CN1598624A - Polarization membrane and manufacturing method thereof,polarizer and optical laminate - Google Patents
Polarization membrane and manufacturing method thereof,polarizer and optical laminate Download PDFInfo
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- CN1598624A CN1598624A CNA2004100851626A CN200410085162A CN1598624A CN 1598624 A CN1598624 A CN 1598624A CN A2004100851626 A CNA2004100851626 A CN A2004100851626A CN 200410085162 A CN200410085162 A CN 200410085162A CN 1598624 A CN1598624 A CN 1598624A
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- boric acid
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00634—Production of filters
- B29D11/00644—Production of filters polarizing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133753—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers with different alignment orientations or pretilt angles on a same surface, e.g. for grey scale or improved viewing angle
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nonlinear Science (AREA)
- Manufacturing & Machinery (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Ophthalmology & Optometry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Polarising Elements (AREA)
- Liquid Crystal (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
Provided is a polarizing film which has few voids and is free of wrinkles and a method for manufacturing the same, and to provide a polarizing plate and an optical laminate. The polarizing film is obtained by treating a polyvinyl alcohol film in order of swelling treatment, dyeing treatment, boric acid treatment and rinse treatment, subjecting the film to uniaxial stretching in a boric acid treatment step and/or a step before the same and further alleviating the stretching of the film by 1 to 5% in the stretching direction in the at least one step after the stretching treatment. The polarizing plate is obtained by pasting a protective film to the at least one surface of the polarizing film. The optical laminate is obtained by pasting at least one kind selected from a retardation plate, a viewing angle improving film and a translucent reflection plate to the polarizing plate pasted with the protective film on the at least one surface.
Description
[technical field]
The present invention relates to light leak (white point (ヌ ケ)) less, do not have the polarizing coating of wrinkle Zhe and manufacture method thereof, the polarizer of laminated diaphragm, any one of further laminated phase difference film, brightness enhancement sheet, field angle improvement film and Transflective film or multiple and optical laminate that constitute on the single face at least of this polarizing coating.
[background technology]
As polarizing coating, all be to use on the polyvinyl alcohol (PVA) mesentery absorption orientation dichromatism pigment all the time.That is, be polarizing coating with iodine as the iodine of dichromatism pigment or be known as dye class polarizing coating of dichromatism pigment etc. with dichroic dye.These polarizing coatings usually on its single face or two sides, are made polarizer by the diaphragms such as adhesive laminated triacetyl cellulose that the aqueous solution by polyvinyl alcohol resin constitutes.
Manufacture method as polarizing coating, for example, in patent documentation 1, put down in writing following method: make the polyethenol series film immersion in water, make it swelling after, dye with above-mentioned dichromatism pigment, and this film that stretches, then, be fixed on the film, the polyvinyl alcohol (PVA) mesentery carried out boric acid handle in order to make iodine, after the washing, carry out drying again.
In addition, in patent documentation 2, put down in writing following method: utilize on one side the aqueous solution that contains above-mentioned dichromatism pigment that the polyvinyl alcohol (PVA) mesentery of dry type uniaxial tension is dyeed, it is relaxed, and further in containing the aqueous solution of boric acid, it is stretched, make polarizing coating.
The polarizing coating that makes like this on its two sides or single face superimposed layer diaphragm, and is assembled into liquid crystal indicator as polarizer.
Yet if at high temperature use described liquid crystal indicator, near the mid point on four limits, light is sewed around the display frame, thereby looks and turn white, and promptly can produce so-called " white point " phenomenon.If produce such white point, near the mid point on four limits, contrast descends around display frame, and display quality reduces.
In order to solve such problem, in patent documentation 3, put down in writing behind the polyvinyl alcohol (PVA) mesentery of the uniaxial tension that washing boric acid is handled, Yi Bian the tension force of regulation is provided, Yi Bian the manufacture method of withering polarizing coating.But, in patent documentation 3, in the method for record, can appear at the problem that produces wrinkle Zhe on the polarizing coating of gained.
[patent documentation 1] spy opens flat 10-153709 communique
[patent documentation 2] spy opens the 2002-182035 communique
[patent documentation 3] spy opens the 2001-174634 communique
[summary of the invention]
The major subjects that the present invention will solve provides polarizing coating and manufacture method, polarizer and the optical laminate that so-called white point is few, do not have wrinkle Zhe.
Present inventors carry out meticulous research repeatedly in order to solve above-mentioned problem, found that the following new fact: the polyvinyl alcohol (PVA) mesentery is carried out swelling processing, dyeing processing, boric acid processing and washing processing successively, and in boric acid treatment process and/or operation before this, carry out uniaxial tension, and further make the stretching of film lax in the operation of at least one after stretch processing, so just, can make white point few and also do not have the wrinkle Zhe polarizing coating, thereby finish the present invention.
