CN104094141B - Polarizing coating and its manufacture method and polarization plates - Google Patents

Polarizing coating and its manufacture method and polarization plates Download PDF

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Publication number
CN104094141B
CN104094141B CN201380006145.6A CN201380006145A CN104094141B CN 104094141 B CN104094141 B CN 104094141B CN 201380006145 A CN201380006145 A CN 201380006145A CN 104094141 B CN104094141 B CN 104094141B
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China
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polarizing coating
film
polyvinyl alcohol
boric acid
resin film
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CN201380006145.6A
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CN104094141A (en
Inventor
李原氾
田崎诚
松元浩二
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Priority to CN201711215716.3A priority Critical patent/CN107861183B/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B29C55/06—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/023—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates or sheets
    • B29C55/026—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates or sheets of preformed plates or sheets coated with a solution, a dispersion or a melt of thermoplastic material
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3008—Polarising elements comprising dielectric particles, e.g. birefringent crystals embedded in a matrix
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2029/00—Use of polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals or derivatives thereof as moulding material
    • B29K2029/04—PVOH, i.e. polyvinyl alcohol
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/0034—Polarising

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

The present invention provides the polarization plates that matcoveredn is formed on a kind of polarizing coating and the polarizing coating; on the polarizing coating; make iodine gas absorption quantity in polyvinyl alcohol resin (PVA) film; Boron contents are in the range of 1~3.5 weight %; when cutting into using absorption axiss as 2mm × 10mm of long side size and being heated 4 hours at 80 DEG C; its convergent force for absorbing on direction of principal axis is below 2.8N, and the b values of orthogonal tone are in the range of -2.2~+0.5.Iodine staining, boric acid processing and washing are implemented to PVA film successively, and uniaxial tension is carried out in the stage in boric acid processing or before it, implements the primary drying that film is dried in the processing of above-mentioned boric acid and between washing, thus can manufacture the polarizing coating.

Description

Polarizing coating and its manufacture method and polarization plates
Technical field
The present invention relates to the manufacture method and polarization plates of the polarizing coating suitable for liquid crystal display device, the polarizing coating.In detail For thin, it is related to and neutral ash can be achieved and durability also excellent polarizing coating, the manufacture method of the polarizing coating and by transparent guarantor Sheath is formed at polarization plates obtained by polarizing coating.
Background technology
Liquid crystal display device has the feature such as low consumption electric power, low voltage operating, lightweight, slim, is used for various displays With in device.In general, the liquid crystal panel for forming liquid crystal display device possesses and is fitted with polarization plates on the surface of liquid crystal cells Composition.Generally, polarization plates have following structures, i.e. include polyethenol series tree in dichroism pigment generation gas absorption quantity The single or double of the polarizing coating (also referred to as polarizer) of fat is laminated with transparent diaphragm.As dichroism pigment, typically may be used Use iodine or dichroic organic dye.
Dichroic organic dye as the dyestuff system polarizing coating of dichroism pigment and is made it be bonded with diaphragm and obtained The durability of dye-containing polarizer, especially excellent heat resistance, therefore, be mainly used in the neck more than the chance that is exposed under high temperature Domain, for example using auto-navigation system as the automobile inside product of representative and the field of liquid crystal projector.On the other hand, iodine is made Iodine system polarizing coating for dichroism pigment and make its be bonded with diaphragm obtained by iodine system polarization plates and dye-containing polarizer phase Than for, polarization property is more excellent, therefore, is used for using television set as in the extensive field of representative.
The manufacture method of polarizing coating of the reference picture 5 to being widely adopted in the past is illustrated.Here, so that iodine is used as into two colors Property pigment in case of illustrate, still, for using dichroic organic dye in the case of dichroism pigment, only Iodine in the following description is changed into dichroism pigment, then it is substantially the same below.
Reel film 10 comprising polyvinyl alcohol resin is unreeled first with roller 11 is released, and is then directed to water In swelling groove 13 as swelling bath, here, being immersed in swelling bath (water) to implement swelling treatment.After implementing swelling treatment Film is directed to using the aqueous solution comprising iodine as in the staining trough 15 of dye bath, is dyed herein, adsorbs iodine.Then, it is imported into To using the aqueous solution comprising boric acid as in the fixing groove 17 of processing bath, the polyvinyl alcohol resin of iodine is adsorbed with herein by boron Acid and crosslink, iodine is fixed.
Handled in boric acid or in the stage before it, can implement what is be orientated for making iodine to polyvinyl alcohol resin film Uniaxial tension.The uniaxial tension can in fixing groove 17 with boric acid processing carry out simultaneously, can also in staining trough 15 with dye Color is carried out simultaneously, can also simultaneously be carried out with dyeing and be handled with boric acid respectively in both staining trough 15 and fixing groove 17 Carry out simultaneously, can also stretch slot be set between staining trough 15 and fixing groove 17 and separately carried out with both, furthermore it is also possible to Before staining trough 15, generally it is independently arranged drawing mechanism before groove 13 is swelled and is carried out in a manner of dry type.
The film after boric acid processing is implemented to be then introduced into using water as in the rinsing bowl 19 of water washing bath, here, will be attached In on film but the foreign matter such as the medicine such as loose iodine or boric acid and rubbish is washed off, it is finally, right using final drying oven 23 Film implements drying.It is taken up by polarizing coating 30 obtained by final drying oven 23 in takers-in 27.Fig. 5, which is shown, will adsorb iodine The temporary transient form batched when takers-in 27 of polarizing coating 30 obtained by polyvinyl alcohol resin film is oriented in, still, here, not entering Row is batched and supplied to the process of ensuing attaching diaphragm, and the situation for continuously producing polarization plates is also implemented extensively.
For the conventional iodine system polarizing coating thus produced, it can not say that it includes heat resistance, humidity resistance exists Interior durability is necessarily abundant.Therefore, in Japanese Unexamined Patent Publication 7-198939 publications (patent document 1), especially for changing The humidity resistance of the kind polarizing coating comprising polyvinyl alcohol resin, it is proposed that following methods：More than 2 boric acid are set to handle work Sequence, and in each process by polyvinyl alcohol resin film immersion in the different treatment fluid of boron compound concentration so that it is relative Contain the weight % of boron atom 4.5~7 for the gross weight of polyvinyl alcohol resin film.
By improving the Boron contents in polarizing coating as described above, it is improved so as to can obtain the degree of cross linking, and even in Placed for a long time in hot and humid environment, its degree of polarization reduces also few polarizing coating.But because the degree of cross linking improves, therefore The convergent force of polarizing coating during heating becomes big.Therefore, will make the polarizing coating be bonded with diaphragm obtained by polarization plates fit in In the state of glass plate or liquid crystal panel, be alternately repeated carry out the testing of high temperature and low temperature, so-called thermal cycling test when, have When polarizing coating be broken along draw direction.
Therefore, following methods are proposed in Japanese Unexamined Patent Publication 2009-104062 publications (patent document 2)：Reduce and be used for Boric acid amount in the boric acid processing bath of boric acid treatment process, and boric acid treatment process is divided into 2 stages, make second stage Boric acid amount in boric acid processing bath further tails off and makes temperature that the boric acid of second stage handles also step-down, thus makes polarizing coating In Boron contents tail off so that polarizing coating durability improve.Thus, following polarizing coatings be can obtain：Boron in polarizing coating contains Scope of the amount in 3~3.9 weight %, and cut into using absorption axiss (tensile axis) direction of polarizing coating as short side 2mm × 8mm size, 80 DEG C are heated to, now, the convergent force in the direction orthogonal with absorption axiss is below 2.8N.For such polarization For film, the convergent force in the direction orthogonal with tensile axis is small, therefore, not easy to break in thermal cycling test, thus durability is excellent It is different.
