CN106796321B - The manufacturing method of polarizing film and polarizing film - Google Patents
The manufacturing method of polarizing film and polarizing film Download PDFInfo
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- CN106796321B CN106796321B CN201580055184.4A CN201580055184A CN106796321B CN 106796321 B CN106796321 B CN 106796321B CN 201580055184 A CN201580055184 A CN 201580055184A CN 106796321 B CN106796321 B CN 106796321B
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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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—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
- G02B5/305—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 including organic materials, e.g. polymeric layers
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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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
Abstract
The present invention relates to polarizing films, more specifically be related to following polarizing film: the weight ratio of iodine and potassium element i.e. potassium element/iodine is 0.12~0.18, and include the boron element of 3~4.5 weight %, significantly excellent degree of polarization and heat resistance are thus shown simultaneously.
Description
Technical field
The present invention relates to polarizing film and its manufacturing methods.
Background technique
Liquid crystal display device (LCD), electroluminescent (EL) display device, plasm display device (PDP), field emission
Polarization plates used in various image display devices as display device (FED), Organic Light Emitting Diode (OLED etc.) are usual
It goes forward side by side including making iodine based compound or dichroism polarization material be adsorbed in polyethenol series (polyvinyl alcohol, PVA) film
Polarizing film made of row orientation, the polarization plates have following multi-ply construction: stacking gradually on the face of a side of polarizing film
Polaroid protective film, the bonding that polaroid protective film is stacked gradually on the face of another party of polarizing film, is engaged with liquid crystal cells
Oxidant layer and mold release film.
The polarizing film of the polarization plates image excellent for the reproducibility for being applied to image display device to provide color is constituted,
And it requires to have both high transmissivity and degree of polarization.In addition, with application from image display device to each field extension, it is large-scale
Changing tendency becomes more significant, generates at high operating temperatures for a long time using various image display devices such as liquid crystal display devices
Situation is not only to improve polarization property and the requirement of optical property increases, and the requirement for improving durability also increases, and ties
Fruit is to become very harsh for the condition of the performance of polarization plates.Moreover, current pursue has suitable for various environment and use
The image display device of the characteristic on way pursues the optical durability including tone variations under the high temperature conditions.
The manufacturing method of polarizing film is disclosed in KR published patent the 2009-70085th, but could not enough propose to be directed to
The alternative scheme of above-described problem.
Citation
Patent document
Patent document 1: KR published patent the 2009-70085th
Summary of the invention
Problems to be solved by the invention
The purpose of the present invention is to provide the polarizing films with excellent heat resistance and degree of polarization.
Solution for solving the problem
Technical solution 1 is related to a kind of polarizing film, which is characterized in that weight ratio, that is, potassium element/iodine of iodine and potassium element
Element is 0.12~0.18, and the content of boron element is 3~4.5 weight %.
On the basis of above-mentioned technical proposal 1, the polarizing film of technical solution 2 is configured to, the weight of iodine and potassium element
Than being 0.14~0.16.
On the basis of above-mentioned technical proposal 1 or 2, the polarizing film of technical solution 3 is configured to, and the content of boron element is 3.5
~4.0 weight %.
On the basis of any one of above-mentioned technical proposal 1 to 3, the polarizing film of technical solution 4 is configured to, and transmissivity is
43% or less.
Technical solution 5 is related to a kind of polarization plates comprising in the polarizing film of any one of above-mentioned technical proposal 1~4
The protective film of at least one side stacking.
Technical solution 6 is related to a kind of image display device, has the polarization plates of above-mentioned technical proposal 5.
Technical solution 7 is related to a kind of manufacturing method of polarizing film comprising is swollen, is contaminated with film to polarizing film formation
Color, crosslinking, extension, complementary color and the step of drying,
The manufacturing method of the polarizing film is characterized in that,
The content of the boronic acid compounds of the crosslinked fluid of the cross-linking step is 3~4.5 weight %, and the content of potassium iodide is 11
~13 weight %,
The content of the boronic acid compounds of the complementary color liquid of the complementary color step is 1.5~2.5 weight %, and the content of potassium iodide is
4~8 weight %.