Promptly, polarizing coating of the present invention makes by following: the polyvinyl alcohol (PVA) mesentery is carried out swelling processing, dyeing processing, boric acid processing and washing processing successively, and in boric acid treatment process and/or operation before this, carry out uniaxial tension, and further make the stretching of film along draw direction lax 1～5% in the operation of at least one after stretch processing.
The manufacture method of the polarizing coating that the present invention relates to is characterised in that: it is that the polyethenol series film is carried out swelling processing, dyeing processing, boric acid processing and washing processing continuously successively, carry out the manufacture method of the polarizing coating of uniaxial tension in boric acid treatment process and/or operation before this, the stretching that makes above-mentioned film at least one operation after stretch processing is along draw direction lax 1～5%.
In the present invention, above-mentioned boric acid treatment process can be made up of a plurality of boric acid treatment process, in this case, above-mentioned film can stretch in initial boric acid treatment process, and from after boric acid treatment process at least one operation among the operation of washing step, the stretching of above-mentioned film is relaxed.
In addition, polarizer of the present invention is the polarizer of laminated diaphragm on the single face at least of above-mentioned polarizing coating.This diaphragm also can possess any one function of phase difference film, brightness enhancement sheet, field angle improvement film and Transflective film.Perhaps, also can be on single face the is laminated at least above-mentioned polarizer of diaphragm, the laminated optical laminate that is selected from least a of phase difference film, brightness enhancement sheet, field angle improvement film and Transflective sheet and makes.
According to the present invention, the stretching by making film at least one operation after stretch processing is lax 1～5% along draw direction, can obtain to make the effect of the few and Zhe that do not wrinkle of white point on the gained polarizing coating.By in liquid crystal indicator, using polarizer of the present invention, optical laminate, can obtain slim and high-quality liquid crystal display.
[embodiment]
Below, the present invention is described in detail.
Form the polyvinyl alcohol resin of polyvinyl alcohol (PVA) mesentery of the present invention, generally can exemplify and the polyvinyl acetate esters resin is carried out saponification obtain.Saponification degree be 85 moles of % or more than, be preferably 90 moles of % or more than, 99 moles of %～100 mole % more preferably.As the polyvinyl acetate esters resin, except polyvinyl acetate, can enumerate vinyl acetate and the multipolymer that can carry out other monomers of copolymerization with it as the simple polymkeric substance of vinyl acetate, for example, ethylene-vinyl acetate ester copolymer etc.As other monomers that can carry out copolymerization, for example, can enumerate unsaturated carboxylic acid class, olefines, vinyl ethers, unsaturated sulfonic acid class etc.The degree of polymerization of polyvinyl alcohol resin is 1000～10000, is preferably about 1500～5000.
Can also carry out modification to these polyvinyl alcohol resins, for example, can use by aldehydes and carry out modified polyethylene alcohol formal, polyvinyl acetal, polyvinyl butyral etc.Usually, as the parent material that polarizing coating is made, used thickness is 20 μ m～100 μ m, be preferably this film that does not stretch of polyvinyl alcohol resin film of 30 μ m～80 μ m.Industrial, the width of film is that 1500mm～4000mm is practical.
This film that does not stretch is stretched,, carry out drying and the thickness of the polyethenol series polarizing coating that makes, for example be about about 5～50 μ m Yi Bian carry out successively that swelling is handled, dyeing processings, water-fastization processing, tone adjustment are handled, the washing processing.
Polarizing coating of the present invention is the polyethenol series monadic stretching membrane that makes dichromatism pigment absorption orientation, and its manufacture method is divided from big aspect 2 kinds.The 1st kind of method is in air or inert gas, the polyvinyl alcohol (PVA) mesentery is carried out uniaxial tension after, carry out solution-treated according to the order that swelling is handled, dyeing is handled, boric acid is handled and washing is handled, carry out dry method at last.The 2nd kind of method is in aqueous solution, the polyvinyl alcohol (PVA) mesentery that does not stretch is carried out solution-treated according to the order that swelling is handled, dyeing is handled, boric acid is handled and washing is handled, in the operation before boric acid treatment process and/or boric acid treatment process, carry out the wet type uniaxial tension, carry out dry method at last again.
In any one method, uniaxial tension can carry out in 1 operation, also can carry out in 2 or above operation, preferably carries out in a plurality of operations.Drawing process can adopt known method, for example, stretches the hot-rolling pulling method of putting down in writing as No. 2731813 communiques of patent, stenter pulling method etc. by producing between 2 niprolls that make transport membrane between the roller that difference stretches.In addition, the order of operation as described above in proper order, has no particular limits for the quantity of handling bath and treatment conditions etc. basically, thereby without limits.
In addition, can certainly freely insert the operation that does not have record in the above-mentioned operation for other purposes.Example as such operation, after can being set forth in boric acid and handling, the dip treating (iodide processing) of being undertaken by not borated iodide aqueous solution or contain dip treating (zinc processing) operation that the aqueous solution of zinc chloride etc. carries out etc. by boronic acid containing not.