On the other hand, especially for iodine system polarizing coating and polarization plates, for energy when applied to liquid crystal display device Original color is enough shown, and wishing transmitted light turns into neutral ash, i.e. muted color.For example, in Japanese Unexamined Patent Publication 2002-169024 The white displays for realizing neutral ash and the iodine system polarization plates of black display and its manufacture are shown in number publication (patent document 3) Method.
The content of the invention
Although the method according to being proposed in above-mentioned patent document 2 can obtain the polarizing coating of excellent in te pins of durability, but transmitted light Orthogonal tone shifted sometimes from neutral ash to blueness, now, become naturally and feel that the image for blueness is shown.So Sensation for blueness polarization plates easily boric acid processing used in processing bath boric acid concentration it is too low in the case of or boric acid Obtained in the case that washing after processing is excessive.That is, if the Boron contents in polarizing coating tail off, polarizing coating or polarization plates it is orthogonal Tone is in easily to the trend of blue shift.
One of problem of the present invention is, there is provided assigns the polarization plates and just for the excellent in te pins of durability of thermal cycling test Tone is handed over to turn into the polarizing coating and its manufacture method of neutral ash.Another problem of the present invention is, there is provided is formed at protective layer The polarizing coating and the still excellent in te pins of durability for thermal cycling test and orthogonal tone turn into the polarization plates of neutral ash.
That is, according to the present invention, it is possible to provide following polarizing coatings：Make iodine gas absorption quantity in polyvinyl alcohol resin film, Boron contents In the range of 1~3.5 weight %, cut into by absorb direction of principal axis be set to long side 2mm × 10mm size and in 80 DEG C During heating 4 hours, its convergent force on direction of principal axis is absorbed be below 2.8N, and the b values of orthogonal tone in -2.2~+ In the range of 0.5.
For the polarizing coating, preferably above-mentioned convergent force is below 2.1N, additionally, it is preferred that the b values of orthogonal tone be in- In the range of 1.0~0.
For above-mentioned polarizing coating, it can be manufactured by following methods：Polyvinyl alcohol resin film is implemented successively to make iodine Dyeing process, boric acid treatment process and the washing step of absorption, and in above-mentioned boric acid treatment process or stage before it Implement the stretching process of progress uniaxial tension, between above-mentioned boric acid treatment process and washing step, implement to polyethenol series The primary drying process that resin film is dried.
In the method, primary drying process is preferably carried out as follows：The primary drying work will entered The moisture rate of polyvinyl alcohol resin film before sequence is set to W0, will after the primary drying process and enter washing step before The moisture rate of polyvinyl alcohol resin film be set to W1When, make following formula (1) represent moisture slip turn into 5~95 weight %, In the range of 30~80 weight %.
Moisture slip=((W0-W1)/W0〕×100 (1)
In addition, primary drying process is carried out 1~100 second preferably at a temperature of 40~300 DEG C.The primary drying process is excellent Choosing utilizes and the method for hot blast is blowed to polyvinyl alcohol resin film, makes the method for its direct contact heating component and it is shone The one kind or two or more method penetrated in the method for emittance is carried out.
In these methods, by implementing final drying process to the polyvinyl alcohol resin film after washing step, So as to obtain target polarization film.
In addition, according to the present invention, it may also provide and possess above-mentioned any polarizing coating and be formed at the polarizing coating at least The polarization plates of the protective clear layer of one side.
For the present invention polarizing coating for, even if when being placed in hot environment, convergent force is also small, thus with for Characteristic as the excellent in te pins of durability of thermal cycling test, also, orthogonal tone will not exceedingly be offset to blueness, for neutral ash. The polarization plates formed with protective clear layer are similarly neutral ash and excellent in te pins of durability on the polarizing coating.In addition, according to this hair Bright method, it may be advantageous to produce above-mentioned such neutral ash and the polarizing coating of excellent in te pins of durability.
Brief description of the drawings
Fig. 1 is the top view for the state for schematically showing test film when obtaining convergent force.
Fig. 2 is the diagrammatic cross-section of the preferred disposition example of the device in the manufacture method for represent polarizing coating.
Fig. 3 is the diagrammatic cross-section for representing the example that the layer of the polarization plates of the present invention is formed.
Fig. 4 is the section signal for representing the example that the layer for the liquid crystal panel and liquid crystal display device for possessing polarization plates is formed Figure.
Fig. 5 is the diagrammatic cross-section of the configuration example of the device in the manufacture method for represent conventional polarizing coating.
Embodiment
Hereinafter, for embodiments of the present invention, illustrated while suitably with reference to drawing.It should be noted that this hair Bright to be not exposed to the restriction such as component described below, configuration, these components, configuration etc. can be appropriate according to purport of the invention Ground changes.
[polarizing coating]
The polarizing coating of the present invention is iodine gas absorption quantity in the polarizing coating of polyvinyl alcohol resin film.First, to the polarizing coating Illustrate.
Polyvinyl alcohol resin film is used as the resin film of the base material of polarizing coating, is by polyvinyl acetate specifically It is the film of resin obtained by resin saponification.As polyvinyl acetate system resin, the homopolymerization as vinyl acetate can be included The polyvinyl acetate of thing, in addition, it can also include vinyl acetate and the copolymerization for the other monomers that can be copolymerized with it Thing etc..As can with the other monomers of vinyl acetate copolymerization, have for example unsaturated carboxylic acid class, olefines, vinyl ethers, Unsaturated sulfonic acid class, the acrylic amide with ammonium etc..
The saponification degree of polyvinyl alcohol resin is usually 85~100 moles of % or so, preferably 98 moles of more than %.Poly- second Enol system resin can be modified, such as also can be used through the modified polyvinyl formal of aldehydes, polyvinyl acetal Deng.The degree of polymerization of polyvinyl alcohol resin is usually 1000~10000 or so, and preferably 1500~5000 or so.
The material that polyvinyl alcohol resin film is formed can be as the reel of polarizing coating.Polyvinyl alcohol resin is film-made Method be not particularly limited, can be film-made using known method.The thickness of polyethenol series reel film does not also limit especially It is fixed, such as the appropriate selection from 20~150 μm or so of scope.
Iodine gas absorption quantity is set to can be used as polarizing coating in film obtained by such polyvinyl alcohol resin film.Specifically, lead to The dyeing process for implementing to adsorb iodine to polyvinyl alcohol resin film is crossed, the iodine adsorbed is fixed in resin and makes resin The washing step that the medicine or foreign matter washing of the boric acid treatment process of crosslinking and the film that will attach to after boric acid processing remove, And implement to carry out the stretching process of uniaxial tension in boric acid treatment process or process before it, thus can manufacture polarization Film.For the manufacture method, illustrate in detail below.
The polarizing coating of the present invention is that the convergent force for making absorption direction of principal axis diminishes, and orthogonal tone is turned into neutral grey polarization Film.Therefore, in the range of Boron contents are set into 1~3.5 weight %, cut into will absorb 2mm of the direction of principal axis as long side × 10mm size and in 80 DEG C heating 4 hours when, the convergent force absorbed on direction of principal axis is set to below 2.8N, in addition, will just The b values of tone are handed over to be set in the range of -2.2~+0.5.