On the basis of above-mentioned technical proposal 7, the manufacturing method of the polarizing film of technical solution 8 is configured to, the dyeing step
The content of the boronic acid compounds of rapid dyeing liquor is 0.3~5 weight %.
On the basis of above-mentioned technical proposal 7 or 8, the manufacturing method of the polarizing film of technical solution 9 is configured to, described inclined
It shakes in piece, weight ratio, that is, potassium element/iodine of iodine and potassium element is 0.12~0.18, and the content of boron element is 3~4.5
Weight %.
On the basis of any one of above-mentioned technical proposal 7 to 9, the manufacturing method of the polarizing film of technical solution 10 is constituted
For the transmissivity of the polarizing film is 43% or less.
On the basis of any one of above-mentioned technical proposal 7 to 10, the manufacturing method of the polarizing film of technical solution 11 is constituted
To carry out the second extension with film to polarizing film formation with 1.01~1.1 times of ratio of elongation in the complementary color step.
Invention effect
The excellent heat resistance of polarizing film of the invention.Even if as a result, in the case where being exposed to hot conditions for a long time,
It can make to generate a possibility that reddening phenomenon minimum.Especially, polarizing film of the invention is showed when not having high-transmission rate
The heat resistance further improved out.
Polarizing film of the invention shows the degree of polarization significantly improved.
Specific embodiment
The present invention relates to a kind of polarizing film, the polarizing film by be configured to iodine and potassium element weight ratio (potassium element/
Iodine) it is 0.12~0.18 and includes the boron element of 3~4.5 weight %, significantly excellent degree of polarization is thus shown simultaneously
And heat resistance.
Hereinafter, the present invention will be described in detail.
<polarizing film>
In polarizing film of the invention, the weight ratio of iodine and potassium element is 0.12~0.18, and the content of boron element is 3
~4.5 weight %.
If the weight ratio of iodine and potassium element, less than 0.12, degree of polarization reduces, if more than 0.18, it is sudden and violent for a long time
Iodine is decomposed and is possible to generate the phenomenon that reddens when being exposed to high temperature.From having excellent this side of degree of polarization and heat resistance simultaneously
Face is set out, and can also be preferably 0.14~0.16.
If the content of boron element is less than 3 weight %, the PVA-I with short-wavelength absorption region3Complex compound production quantity is few
Therefore degree of polarization reduces, and is possible to generate the phenomenon that reddens if more than 4.5 weight %.In addition, if the content of boron element is 4.5 weights
% or more is measured, then thermal shock resistance reduces, and is possible to crack in thermal shock experiment.There is excellent polarization from simultaneously
Degree, heat resistance and thermal shock resistance this aspect are set out, and can also be preferably 3~4.4 weight %, and more preferably 3.5~4.0
Weight %.
The transmissivity of polarizing film of the invention may be 43% or less.In the case where transmissivity is 43% situation below, energy
Enough maximize the improvement of the heat resistance and thermal shock resistance.
Polarizing film of the invention is also possible to by including carrying out aftermentioned swelling, dyeing, friendship with film to polarizing film formation
Connection and dry step and the polarizing film produced.
As long as the film that polarizing film formation can be dyed with film by dichroic substance, that is, iodine etc., type do not have
Be particularly limited to, for example, can enumerate polyvinyl alcohol film, it is partly-hydrolysed after polyvinyl alcohol film, polyethylene terephthalate film,
Film after vinyl-vinyl acetate copolymer film, ethylene vinyl alcohol copolymer film, cellulose membrane, they partly-hydrolysed etc. this
The hydrophilic macromolecule film of sample, or the polyvinyl alcohol mesentery after dehydration, desalination acid treated polyvinyl alcohol can be enumerated
Polyenoid alignment films etc. as mesentery etc..In them, from the effect not only strengthened in face to the uniformity of degree of polarization
It is excellent and set out to the dyeing compatibility of iodine also this excellent point, preferred polyvinyl alcohol mesentery.
