content in patent document 1: being configured at the visible side of the liquid crystal cells of liquid crystal display device or more In the polarizer of backlight side, the elasticity modulus of the longitudinal direction of each polarizer is controlled, and consider the placement of polarizer up and down Difference is arranged to the elasticity modulus of upper and lower polarizer, so as to improve the warpage of liquid crystal display device in the difference of environment.In addition, specially It is conceived to the difference of the absorption axis direction of polarizer and the convergent force of light transmission axis direction in sharp document 2, reduces high temperature or high temperature is high The convergent force of the polarizer of contraction principal direction when wet, so as to improve the warpage of display equipment.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2006-267503 bulletin
Patent document 2:WO2014-204165
Summary of the invention
Problems to be solved by the invention
However, in patent document 1, patent document 2, by for temperature change strain, with moisture absorption/moisture releasing Strain is controlled and carries out improvement research, and low using glass transition temperatures such as pet films Film in the case where be considered as not accounting for but the influence of the residual strain (percent thermal shrinkage) that film has originally.
That is, the problem to be solved by the present invention is to provide: can highly control in liquid crystal display device by polarizer/liquid The liquid crystal display device of the curling for the laminated body that brilliant unit/polarizer is formed.
The solution to the problem
Liquid crystal display device is filled usually on a face of liquid crystal cells with the light transmission axis direction of polarizing film and liquid crystal display The longitudinal direction set become parallel mode be laminated with polarizer, in another face with the absorption axis direction and liquid crystal of polarizing film The long side of showing device becomes parallel mode and is laminated with polarizer.It is deeply ground using commercially available various liquid crystal display devices Study carefully, as a result the inventors of the present invention have found: being shunk since the big polarizing film of convergent force absorbs axis direction as the polarizer of long side And in the problem of being easy to produce the shape factor of curling (curling general be easy in the long side direction generate), liquid crystal display panel up and down Influenced brought by the asymmetric composition of polarizer and liquid crystal display panel the polarizer up and down for being configured at crossed nicols polarizing film The polarizer side that light transmission shaft becomes long side becomes convex, this is the essence of problem.
In turn, it has made intensive studies, the results showed that, polarizing film light transmission shaft becomes the longitudinal direction of the polarizer of long side Convergent force can be controlled according to the residual strain of protective film, by the convergent force, can control the curling of liquid crystal display device.
Herein, the measuring method of the convergent force of polarizer is illustrated.In general, the convergent force of film is as follows: making With TMA etc., initial length is set under the low state of temperature of on-test, under minimum load, is keeping the length initially grown The power of shrinkage direction in the state of constant in measurement heating.However, in temperature-rise period, due to the conformation change with polymer The recovery of the residual strain of change and generate contraction (hereinafter, brief note be heat-shrinked), while the free body by heating up by polymer Product possessive volume increases and generates thermal expansion (hereinafter, brief note thermally expands), therefore, in the glass transition temperature of polyester film It spends in the temperature region of (such as~Tg+50 DEG C or so) nearby, often becomes the relationship of thermal contraction < thermal expansion, therefore, as thin Film integrally expands, and can not observe convergent force.
Research the result shows that, even if do not generate convergent force in TMA temperature-rise period, in TMA cooling procedure In also generate convergent force.This is because, strain caused by thermal expansion is reversible change, therefore, restore after heating is cooling to Reset condition, but in temperature-rise period with meeting contracted thermal contraction degree, it is cooled down with the state that size is small, therefore, Thermal stress is generated in cooling procedure.I.e., it is possible to convert the strain of thermal stress to the percent thermal shrinkage of film, contraction after cooling Power is embodied with following formula.It should be noted that the percent thermal shrinkage in the present invention includes the moisture rate variation in heat treatment.
Convergent force (N/m)
=film thickness (mm) × elasticity modulus (N/mm2) × percent thermal shrinkage (%) ÷ 100 × 1000
That is, the representative present invention is as described below.
Item 1.
A kind of liquid crystal display device, with liquid crystal cells, the polarizer A in a face for being pasted on liquid crystal cells, stickup Polarizer B in another face of liquid crystal cells, which is characterized in that
Aforementioned polarizer A is such as flowering structure: the light transmission axis direction of polarizing film is parallel with the longitudinal direction of liquid crystal display device, It is laminated with polyester film in at least single side of polarizing film,
Aforementioned polarizer B is such as flowering structure: the absorption axis direction of polarizing film is parallel with the longitudinal direction of liquid crystal display device, It is laminated with protective film in at least single side of polarizing film,
The convergent force F of the longitudinal direction of the liquid crystal display device of aforementioned polyester filmfAnd polarization possessed by polarizer B The convergent force F of the longitudinal direction of the liquid crystal display device of piecepMeet following formula (1).
(1) 0.1≤F of formulaf/Fp≤2
(wherein, convergent force FfIt (N/m) is thickness (mm) × elasticity modulus (N/mm of polyester film2) × percent thermal shrinkage (%) ÷ 100 × 1000, convergent force FpIt (N/m) is thickness (mm) × elasticity modulus (N/mm of the polarizing film of polarizer B2) × be heat-shrinked Rate (%) ÷ 100 × 1000.)
Item 2.
According to liquid crystal display device described in item 1, which is characterized in that the long side of the liquid crystal display device of aforementioned polyester film The elasticity modulus in direction is 1000~9000N/mm2。
Item 3.
The liquid crystal display device according to item 1 or 2, which is characterized in that the liquid crystal display device of aforementioned polyester film The percent thermal shrinkage of longitudinal direction is 0.1~5%.
Item 4.
The liquid crystal display device according to any one of item 1~3, which is characterized in that aforementioned polyester film with a thickness of 40~200 μm.
Item 5.
The liquid crystal display device according to any one of item 1~4, which is characterized in that the orientation master of aforementioned polyester film Axis is 15 degree or less relative to the longitudinal direction of liquid crystal display device or the inclination angle of short side direction.
Item 6.
The liquid crystal display device according to any one of item 1~5, which is characterized in that the contraction master of aforementioned polyester film Axis is 15 degree or less relative to the longitudinal direction of liquid crystal display device or the inclination angle of short side direction.
Item 7.
A kind of liquid crystal display panel, with liquid crystal cells, a face for being pasted on liquid crystal cells polarizer A, be pasted on liquid The polarizer B in another face of brilliant unit, wherein
Aforementioned polarizer A is such as flowering structure: the light transmission axis direction of polarizing film is parallel with the longitudinal direction of polarizer A, inclined At least single side of vibration piece is laminated with polyester film,
Aforementioned polarizer B is such as flowering structure: the absorption axis direction of polarizing film is parallel with the longitudinal direction of polarizer B, inclined At least single side of vibration piece is laminated with protective film,
The convergent force F of the longitudinal direction of the polarizer A of aforementioned polyester filmf, it is inclined with polarizing film possessed by polarizer B The convergent force F of the longitudinal direction of tabula rasa BpMeet following formula (1).
(1) 0.1≤F of formulaf/Fp≤2
(wherein, convergent force FfIt (N/m) is thickness (mm) × elasticity modulus (N/mm of polyester film2) × percent thermal shrinkage (%) ÷ 100 × 1000, convergent force FpIt (N/m) is thickness (mm) × elasticity modulus (N/mm of the polarizing film of polarizer B2) × be heat-shrinked Rate (%) ÷ 100 × 1000.)