The reasons why for the Boron contents in polarizing coating are set in the range of 1~3.5 weight %, illustrates.If polarizing coating In Boron contents be less than 1 weight %, then be difficult to obtain enough water resistances, on the other hand, if Boron contents more than 3.5 weight %, Then when implementation polarization plates carry out thermal cycling test, rupture is easily produced on the absorption direction of principal axis of polarizing coating.For body Reveal excellent water resistance and heat-resisting cyclicity, preferably by the Boron contents in polarizing coating be set to 2 weight % in above range with Upper and below 3 weight %.It is believed that the boron in polarizing coating is with boric acid (H3BO3) form exist in the state of free, Huo Zhe The unit of boric acid and polyvinyl alcohol formed cross-linked structure in the state of exist, Boron contents mentioned here be include as described above with Boron atom (B) amount of itself including situation existing for the state of compound.
Boron contents in polarizing coating can for example utilize high-frequency inductive coupling plasma body (Inductively Coupled Plasma：ICP) ICP Atomic Emission Spectrophotometer method quantifies to the boron amount in polarizing coating, the weight with boron relative to the weight of polarizing coating The form for measuring percentage calculates.
Then, for using the absorption direction of principal axis of polarizing coating as long side 2mm × 10mm size will be cut into and in 80 When being heated 4 hours at DEG C, absorb the reasons why the convergent force of direction of principal axis is set to below 2.8N and illustrate.If the convergent force exceedes 2.8N, then when implementation polarization plates carry out thermal cycling test, rupture is easily produced on the draw direction of polarizing coating.The receipts Contracting power is ideally zero, but due to being difficult to make the convergent force be zero, therefore, preferably 0.1~2.8N in actual applications In the range of.
In Fig. 1 by schematical top view to show to obtain the convergent force when test film state.That is, from polarizing coating On, the test film 1 of 2mm × 10mm size is cut using its direction of absorption axiss 5 as long side.For the test film 1, 10mm long side turns into the direction of absorption axiss 5, and 2mm short side turns into the direction orthogonal with absorption axiss 5.Absorption in polarizing coating Axle 5 is stretching direction of principal axis.The test film 1 is warming up to 80 DEG C and heated 4 hours.Now, obtain on the direction of absorption axiss 5 Caused convergent force S.Convergent force S specifically obtains using following method.That is, experiment dimensions indicated above cut Piece 1 is placed in thermo-mechanical analysis device (Thermo-Mechanical Analyzer：TMA in).Then, obtain by the chi In the state of very little holding is constant, caused, long side direction convergent force when 80 DEG C of heating 4 hours (240 minutes).As heat The commercially available product of mechanical analysis device (TMA), it can include for example by SII Nano Technology (strain) sale “EXSTAR-6000”。
Next, the reasons why in the range of the b values of the orthogonal tone in polarizing coating are set into -2.2~+0.5, is said It is bright.If the b values of the orthogonal tone are less than -2.2, hue shift to blueness, on the other hand, if the value exceedes+0.5, tone Yellow is offset to, therefore, deviates neutral ash in any case.B values mentioned here are the values in Lab color specification systems.As Similar to the concept of Lab color specification systems, there are JIS Z8729：2004 " method for expressing-the L of color*a*b*Color specification system and L* u*v*Table color The L of system " defined*a*b*Color specification system, but Lab color specification systems are used in the present invention.
Orthogonal tone refers to, make 2 polarization plates according to the orthogonal mode of respective absorption axiss it is overlapping in the state of, from one The tone of the light transmitted during the face irradiation light of side from the face of the opposing party.Here tone in Lab color specification systems can with a values and B values represent, the light C of standard can be used to determine.It should be noted that in the present invention, although being provided for polarizing coating The b values of orthogonal tone, but the actual measurement of orthogonal tone is that transparent protective film is fitted with the two sides of polarizing coating (in reality described later Apply in example is tri acetyl cellulose membrane) polarization plates in the state of carry out.Now, transparent protective film substantially can be considered that its is saturating It is 100% to penetrate rate, and therefore, the orthogonal tone of polarization plates can be considered identical with the orthogonal tone of polarizing coating.Lab color specification systems such as JIS K5981：As described in " 5.5 promote atmospheric exposure test " of 2006 " synthetic resin powder films ", with the bright of Hunter Index L and tone a and b is spent to represent.The b values of orthogonal tone can be by JIS Z8722：2009 " assay method-reflections of color And transparent objects color " in defined tristimulus values X, Y and Z and calculated by following formula.
B=7.0 (Y-0.847Z)/Y1/2
Given to this invention, Boron contents be in 1~3.5 weight % in the range of, the convergent force that absorbs on direction of principal axis be The polarizing coating that the b values of below 2.8N and orthogonal tone are in the range of -2.2~+0.5 can be manufactured by method described later. That is, in the manufacturing process of polarizing coating, by being set once between boric acid treatment process and the washing step carried out after it Drying process, although so as to Boron contents it is fewer and absorb direction of principal axis on convergent force it is small, can also produce orthogonal Tone is about the polarizing coating of neutral ash.Polarizing coating of the orthogonal tone for neutral ash can be produced by implementing primary drying process The reasons why it is unclear, such as the reasons why as described below can be speculated as.
That is, the cross-linking reaction of polyvinyl alcohol resin and boric acid is by the way that moisture is removed to carry out.On the other hand, as above institute State, the orthogonal tone of polarizing coating because the Boron contents in film tail off and to blue shift.Therefore, if at by iodine staining and boric acid The washing of film after reason is excessive, then the Boron contents in film tail off, and orthogonal tone becomes easily to blue shift.By at boric acid Primary drying process is set between science and engineering sequence and washing step, therefore dries film, so as to the situation phase with being not provided with the process Than that can promote the cross-linking reaction of polyvinyl alcohol resin and boric acid, especially can form both on film surface and fully hand over Join the layer (cross-linked layer) formed.It is believed that：By the cross-linked layer on the surface, so as to make polyethylene in ensuing washing step Boric acid inside alcohol resin film becomes to be not easy to outside dissolution, thus can suppress the reduction of Boron contents, obtains orthogonal tone base It is the polarizing coating of neutral ash in sheet.
[manufacture method of polarizing coating]
It is discussed above, Boron contents are few, the convergent force on direction of principal axis is absorbed is small and orthogonal tone is substantially neutrality The polarizing coating of ash can be manufactured by following methods as previously described, and methods described is：To the polyvinyl alcohol resin film as reel Implement dyeing process, boric acid treatment process and the washing step for adsorbing iodine successively, and before boric acid treatment process or its Stage in implement carry out uniaxial tension stretching process, between boric acid treatment process and washing step implement to polyvinyl alcohol The primary drying process that resin film is dried.Now, set preferably before dyeing process makes polyethenol series using water The swelling process of resin membrane swelling.In addition, final drying process is generally set after washing step.
Fig. 2 shows the preferred disposition of the device in the manufacture method of the polarizing coating of the present invention in the form of diagrammatic cross-section Example.Fig. 2 is only different at following aspects compared with the Fig. 5 for the expression prior art being illustrated before, i.e. is carrying out at boric acid Between the fixing groove 17 of science and engineering sequence and the rinsing bowl 19 of progress washing step afterwards, it is configured with and carries out above-mentioned primary drying work The primary drying stove 21 of sequence.While with reference to the figure, while being illustrated to the manufacture method of polarizing coating of the present invention.