In polarizing film of the invention, carried out in a manner of making the weight ratio of iodine and potassium element be in above-mentioned range
The method of adjusting is not particularly limited, such as can be inclined by the concentration of the potassium iodide of change crosslinked fluid or complementary color liquid or change
Vibration piece formation is adjusted with the residence time that film is detained in crosslinking slot or complementary color slot.Likewise it is possible to pass through change crosslinked fluid
Or the delay that the concentration or change polarizing film formation film of the boronic acid compounds of complementary color liquid are detained in crosslinking slot or complementary color slot
Time is adjusted to the content that polarizing film has the boron element, but not limited.
<polarization plates>
In addition, present invention offer is laminated with the polarization plates of protective film in at least one side of the polarizing film.
For the type of the protective film, as long as the transparency, mechanical strength, thermal stability, water preventing ability, isotropism
It is just not particularly limited etc. excellent film, if lifting specific example, polyethylene terephthalate, poly- isophthalic diformazan can be enumerated
The polyester based resins such as sour glycol ester, polybutylene terephthalate (PBT)；The celluloses such as diacetyl cellulose, triacetyl cellulose
It is resin；Polycarbonate-based resin；The polyacrylic based resins such as poly- (methyl) ethyl acrylate, poly- (methyl) ethyl acrylate；
The phenylethylene resin series such as polystyrene, acrylonitritrile-styrene resin；Polyethylene, has ring system or norbornene structure at polypropylene
The polyolefin-based resins such as polyolefin, the ethylene propylene copolymer made；The polyamide resins such as nylon, aromatic polyamide；Acyl is sub-
Amine system resin；Polyether sulfone system resin；Sulfone system resin；Polyether-ketone system resin；Polyphenylene sulfide system resin；Vinyl alcohol resin；Inclined chlorine
Vinylite；Vinyl butyral system resin；Aromatic ester system resin；Polyformaldehyde system resin；The heat as epoxy system resin etc.
The film that plastic resin is constituted, also can be used the film being made of the blend of the thermoplastic resin.Further, it is possible to use by
What the heat-curing resin or ultraviolet curing resin of (methyl) acrylic acid series, polyurethane series, epoxy, silicon systems etc. were constituted
Film.Wherein particularly, if considering polarization characteristic or durability, preferably have and (saponification) is saponified by alkali etc.
The cellulose mesentery on surface afterwards.In addition, protective film can also have both the function of following optical layers.
The construction of the polarization plates is not particularly limited, and is also possible to meet the various optics layer stackups of necessary optical characteristics
The polarization plates made of on polarizing film.For example, it is also possible to have polarizing film at least one party surface layer be laminated with to polarizing film into
The construction of the protective film of row protection, polarizing film at least one party face or protective film on be laminated with hard conating, anti-reflection layer, anti-
The construction of the surface-treated layers such as adhesive layer, barrier layer, antiglare layer, polarizing film at least one party face or protective film upper layer
It is laminated with the construction of the aligned liquid-crystal layer or other function film that compensate to visual angle.Alternatively, it is also possible to being to form various images
Optical film as used polarization converter, reflector, half transmitting plate including 1/2 wavelength plate or 1/4 when display device
The phase plate of wavelength plate equiwavelength plate (including λ plate), compensation film for angular field of view, more than one in brightness enhancement film are as optical layer tegillum
Folded construction.More specifically, the surface layer as the side in polarizing film is laminated with the polarization plates of the construction of protective film, it is preferred to use
The reflection type polarizer or Semitransmissive polarization plates of reflector or half-transmitting reflector are laminated on the protective film being laminated,
It is laminated with the ellipse or circular polarization plate of phase plate on the protective film being laminated, view is laminated on the protective film being laminated
The wide viewing angle polarization plates of angle compensation layer or compensation film for angular field of view, or it is laminated on the protective film being laminated the polarization plates of brightness enhancement film
Deng.