Item 8.
According to liquid crystal display panel described in item 7, which is characterized in that the bullet of the longitudinal direction of the polarizer A of aforementioned polyester film Property modulus be 1000~9000N/mm2。
Item 9.
The liquid crystal display panel according to item 7 or 8, which is characterized in that the longitudinal direction of the polarizer A of aforementioned polyester film Percent thermal shrinkage is 0.1~5%.
Item 10.
The liquid crystal display panel according to any one of item 7~9, which is characterized in that aforementioned polyester film with a thickness of 40~ 200μm。
Item 11.
The liquid crystal display panel according to any one of item 7~10, which is characterized in that the orientation main shaft phase of aforementioned polyester film The inclination angle of longitudinal direction or short side direction for liquid crystal display panel is 15 degree or less.
Item 12.
The liquid crystal display panel according to any one of item 1~5, which is characterized in that the contraction main shaft phase of aforementioned polyester film The inclination angle of longitudinal direction or short side direction for liquid crystal display panel is 15 degree or less.
The effect of invention
Following liquid crystal display device can be provided: alleviate generated under high temperature or hot and humid environment by polarizer/ The curling for the laminated body (liquid crystal display panel) that liquid crystal cells/polarizer is formed.
Specific embodiment
The picture of liquid crystal display device is usually rectangle, has long side and short side.In this specification, " liquid crystal display dress The longitudinal direction set " refers to, the direction parallel with the long side of liquid crystal display device, with " longitudinal direction of polarizer A ", " polarisation The longitudinal direction of plate B ", " longitudinal direction of polarizing film possessed by polarizer B ", " the long side side of the polyester film of polarizer A To " identical.As a result, in this specification, " longitudinal direction of liquid crystal display device " can be referred to as " the long side side of polarizer A To ", " longitudinal direction of polarizer B ", " longitudinal direction of polarizing film possessed by polarizer B ", " possessed by polarizer A gather The longitudinal direction of ester film "." short side direction of liquid crystal display device " refers to, the side parallel with the short side of liquid crystal display device To the direction vertical with longitudinal direction.
Liquid crystal display device of the invention at least includes the polarizer of liquid crystal cells, a face for being pasted on liquid crystal cells A, it is pasted on the polarizer B in another face of liquid crystal cells.Liquid crystal cells can usually be pasted with polarizer by adhesive layer. In liquid crystal display device, in addition to liquid crystal cells, polarizer A, polarizer B, the usually liquid crystal display dress such as backlight can also be included Member of formation used in setting.Liquid crystal cells have the structure with 2 glass substrate clamping liquid crystal.In one embodiment, constitute The preferred 0.7mm of the thickness of the glass substrate of liquid crystal cells hereinafter, 0.6mm hereinafter, 0.5mm hereinafter, 0.4mm hereinafter, 0.3mm with Under or 0.25mm or less.
Polarizer A has the following structure: the light transmission axis direction of polarizing film is parallel with the longitudinal direction of liquid crystal display device (that is, meaning parallel with the longitudinal direction of polarizer A is identical with the light transmission axis direction of polarizing film), in at least single side layer of polarizing film It is laminated with polyester film (using as polaroid protective film).With the face of the one side opposite side for being laminated with polyester film of polarizing film On, the low protective film of the retardations such as TAC film, cyclic olefin film, acrylic film, optical compensating film can be laminated. Herein, the low protective film of retardation for example can be retardation be 500nm hereinafter, 400nm hereinafter, 300nm hereinafter, 200nm with Under, 100nm is hereinafter, or 50nm protective film below.In addition, being only laminated with polyester in the single side of polarizing film for polarizer A Film, protective film is not laminated for another face of polarizing film, the structure of optical compensating film is also one of preferred form.Polyester Film can be configured at the liquid crystal cell side of polarizing film, be located at any one of distal side (outside) (or two sides) with liquid crystal cells, But preferred disposition is in being located at distal side (outside) with the liquid crystal cells of polarizing film.
The light transmission axis direction of polarizing film is parallel with the longitudinal direction of liquid crystal display device to be ideally substantially parallel, but is Allow the concept of a small amount of deviation.That is, the light transmission axis direction of polarizing film and the longitudinal direction angulation of liquid crystal display device are excellent Select 7 degree or less, preferably 5 degree or less, preferably 3 degree or less, preferably 2 degree or less, preferably 1 degree or less, most preferably 0 degree.
Polarizer B is such as flowering structure: the absorption axis direction of polarizing film it is parallel with the longitudinal direction of liquid crystal display device (that is, With the absorption axiss of polarizing film, meaning parallel with the longitudinal direction of polarizer B is identical), protection is laminated in at least single side of polarizing film Film.The low protective film of the retardations such as TAC film, cyclic olefin film, acrylic film, optics can be laminated on protective film Compensation film.Herein, the low protective film of retardation for example can be retardation be 500nm hereinafter, 400nm hereinafter, 300nm with Under, 200nm hereinafter, 100nm hereinafter, or 50nm protective film below.Alternatively, it is also possible to which the laminated polyester film of protective film will be used as It is laminated on polarizing film.In the case where using polyester film, preferably it is laminated in and is located at distal side with the liquid crystal cells of polarizing film.
Polarizer B can be following structure: being laminated with polyester film in the single side of polarizing film, be laminated in another surface layer State protective film, optical compensating film.In addition, for polarizer B, polyester film only is laminated in the single side of polarizing film, is being polarized Protective film is not laminated for another face of piece, the structure of optical compensating film is also one of preferred form.
The absorption axis direction of polarizing film is parallel with the longitudinal direction of liquid crystal display device to be ideally substantially parallel, but is permitted Perhaps a small amount of deviation.That is, polarizing film absorption axis direction and liquid crystal display device preferably 7 degree of longitudinal direction angulation with Under, preferably 5 degree or less, preferably 3 degree or less, preferably 2 degree or less, preferably 1 degree or less, most preferably 0 degree.
Polarizer A can be used for the polarizer of visible side, the polarizer of backlight side according to liquid crystal cells, it is general excellent It is elected to be the polarizer configuration for backlight side.Polarizer B can be used for according to liquid crystal cells the polarizer of visible side, backlight side it is inclined Tabula rasa, it is generally preferable to the polarizer as visible side configures.That is, it is preferred that successively there is back light, polarizer A, liquid crystal The liquid crystal display device of unit, polarizer B.It should be noted that liquid crystal display device may include other structures between them Part.
In liquid crystal display device of the invention, it is generally desirable to 0.1≤Ff/Fp≤2。Ff/FpLower limit value preferably 0.2 or 0.3。Ff/FpUpper limit value preferably 1.9,1.8,1.7,1.6,1.5,1.4,1.3,1.2,1.1,1.0,0.9,0.8 or 0.7.One is real It applies in mode, preferably 0.1≤Ff/Fp≤1.0、0.1≤Ff/Fp<1.0、0.1≤Ff/Fp≤0.9、0.1≤Ff/Fp≤0.8、0.2 ≤Ff/Fp≤ 0.8 or 0.3≤Ff/Fp≤0.7。
Herein, FfRefer to, the convergent force of the longitudinal direction of the liquid crystal display device of the polyester film of polarizer A uses polyester Film thickness (mm) × elasticity modulus (N/mm2) × percent thermal shrinkage (%) ÷ 100 × 1000 is defined.FpRefer to, polarizer B's is inclined The convergent force of the longitudinal direction of the liquid crystal display device of vibration piece, with thickness (mm) × elasticity modulus (N/ of the polarizing film of polarizer B mm2) × percent thermal shrinkage (%) ÷ 100 × 1000 is defined.Convergent force FfAnd FpFormula in, elasticity modulus and percent thermal shrinkage are liquid The value of the longitudinal direction of crystal device.The convergent force of polarizer B mainly by polarizing film embody, according to the thickness of polarizing film, Film forming condition and convergent force change.It is therefore desirable to adjust the convergent force of polyester film used in polarizer A according to it.