Device shown in Fig. 2 is formed as follows：Reel film 10 comprising polyvinyl alcohol resin from release roller 11 Unreeled, pass sequentially through for carry out swelling treatment swelling groove 13, for carry out dye processing staining trough 15 and be used for into The fixing groove 17 of row boric acid processing.Film after fixing groove 17 passes through the primary drying for carrying out above-mentioned primary drying Stove 21 and by primary drying, then unreacted iodine or boric acid etc. are washed off by rinsing bowl 19, dried finally by final Stove 23 is dried, so as to obtain polarizing coating 30.Although moreover, not expressing in figure, in fixing groove 17 or it is previous real Apply uniaxial tension.For the polarizing coating 30 of gained, though it is shown that batching in the form of takers-in 27, but also may be used herein Supplied with not batching to the process of ensuing attaching diaphragm.In addition, Fig. 2 is shown sets swelling groove 13, dyeing respectively The example of 19 each groove 15, fixing groove 17 and rinsing bowl grooves, but can be set for a certain processing as needed more Individual groove.
The reel film 10 comprising polyvinyl alcohol resin of raw material as polarizing coating is generally around in releasing as shown in the drawing Roller 11 and turn into roll, and the state for strip is unreeled by the releasing roller 11.Reel film 10 comprising polyvinyl alcohol resin Thickness be usually in the range of 20~100 μm, be preferably in the range of 30~80 μm, in addition, its industrial practical application In the range of width is 1500~6000mm.
(1) it is swelled process
The swelling process for carrying out swelling treatment is the process for making reel film be connect with water and being swelled it.The swelling treatment can go out In remove the foreign matter for being attached to film surface, except striping in the plasticizer such as contained glycerine, assign easy dyeing in subsequent handling, The purpose of plasticising of film and carry out.The condition of swelling treatment can produce film in the range of it can realize above-mentioned purpose and not Determined in the range of the undesirable conditions such as extreme dissolving, devitrification.Specifically, by by the reel film comprising polyvinyl alcohol resin 10 are immersed in such as 10~50 DEG C of temperature, preferably 20~50 DEG C of processing bath and carry out swelling treatment.The time of swelling treatment Usually 5~300 seconds, preferably 20~240 seconds.
Generally, it is swelled in process, as shown in the drawing, is transported in the more deflector rolls of interior configuration of swelling groove 13 for accommodating processing bath Polyvinyl alcohol resin film.Further, since the problems such as film occurs to be swelled and easily make film produce fold in the direction of the width, therefore The fold of film is being eliminated preferably by amplitude-expanding device known to Stretching rollers, propellers, crowned roll, guide, stent folder, roller etc. While transport film.And then in order that bath in film conveyance stabilize, using in water spray control swelling groove 13 in water Stream or and with EPC devices (Edge Position Control devices：Detect the end of film and prevent the dress of the warpage of film Put) etc. be also useful.
In process is swelled, swelling can also occur in the conveyance direction of film and expand for film, therefore, in order to eliminate conveyance direction On film relaxation, the methods of preferably for example taking the speed of front and rear carrying roller for being pointed to be swelled groove 13 to be controlled.Tool For body, preferably the peripheral speed for the outlet side carrying roller for being swelled groove 13 is removed relative to entrance side according to the temperature of processing bath The ratio between peripheral speed of roller is sent to be set to 1.2~2 times or so.In addition, if needing, single shaft drawing can also be implemented in the process Stretch.
The processing used in groove 13 is swelled is bathed in addition to pure water or in the range of 0.01~10 weight % Add the aqueous solution obtained by boric acid or chloride, other inorganic salts, water-miscible organic solvent, alcohols etc..But for above-mentioned Purpose, preferably using the pure water for being substantially free of solvent components.The pure water for not having solvent components can be by carrying out to common water Method of reverse osmosis membrane processing etc. obtains.
Then process, the also settable water retting process by polyvinyl alcohol resin film immersion in water are swelled.As above institute State, in process is swelled, although film is swelled on width and the two directions of conveyance direction, by behind Water retting process is set, it is possible to adjusting the water suction state on the width of film, improves the mechanical properties of film, Jin Ergai The uniformity of the optical characteristics of the polarizing coating of kind final gained.It is preferably to be substantially free of for the processing bath in water retting processing The pure water of solvent components, in addition, its temperature is preferably in the range of 10~50 DEG C.
(2) dyeing process
Dyeing process makes iodine to be dyed in the aqueous solution (dye bath) comprising iodine to polyvinyl alcohol resin film It is adsorbed in polyvinyl alcohol resin film and carries out.The dyeing process is usually carried out：Will after being swelled process, according to circumstances It is immersed in the staining trough 15 for containing dye bath as shown in the figure further across the polyvinyl alcohol resin film after water retting process In.The condition of dyeing processing can be in the range of it can make iodine be adsorbed in polyvinyl alcohol resin film, and not produce the extreme of film Determined in the range of a problem that dissolving, devitrification.
The dye bath used in dyeing process can include the parts by weight of iodine 0.003~0.2 relative to the parts by weight of water 100 And the aqueous solution of the parts by weight of KI 0.1~10.In addition, instead of KI, and other iodate of zinc iodide etc can be used Thing, can also be on the basis of KI and with other iodide.Furthermore, it is possible to make the iodide such as boric acid, zinc chloride, cobalt chloride Compound in addition coexists.In the case of the composition beyond comprising iodine, as long as contain relative to the parts by weight of water 100 The aqueous solution more than parts by weight of iodine 0.003, so that it may be considered as dye bath.The temperature (dyeing temperature) of dye bath is usually 10~50 DEG C, be preferably 20~40 DEG C, the time (dyeing time) for being additionally carried out dyeing processing is usually 10~600 seconds, be preferably 30~ 200 seconds.
In dyeing process, in order to transport polyethenol series tree while eliminating the fold of film in the same manner as process with being swelled Adipose membrane, also can the amplitude-expanding device such as appropriately configured Stretching rollers, propellers, crowned roll, guide, roller, using these devices In the case of, as long as being arranged at the inside and/or its gateway of staining trough 15.
(3) boric acid treatment process
Boric acid treatment process is entered for the aqueous solution of the utilization comprising boric acid to the polyvinyl alcohol resin film after iodine staining Row processing, is crosslinked polyvinyl alcohol resin, and adsorbed iodine is fixed in resin and is carried out.The process generally passes through Polyvinyl alcohol resin film immersion after dyed process is entered in the fixing groove 17 for containing the processing bath comprising boric acid OK.
Bath used in boric acid processing (boric acid processing bath) can include boric acid 0.5~15 relative to the parts by weight of water 100 The aqueous solution of parts by weight.If the content of the boric acid in boric acid processing bath is very few, exists and be difficult to obtain sufficient cross-linking effect Trend, iodine is from polyvinyl alcohol resin film dissolution in washing step described later etc., and the orthogonal tone of polarizing coating is easily to blueness Skew.On the other hand, if the content of boric acid is excessive, become big in the presence of the convergent force absorbed in a heated condition on direction of principal axis and become Gesture, implement durability after polarization plates, especially for thermal cycling test reduces sometimes.In the present invention, due to inciting somebody to action Boron contents in polarizing coating are set to 1~3.5 weight % less slightlyly, and therefore, the content of the boric acid in boric acid processing bath is in above-mentioned model Also it is less slightly in enclosing, specifically, is set to 1~3.5 parts by weight relative to the parts by weight of water 100, is particularly preferably set to 2~3.5 weights Measure the scope of part.