The swelling operation for the foreign matter that removes the striping surface, remove plastifier in the striping, provide the easy dyeing in the subsequent handling, the plasticized of film etc. to carry out.Be set in treatment conditions in the scope that can reach these purposes and in the scope of defectives such as the excessive dissolution that does not cause basilar memebrane, devitrification.When making the film swelling that in gas, stretches in advance, film is flooded in for example 20 ℃～70 ℃, preferred 30～60 ℃ aqueous solution.The dip time of film is 30 seconds～300 seconds, more preferably about 60～240 seconds.To from initial just not the former anti-film of stretching carry out under the situation of swelling, film is flooded in for example 10 ℃～50 ℃, preferred 20～40 ℃ aqueous solution.The dip time of film is 30 seconds～300 seconds, more preferably about 60～240 seconds.
In the swelling treatment process, on film, produce problems such as wrinkle Zhe owing to be easy to generate the swelling of film broad ways, the preferred wrinkle Zhe that uses known expanding apparatus such as stenter, double-screw bolt roller (spiral roll), crowned roll (crown roll), cloth guider (cross guider), roller (bend bar), stenter cloth gripper to eliminate film on one side, on one side transport membrane.In order to reach in bath the purpose of transport membrane stably, utilize the current of the swelling of spray control under water in bathing, perhaps coupling EPC device (marginal position control device: detect the end of film and prevent the device that film crawls) etc. is of great use.In this operation,,, for example, preferably take the means such as speed of the conveying roller of control and treatment groove front and back for the film of eliminating throughput direction speeds to hang down because film also enlarges along the direction swelling of film traveling.In addition, employed swelling is handled and is bathed, except pure water, can also use the aqueous solution of the boric acid (it is described that the spy opens flat 10-153709 communique) that adds 0.01 weight %～10 weight % scopes, chloride (it is described that the spy opens flat 06-281816 communique), mineral acid, inorganic salts, water-miscible organic solvent, alcohols etc.
Utilize dyeing process that the dichromatism pigment carries out the dichromatism pigment adsorbs orientation etc. on film purpose to be carried out in order to reach.Be set in treatment conditions in the scope that can reach these purposes and in the scope that does not cause defectives such as basilar memebrane excessive dissolution, devitrification.When using iodine as the dichromatism pigment, for example, under 10 ℃～45 ℃, preferred 20 ℃～35 ℃ temperature, and in weight ratio, under the concentration of iodine/KI/ water=0.003～0.2/0.1～10/100, carry out 30 seconds～600 seconds, be preferably 60～300 seconds dip treating.Can use other iodide, for example zinc iodide etc. replaces potassium iodide.In addition, other iodide and potassium iodide can also be used simultaneously.In addition, can also with compound such as the coexistences such as boric acid, zinc chloride, cobalt chloride beyond the iodide.When adding boric acid, containing on the iodine this point, be different from following boric acid and handle.With respect to the water of 100 weight portions,, just can be regarded as staining trough as long as contain 0.003 weight portion or above iodine.
When using water-soluble dichroic dye as the dichromatism pigment, for example, under 20 ℃～80 ℃, preferred 30 ℃～70 ℃ temperature, and in weight ratio, under the concentration of dichroic dye/water=0.001～0.1/100, carry out 30 seconds～600 seconds, be preferably 60 seconds～300 seconds dip treating.Employed dichroic dye aqueous solution can also contain dyeing assistant etc., for example, can contain inorganic salts, surfactants etc. such as sodium sulphate.Dichroic dye can be used separately, also two kinds or above dichroic dye can be used simultaneously.
As mentioned above, can also be in staining trough stretched film.The method that stretching utilizes the niproll make before and after the staining trough to have difference etc. is carried out.In addition, also can with the swelling operation similarly in dye bath and/or bathe the place, gateway stenter, double-screw bolt roller, crowned roll, cloth guider, roller etc. are set.
It is by containing with respect to 100 weight parts waters in the aqueous solution of 1～10 weight portion boric acid of having an appointment, the polyvinyl alcohol (PVA) mesentery with the dichromatism pigment dyeing being flooded implement that boric acid is handled.When the dichromatism pigment is iodine, preferably contain the iodide of 1～30 weight portion of having an appointment.
As iodide, can enumerate potassium iodide, zinc iodide etc.In addition, can also with compound such as the coexistences such as zinc chloride, cobalt chloride, zirconium chloride, sodium thiosulfate, potassium sulfite, sodium sulphate beyond the iodide.
It is in order to implement by the purpose of crosslinked and water-fast change or tone adjusting (prevent with blue cast etc.) etc. that this boric acid is handled.With under by the crosslinked and water-fast situation that turns to purpose, as required, except boric acid, perhaps can be with boric acid, use borax, glyoxal, crosslinking chemical such as glutaraldehyde.