Polyester film used in polarizer A is preferably, and the elasticity modulus of the longitudinal direction of liquid crystal display device is 1000~9000N/mm2.The convergent force of polyester film can be controlled with elasticity modulus, but in order to improve the long side of liquid crystal display device The elasticity modulus in direction, it is necessary to be highly orientated along the longitudinal direction of liquid crystal display device and improve crystallinity.Therefore, long side The elasticity modulus in direction is more than 9000N/mm2In the case where, the problems such as being easily broken off, is obviously changed, therefore, the preferred 9000N/ of the upper limit mm2, more preferable 8000N/mm2, further preferred 7000N/mm2.On the other hand, it is orientated low and in the case that crystallinity is low, volume When being taken at roller, the roller due to being originated from uneven thickness is concave-convex and film deforms, and causes flatness bad.Elasticity modulus as a result, The preferred 1000N/mm of lower limit2, more preferable 1500N/mm2, further preferred 1800N/mm2.Elasticity modulus can use aftermentioned reality Apply the method measurement used in example.
Polyester film used in polarizer A is preferably, and liquid crystal display when heat treatment in 30 minutes is carried out at 100 DEG C The percent thermal shrinkage of the longitudinal direction of device is 0.1~5%.The lower limit of percent thermal shrinkage preferably 0.3% or more, preferably 0.4% or more, It is preferred that 0.5% or more, preferably 0.7% or more.The upper limit of percent thermal shrinkage preferably 4% or less, preferably 3% or less, preferably 2% with Under.Percent thermal shrinkage is lower than in the case where 0.1%, that is, in the range of 0.01~0.099%, it is difficult to control heat with not fluctuating Shrinking percentage.In addition, when percent thermal shrinkage being made to be higher than 5%, as be described hereinafter, it is necessary to further reduction crystallinity, glass transition temperature, A problem that flatness is bad as a result, becomes obvious.Percent thermal shrinkage can be measured with aftermentioned method used in the examples.
Polyester film used in polarizer A is preferably, with a thickness of 40~200 μm.The thickness of polyester film is lower than 40 μ It in the case where m, is easily broken, in addition, being easy to cause flatness bad since rigidity is insufficient.In addition, in the case where thin, with it The elasticity modulus or percent thermal shrinkage of longitudinal direction must be correspondingly improved, but it has been observed that also has the upper limit in each parameter, therefore, in fact 40 μm are lower limit in matter.In addition, in the case that film thickness is more than 200 μm, corresponding to which the elasticity modulus of longitudinal direction or The unevenness of percent thermal shrinkage becomes larger, and not only its control is difficult, but also cost increase.The thickness of polyester film can use aftermentioned implementation The method measurement used in example.
Polyester film used in polarizer A it is desirable that polyester film orientation main shaft and liquid crystal display device length The inclination angle of edge direction or short side direction is 15 degree or less.Oriented polyester film usually in pellicular front flexible modulus it is each to different Property, but the anisotropy of the elasticity modulus of oriented polyester film and optical anisotropy are generally consistent.Therefore, for each from optics The orientation main shaft of anisotropy judgement, by make with 15 degree of the inclination angle of the longitudinal direction of liquid crystal display device or short side direction with Under, the high direction of elasticity modulus close to liquid crystal display device longitudinal direction or short side direction, therefore, for as of the invention The curling for the laminated body that the inhibition of purpose is formed by polarizer/liquid crystal cells/polarizer is effective.It is orientated main shaft and liquid crystal In the case that the longitudinal direction of showing device or the inclination angle of short side direction are more than 15 degree, the tendency in an inclined direction crimped becomes Obviously.More preferable 10 degree of the inclination angle hereinafter, 9 degree hereinafter, or 8 degree or less.The orientation main shaft of polyester film can be according to aftermentioned Measuring method measurement used in the examples.
Polyester film used in polarizer A is it is desirable that contraction main shaft for polyester film, with liquid crystal display device Longitudinal direction or short side direction inclination angle be 15 degree or less.Oriented polyester film usually has each of percent thermal shrinkage in pellicular front Anisotropy, in addition, there are inclination angles on shrinking main shaft.The inclination angle for shrinking main shaft and longitudinal direction or short side direction is greater than 15 degree In the case of, the tendency crimped on inclined direction becomes apparent, not preferably.Therefore, the receipts of polyester film used in polarizer A Preferably 15 degree or less, more preferable 10 degree of inclination angle of the longitudinal direction or short side direction of contracting main shaft and liquid crystal display device or less, 9 degree Below or 8 degree or less.Shrinking main shaft can measure according to aftermentioned measuring method used in the examples.
From the viewpoint of the rainbow spot observed on the picture for inhibiting liquid crystal display device, polyester used in polarizer A Film is preferably, and retardation is in particular range in face.In face the preferred 3000nm or more of the lower limit of retardation, 5000nm with Upper, 6000nm or more, 7000nm or more or 8000nm or more.The preferred 30000nm or less of the upper limit of retardation in face, more preferably 18000nm or less, further preferred 15000nm or less.It should be noted that also using polyester film as guarantor in polarizer B In the case where cuticula, preferably the polyester film also has retardation in the face of above range.
The retardation of polyester film can also measure biaxially oriented refractive index and thickness and find out, or also can be used The commercially available automatic double refraction determining dress of KOBRA-21ADH (Oji Scientific Instruments Co., Ltd.) etc It sets and finds out.It should be noted that refractive index can use Abbe refractometer (measurement wavelength 589nm) and find out.
For polyester film used in polarizer A, the ratio between the retardation (Rth) of retardation (Re) and thickness direction in face (Re/Rth) preferably 0.2 or more, preferably 0.3 or more, preferably 0.4 or more, preferably 0.5 or more, more preferable 0.5 or more, further It is preferred that 0.6 or more.The ratio between retardation and thickness direction retardation amount (Re/Rth) are bigger in above-mentioned face, and birefringent effect more increases Isotropism has the tendency that the iris color spot as caused by viewing angle becomes difficult to generate.Complete uniaxiality (1 axis Symmetrically) in film, the ratio between above-mentioned retardation and thickness direction retardation amount (Re/Rth) become 2.0, therefore above-mentioned retardation and thickness The upper limit for spending the ratio between direction retardation (Re/Rth) is preferably 2.0.The upper limit of preferred Re/Rth is 1.2 or less.It needs to illustrate , thickness direction phase difference refers to, 2 birefringent △ Nxz, △ Nyz when by from thickness direction cross-section observation film distinguish Multiplied by being averaged for phase difference obtained from film thickness d.It should be noted that also using polyester film as guarantor in polarizer B In the case where cuticula, it is also preferred that the ratio between retardation (Re) and the retardation (Rth) of thickness direction (Re/ in the face of the polyester film It Rth) is above range.