Boric acid processing bath preferably contains iodide on the basis of boric acid, and its amount is usually relative to the parts by weight of water 100 5~20 parts by weight, it is preferably 8~15 parts by weight.If the content of the iodide in boric acid processing bath is few, the orthogonal color of polarizing coating Capacity transfer is easily to blue shift.On the other hand, if iodide containing quantitative change it is more, hinder the cross-linking reaction based on boric acid sometimes, That is, the orthogonal tone of polarizing coating is easily to blue shift.
Can be KI, zinc iodide etc. for this iodide.Alternatively, it is also possible to make the compound beyond iodide exist Is coexisted in boric acid processing bath, as its example, can include zinc chloride, cobalt chloride, zirconium chloride, sodium thiosulfate, potassium sulfite, Sodium sulfite, potassium sulfate, sodium sulphate etc..In addition, as needed can with boric acid be used together the boric acid such as glyoxal, glutaraldehyde with Outer crosslinking agent.
Boric acid processing is generally carried out at 50~70 DEG C, is preferably carried out at a temperature of 53~65 DEG C.If temperature is too low, The progress of cross-linking reaction easily becomes insufficient, on the other hand, if temperature is too high, easily causes the disconnected of film in boric acid processing bath Split, processing stability easily significantly reduces.In addition, the time of boric acid processing be usually 10~600 seconds, be preferably 20~300 seconds, More preferably 20~100 seconds.
Boric acid treatment process can also be carried out in single fixing groove 17, can also be such as the patent document of recited earlier Shown in 2 (Japanese Unexamined Patent Publication 2009-104062 publications) like that, carried out using several fixing grooves with multiple stages.In this feelings Under condition, the concentration of the fixing groove of the boric acid concentration of initial fixing groove preferably than setting afterwards is high.
Polyvinyl alcohol resin film can be in boric acid treatment process by uniaxial tension.Stretch processing describes in detailed below, Implement generally along the travel direction (conveyance direction) of machinery.In the case of uniaxial tension being carried out in boric acid treatment process, Its stretching ratio is preferably set in the range of such as 1.2~3 times.Uniaxial tension now can use what is configured at spaced intervals Multigroup roller, carried out with the multistage.
(4) stretching process
Stretching process is to be used to polyvinyl alcohol resin film is carried out uniaxial tension and makes it be orientated and along the orientation side To the process for being orientated iodine, can be carried out in the stage in the above-mentioned boric acid treatment process being illustrated or before this.Specifically For, the stretching process can in any at least one process in swelling process, dyeing process and boric acid treatment process or it In any process last stage carry out.Enter in any process in swelling process, dyeing process and boric acid treatment process During row uniaxial tension, such as the side of difference can be assigned by the carrying roller of the carrying roller to groove entrance side and groove outlet side Method etc. is carried out.On the other hand, when the last stage for being swelled process, dyeing process or boric acid treatment process carrying out uniaxial tension, The wet tensile that stretch slot is set before each operation can be used, the method stretched in atmosphere, side can also be used The dry type stretchings such as the method stretched with the roller contact edge after heating.
Stretch processing is preferably at least carried out in boric acid treatment process, further preferably in dyeing process and boric acid processing work Carry out in the two processes of sequence, especially more preferably carried out in swelling process, dyeing process and each process of boric acid treatment process. When implementing stretch processing in these processes, carried out under state during processing of the polyvinyl alcohol resin film immersion in groove is bathed Uniaxial tension.If reference picture 2 illustrates, when uniaxial tension is carried out in boric acid treatment process, the boron in fixing groove 17 Carry out in acid treatment bath, similarly, when uniaxial tension is carried out in dyeing process, carried out in the dye bath in staining trough 15, When carrying out uniaxial tension in being swelled process, carried out in the processing bath in swelling groove 13.
For the polyvinyl alcohol resin film after all stretching process, preferably stretch its final accumulation Multiplying power reaches 4.5~8 times, more preferably up to 5~7 times.Here, accumulation stretching ratio refers to, the reel that roller 11 unreels is released Which kind of length the datum length of the stretching direction of principal axis of film 10 reaches in the film after all stretching process terminate.Except in boric acid Then it is also to include these in the case of also being stretched in swelling process, dyeing process beyond being stretched in treatment process It is stretching in interior value.For example, for reel film, if the length of stretching direction of principal axis is 1m part at all stretchings Reason turns into 5m after terminating, then accumulation stretching ratio now is 5 times.
(5) primary drying process
In the present invention, primary drying process can be carried out between boric acid treatment process and washing step described later.This one Secondary drying process is to add to ratio, the i.e. moisture rate of the moisture contained by the polyvinyl alcohol resin film after perboric acid is handled Carried out with adjustment.
Here, moisture rate refers to, the moisture in film is (heavy relative to the ratio of the dry weight of polyvinyl alcohol resin film Measure %), moisture rate can be dried to be measured by sample obtained by the part by cutting film in heated oven etc..Specifically For, by the weight before the drying of the sample cut out and dried weight, defined using following formula (2).
Moisture rate=[(weight-dried weight before drying)/dried weight] × 100 (2)
For the moisture slip as defined in previous formula (1), it is will to be calculated once using above formula (2) The moisture rate of polyvinyl alcohol resin film before drying process is set to W0, by the polyvinyl alcohol resin film after primary drying process Moisture rate be set to W1When, the value that is calculated by both.
In primary drying process, preferably reach 5 according to the moisture slip for making above-mentioned polyvinyl alcohol resin film~ 95 weight %, the mode for further reaching 30~80 weight % are dried.If moisture slip is less than 5 weight %, poly- second The drying of enol resin film becomes insufficient, the orthogonal tone of polarizing coating of gained be present easily to the trend of blue shift. On the other hand, if moisture slip is higher than 95 weight %, the drying of polyvinyl alcohol resin film becomes over, and gained be present The convergent force absorbed on direction of principal axis of polarizing coating becomes big, and the trend of rupture etc. easily occurs for polarization plates.
If reference picture 2 illustrates to primary drying process, the film from fixing groove 17 out, which is directed to, once to be done In dry stove 21, heated herein, be subjected to primary drying processing.Heating now can be for example, by polyvinyl alcohol resin Film blows the method for hot blast, makes method that polyvinyl alcohol resin film directly contacts with generating component, to polyvinyl alcohol resin Method of film illumination radiation energy etc. is carried out.
When blowing hot blast, such as using the hot-blast spray nozzle of injection hot blast as heating arrangements, thus mechanism is directly to poly- second Enol resin film sprays hot blast.Using this method, the surface of polyvinyl alcohol resin film can be made using hot blast It is dried while moisture distributes, therefore, enables in particular to that effectively film surface is dried.
In the case where making polyvinyl alcohol resin film directly be contacted with generating component, such as by the roller (hot-rolling) after heating As heating arrangements, polyvinyl alcohol resin film is wound on the roller to be heated to film.According to this method, make poly- second Enol resin film is directly contacted with generating component, therefore the heating-up temperature of film can be made uniform, thus is not likely to produce and is dried not It is even etc..
In the case of illumination radiation energy, such as using infrared heater as heating arrangements, by thus to poly- second Enol resin film illumination radiation energy, is dried film self-heating.According to this method, make polyethenol series tree Adipose membrane self-heating is dried, therefore the inside that can include film is equably heated to overall inside.
Above-mentioned method can individually be implemented, and can also combine different a variety of methods.In addition, in order to polyethylene The two sides of alcohol resin film is dried, and it is preferred that setting above-mentioned heating arrangements in the both sides of film.