In addition, also call titles such as water-fastization processing, crosslinking Treatment, immobilization processing sometimes handling with the water-fast boric acid that turns to purpose.In addition, also the boric acid that is adjusted to purpose with tone is handled titles such as being called complementary color is handled, the processing of dyeing again sometimes.
This boric acid is handled, and according to the not special difference of its purpose, is usually undertaken by the concentration that suitably changes boric acid and other additives, the temperature that processing is bathed.
Under the situation of former anti-film being carried out swelling, dyeing, boric acid processing, handling when boric acid is with by crosslinked and water-fast when turning to purpose, use is handled bath with respect to the boric acid that 100 weight parts waters contain about 3～10 weight portion boric acid, about 1～20 weight portion iodide, usually, under 50 ℃～70 ℃, preferred 55 ℃～65 ℃ temperature, carry out.Dip time was generally about 30～600 seconds, was preferably 60～420 seconds, more preferably 90～300 seconds.
In addition, the film that stretches is in advance dyeed, when boric acid is handled, boric acid is handled the temperature of bathing and is generally 50～85 ℃, is preferably 55 ℃～80 ℃.
Can also after handling, carry out being adjusted to the boric acid processing of purpose with tone with the water-fast boric acid that turns to purpose.For example, when dichroic dye is iodine,, use the boric acid processing bath that contains the boric acid of 1～5 weight portion of having an appointment, about 3～30 weight portion iodide with respect to 100 weight parts waters, generally under 10 ℃～45 ℃ temperature, carry out for this purpose.Dip time was generally about 3～300 seconds, was preferably 10～240 seconds.
Compare with handling with the water-fast boric acid that turns to purpose, it generally is to carry out under lower boric acid concentration, higher iodide concentration and lower temperature that the boric acid that is adjusted to purpose with tone is handled.
These boric acid are handled and also can be carried out in a plurality of operations, carry out in 2～5 operations mostly usually.At this moment, the aqueous solution of employed each boric acid treatment trough is formed, temperature can be identical with above-mentioned scope, also can be different.Above-mentioned handle and handle with the water-fast boric acid that turns to purpose with the boric acid that form and aspect are adjusted to purpose also can in a plurality of operations, carry out respectively.
In the boric acid treatment process, also can similarly carry out the stretching of film with dyeing process.Final accumulation draw ratio is approximately 4.5～7.0 times, is preferably 5.0～6.5 times.
After boric acid is handled, wash processing.For example, wash processing: will be adjusted to purpose with water-fastization and/or tone and carry out polyethenol series film immersion that boric acid handles in water, and, perhaps flood simultaneously and spray with the form spray water of spray by following.Water temperature in washing is handled is generally about 2～40 ℃, and dip time can be 2-120 about second.After the washing, in drying oven, under about 40～100 ℃ temperature, carry out after about 60～600 seconds washing dry.
In the present invention, in the operation after stretch processing, the stretching that makes film is along draw direction lax 1～5%.
Under the situation that dyeing stretches in the treatment process, from thereafter boric acid treatment process begin up at least one operation of washing treatment process, making stretch lax.Finish under the situation of stretching in the operation before the dyeing treatment process, what stretch at least one operation of the later operation that comprises dyeing treatment process and boric acid treatment process is lax.
When the boric acid treatment process is made up of a plurality of boric acid treatment process, the above-mentioned film that in initial boric acid treatment process, stretches, and the subsequent boron acid treatment operation from the boric acid treatment process of carrying out stretch processing begin up at least one operation of washing step, to stretch lax.
After carrying out the boric acid processing, carry out under the situation of above-mentioned iodide processing or zinc processing, what can also stretch in these operations is lax.
Specifically, make polyvinyl alcohol (PVA) mesentery lax contraction in handling bath of stretching.Relaxation rate (being shrinkage factor) preferably 1～5%.If relaxation rate is lower than 1%, do not have and reduce the effect that white point produces, on the contrary,, on the polyvinyl alcohol (PVA) mesentery, produce wrinkle Zhe if surpass 5%, probably can not be used for optical applications.Lax can carrying out in 1 operation also can carry out in a plurality of operations.Under the situation of in a plurality of operations, carrying out, with before lax and the total relaxation rate after lax be set at 1～5%.
Close diaphragm with bonding agent on the upper strata of one side at least of the polarizing coating of making like this, thereby make polarizer.
As diaphragm, the film that can enumerate film that the acetylcellulose resinoid by triacetyl cellulose and diacetyl cellulose and so on constitutes, constitute by the polyester resin of polyethylene terephthalate and poly (ethylene naphthalate), poly terephthalic acid Aden ester and so on, the film that constitutes by polycarbonate resin, the film that constitutes by the cycloolefin resinoid.As commercially available thermoplasticity cycloolefin resinoid, for example, the Topas (registered trademark) that sells by German Ticona company, the Arton (registered trademark) that sells by JSR Corporation, the Zeonor that sells by Japanese ZeonCorporation and Zeonex (all being registered trademark), the Apel (registered trademark) that sells by Mitsui Chemicals (strain) etc.If as diaphragm, when the system film, suitably adopt known method such as solvent cast method, extrusion by melting with the film that obtains with this cycloolefin resinoid system film.The cycloolefin resin film of system film also is commercially available, for example, by Sekisui Chemical Co., " the エ ス シ-Na " and " SCA40 " that Ltd sells etc.