For polyester film used in polarizer A, from the viewpoint of further suppressing iris color spot, polyester film NZ coefficient preferably 2.5 or less, more preferable 2.0 or less, further preferred 1.8 or less, still more preferably 1.6 or less.Moreover, complete In full uniaxiality (axial symmetry) film, NZ coefficient becomes 1.0, and therefore, the lower limit of NZ coefficient is 1.0.However, with close There is the significantly reduced tendency of mechanical strength in the direction vertical with differently- oriented directivity in a complete axis (axial symmetry) film, Therefore, it is necessary to pay attention to.It should be noted that also used in polarizer B polyester film as protective film in the case where, it is also preferred that should The NZ coefficient of polyester film is in above range.
NZ coefficient is used | Ny-Nz |/| Ny-Nx | it indicates, Ny indicates the refractive index of the slow-axis direction of polyester film, Nx table herein Show that the refractive index (refractive index of fast axis direction) in the direction orthogonal with slow axis, Nz indicate the refractive index of thickness direction.Use molecule Orientation meter (Oji Scientific Instruments Co., Ltd. system, MOA-6004 type molecularly oriented meter) finds out film Axis of orientation, using Abbe refractometer (ATAGO CO., LTD, system, NAR-4T, measurement wavelength 589nm) find out orientation axis direction and The refractive index (Ny, Nx, wherein Ny > Nx) of the twin shaft in orthogonal to that direction and the refractive index (Nz) of thickness direction.It can will be as This value found out is substituting to | Ny-Nz |/| Ny-Nx | find out NZ coefficient.
In addition, for polyester film used in polarizer A, from the viewpoint of further suppressing iris color spot, polyester It is the value of the Ny-Nx of film preferably 0.05 or more, more preferable 0.07 or more, further preferred 0.08 or more, still more preferably 0.09 or more, most preferably 0.1 or more.The upper limit is not particularly limited, in the case where PET series film, on Limit preferably 1.5 or so.Also used in polarizer B polyester film as protective film in the case where, it is also preferred that the Ny- of the polyester film The value of Nx is in above range.
Polyester film used in polarizer A can be obtained by arbitrary polyester resin.The type of polyester resin is without spy It does not limit, any polyester resin obtained from being condensed dicarboxylic acids and glycol can be used.It should be noted that in polarizer B Also use polyester film as protective film in the case where, polyester film is also the same.
As the dicarboxylic acid component that can be used in the manufacture of polyester resin, for example, terephthalic acid (TPA), isophthalic two Formic acid, phthalic acid, 2,5- naphthalene dicarboxylic acids, 2,6 naphthalene dicarboxylic acid, 1,4- naphthalene dicarboxylic acids, 1,5- naphthalene dicarboxylic acids, diphenyl carboxylic Acid, diphenoxyethanedicarboxylic acid, diphenyl sulfone carboxylic acid, anthracene dicarboxylic acids, 1,3- cyclopentane dicarboxylic acid, 1,3- hexamethylene dicarboxyl Acid, 1,4- cyclohexane dicarboxylic acid, hexahydro terephthalic acid, hexahydro M-phthalic acid, malonic acid, dimethyl malonic acid, succinic acid, 3,3- diethyl succinic acid, glutaric acid, 2,2- dimethylated pentanedioic acid, adipic acid, 2- methyl adipic acid, trimethyladipic acid, heptan Diacid, azelaic acid, dimeric dibasic acid, decanedioic acid, suberic acid, dodecanedicarboxylic acid etc..
As the diol component that can be used in the manufacture of polyester resin, for example, ethylene glycol, propylene glycol, six methylenes Base glycol, neopentyl glycol, 1,2- cyclohexanedimethanol, 1,4 cyclohexane dimethanol, decamethylene glycol, 1,3- propylene glycol, 1, Bis- (4- hydroxy phenyl) propane of 4- butanediol, 1,5- pentanediol, 1,6-HD, 2,2-, bis- (4- hydroxy phenyl) sulfones etc..
The dicarboxylic acid component and diol component for constituting polyester resin can be used one kind or two or more.As composition polyester The suitable polyester resin of film, for example, polyethylene terephthalate, polypropylene terephthalate, poly- Mutual-phenenyl two acid bromide two alcohol ester, polyethylene naphthalate etc. can more preferably enumerate polyethylene terephthalate, gather (ethylene naphthalate), they can further include other copolymer compositions.The transparency of these resins is excellent and hot special Property, mechanical property are also excellent.In particular, polyethylene terephthalate can reach high elastic modulus, in addition, percent thermal shrinkage Control is relatively easy to, and is suitable raw material therefore.
In the case where the percent thermal shrinkage for needing highly to improve polyester film, it is generally desirable to, addition copolymer composition makes to crystallize It spends moderately low.In addition, elastic strain, the ratio of permanent strain are high for deformation below near glass transition temperature, Therefore, it is difficult to highly improve percent thermal shrinkage.Therefore, as needed, importing the low ingredient of glass transition temperature is also Preferred embodiment.Specifically, for propylene glycol, 1,3- propane diol etc..
(imparting of functional layer)
Polarizer A used in liquid crystal display device of the invention is it is desirable that the percent thermal shrinkage in polyester film remains In the state of it is integrated with the glass plate of liquid crystal cells, therefore, assign adhesive layer, hard conating, antiglare layer, anti-reflection layer, low In the case where the functional layers such as reflecting layer, low anti-reflection layer and antireflection antiglare layer, antistatic layer, ideal embodiment be by Drying temperature is set as lower or is carried out using small methods of thermal histories such as UV irradiation, electron beam irradiations.In addition, in order to These functional layers are assigned in the film making process of polyester film, and polarisation can be made in the case where not damaging the percent thermal shrinkage improved Plate A is integrated with the glass plate of liquid crystal cells, is more preferably embodiment therefore.
(manufacturing methods of oriented polyester films)
Polyester film used in the present invention can be manufactured according to the manufacturing method of general polyester film.Such as it can lift Following method out: it will make the No yield point polyester of polyester resin melting and extrusion molding sheet more than glass transition temperature At a temperature of, stretched along longitudinal direction using the speed difference of roller, then, transversely stretched using stenter, implement heat treatment. It can may be biaxially oriented film for single axle drawn membrane.It should be noted that MD refers to Machine Direction's Referred to as, in this specification, sometimes referred to as film conveying direction, length direction, longitudinal direction.In addition, TD refers to Transverse The abbreviation of Direction, in this specification, sometimes referred to as width direction, transverse direction.
The polyester film used in polarizer A as polaroid protective film preferably adjusts convergent force FfSo that becoming 0.1Fp≤ Ff≤2Fp。
(method of adjustment of the elasticity modulus of polyester film)
Elasticity modulus for the polyester film used in polarizer A as polaroid protective film, polarizing film light transmission shaft side Under MD unanimous circumstances when being film-made to (that is, longitudinal direction of liquid crystal display device) and polyester film, stretched polyester can be used The elasticity modulus of the known method adjustment MD of film, under TD unanimous circumstances when polyester film film, Ke Yiyong The elasticity modulus of the known method adjustment TD of oriented polyester film.
Specifically, the direction be draw direction in the case where, stretching ratio can be set as higher, the direction be with In the case where draw direction orthogonal direction, stretching ratio can be set as lower.