Primary drying for example can also in movement film impose heater it is hot in the form of it is (outside in ambiance Gas) in carry out, but in this case, the efficiency of heating surface caused by easily producing extraneous gas is low, the disorder of extraneous gas Caused drying mark etc..In order to prevent the above situation, as shown in Fig. 2 it is preferred that being carried out in the inside of drying oven 21, particularly preferably Carried out in the closed system for closing the inside of drying oven.For the method using hot blast or emittance, Influence caused by extraneous gas easily becomes big, therefore preferably implements drying process in closed system.But with hot-rolling Deng the method directly contacted like that, the influence of extraneous gas it is small in the case of, can also not by the inside closing of drying oven or It is dried in the open system for being not provided with drying oven itself.
Drying temperature in primary drying process is preferably 40~300 DEG C, particularly preferably 50~100 DEG C.It is dry for this For dry temperature, if closed system as described above, then the temperature measured in drying oven may be defined as.In addition, if For open system, then heating arrangements (hot-rolling etc.) temperature of itself is may be defined as.
Drying time in primary drying process is 1~100 second or so, is preferably 3~30 seconds.For the drying time Speech, if closed system, then it may be defined as entering in drying oven untill it comes out from polyvinyl alcohol resin film Time, it is open system such as to cross, then may be defined as being in the hot position that may be heated mechanism from polyvinyl alcohol resin film Nearby or with heating arrangements contact start, until leave to the hot position for being not easily susceptible to heating arrangements or not with heating arrangements Time untill contact.
Primary drying process can be carried out using a kind of heating arrangements with a stage, can also continuously set several add Heat engine structure and with multiple stages carry out.In addition, in the case where being dried with multiple stages, the drying temperature in each stage can be with It is identical or different, it is preferred that becoming higher mode according to drying stage drying temperature more rearward sets thermograde.
(6) washing step
Washing step is carried out to be washed to the polyvinyl alcohol resin film after primary drying process. Specifically, the removing of the medicaments such as unnecessary boric acid or the iodine of polyvinyl alcohol resin film can be will attach to using the washing process. The condition of washing process is：The temperature of water is usually 2~40 DEG C, processing time is usually 2~120 seconds.
As the method for washing, it can include for example by method of the polyvinyl alcohol resin film immersion in water and make Method that water is sprayed in the form of spraying to polyvinyl alcohol resin film etc..In addition, can also and it be implemented with these methods Washing process.
Washing step can be configured a rinsing bowl as illustrated in fig. 2 and be carried out with a stage, can also be matched somebody with somebody in series Put several rinsing bowls and carried out with multiple stages.In the case where carrying out washing step with multiple stages, can be configured at The aqueous solution of inorganic salts is used in any processing bath of upstream.The inorganic salt such as can be from KI, sodium iodide, zinc iodide, chlorine Change and select to use in zinc, sodium sulphate, sodium sulfite etc..In addition, one kind can be used only in these inorganic salts, can also and use more Kind.
In washing step, in order to transport polyethenol series tree while except the fold of striping in the same manner as swelling process Adipose membrane, and assign tension force along the mechanical travel direction preferably for polyvinyl alcohol resin film.Tension force now is for example excellent Elect 300~1000N/m as.
The conveyance speed of polyvinyl alcohol resin film in washing step can suitably select optimal speed, such as can set For speed 5~30m/ minutes of dividing a word with a hyphen at the end of a line.If making the conveyance speed of polyvinyl alcohol resin film become to be above 30m/ minutes, film be present The trend easily skidded on roller, the trend for easily producing a problem that being difficult to stable stretching be present.
Alternatively, it is also possible to implement uniaxial tension processing in washing step.In the case of being stretched herein, it is stretched again Rate can for example be set to 1.05~1.2 times.
(7) final drying process
Final drying process is to dry it in order to be heated to the polyvinyl alcohol resin film after washing step and come Carry out.Thus, the polarizing coating as object can be obtained.As the drying method carried out in final drying process, It may be used at method cited in above-mentioned primary drying process.
The condition of final drying process is preferably set to：40~100 DEG C are remained in temperature, is preferably maintained at 50~100 DEG C Drying oven in, processing time be 30~600 seconds or so.It should be noted that drying can be implemented using multiple drying ovens Processing.In this case, the temperature of each drying oven can be with identical or different, preferably according to the drying oven of section more rearward, stove The mode that interior temperature becomes higher sets thermograde.
Polarizing coating after final drying process can batch as needed to be protected in takers-in 27 as shown in Figure 2 Pipe, or do not batched herein, but the process for being directly fed to ensuing attaching diaphragm, until producing inclined The surface of vibrating diaphragm forms the polarization plates of matcoveredn.It should be noted that the thickness of the polarizing coating of final gained can be set to such as 2 ~40 μm or so.
[polarization plates]
The polarizing coating of the invention manufactured by method more than, can form protective layer on its at least one face, from And polarization plates are made.Fig. 3 shows the layer configuration example of the polarization plates of the present invention with diagrammatic cross-section.As shown in the drawing, polarization plates 40 Possess polarizing coating 30 and the protective layer 35 formed at least one face of the polarizing coating.Protective layer 35 is that have to prevent from polarizing The abrasion on the surface of film 30, the component for strengthen etc. function, are preferably made up of transparent resin.Although protective layer 35 can also be only A face of polarizing coating 30 is arranged at, it is preferred that as illustrated, being formed at the two sides of polarizing coating 30.
Protective layer 35 can for membranaceous diaphragm or make to have and utilize active-energy transparent resin film Cured layer obtained by solidification occurs for the resin for the property that ray etc. is solidified.
As the example of the transparent resin for diaphragm, the acrylic acid series such as methyl methacrylate system resin can be included Resin, olefin-based resin, polyvinyl chloride resin, cellulose-based resin, phenylethylene resin series, acrylonitrile-butadiene-styrene (ABS) Based copolymerized resin, acrylonitrile-styrene based copolymerized resin, polyvinyl acetate system resin, Vingon system resin, polyamide It is resin, polyacetals system resin, polycarbonate-based resin, Noryl system resin, polyester based resin (poly terephthalic acid fourth Diol ester system resin, PET series resin etc.), polysulfones system resin, polyether sulfone system resin, polyacrylate It is resin, polyamidoimide system resin, polyimides system resins, epoxy system resin, oxetanes system resin etc..These trees Fat can contain additive in the range of the transparency, the cementability with polarizing coating is not damaged.As in general protective layer 35, on In the resin stated, preferably using cellulose-based resin, especially triacetyl cellulose.
In the case where being formed protective layer 35 with cured layer, curability compound can be the curability of cationically polymerizable Compound or free-radical polymerised curability compound.Example as the curability compound of cationically polymerizable Son, can include epoxide of the intramolecular at least with an epoxy radicals, in intramolecular at least with an oxa- ring Oxetane compound of butane ring etc..In addition, the example as free-radical polymerised curability compound, can be included At least there are (methyl) acrylic compounds of (methyl) acryloxy etc. in intramolecular.It is such to contain curability The hardening resin composition of compound is solidified by the irradiation or heating of active energy beam, transparent so as to provide The excellent protective clear layer such as property, mechanical strength, heat endurance.
The thickness of protective layer is preferably relatively thin used in the polarization plates of the present invention, but the intensity decreases if excessively thin, processing Property deterioration, on the other hand, if blocked up, easily produce the transparency reduce or stacking after needed for hardening time it is elongated the problems such as. Therefore, the appropriate thickness of protective layer is, for example, 5~200 μm, preferably 10~150 μm, more preferably 10~100 μm.