Problems such as the thickness of diaphragm is preferably thin, but if too thin, strength degradation, processability variation on the other hand, if too thick, will produce the transparency and descend, and the curing time that needs after perhaps laminated is elongated.Therefore, the suitable thickness of diaphragm is preferably 10～150 μ m, more preferably 20～100 μ m for for example about 5～200 μ m.
In order to improve the cohesiveness between bonding agent and polarizing coating and/or the diaphragm, can also carry out surface treatments such as corona treatment, flame treatment, plasma treatment, ultraviolet ray irradiation, priming paint coating processing, saponification processing to polarizing coating and/or diaphragm.
Can also be separately or prevent dazzling surface treatments such as optical processing, antireflection processing, hard conating processing, antistatic treatment, antifouling processing in combination to diaphragm.In addition, diaphragm and/or diaphragm sealer can also contain ultraviolet light absorber or plastifier such as phenyl phosphate compounds, phthalate compound such as benzophenone compound, benzotriazole compound.
This protective film can also be combined on the single face of polarizing coating, also can be laminated in two-sided on.
Polarizing coating and diaphragm adopt bonding agents such as hydrosolvent class bonding agent, organic solvent class bonding agent, hot melt class bonding agent, solvent-free class bonding agent to carry out laminated.As hydrosolvent class bonding agent, for example, can enumerate polyvinyl alcohol resin aqueous solution, water system two-component-type ammonia ester class emulsion binding agent etc., as organic solvent class bonding agent, for example, can enumerate two-component-type ammonia ester class bonding agent etc., as solvent-free class bonding agent, for example, can enumerate one-pack type ammonia ester class bonding agent etc.Adhesive surface with polarizing coating is carried out under the situation of acetylcellulose class film as diaphragm of hydrophilicity-imparting treatment using by saponification processing etc., the polyvinyl alcohol resin aqueous solution is by suitably as bonding agent.For the polyvinyl alcohol resin that uses as bonding agent, the alcotex that makes except the polyvinyl acetate as the simple polymkeric substance of vinyl acetate being carried out saponification handle, also have to vinyl acetate and with it the multipolymer of other monomers of copolymerization carry out that saponification is handled and the ethenol system copolymer that makes, further have those hydroxyls are carried out partially modified modified polyvinylalcohol based polymer etc.In this bonding agent, can also use polyaldehyde, soluble epoxide compound, melamine compounds etc. as adjuvant.
Not restriction especially of method for laminated light polarizing film and diaphragm; for example; can be set forth on the surface of polarizing coating or diaphragm coating adhesive equably, another tunic on folded again on the coated face, by roller etc. carry out laminated, carry out dry method etc. again.
Usually, bonding agent is after preparation, is coated with under 15～40 ℃ temperature, and laminated temperature is generally about 15～30 ℃.Carry out dried after laminated, thereby remove the water equal solvent that contains in bonding agent, the baking temperature of this moment is generally 30～85 ℃, is preferably 40～80 ℃.Then, can 15～85 ℃, be preferably 20～50 ℃, more preferably under 35～45 ℃ the temperature environment, carry out common about 90 days maintenance, bonding agent is solidified.Because this curing time is long, the throughput rate variation, therefore, curing time is about 1～30 day, is preferably 1～7 day.
Like this, make by adhesive phase, the single face of polarizing coating or two-sided the polarizer of laminated diaphragm.
In the present invention, diaphragm can also have function as phase difference film, as the function of brightness enhancement sheet, as the function of reflectance coating, as the function of Transflective film, as the function of diffuser, as the optical functions such as function of optical compensation films.In this case; for example by optical functional films such as laminated phase difference film, brightness enhancement sheet, reflectance coating, Transflective film, diffuser, optical compensation films on the diaphragm surface; can make it possess such function; in addition, give such function can also for diaphragm itself.In addition, can also make diaphragm itself have multiple function as the diffuser of the function with brightness enhancement sheet etc.