(method of adjustment of the percent thermal shrinkage of polyester film)
Percent thermal shrinkage for the polyester film used in polarizer A as polaroid protective film, the light transmission shaft of polarizing film It, can be poly- with stretching under MD unanimous circumstances when direction (that is, longitudinal direction of liquid crystal display device) and polyester film are film-made The percent thermal shrinkage of the known method adjustment MD of ester film can be under TD unanimous circumstances when being film-made with polyester film With the percent thermal shrinkage of the known method adjustment TD of oriented polyester film.
In the case where the percent thermal shrinkage for adjusting the MD of polyester film, for example, in stretching the cooling procedure after heat fixation, Method of the interval of the fixture and adjacent fixture that expand clamping thin-film width direction end to be stretched along MD；Reduce folder Tool interval is to make its contraction along MD, it is possible thereby to be adjusted.In addition, in stretching the cooling procedure after heat fixation, from The fixture for clamping thin-film width direction end will be in the case where film cutting or separation, and the power of film is collected in adjustment, to make thin Film is stretched or is shunk along MD, it is possible thereby to be adjusted.Moreover, film after offline process in, in order to assign functional layer Deng and in the case where being heated up, percent thermal shrinkage changes in heating cooling procedure, and therefore, adjustment collects the power of film simultaneously It is set to stretch or shrink along MD, to can also be adjusted.
In the case where the percent thermal shrinkage for adjusting the TD of polyester film, for example, in stretching the cooling procedure after heat fixation, Expand the fixture of clamping thin-film width direction end and the interval of the fixture for the opposite side for being located at width direction to carry out along TD The method of stretching；Reduce to make its contraction along TD, it is possible thereby to be adjusted.
In addition, being received it is desirable that implementing heat in target temperature regime of the invention in any situation in MD or TD The adjustment of shrinkage.
(method of adjustment at the inclination angle of the contraction main shaft of polyester film)
The inclination angle of the contraction main shaft for the polyester film that polaroid protective film as polarizer A uses can be such as PCT/ Disclosed in JP2014/073451 (WO2015/037527) like that, in the stretching heat treatment based on stenter of polyester film It is adjusted in the offline process after cooling procedure or film afterwards.Specifically, generating in cooling process with incomplete The contraction of the stretching of heat fixation removal and with cooling thermal stress, due to the two on film conveying direction harmony and produce Raw introducing to the upstream side or introducing downstream, generate the phenomenon that shrinking inclined main axes.Inclining for main shaft is shunk in order to reduce Angle, it is necessary to the convergent force of the film conveying direction in cooling process (with the convergent force of stretching and with cooling convergent force It is total) become uniform mode and be adjusted.In order to make it uniformly, it is generally desirable to, on film conveying direction, in convergent force Make its contraction along film conveying direction in high temperature region；Or, on film conveying direction, in the low temperature region of convergent force It is middle to be stretched along film conveying direction.The method shunk or stretched can be by a conventionally known method.In addition, by film In the case where end cutting or separation, in the temperature region that has separated of cutting hereinafter, free shrink in the width direction, the temperature Region percent thermal shrinkage below becomes smaller, therefore needs to pay attention to.
(method of adjustment at the inclination angle of the orientation main shaft of polyester film)
The adjustment at the inclination angle of the orientation main shaft of the polyester film used in polarizer A as polaroid protective film can be such as day Disclosed in this Patent 2014-11438 (special open 2015-136922) or Japanese Patent Application 2012-552162 (WO2013/031511) Like that, in oriented polyester film benefit by a conventionally known method.For the inclination angle of direction of adjustment main shaft, it is preferred that Keep the convergent force for stretching the film conveying direction in heat fixation section uniform.Utilize the stretching heat fixation section of stenter In, due to stretched based on MD residual stress, TD stretch Poisson stress and there are convergent forces on film conveying direction Distribution generates to the upstream side or therefore the introducing in downstream side generates inclination angle (so-called bow phenomenon) on orientation main shaft.In order to Keep the convergent force on film conveying direction uniform, known method can be used.Specifically, gathering meeting to meet to stretch It, can be according to considering MD's and TD on the basis of stretching condition needed for optical characteristics required by ester system polaroid protective film The harmony of stretching ratio, stenter size Elevated Temperature Conditions, stretch the reduction of distance between adjacent fixture in heat fixation It is generated contraction and reach.
Embodiment
It, can also be with hereinafter, further illustrate the present invention referring to embodiment, but the present invention is not limited by the following examples It is suitable for change in the range of can be suitble to purport of the invention to implement, these are all contained in protection scope of the present invention In.
(1) convergent force
The convergent force of polarizing film and polyester film is calculated as follows.It should be noted that film thickness, elasticity modulus, Percent thermal shrinkage is the measured value of following middle explanation.
Convergent force (N/m)
=film thickness (mm) × elasticity modulus (N/mm2) × percent thermal shrinkage (%) ÷ 100 × 1000
(2) film thickness
The thickness (mm) of polarizing film and polyester film measures as follows: after standing 168 hours in the environment of 25 DEG C, 50RH% It is measured with electric micrometer (Fine Liu off Co., system, Miritoron 1245D), is mm by unit conversion.
(3) elasticity modulus
The elasticity modulus of polarizing film and polyester film is as follows: after standing 168 hours in the environment of 25 DEG C, 50RH%, according to According to JIS-K7244 (DMS), carried out with the measurement of dynamic viscoelasticity device (DMS6100) of Seiko Instruments Inc. Evaluation.Under conditions of distance is 5mm between stretch mode, driving frequency 1Hz, chuck, heating rate is 2 DEG C/min, measurement 25 DEG C~120 DEG C of temperature dependency, average by 30 DEG C~100 DEG C of storage modulus are used as elasticity modulus.It needs to illustrate It is to measure the elasticity modulus in the direction parallel with the longitudinal direction of liquid crystal display device.
(4) inclination angle of percent thermal shrinkage and contraction main shaft
The percent thermal shrinkage of polarizing film and polyester film and the inclination angle for shrinking main shaft are as follows: in the environment of 25 DEG C, 50RH% After standing 168 hours, the circle of diameter 80mm is drawn, with picture size analyzer (Keyence Corporation Image Measure IM6500) diameter of a circle is measured 1 ° everyly, as the length before processing.Then, old with the gill for being set as 100 DEG C Change insulating box and carry out heat treatment in 30 minutes, later, in the environment of being set as 25 DEG C of room temperature it is cooling after ten minutes, using with place Same method before managing, every 1 ° of ground evaluated, as treated length.
Percent thermal shrinkage in the present invention refers to, fills in the percent thermal shrinkage calculated with following calculating formula, with liquid crystal display The value that the value in the parallel direction of the longitudinal direction set defines.
Length × 100 before percent thermal shrinkage=(length-treated length) before processing/processing
The inclination angle for shrinking main shaft is that the percent thermal shrinkage of every 1 ° of ground measurement becomes maximum angle, with apart from longitudinal direction or short The inclination angle of edge direction defines.That is, the inclination angle for shrinking main shaft becomes 0~45 ° of range.
(5) it is orientated the inclination angle of main shaft
For the inclination angle of the orientation main shaft of polyester film, molecularly oriented meter (Oji Scientific is used Instruments Co., Ltd. system, MOA-6004 type molecularly oriented meter) measurement orientation main shaft, with apart from longitudinal direction or short side The inclination angle in direction defines.That is, the inclination angle of orientation main shaft becomes 0~45 ° of range.