In the case where using diaphragm as protective layer 35, it is bonded usually using adhesive on the surface of polarizing coating 30 Diaphragm.As adhesive, epoxy system resin, oxetanes system resin, carbamate system resin, cyanoacrylate can be used The adhesive as adhesive component such as acid esters system resin, acrylamide resin.From improve rapidly-curable and with this phase From the viewpoint of the productivity of the polarization plates of companion, as the example for the preferable adhesive for forming gluing oxidant layer, profit can be included The active energy ray-curable adhesive solidified with the irradiation of active energy beam.For example, using epoxide as Curability composition and thereto coordinate optical free radical polymerization initiator obtained by material be preferable active energy ray-curable One of adhesive.In addition, from the viewpoint of making gluing oxidant layer thinning, as adhesive, water system adhesive also can be used, will Adhesive component be dissolved in water or make adhesive component be dispersed in water obtained from adhesive.It is gluing as preferable water system Agent, it can include and for example be used as the water system composition of principal component using polyvinyl alcohol resin or carbamate resins.
When transparent protective film is fitted in into polarizing coating 30 by adhesive, in order to improve adhesive and polarizing coating and/or The cementability of diaphragm, implement the scorching processing of sided corona treatment, fire, corona treatment, ultraviolet to polarizing coating and/or transparent protective film The surface treatment such as line processing, primary coat coating process, saponification process is also effective.
When using cured layer as protective layer 35, such as can be by the way that hardening resin composition is coated on into polarizing coating Surface and irradiation using active energy beam etc. make the method that it solidifies to form protective layer.Hardening resin composition Coating can use the various coating methods such as scraper, bar, die coating machine, comma coater, gravure coater.
For protective layer 35, also the defencive function for not only possessing polarizing coating 30 can be used also to have other various functions concurrently Functional membrane.As the function of film as described above, for example anti-dazzle, antireflection, low reflection, antifouling, antistatic can be included Deng.In addition, by making protective layer 35 show phase difference, so as to which the phase separation layer for having defencive function concurrently can also be made.
[liquid crystal display device]
Polarization plates 40 discussed above can be used as the member of formation of liquid crystal panel.Fig. 4 is to represent liquid crystal panel 60 and answer The diagrammatic cross-section of the example formed with the Primary layer of its liquid crystal display device 90.Liquid crystal display device is carried out with reference to the figure Illustrate, polarization plates 40 are bonded to liquid crystal cells 50 and turn into liquid crystal as the component parts of liquid crystal panel 60, liquid crystal panel 60 The member of formation of display device 90.In general, liquid crystal panel 60 by liquid crystal cells 50, fit in the back side of liquid crystal cells 50 The polarization plates 40 of side and fit in another polarization plates 41 of visuognosis side of liquid crystal cells 50 and form.Fig. 4 shows Fig. 3 Shown polarization plates 40 of the invention are configured at the example of the rear side of liquid crystal cells 50, but can naturally also be configured at vision Recognize side.
Liquid crystal display device 90 can be made up of liquid crystal panel 60, light diffusing sheet 70 and backlight 80.In liquid crystal display device 90 In, liquid crystal panel 60 configures in the way of polarization plates 40 turn into the side of backlight 80, i.e. is spread according to a protective layer 35 and light Plate 70 opposed mode configures.Polarization plates 40 can fit in liquid crystal cells 50 by adhesive phase 38.Here, rear side is Refer to, liquid crystal panel 60 is equipped on to the side of backlight 80 during liquid crystal display device 90.In addition, visuognosis side refers to liquid crystal panel The opposite side of 60 backlight 80 when being equipped on liquid crystal display device 90.
Illustrated for the part for forming liquid crystal display device.Liquid crystal cells 50 are by being sealed between glass substrate Unit obtained by liquid crystal material is entered and has been subject to electric control, so as to show the element of image.As liquid crystal cells, VA moulds can be used Formula, IPS patterns, used blue phase liquid crystal liquid crystal drive pattern etc. known to pattern.
Light diffusing sheet 70 is the optical component for having the function of making the light from backlight 80 spread, deliver to liquid crystal panel 60. Light diffusing sheet 70 for example can by the particle as light diffusing agent is dispersed in thermoplastic resin and assign light diffusing material, Material that is concavo-convex and assigning light diffusing is formed on the surface of thermoplastic resin film, sets and disperses on the surface of thermoplastic resin film There is the coating layer of the resin combination of particle and assign the composition such as material of light diffusing.Light diffusing sheet 70 generally can be made into 0.1 ~5mm or so thickness.
Backlight 80 is for the device to the irradiation light of liquid crystal cells 50, there is edge-light (エ ッ ジ ラ イ ト) mode, full run-down type Mode etc..For the backlight of edge-light mode, using light sources such as the cold-cathode tubes or LED for being configured at side, pass through leaded light Plate and to the irradiation light of liquid crystal cells 50.In addition, for the backlight of full run-down type mode, light source is configured at liquid crystal cells 50 Immediately below rear side and to liquid crystal cells irradiation light.The species of backlight can suitably select and apply the use according to liquid crystal display device Backlight species needed for way.
Can also be set between light diffusing sheet 70 and liquid crystal panel 60 brightness improving piece (as reflective polarizing film by " DBEF " etc. of 3M companies sale), light diffusing sheet etc. other show the piece or film of optical functional.Other show optics work( The piece or film of energy property can also configure more than 2 as needed and configure as needed a variety of.
Embodiment
Embodiment described below come to the present invention further specifically illustrate, but the present invention do not implemented by these The restriction of example.In example, % and part of content or usage amount are represented, is then weight basis unless otherwise specified.
[embodiment 1]
Implement following each processing to the reel film comprising polyvinyl alcohol, manufacture polarizing coating.As reel film, it is polymerization Degree 2400,99.9 moles of % of saponification degree, the polyvinyl alcohol film of 60 μm of thickness, use by (strain) Kuraray sale " Kuraray Vinylon VF-PE#6000 " (trade name).
First, by above-mentioned reel film immersion in the pure water of 30 DEG C of temperature 68 seconds and make its swelling, then in iodine/iodate The weight of potassium/water than being dyed for 80 seconds in the aqueous solution for 0.063/2/100 in 30 DEG C of dippings.Then, in KI/boron The weight of acid/water in 56 DEG C of dippings in the aqueous solution for 11/2/100 than carrying out boric acid processing in 71 seconds.
The film after boric acid processing is set to carry out primary drying by drying oven.In the drying oven, by nozzle to film two Face blows hot blast, and the wind speed from the hot blast of nozzle blowout is 15.5m/ seconds, air quantity 4m3/ minute.The temperature of drying oven is set to 80 DEG C, the holdup time is set to 2 seconds.After primary drying, film is impregnated 2 seconds in 10 DEG C of the rinsing bowl full of pure water and washed Wash.Finally, dried 3 minutes in 60 DEG C, so as to produce iodine gas absorption quantity in the polarizing coating of polyvinyl alcohol.In the meantime, mainly Stretch processing is carried out in dyeing process and boric acid treatment process, the accumulation stretching ratio from reel film is 5.8 times.
[embodiment 2~10]
Change temperature and the holdup time of primary drying as shown in table 1, in addition, identical is carried out with embodiment 1 Operation, produces polarizing coating.
[comparative example 1]
Film after not carrying out primary drying and handling boric acid is imported into rinsing bowl immediately, in addition with embodiment 1 Identical operation is carried out, produces polarizing coating.
[comparative example 2]
The composition of the aqueous solution handled for boric acid is changed into KI/boric acid/water using weight ratio meter as 11/4/100, In addition, carry out operating with the identical of comparative example 1, produce polarizing coating.