Such polarization plates can be applied not only to common liquid crystal display device, and can be aobvious suitable for electroluminescent
The various image display devices such as showing device, plasm display device, field-emission display device.
<manufacturing method of polarizing film>
The manufacturing method of polarizing film of the invention include polarizing film formation is swollen with film, is dyed, is crosslinked, is extended,
Complementary color and the step of drying.
The number of occurrence, process conditions of each manufacturing step of polarizing film of the invention etc. are without departing from the purpose of the present invention
Just be not particularly limited, extend step can be carried out by independent step, or with one in swelling, dyeing and cross-linking step
A above step simultaneously carries out.
Polarizing film formation is not particularly limited with film, may be exemplified film above-mentioned, preferably polyvinyl alcohol mesentery.
Hereinafter, the present invention will be described in detail one realizes the manufacturing method of the polarizing film of example.
Swelling step
Swelling step is the steps of: forming polarizing film before being dyed to the polarizing film formation not extended with film
With film immersion in by being swollen the swelling slot being full of with aqueous solution, for removing the dirt accumulated on the surface of polarizing film formation film
Angstrom, impurity as anti-sticking agent, make polarizing film formation membrane swelling and improve extension efficiency, also inhibit dyeing inhomogeneities and
Improve the physical property of polarizing film.
As swelling aqueous solution, it usually can be used alone water (pure water, deionized water), or raising high score
The processability of sub- film and add a small amount of glycerol.
Comprising glycerol, content is not particularly limited, such as can be in the total weight of swelling aqueous solution
For 5 weight % or less.
The temperature of swelling slot is not particularly limited, such as can be 20~45 DEG C, and preferably 20~40 DEG C.In the temperature of swelling slot
In the case that degree is in above-mentioned range, extension and dyeing efficiency later is excellent, can prevent from being drawn by excessive swelling
The expansion of the film risen.
The execution time (swelling slot dip time) of swelling step is not particularly limited, for example, can be 180 seconds hereinafter, it is preferred that
It is 90 seconds or less.In the case where swelling slot dip time is in above-mentioned range, being able to suppress becomes because being swollen excessively
The case where saturation state, can prevent the fracture as caused by the softening of polarizing film formation film, the absorption of iodine in staining procedure
Become uniformly, to can be improved degree of polarization.
Swelling step and extend step and can carry out together, ratio of elongation in this case may be about 1.1~3.5 times, excellent
It is selected as 1.5~3.0 times.Fold is generated sometimes in the case where above-mentioned ratio of elongation is less than 1.1 times, more than 3.5 times
Initial optical characteristics are likely to decrease.
In swelling step, can in bath and/or bath entrance be provided with spreader roll, propellers, crowned roll, selvage guide
Device, roller etc..
Staining procedure
Staining procedure is to be full of polarizing film formation in by the dyeing liquor comprising dichroic substance such as iodine with film immersion
Staining trough and make polarizing film formation film adsorb iodine the step of.
Dyeing liquor can also also include water, water-miscible organic solvent or their mixed solvent and iodine.The concentration of iodine exists
It can be 0.4~400mmol/L, preferably 0.8~275mmol/L, more preferably 1~200mmol/L in dyeing liquor.
Dyeing liquor can be also comprising iodide as dissolving adjuvant in order to improve dyeing efficiency.
The type of iodide is not particularly limited, for example, can enumerate potassium iodide, lithium iodide, sodium iodide, zinc iodide, silver iodide,
Lead iodide, cupric iodide, barium iodide, calcium iodide, stannic iodide, titanium iodide etc., from this high point of the solubility relative to water, preferably
Potassium iodide.They can be used alone or mix and use two or morely.