(6) crimp height
In the production of the liquid crystal display panel made in aftermentioned each embodiment, " glass substrate with a thickness of 0.4mm will be used The IPS type liquid crystal cells of 50 inch dimensions " replace with " length of short side direction is 125mm, the length of longitudinal direction be 220mm, With a thickness of the glass plate of 0.4mm ", it in addition to this, operates in the same way, makes evaluation liquid crystal display panel.Then, for evaluation liquid Crystal panel carries out heat treatment in 30 minutes with the Geer -Evans-oven for being set as 100 DEG C, later, be set as 25 DEG C of room temperature, In the environment of 50%RH it is cooling after ten minutes, make it is convex it is lateral under be placed in horizontal plane, will most with the height at Measure measurement 4 Big value is used as crimp height.In addition, being that 5mm or less is used as good range by maximum crimp height.Curling is should be with curvature body Existing phenomenon, but for simplicity, highly to be evaluated.In addition, the rigidity relative to sample, crimps existing when sample becomes large-sized As becoming bowl-type, and the non-constant phenomenon of curvature is generated in film sometimes, but the result of the present embodiment confirmed whole songs Rate is constant.
(7) refractive index of polyester film
Using molecularly oriented meter, (Oji Scientific Instruments Co., Ltd. system, MOA-6004 type molecule are taken To meter), the slow-axis direction of film is found out, parallel mode is become with test sample long side with slow-axis direction and cuts out 4cm × 2cm Rectangle, as test sample.For the sample, Abbe refractometer (ATAGO CO., LTD, system, NAR-4T, survey are utilized The long 589nm of standing wave) finding out the refractive index of orthogonal twin shaft, (refractive index of slow-axis direction: Ny, fast axle are (orthogonal with slow-axis direction The refractive index in direction): Nx) and the refractive index of thickness direction (Nz).NZ coefficient is found out using these values.
(8) retardation (Re)
Retardation is the anisotropy (△ Nxy=| Nx-Ny |) and film by the refractive index of the orthogonal twin shaft on film The parameter that the product (△ Nxy × d) of thickness d (nm) defines, is to indicate optical isotropism, anisotropic standard.Twin shaft The anisotropy (△ Nxy) of refractive index is found out by the following method.Use molecularly oriented meter (Oji Scientific Instruments Co., Ltd. system, MOA-6004 type molecularly oriented meter), find out the slow-axis direction of film, with slow-axis direction with Test sample long side becomes the rectangle that parallel mode cuts out 4cm × 2cm, as test sample.For the sample, benefit The refractive index for finding out orthogonal twin shaft with Abbe refractometer (ATAGO CO., LTD, system, NAR-4T, measurement wavelength 589nm) is (slow The refractive index of axis direction: Ny, the refractive index in the direction orthogonal with slow-axis direction: Nx) and thickness direction refractive index (Nz), will Anisotropy (△ Nxy) of the refractive index absolute value of the difference (| Nx-Ny |) of aforementioned twin shaft as refractive index.The thickness d of film It (nm) is nm by unit conversion with electric micrometer (Fine Liu off Co., system, Miritoron 1245D) measurement.By reflecting The product (△ Nxy × d) of the thickness d (nm) of the anisotropy (△ Nxy) and film of rate finds out retardation (Re).
(9) thickness direction retardation amount (Rth)
Thickness direction retardation amount be 2 when indicating from film thickness direction cross-section observation birefringent △ Nxz (=| Nx-Nz |), △ Nyz (=| Ny-Nz |) is respectively multiplied by the average parameter of retardation obtained from film thickness d.Using with retardation Same method is measured, Nx, Ny, Nz and film thickness d (nm) are found out, calculating (△ Nxz × d) is averaged with (△ Nyz × d's) Value, finds out thickness direction retardation amount (Rth).
(Production Example 1- polyester A)
It heats up to esterification reaction tank, at the time of reaching 200 DEG C, puts into 86.4 mass parts of terephthalic acid (TPA) and second two 64.6 mass parts of alcohol, investment is as 0.017 mass parts of antimony trioxide of catalyst, magnesium acetate 4 hydrate 0.064 while stirring Mass parts, 0.16 mass parts of triethylamine.Then, pressurization heating is carried out, is pressurizeed under conditions of gauge pressure 0.34MPa, 240 DEG C After esterification, esterification reaction tank is made to be restored to normal pressure, adds 0.014 mass parts of phosphoric acid.In turn, 260 were warming up to 15 minutes DEG C, add 0.012 mass parts of trimethyl phosphate.Then after 15 minutes, decentralized processing is carried out with high pressure dispersing machine, after 15 minutes, Gained esterification reaction product is transplanted in polycondensation reaction tank, carries out polycondensation reaction at 280 DEG C, under decompression.
After polycondensation reaction, it is filtered processing with the NASLON filter that 95% cut-off diameter is 5 μm, from nozzle It is extruded as strand form, cooling is carried out using the cooling water for having carried out filtration treatment (aperture: 1 μm or less) in advance, solidifies, be cut into Partical.The inherent viscosity of gained pet resin (A) is 0.62dl/g, is contained substantially no nonactive Particle and internal precipitation particle.(hereinafter abbreviated as PET (A).)
(Production Example 2- polyester B)
By dry ultraviolet absorbing agent (2,2 '-(1,4- phenylene) bis- (4H-3,1- benzoxazin-4-ones) 10 mass Part, 90 mass parts of PET (A) (inherent viscosity 0.62dl/g) mixing without containing particle, using mixing extruder, are contained The pet resin (B) of ultraviolet absorbing agent.(hereinafter abbreviated as PET (B))
(preparation of the modified coating fluid of Production Example 3- cementability)
Ester exchange reaction and polycondensation reaction are carried out by conventional method, and preparation is as dicarboxylic acid component (relative to dicarboxyl Sour component is whole) 46 moles of % of terephthalic acid (TPA), 46 moles of % and 5- sulfoisophthalic acid sodium of M-phthalic acid, 8 moles of %, The water of the composition of (relative to diol component entirety) ethylene glycol 50 moles of % and 50 moles of % of neopentyl glycol as diol component The copolymer polyester resin of dispersibility alkali containing metal sulfamate.Then, by 51.4 mass parts of water, 38 mass parts of isopropyl alcohol, positive fourth After 5 mass parts of base cellosolve, the mixing of 0.06 mass parts of nonionic surfactants, carries out heating stirring and add after reaching 77 DEG C 5 mass parts of copolymer polyester resin for entering above-mentioned water dispersible alkali containing metal sulfamate continue to stir to the block disappearance of resin, will Aqueous resin dispersion liquid is cooled to room temperature, and obtains the uniform water dispersible copolymer polyester resin of 5.0 mass % of solid component concentration Liquid.In turn, make aggregation silica dioxide granule (FUJI SILYSIA CHEMICAL LTD. system, SILYSIA 310) 3 mass parts After being scattered in 50 mass parts of water, it is added SILYSIA's 310 into above-mentioned 99.46 mass parts of water dispersible copolymer polyester resin liquid 20 mass parts of water are added in 0.54 mass parts of aqueous dispersions while stirring, obtain the modified coating fluid of cementability.