For example, by carrying out,, can give function to said protection film as phase difference film perhaps by carrying out as No. 3168850 described processing such as communique of patent as No. 2841377 communique of patent, No. 3094113 described stretch processing such as communique of patent.In addition; open 2002-169025 communique or spy as the spy and open the described method of 2003-29030 communique and form micropore by utilizing; in addition, by overlapping selection reflection kernel wavelength different 2 layers or above cholesteric, can give the function of brightness enhancement sheet to said protection film.By on said protection film, utilizing evaporation or sputter etc. to form metal film, can give function as reflectance coating or Transflective film.By on said protection film, being coated with the resin solution that contains particulate, can give function as diffuser.In addition,, and make it orientation, can give function as optical compensation films by liquid crystal compounds such as coating dish type molecule liquid crystal compounds on said protection film.In addition, can also use suitable adhesive, with brightness enhancement sheet, trade names such as trade name: DBEF (ス リ-エ system (strain) produce): commercially available optical functional films such as WV film field angle such as (Fuji's description Off イ Le system (strain) are produced) improvement film, trade name: ス ミ カ ラ イ ト (registered trademark) (Sumitomo Chemical (strain)) equiphase difference sheet directly are laminated on the polarizing coating.
Below, by illustrative embodiments the present invention is specifically described, but the present invention is not limited to these
Embodiment.
[embodiment 1]
With thickness is that the polyvinyl alcohol film (99.9 moles of saponification degrees are more than the % for Network ラ レ PVC ニ ロ Application VF-PS#7500, the degree of polymerization 2400) of 75 μ m places 30 ℃ pure water, makes film lax and keep tense situation, floods about 130 seconds, makes film swelling fully.
Then, on one side with film immersion processings of dyeing in the weight ratio of iodine/potassium iodide/water is the aqueous solution of 0.02/1.5/100, uniaxial tension carries out on one side.Then, film immersion in the weight ratio of potassium iodide/boric acid/water be 10/5/100 60 ℃ aqueous solution carried out boric acid handle on one side, carry out uniaxial tension on one side, up to being 5.9 times from the former anti-accumulation draw ratio that begins.
Then, be about 30 seconds of dipping in 10/3/100 the aqueous solution in the weight ratio of potassium iodide/boric acid/water under 40 ℃ on one side with film, carry out the 2nd hypoborous acid and handle, the stretching that makes film on one side is along lax about 3% (therefore, last draw ratio is 5.9 * 0.97=5.72 times) of draw direction.At last, in 10 ℃ pure water after washing about 10 seconds, 60 ℃ dry 2 minutes down, making iodine is polarizing coating.In any operation, all do not produce wrinkle Zhe.
Two sided coatings polyethenol series bonding agent at this polarizing coating; and with diaphragm [tri acetyl cellulose membrane that saponification is handled is carried out on the surface; " Off ジ Star Network (registered trademark) T80UNL ", Fuji description Off イ Le system (strain) is produced; thickness 80 μ m] be laminated on the two sides; drying is 5 minutes under 60 ℃, thereby makes polarizer.
On the single face of this polarizer, be coated with acrylic adhesives, make its absorption axes be miter angle and be cut into rectangle (120mm * 90mm) with respect to long limit.By the mode that forms Nicol crossed respectively laminated 2 this polarizers on transparency glass plate two-sided, utilize naked eyes to observe.As a result, the part of laminated polarizer seems to be even black on the glass plate two sides, does not observe light and leaks (white point).Under 80 ℃ dry heat condition, the glass sheet of laminated this polarizer was left standstill 240 hours, utilize naked eyes to observe then, it is smaller that near the light the center on each limit of polarizer leaks (white point).
[embodiment 2]
Handle, when washing, make the stretching of film to relax about 3% (therefore, final draw ratio is 5.9 * 0.97=5.72 times) in addition along draw direction except not carrying out the 2nd hypoborous acid, operation similarly to Example 1, making iodine is polarizing coating.In any operation, all do not produce wrinkle Zhe.
Operate in the laminated diaphragm in two sides of this polarizing coating similarly to Example 1, thereby form polarizer.Operate similarly to Example 1 this polarizer is carried out the observation that light leaks (white point), the result is identical with embodiment 1.
[embodiment 3]
Except being to carry out the 2nd hypoborous acid in about 30 seconds in 10/5/100 60 ℃ the aqueous solution to handle in the weight ratio of potassium iodide/boric acid/water on one side with film immersion, the stretching that makes film on one side is along draw direction lax about 1%, and further washing on one side, make the stretching of film relax about 2% (therefore on one side along draw direction, final stretching ratio 5.9 * 0.99 * 0.98=5.72 is doubly) in addition, operation similarly to Example 1, making iodine is polarizing coating.In any operation, all do not produce wrinkle Zhe.
Operate in the laminated diaphragm in two sides of this polarizing coating similarly to Example 1, form polarizer.Operation is similarly to Example 1 carried out the observation that light leaks (white point) to this polarizer, and the result is identical with embodiment 1.