[evaluation test]
Film in the polarizing coating produced in embodiment and comparative example for more than or manufacture way, utilizes following method Physical property measurement is carried out, is evaluated.
(a) the moisture rate measure of film and calculating for the moisture slip in primary drying
A part will be cut out into the film before rinsing bowl from each example, moisture rate test sample is made.Measure Initial stage (before drying) weight of the sample, it is then placed in drying oven " the MODEL DK-42 " of YAMATO science (strain) system In, it is dried under conditions of 105 DEG C, 1 hour, then, is taken out from drying oven, determines dried film weight.So Afterwards, according to previous formula (2) by before drying and dried film weight obtains the moisture rate of film.The ratio of primary drying is being not carried out Compared with example 1, each embodiment will be can be considered into the moisture rate of the film of (that is, the state that boric acid processing terminates) before rinsing bowl In will enter primary drying before (that is, the state that boric acid processing terminates) film moisture rate, therefore, be set to W0, will The moisture rate of film before will carrying out rinsing bowl in each embodiment (that is, after primary drying) is set to W1, by these values Substitute into previous formula (1), calculate the moisture slip caused by the primary drying of each embodiment.Result is summarized in table 1.
(b) measure of the b values of orthogonal tone
The two sides coating thickness of obtained polarizing coating is 80 μm of the diaphragm formed by triacetyl cellulose in each case, Produce polarization plates.Using 2 thus obtained by polarization plates, crossed nicols is configured in a manner of making absorption axiss mutually orthogonal (Network ロ ス ニ Us Le), the b values of orthogonal tone are determined using the spectrophotometer " V-7100 " of Japan's light splitting (strain) system.Will As a result it is summarized in table 1.
(c) Boron contents of polarizing coating
By high-frequency inductive coupling plasma body (ICP) ICP Atomic Emission Spectrophotometer method to the boron in obtained polarizing coating in each example (B) amount is quantified, and calculates weight percent of the boron for the weight of polarizing coating, the boron being set in polarizing coating contains Amount.ICP ICP Atomic Emission Spectrophotometers use " ICPS-8100 " of (strain) Shimadzu Seisakusho Ltd..Result is summarized in table 1.
(d) convergent force (MD convergent forces) on direction of principal axis is absorbed
By obtained polarizing coating in each example, direction of principal axis (MD) will be absorbed as long side, wide 2mm and long 10mm by cutting out Size, test sample is made.In thermo-mechanical analysis device (TMA) " EXSTAE- of SIINanoTechnology (strain) systems 6000 " the above-mentioned samples of placement, in the state of size is kept into constant, determine caused suction when heating 240 minutes for 80 DEG C Receive the convergent force (MD convergent forces) of direction of principal axis (long side direction, i.e. MD).Result is summarized in table 1.
Table 1
As shown in Table 1, the embodiment 1~10 of primary drying has been carried out and has been carried out using identical method to boric acid The comparative example 1 for not carrying out primary drying untill processing is compared, the b values of orthogonal tone near zero, specifically for -2.0~ In the range of+0.4.It follows that by carrying out primary drying, so as to which the b values of the orthogonal tone of the polarizing coating of gained will not be big Width to blue shift, so as to which good neutrality ash can be realized.
In addition, for embodiment 7 and 8 of the moisture slip caused by primary drying less than 20%, the b of orthogonal tone It is worth for below -1.8, slightly to blue shift.On the other hand, 80% implementation is higher than for the moisture slip caused by primary drying For example 9 and 10, MD convergent forces are more than 2.2N, and are slightly become big.On the other hand, subtract for the moisture caused by primary drying Few rate is for the embodiment 1~6 in the range of 30~80%, and the b values of orthogonal tone are in the range of -1~0, and MD is received Contracting power is below 2.1N.It follows that primary drying is carried out by way of being 30~80% according to moisture slip, so that The polarizing coating of gained is provided with good characteristic in orthogonal tone and convergent force these two aspects.
If it should be noted that the different comparative example 1 of the boric acid concentration in boric acid processing bath is compared with comparative example 2 Compared with then for the comparative example 2 of the aqueous solution high using boric acid concentration, the Boron contents in its polarizing coating become more, orthogonal tone B values close to zero, but MD convergent forces are up to 3.5N.It follows that the Boron contents in polarizing coating are more, then the contraction of polarizing coating Power is bigger, easier to rupture.
More than, according to the present invention, the problem of can obtaining in terms of lower shrinkage and tone few polarizing coating and polarization plates.Moreover, The polarization plates can be effectively applied to using liquid crystal display device as in the various display devices of representative.
Symbol description
1 ... obtains test film during convergent force
The absorption axiss of 5 ... test films
S ... convergent forces
The reel film of 10 ... polyvinyl alcohol resins
11 ... release roller
13 ... swelling grooves
15 ... staining troughs
17 ... fixing grooves
19 ... rinsing bowls
21 ... primary drying stoves
23 ... final drying ovens
27 ... takers-ins
30 ... polarizing coatings
35 ... protective layers
38 ... adhesives
40,41 ... polarization plates
50 ... liquid crystal cells
60 ... liquid crystal panels
70 ... light diffusing sheets
80 ... backlights

Claims (7)

  1. A kind of 1. polarizing coating, it is characterised in that it is iodine gas absorption quantity in the polarizing coating of polyvinyl alcohol resin film,
    Boron contents be in 1~be less than 2.5 weight % in the range of,
    Direction of principal axis will be absorbed as 2mm × 10mm sizes of long side and when heating 4 hours for 80 DEG C being cut into, and it is absorbing Convergent force on direction of principal axis is below 2.1N, and
    The b values of orthogonal tone are in the range of -1.0~0.
  2. 2. the manufacture method of the polarizing coating described in a kind of claim 1, it is characterised in that be successively to polyvinyl alcohol resin film Implement dyeing process, boric acid treatment process and the washing step for adsorbing iodine, and before the boric acid treatment process or its Stage in implement carry out uniaxial tension stretching process, so as to manufacture the method for polarizing coating, wherein,
    Between the boric acid treatment process and the washing step, implement what the polyvinyl alcohol resin film was dried Primary drying process,
    The primary drying process is carried out as follows：By the polyvinyl alcohol before will entering the primary drying process The moisture rate of resin film is set to W0, by the polyethenol series after the primary drying process and before washing step is entered The moisture rate of resin film is set to W1When, in the range of the moisture slip shown in following formula (1) is turned into 5~95 weight %,
    Moisture slip=((W0-W1)/W0〕×100 (1)。
  3. 3. manufacture method according to claim 2, wherein,
    The primary drying process is carried out in the way of the moisture slip turns into the range of 30~80 weight %.
  4. 4. the manufacture method according to Claims 2 or 3, wherein,
    The primary drying process is carried out 1~100 second at a temperature of 40~300 DEG C.
  5. 5. the manufacture method according to Claims 2 or 3, wherein,
    The primary drying process utilizes to be selected from and blows the method for hot blast to the polyvinyl alcohol resin film, makes the polyethylene The method of the direct contact heating component of alcohol resin film and the method to the polyvinyl alcohol resin film illumination radiation energy At least one of method carry out.
  6. 6. the manufacture method according to Claims 2 or 3, wherein,
    Implement final drying process for the polyvinyl alcohol resin film after the washing step.
  7. A kind of 7. polarization plates, it is characterised in that
    Possess the polarizing coating described in claim 1 and be formed at the protective clear layer of at least one side of the polarizing coating.
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