(embodiment 1)
By PET (A) resin granular material 90 mass parts as base film middle layer raw material without particle and contain purple 10 mass parts of PET (B) resin granular material of ultraviolet absorbers are carried out 6 hours at 135 DEG C after being dried under reduced pressure (1Torr), to extrusion Machine 2 (II layers of middle layer use) supply, in addition, by conventional method by PET (A) it is dry and respectively to extruder 1 (I layers of outer layer and Outer layer III use) supply, it is melted at 285 DEG C.2 kinds of polymer are used to filter material (the nominal filter essence of stainless steel sintered body respectively 10 μm of particles 95% are spent to end) it is filtered, it is laminated using 2 kind of 3 laminated stream block, after being extruded as sheet from tube head, use Electrostatic application casting is wrapped on 30 DEG C of surface temperature of curtain coating drum (casting drum) and is cooled and solidified, and production is not drawn Stretch film.At this point, adjusting the discharge rate of each extruder in such a way that I layers, II layers, the ratio of III layers of thickness become 10:80:10.
It then, is 0.08g/m with the coating weight after drying by reverse roll method2Mode be coated with above-mentioned cementability is modified Liquid be applied to the non-stretched PET film it is two-sided it is upper after, dry 20 seconds at 80 DEG C.
The non-stretched film for being formed with coating layer is directed into tentering stretching-machine, while with the end of fixture clamping film, While importeding into 105 DEG C of temperature of hot wind region, 4.0 times are stretched to along TD.Then, it is heat-treated with 180 DEG C, 30 seconds of temperature, Later, it will be cooled to 100 DEG C of film and stretch 1% along MD, later, open the folder for clamping the both ends for the film for being cooled to 60 DEG C Tool, is collected with the tension of 350N/m, the huge volume formed by about 80 μm of film thickness of uniaxial orientation PET film is acquired, by institute It obtains huge volume and carries out 3 equal parts, obtain 3 cuttings volumes (L (left side), C (center), R (right side)).It rolls up to obtain by the cutting positioned at R Polaroid protective film 1 (uses the central portion of the cutting volume positioned at R as polaroid protective film 1).
In the list of the polarizing film (convergent force of the absorption axis direction of polarizing film is 5100N/m) comprising PVA and iodine and boric acid Side becomes parallel mode with the MD of film with the light transmission shaft of polarizing film and adheres to polaroid protective film 1.In addition, in polarizing film Opposite face adheres to TAC film (80 μm of Fujifilm Corporation system, thickness).In this way, production longitudinal direction and polarization The consistent polarisation of absorption axis direction of the consistent polarizer (polarizer A) of the light transmission axis direction of piece and longitudinal direction and polarizing film Plate (polarizer B).In such a way that polaroid protective film 1 becomes and is located at distal side (opposite side) with liquid crystal cells, by PSA, divide Not using thickness 0.4mm glass substrate 50 inch dimensions IPS type liquid crystal cells visible side paste polarizer B, Light source side pastes polarizer A, makes liquid crystal display panel.The liquid crystal display panel is packed into shell, to make liquid crystal display device.
(embodiment 2)
In the film of the polaroid protective film 1 of embodiment 1, it will be cooled to 100 DEG C of film and stretch along its length 2.5%, it in addition to this, is operated in the same way with polaroid protective film 1, obtains polaroid protective film 2.In embodiment 1, by polarizing film Protective film 1 replaces with polaroid protective film 2, in addition to this, operates similarly with example 1, and makes liquid crystal display device.
(embodiment 3)
In the film of the polaroid protective film 1 of embodiment 1, it will be cooled to 100 DEG C of film and stretch 4% along its length, In addition to this, it is operated in the same way with polaroid protective film 1, obtains polaroid protective film 3.In embodiment 1, by absorption axis direction Convergent force is that the polarizing film of 5100N/m replaces with the polarizing film of 11200N/m, polaroid protective film 1 is replaced with to polarizing film protection In addition to this film 3 operates similarly with example 1, make liquid crystal display device.
(embodiment 4)
As I layers, II layers and III layers of raw material, using the blend of PET (A) 90 mass % and PBT10 mass %, and It will be cooled to 100 DEG C of film and stretch 4% along its length, in addition to this, operated in the same way with polaroid protective film 1, made Polaroid protective film 4.In embodiment 1, replace with 11200N/m's by the polarizing film that the convergent force of absorption axis direction is 5100N/m Polaroid protective film 1 is replaced with polaroid protective film 4 by polarizing film, in addition to this, is operated similarly with example 1, and liquid is made Crystal device.It should be noted that PBT uses Mitsubishi Engineering-Plastics Corporation system NV5020(0.52dl/g)。
(embodiment 5)
The revolving speed of casting roll is adjusted to make 50 μm of film thickness after stretching, in addition to this, with polaroid protective film 1 It operates in the same way, obtains polaroid protective film 5.In embodiment 1, polaroid protective film 1 is replaced with into polaroid protective film 5, is removed It except this, operates similarly with example 1, makes liquid crystal display device.
(embodiment 6)
It will be cooled to 100 DEG C of film and stretch 2.5% along its length, in addition to this, in the same manner as polaroid protective film 5 Operation, obtains polaroid protective film 6.In embodiment 1, polaroid protective film 1 is replaced with into polaroid protective film 6, in addition to this, It operates similarly with example 1, makes liquid crystal display device.
(embodiment 7)
It will be cooled to 100 DEG C of film and stretch 4% along its length, in addition to this, grasped in the same manner as polaroid protective film 5 Make, obtains polaroid protective film 7.
It is that the polarizing film of 5100N/m replaces with the polarization of 11200N/m by the convergent force of absorption axis direction in embodiment 1 Polaroid protective film 1 is replaced with polaroid protective film 7 by piece, in addition to this, is operated similarly with example 1, and liquid crystal is made Showing device.
(embodiment 8)
The revolving speed of casting roll is adjusted to make 160 μm of film thickness after stretching, in addition to this, with polaroid protective film 1 operates in the same way, and obtains polaroid protective film 8.In embodiment 1, polaroid protective film 1 is replaced with into polaroid protective film 8, is removed It except this, operates similarly with example 1, makes liquid crystal display device.
(embodiment 9)
It will be cooled to 100 DEG C of film and stretch 2.5% in the width direction, in addition to this, in the same manner as polaroid protective film 8 Operation, obtains polaroid protective film 9.Then, it is replaced with by the polarizing film that the convergent force of absorption axis direction is 5100N/m The polarizing film of 11200N/m；Become parallel mode with the TD of polaroid protective film with the light transmission shaft of polarizing film to paste, production is inclined Tabula rasa A and polarizer B；With polaroid protective film 1 is replaced with into polaroid protective film 9, in addition to this, similarly to Example 1 Operation, obtains liquid crystal display device.
(embodiment 10)
4.0 times are stretched along MD, stretches 1.0 times along TD, in addition to this, are operated in the same way, are obtained partially with polaroid protective film 1 Shake piece protective film 10.In embodiment 1, polaroid protective film 1 is replaced with into polaroid protective film 10, in addition to this, with embodiment 1 It operates in the same way, makes liquid crystal display device.
(embodiment 11)
It will be cooled to 100 DEG C of film and stretch 1.5% along MD, in addition to this, operated in the same way with polaroid protective film 10, Obtain polaroid protective film 11.In embodiment 1, polaroid protective film 1 is replaced with into polaroid protective film 11, in addition to this, with Embodiment 1 operates in the same way, and makes liquid crystal display device.