[embodiment 4]
In air, use 125 ℃ hot-rolling, making thickness is that the polyvinyl alcohol film (99.9 moles of saponification degrees are more than the % for Network ラ レ PVC ニ ロ Application VF-PS#7500, the degree of polymerization 2400) of 75 μ m stretches 4.9 times.This dry type stretching film is placed 60 ℃ pure water, film is not relaxed and the maintenance tense situation, flooded about 60 seconds, make the abundant swelling of film.Then, be in the aqueous solution of 0.05/5.0/100 dipping about 60 seconds dye processing in the weight ratio of iodine/potassium iodide/water with film under 28 ℃.Make the state that film does not relax and maintenance is nervous in the dyeing course.Then, film immersion in the weight ratio of potassium iodide/boric acid/water be 6/7.5/100 73 ℃ aqueous solution carried out boric acid handle on one side, carry out uniaxial tension on one side, up to being 5.3 times from the former anti-accumulation draw ratio that begins.Then, do not carry out the 2nd hypoborous acid and handle, wash about 10 seconds in 10 ℃ pure water, when washing, the stretching that makes film is along lax about 2% (therefore, final draw ratio 5.3 * 0.98=5.19 doubly) of draw direction.Drying is 2 minutes under 60 ℃, and making iodine is polarizing coating.In any operation, all do not produce wrinkle Zhe.
Operation similarly to Example 1 at the laminated diaphragm in the two sides of this polarizing coating, thereby forms polarizer.Operation is similarly to Example 1 carried out the observation that light leaks (white point) to this polarizer, and the result is identical with embodiment 1.
[comparative example 1]
Except the stretching that does not make film in the 2nd hypoborous acid treatment process is lax, operates similarly to Example 1, thereby make polarizer.In any operation, all do not produce wrinkle Zhe.
Operation similarly to Example 1, laminated this polarizer on glass plate two-sided utilizes naked eyes to observe, and the part of laminated polarizer seems to be even black on the glass plate two sides, does not observe light and leaks (white point).Under 80 ℃ dry heat condition, the glass plate of laminated this polarizer was left standstill 240 hours, utilize naked eyes to observe then, it is bigger than the polarizer of embodiment 1～4 that near the light the center on each limit of polarizer leaks (white point).
[comparative example 2]
Except the stretching that in the 2nd hypoborous acid treatment process, makes film along draw direction lax 6%, operate similarly to Example 1, in the relaxation processes process, wrinkle Zhe appears on film, can be used as the good polarizing coating of outward appearance that optical applications uses thereby can not make.
Claims (6)
1. polarizing coating, make by following: the polyvinyl alcohol (PVA) mesentery is handled by the order that swelling is handled, dyeing is handled, boric acid is handled and washing is handled, carry out uniaxial tension in boric acid treatment process and/or operation before this, the stretching that further makes film in the operation of at least one after stretch processing is along draw direction lax 1～5%.
2. the manufacture method of a polarizing coating, it is characterized in that: the polyethenol series film is being handled by the order that swelling is handled, dyeing is handled, boric acid is handled and washing is handled continuously, carry out in boric acid treatment process and/or operation before this in the manufacture method of polarizing coating of uniaxial tension, the stretching that makes above-mentioned film at least one operation after stretch processing is along draw direction lax 1～5%.
3. the manufacture method of polarizing coating as claimed in claim 2, wherein above-mentioned boric acid treatment process comprises a plurality of boric acid treatment process, above-mentioned film stretches in initial boric acid treatment process, in boric acid treatment process at least one operation in the operation of washing step hereafter, the stretching of above-mentioned film is relaxed.
4. a polarizer is made by closing diaphragm on the upper strata of one side at least of polarizing coating as claimed in claim 1.
5. polarizer as claimed in claim 4, wherein said protection film possesses any function of phase difference film, brightness enhancement sheet, field angle improvement film and Transflective film.
6. optical laminate is by with described polarizer of claim 4 and at least a laminated the making that is selected from phase difference film, brightness enhancement sheet, field angle improvement film and Transflective film.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP318418/03 | 2003-09-10 | ||
| JP318418/2003 | 2003-09-10 | ||
| JP2003318418A JP2005084506A (en) | 2003-09-10 | 2003-09-10 | Polarizing film, its manufacturing method, polarizing plate, and optical laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1598624A true CN1598624A (en) | 2005-03-23 |
| CN100397110C CN100397110C (en) | 2008-06-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100851626A Active CN100397110C (en) | 2003-09-10 | 2004-09-08 | Polarization membrane and manufacturing method thereof,polarizer and optical laminate |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2005084506A (en) |