The content of the iodide is not particularly limited, such as can be 0.01~10 weight in the total weight of dyeing liquor
Measure %, preferably 0.1~5 weight %.
Dyeing liquor used in staining procedure of the invention can also also include boronic acid compounds.Pass through the dyeing liquor packet
Boracic acid compound increases polarizing film shape so as to improve the residence time of boronic acid compounds before carrying out cross-linking reaction
At the formation rate of the complex compound with the dichroic substance in film.Thereby, it is possible to improve the tone durability of polarizing film, improve polarization
Degree.
The concentration of boronic acid compounds in the dyeing liquor is not particularly limited, such as can be in the total weight of dyeing liquor
0.3~5 weight %, preferably 0.5~3 weight %.Feelings of the concentration of boronic acid compounds in dyeing liquor less than 0.3 weight %
Under condition, iodo-complexes forms increased effect and reduces, more than 5 weight %, it is possible to the rising of stress and send out
Raw cutting.
The type of the boronic acid compounds is not particularly limited, for example, the boronic acid compounds can enumerate boric acid, Boratex,
Potassium borate and lithium borate etc. can be preferably boric acid.They may be used alone or in combination two or more.
The temperature of staining trough is not particularly limited, such as can be 5~42 DEG C, preferably 10~35 DEG C.
Time by polarizing film formation with film immersion in staining trough is not particularly limited, such as can be 1~20 minute, can also
To be preferably 2~10 minutes.
Extension step can be simultaneously carried out with staining procedure, ratio of elongation in this case can be 1.01~2.0 times, excellent
It is selected as 1.1~1.8 times.
In addition, the accumulative ratio of elongation of the polarizing film until being swollen and extending step is preferably 1.2~4.0 times.Institute
In the case where accumulative ratio of elongation is stated less than 1.2 times, film generates fold sometimes, more than 4.0 times, initial optical characteristics
It is likely to decrease.
Cross-linking step
Cross-linking step be in order to realize the iodine molecule based on physical absorption dyeability not because external environment reduce due to incite somebody to action
Polarizing film formation after dyeing is with film immersion in adsorbed iodine molecule is fixed in crosslinked fluid the step of.
Crosslinked fluid used in cross-linking step of the invention includes boronic acid compounds.It include boration by the crosslinked fluid
Close object, so as to improve cross-linking efficiency and inhibit the film in process fold generation, form the orientation of dichroic substance and
Improve optical characteristics.
Dichroic dye, that is, iodine causes iodine molecule de- because of hygrothermal environment sometimes in the case where cross-linking reaction is unstable
From therefore it is required that sufficient cross-linking reaction.
Cross-linking step of the invention can be carried out by the first cross-linking step and the second cross-linking step, can also be in institute
It include boronic acid compounds in the used crosslinked fluid of the step of stating more than one in cross-linking step.
The concentration of boronic acid compounds in the crosslinked fluid is 3~4.5 weight %, preferably 4~4.5 weight %.If handing over
Join the concentration of the boronic acid compounds in liquid less than 3 weight % then degree of polarization reduction, is possible to if more than 4.5 weight % because excessively
Crosslinking bond and so that tension is risen and is cut off.
Boronic acid compounds identical with the boronic acid compounds used in staining procedure also can be used in boronic acid compounds.
The organic solvent that crosslinked fluid of the invention may include the water as solvent and can be soluble in one another together with water,
May be the uniformity of the degree of polarization in the face of polarizing film and prevent the desorption for the iodine caught and also comprising a small amount of iodine
Change potassium.
The concentration of potassium iodide in the crosslinked fluid is 11~13 weight %, preferably 12~13 weight %.If crosslinked fluid
Less than 11 weight %, then degree of polarization reduces the concentration of interior potassium iodide, and heat resistance reduces if more than 13 weight %, for a long time
When being exposed to high temperature, it is possible to produce redden phenomenon.
In addition to this, in the range of not damaging the purpose of the present invention, crosslinked fluid can also also include iodide above-mentioned.