(embodiment 12)
It will be cooled to 100 DEG C of film and stretch 2.5% along MD, in addition to this, operated in the same way with polaroid protective film 10, Obtain polaroid protective film 12.
It is that the polarizing film of 5100N/m replaces with the polarizing film of 11200N/m by the convergent force of absorption axis direction；With will polarize Piece protective film 1 replaces with polaroid protective film 12, in addition to this, operates similarly with example 1, obtains liquid crystal display device.
(embodiment 13)
As I layers, II layers and III layers of raw material, the blend of 90 mass % of PET (A) and 10 mass % of PBT are used； With will be cooled to 100 DEG C of film along MD and stretch 3%, in addition to this, operated in the same way with polaroid protective film 10, obtained partially Shake piece protective film 13.
It is that the polarizing film of 5100N/m replaces with the polarizing film of 11200N/m by the convergent force of absorption axis direction；With will polarize Piece protective film 1 replaces with polaroid protective film 13, in addition to this, operates similarly with example 1, obtains liquid crystal display device. It should be noted that PBT uses Mitsubishi Engineering-Plastics Corporation NV5020 (0.52dl/g)。
(embodiment 14)
The revolving speed of casting roll is adjusted to make 50 μm of film thickness after stretching, will be cooled to 100 DEG C of film along MD 1.5% is stretched, in addition to this, is operated in the same way with polaroid protective film 10, obtains polaroid protective film 14.Polarizing film is protected Film 1 replaces with polaroid protective film 14, in addition to this, operates similarly with example 1, obtains liquid crystal display device.
(embodiment 15)
It will be cooled to 100 DEG C of film and stretch 2% along MD, in addition to this, operate in the same way, obtain with polaroid protective film 14 To polaroid protective film 15.Polaroid protective film 1 is replaced with into polaroid protective film 15, in addition to this, similarly to Example 1 Operation, obtains liquid crystal display device.
(embodiment 16)
It will be cooled to 100 DEG C of film and stretch 5% along TD, in addition to this, operate in the same way, obtain with polaroid protective film 14 To polaroid protective film 16.Then, viscous as parallel mode with the direction TD of polaroid protective film with the light transmission shaft of polarizing film Patch makes polarizer A and polarizer B；With polaroid protective film 1 is replaced with into polaroid protective film 16, in addition to this, with reality It applies example 1 to operate in the same way, obtains liquid crystal display device.
(embodiment 17)
It will be cooled to 100 DEG C of film and stretch 2% along MD, in addition to this, operate in the same way, obtain with polaroid protective film 10 To polaroid protective film 20.In embodiment 1, polaroid protective film 1 is replaced with into polaroid protective film 20, in addition to this, with reality It applies example 1 to operate in the same way, makes liquid crystal display device.
(embodiment 18)
It will be cooled to 100 DEG C of film and stretch 2.5% along MD, in addition to this, operated in the same way with polaroid protective film 10, Obtain polaroid protective film 21.In embodiment 1, polaroid protective film 1 is replaced with into polaroid protective film 21, in addition to this, with Embodiment 1 operates in the same way, and makes liquid crystal display device.
(comparative example 1)
The fixture for clamping the both ends of film is opened at 95 DEG C in cooling process after stretching heat fixation, except this it Outside, polaroid protective film 17 is got similarly with polaroid protective film 1.Polaroid protective film 1 is replaced with into polaroid protective film 17；Become parallel mode with the TD of polaroid protective film with the light transmission shaft of polarizing film to be pasted, makes polarizer A and polarisation In addition to this plate B is operated similarly with example 1, obtain liquid crystal display device.
(comparative example 2)
It will be cooled to 100 DEG C of film and stretch 0.8% in the width direction, it is in addition to this, same as polaroid protective film 14 Ground operation, obtains polaroid protective film 18.11200N/m is replaced with by the polarizing film that the convergent force of absorption axis direction is 5100N/m Polarizing film；With polaroid protective film 1 is replaced with into polaroid protective film 18；It is protected with the light transmission shaft of polarizing film and polarizing film The TD of film becomes parallel mode and is pasted, in addition to this production polarizer A and polarizer B is grasped similarly to Example 1 Make, obtains liquid crystal display device.
(comparative example 3)
It will be cooled to 100 DEG C of film and stretch 0.3% in the width direction, in addition to this, in the same manner as polaroid protective film 8 Operation, obtains polaroid protective film 19.Replace with 11200N/m's by the polarizing film that the convergent force of absorption axis direction is 5100N/m Polarizing film；With polaroid protective film 1 is replaced with into polaroid protective film 19；With the light transmission shaft and polaroid protective film of polarizing film TD become parallel mode pasted, production polarizer A and polarizer B in addition to this operate similarly with example 1, Obtain liquid crystal display device.
The liquid crystal display device of liquid crystal display panel and comparative example 1~3 for the liquid crystal display device of embodiment 1~18 Liquid crystal display panel carries out heat treatment in 30 minutes with the Geer -Evans-oven for being set as 100 DEG C, later, is being set as room temperature 25 DEG C, it is cooling in the environment of 50RH% observe liquid crystal display panel after ten minutes, curling, but ratio are not observed in acetonideexample 1~16 Compared with observing curling in example 1~3.
The measurement result of each embodiment is shown in table 1.
[table 1]
Industrial availability
The laminated body formed by polarizer/liquid crystal cells/polarizer is highly controlled according to the present invention it is possible to provide The liquid crystal display device of curling.

Claims (6)

1. a kind of liquid crystal display device, with liquid crystal cells, a face for being pasted on liquid crystal cells polarizer A, be pasted on The polarizer B in another face of liquid crystal cells, which is characterized in that
The polarizer A is such as flowering structure: the light transmission axis direction of polarizing film is parallel with the longitudinal direction of liquid crystal display device, inclined At least single side of vibration piece is laminated with polyester film,
The polarizer B is such as flowering structure: the absorption axis direction of polarizing film is parallel with the longitudinal direction of liquid crystal display device, inclined At least single side of vibration piece is laminated with protective film,
The convergent force F of the longitudinal direction of the liquid crystal display device of the polyester filmfAnd the liquid of polarizing film possessed by polarizer B The convergent force F of the longitudinal direction of crystal devicepMeet following formula (1),
(1) 0.1≤F of formulaf/Fp≤2
Wherein, convergent force FfIt (N/m) is thickness (mm) × elasticity modulus (N/mm of polyester film2) × percent thermal shrinkage (%) ÷ 100 × 1000, convergent force FpIt (N/m) is thickness (mm) × elasticity modulus (N/mm of the polarizing film of polarizer B2) × percent thermal shrinkage (%) ÷100×1000。
2. liquid crystal display device according to claim 1, which is characterized in that the liquid crystal display device of the polyester film The elasticity modulus of longitudinal direction is 1000~9000N/mm2。
3. liquid crystal display device according to claim 1 or 2, which is characterized in that the liquid crystal display of the polyester film fills The percent thermal shrinkage for the longitudinal direction set is 0.1~5%.
4. liquid crystal display device described in any one of claim 1 to 3, which is characterized in that the thickness of the polyester film Degree is 40~200 μm.
5. liquid crystal display device according to any one of claims 1 to 4, which is characterized in that the polyester film takes It is 15 degree or less to the inclination angle of main shaft.
6. liquid crystal display device according to any one of claims 1 to 5, which is characterized in that the receipts of the polyester film The inclination angle of contracting main shaft is 15 degree or less.
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