| KR (1) | KR20050026863A (en) |
| CN (1) | CN100397110C (en) |
| TW (1) | TWI368052B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101852879A (en) * | 2009-03-30 | 2010-10-06 | 住友化学株式会社 | The manufacture method of light polarizing film |
| CN101025456B (en) * | 2006-02-24 | 2010-11-03 | 日东电工株式会社 | Method for manufacturing polarizer, polarizer, polarizing plate, optical film, image display device and cleaning device |
| CN101276013B (en) * | 2007-03-29 | 2011-12-14 | 住友化学株式会社 | Manufacturing methods of polarized light film and polarized light piece |
| CN101519502B (en) * | 2008-02-29 | 2012-10-10 | 住友化学株式会社 | Method for manufacturing polarizing film, polarizing sheet and optical laminate |
| CN107111043A (en) * | 2015-11-05 | 2017-08-29 | 住友化学株式会社 | Polarizer and its manufacture method |
| CN107765355A (en) * | 2016-08-18 | 2018-03-06 | 住友化学株式会社 | The manufacture method and manufacture device of polarizing coating |
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| JP2007041576A (en) * | 2005-07-04 | 2007-02-15 | Nitto Denko Corp | Method for producing optically functional film, optically functional film, polarizing plate, optical device and image display |
| JP2007279621A (en) * | 2006-04-12 | 2007-10-25 | Sumitomo Chemical Co Ltd | Polarizing plate and manufacturing method for polarizing plate with tacky adhesive agent |
| JP5257645B2 (en) * | 2007-10-25 | 2013-08-07 | 住友化学株式会社 | Manufacturing method of polarizing film and manufacturing method of polarizing plate |
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| US8198802B2 (en) | 2008-07-25 | 2012-06-12 | Samsung Mobile Display Co., Ltd. | Organic light emitting diode display for suppressing reflection of external light |
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| KR20150111879A (en) | 2014-03-26 | 2015-10-06 | 주식회사 엘지화학 | Methods for manufacturing for polarizing element, polarizing element roll and single sheet type polarizing element having locally bleaching areas |
| KR20170053039A (en) * | 2015-11-05 | 2017-05-15 | 스미또모 가가꾸 가부시키가이샤 | Polarizing plate and display device comprising the same |
| JP2017167565A (en) * | 2017-06-19 | 2017-09-21 | 住友化学株式会社 | Method for manufacturing polarizing plate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59169818A (en) * | 1983-03-16 | 1984-09-25 | Toray Ind Inc | Biaxially orientated film and manufacture thereof |
| JPH04288504A (en) * | 1991-03-18 | 1992-10-13 | Tsutsunaka Plast Ind Co Ltd | Production of polarizing film |
| JP3979688B2 (en) * | 1996-11-07 | 2007-09-19 | 日本合成化学工業株式会社 | Manufacturing method of polarizing film |
| JPH10153709A (en) * | 1996-11-22 | 1998-06-09 | Tokai Rubber Ind Ltd | Production of polarizer film |
| JP2001174634A (en) * | 1999-12-15 | 2001-06-29 | Sumitomo Chem Co Ltd | Method of producing polarizing film |
| TWI251089B (en) * | 2000-06-19 | 2006-03-11 | Nitto Denko Corp | Polarizer, polarizing plate, and liquid crystal display using the same |
| JP2002174729A (en) * | 2000-12-08 | 2002-06-21 | Sumitomo Chem Co Ltd | Polarizing plate, polarizing plate with adhesive and use of the same |
| JP4405075B2 (en) * | 2000-12-19 | 2010-01-27 | 日東電工株式会社 | Polarizing film, manufacturing method thereof, and polarizing plate using the same |
| CN100337134C (en) * | 2001-10-03 | 2007-09-12 | 日东电工株式会社 | Method for producing polaroid and liquid crystal display with poloroid |
-
2003
- 2003-09-10 JP JP2003318418A patent/JP2005084506A/en active Pending
-
2004
- 2004-08-27 TW TW093125844A patent/TWI368052B/en active
- 2004-09-07 KR KR1020040071208A patent/KR20050026863A/en not_active Application Discontinuation
- 2004-09-08 CN CNB2004100851626A patent/CN100397110C/en active Active
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101025456B (en) * | 2006-02-24 | 2010-11-03 | 日东电工株式会社 | Method for manufacturing polarizer, polarizer, polarizing plate, optical film, image display device and cleaning device |
| US8303867B2 (en) | 2006-02-24 | 2012-11-06 | Nitto Denko Corporation | Method for producing polarizer |
| CN101276013B (en) * | 2007-03-29 | 2011-12-14 | 住友化学株式会社 | Manufacturing methods of polarized light film and polarized light piece |
| CN101519502B (en) * | 2008-02-29 | 2012-10-10 | 住友化学株式会社 | Method for manufacturing polarizing film, polarizing sheet and optical laminate |
| CN101852879A (en) * | 2009-03-30 | 2010-10-06 | 住友化学株式会社 | The manufacture method of light polarizing film |
| CN101852879B (en) * | 2009-03-30 | 2014-02-26 | 住友化学株式会社 | Process for producing a polarizing film |
| CN107111043A (en) * | 2015-11-05 | 2017-08-29 | 住友化学株式会社 | Polarizer and its manufacture method |
| CN107765355A (en) * | 2016-08-18 | 2018-03-06 | 住友化学株式会社 | The manufacture method and manufacture device of polarizing coating |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200510791A (en) | 2005-03-16 |
| TWI368052B (en) | 2012-07-11 |
| KR20050026863A (en) | 2005-03-16 |
| CN100397110C (en) | 2008-06-25 |
| JP2005084506A (en) | 2005-03-31 |
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