The temperature of crosslinking slot is not particularly limited, such as can be 20~70 DEG C, preferably 40~60 DEG C.
Time by polarizing film formation with film immersion in crosslinking slot is not particularly limited, such as can be 1 second~15 minutes, excellent
It is selected as 5 seconds~10 minutes.
Extension step can be simultaneously carried out with cross-linking step, in this case, the ratio of elongation of the first cross-linking step can be with
It is 1.4~3.0 times, preferably 1.5~2.5 times.In addition, the ratio of elongation of the second cross-linking step can be 1.01~2.0 times, preferably
It is 1.2~1.8 times.
The accumulative ratio of elongation of first cross-linking step and the second cross-linking step can be 1.5~5.0 times, preferably
1.7~4.5 times.In the case where the accumulative ratio of elongation is less than 1.5 times, the rising effect of cross-linking efficiency is very little, super
In the case where crossing 5.0 times, the fracture of film is generated because of excessive extension, production efficiency is likely to decrease.
Extend step
Extending step can carry out at least one of swelling step, staining procedure, cross-linking step together as previously described,
Or carried out in can exist while transporting film after the above procedure air or non-active gas, it can also be used as use by prolonging
It stretches the independent extension step that the other extension slot that liquid is full of carries out and carries out.Alternatively, can also before swelling step
After extending the polarizing film formation film not extended in air or non-active gas, execution is swollen the film, is dyed, being handed over
Connection, washing and dry step.
Extending can be carried out by a step, can also be carried out by more than two steps, but preferably pass through two
Above step carries out.Extending can be carried out by the way that the methods of all speed differences of niproll are arranged.In addition, same with swelling step
Sample, can be in bath and/or the entrance of bath is provided with spreader roll, propellers, crowned roll, guide, roller etc..
Total accumulative ratio of elongation of the invention is preferably 4.0~7.0 times, and in the present specification, " accumulative ratio of elongation " is to instigate
The ratio of elongation of each step is worth obtained from being multiplied.
Complementary color step
Complementary color step is will be by the film immersion after the cross-linking step in the benefit comprising boronic acid compounds and iodide
Color liquid is come the step of adjusting tone.
Complementary color liquid used in complementary color step of the invention includes boronic acid compounds.
Boronic acid compounds same as the boronic acid compounds used in staining procedure can be used in boronic acid compounds.
The concentration of boronic acid compounds in the complementary color liquid is 1.5~2.5 weight %, preferably 1.8~2.2 weight %.
If the concentration of the boronic acid compounds in complementary color liquid less than 1.5 weight %, can not improve the orientation of iodine, the inhibition of tone variations with
And the improvement of durability is very little, thermal shock resistance reduces if more than 2.5 weight %.
The organic solvent that complementary color liquid of the invention may include the water as solvent and can be soluble in one another together with water,
May be the uniformity of the degree of polarization in the face of polarizing film and prevent the desorption for the iodine caught and also comprising a small amount of iodine
Change potassium.
The concentration of potassium iodide in complementary color liquid is 4~8 weight %, preferably 5~7 weight %.If the concentration of potassium iodide is small
In 4 weight %, then degree of polarization is reduced, and heat resistance lowers if more than 8 weight %, when being exposed to high temperature for a long time, it is possible to produce
Change red phenomenon.
In the manufacturing method of polarizing film of the invention, by by the concentration of the boronic acid compounds of crosslinked fluid and potassium iodide
It is adjusted to range above-mentioned with the boronic acid compounds of complementary color liquid and the concentration of potassium iodide, so that manufactured inclined
The weight ratio (potassium element/iodine) of iodine and potassium element is 0.12~0.18 in vibration piece, and the content of boron element is 3~4.5
Weight %.The advantages of being achieved in is as previously described.
In the case where the dyeing liquor of staining procedure includes the boronic acid compounds of concentration range above-mentioned, the range of Xiang Shangshu
The adjusting of progress becomes to be more easier.
In addition to this, in the range of not damaging the purpose of the present invention, complementary color liquid can also also include iodide above-mentioned.
Moreover, the present invention can also carry out the second extension of polarizing film formation film in complementary color step.
Extended by carrying out second, can be improved the degree of orientation of dichroic substance complex compound and improve stability, thus lead to
Even if the polarizing film crossing method of the invention and manufacturing also can make the decomposition of complex compound most after being exposed to high temperature for a long time
Smallization, tone excellent in te pins of durability.
Described second is extended and can be carried out with 1.01~1.1 times of ratio of elongation.If ratio of elongation is less than 1.01 times, dichroism
The improvement of the degree of orientation of substance complex is very little, if film is possible to break because of excessive extension more than 1.1 times
It splits.
The temperature of complementary color slot is 20~70 DEG C, the dip time of the polarizing film formation film in complementary color slot can for 1 second~
15 minutes, preferably 5 seconds~10 minutes.
Water-washing step
As needed, the manufacturing method of polarizing film of the invention can also further include water-washing step after complementary color completion.
Water-washing step is to remove the polarizing film formation that complementary color is completed in the rinsing bowl that is full of by water lotion with film immersion
The step of unwanted residue of polarizing film formation film is attached in step in front.
Washing can be water (deionized water) with aqueous solution, can also also add iodide into the water (deionized water).
As iodide, iodide identical with the iodide used in staining procedure can be used, it is preferable to use iodine in them
Change sodium or potassium iodide.The content of iodide is not particularly limited, such as can be 0.1~10 in the total weight of washing aqueous solution
Parts by weight can also be preferably 3~8 parts by weight.
The temperature of rinsing bowl is not particularly limited, such as can be 10~60 DEG C, can also be preferably 15~40 DEG C.
Water-washing step can omit, can also whenever staining procedure, cross-linking step, extend as step or complementary color step
Preceding step carries out when completing.Above alternatively, it is also possible to make a round trip, the number of occurrence is not particularly limited.
Drying steps
Drying steps are that the polarizing film formation film after making washing is dry, by inside contracting (neck-in) as caused by drying
And the orientation of caught iodine molecule is further increased come the step of obtaining optical characteristics excellent polarizing film.
As drying means, natural drying can be used, be air-dried, heat drying, microwave drying, the side such as heated-air drying
Method, the most recently newly microwave treatment for being activated to be dried using the water only made in film, is usually mainly handled using hot wind
With far infrared processing.
Temperature when heated-air drying is not particularly limited, preferred to the deterioration for preventing polarizing film with lower temperature into
Row, such as can be 20~90 DEG C, preferably 80 DEG C hereinafter, further preferably 60 DEG C or less.
The execution time of the heated-air drying is not particularly limited, such as can execute 1~10 minute.
The transmissivity of the polarizing film manufactured by the above method can be 43% or less.It is 43% feelings below in transmissivity
Under condition, the improvement of the heat resistance and thermal shock resistance can be made to maximize.
Hereinafter, showing preferred embodiment to help to understand the present invention, but these embodiments are only right
The example that the present invention is illustrated is not intended to limit the technical solution of the application, as known to those skilled in the art can be in the present invention
Scope and technical idea in the range of embodiment is made various changes and is corrected, certainly such deformation and amendment
Belong to the technical solution of the application.
Embodiment and comparative example
1. embodiment 1
Transparent polyvinyl alcohol (PVA) film (PE60, KURARAY company) that do not extend that saponification degree is 99.9% or more is used
25 DEG C of water (deionized water) impregnate 1 point 20 seconds and be allowed to after swelling, in the iodine containing 1.25mM/L, the iodine of 1.25 weight %
Change 30 DEG C of dyeing of the boric acid of potassium and 3 weight % with impregnated in aqueous solution 2 points 30 seconds and dyed.At this point, molten
Respectively with the ratio of elongation of 1.56 times, 1.64 times is extended and is extended into accumulative after staining trough passes through in swollen and staining procedure
Ratio of elongation is 2.56 times.Then, on one side in the potassium iodide containing 11 weight %, 56 DEG C of crosslinking water of the boric acid of 3 weight %
26 seconds (the first cross-linking steps) are impregnated in solution and are allowed to be crosslinked, and are extended on one side with 1.7 times of ratio of elongation.Then,
On one side the potassium iodide containing 11 weight %, the boric acid of 3 weight % 56 DEG C of crosslinking aqueous solution in impregnate 20 seconds (second
Cross-linking step) and be allowed to be crosslinked, extended on one side with 1.34 times of ratio of elongation.Then, on one side in the iodine containing 4 weight %
Change potassium, 1.5 weight % boric acid 40 DEG C of complementary color aqueous solution in impregnate 10 seconds, extend 1.01 times on one side.
At this point, being set as swelling, dyeing and crosslinking, total accumulative ratio of elongation of complementary color step is 6 times.After the completion of crosslinking,
Polyvinyl alcohol (PVA) film is dried 4 minutes using 70 DEG C of ovens and has manufactured polarizing film.
The polarizing film produced two-sided stacking triacetyl cellulose (TAC) film and produce transmissivity be 42.8%
The polarization plates of (deviation 0.2%).
2. embodiment 2~9 and comparative example 1~4
In addition to the boric acid of dyeing liquor, the boric acid and potassium iodide of crosslinked fluid are had adjusted documented by table 1 described as follows like that
Concentration, other than the boric acid of complementary color liquid and the concentration of potassium iodide, polarization plates have been manufactured using method similarly to Example 1.
[table 1]
Experimental example
1. the analysis of the weight ratio (K/I) of iodine and potassium element in polarizing film
The sample 0.15g of polarizing film sample manufactured by embodiment and comparative example is put into the bottle (Vial) of 30mL
And fill up distilled water 20g.
Then, the bottle is made described after being placed on 90 DEG C of thermostat and dissolving polarizing film with 3 hours time
Bottle natural cooling 30 minutes.Sample after natural cooling is put into the liquid of WDXRF equipment (Axios, PANalytical company)
Cup (Liquid cup), measures the weight of iodine and the weight of potassium element, and found out weight ratio.
2. the content analysis of the boron element in polarizing film
The sample 0.15g of polarizing film sample manufactured by embodiment and comparative example is put into the bottle of 30mL and into one
Sample weight is simultaneously set as 25g by step addition ultrapure water, and it is cold to be allowed to nature after being completely dissolved polarizing film in 90 DEG C of thermostat
But.
The beaker that sample inside bottle after natural cooling is moved to 100mL, with mannitol solution to remaining in bottle
The sample cleaning in portion twice, has been put into the beaker of 100mL.Then, the NaOH for titrating 0.1N has found out the content of boron element.
3. optical characteristics (degree of polarization)
After the polarizing film produced is cut to the size of 4cm × 4cm, using UV, visible light light spectral instrument (V-7100,
JASCO corporation) determine transmissivity.At this point, degree of polarization is defined by following mathematical expressions 1.As reference, need to pay attention to degree of polarization
Big influence is brought to contrast there are 0.001 or so error.Contrast reduces if degree of polarization is less than 99.990
And it is difficult to realize black (real black).
[mathematical expression 1]
Degree of polarization (P): [(T1-T2)/(T1+T2)]1/2×100
It should be noted that the unit of degree of polarization (P) is %.
(in formula, T1It is the parallel transmission obtained in the case where configuring the parallel state of absorption axiss for a pair of of polarizing film
Rate, T2It is the orthogonal transmission obtained in the case where configuring the orthogonal state of absorption axiss for a pair of of polarizing film).
4. Evaluation of Heat Tolerance
It will be inclined manufactured by embodiment and comparative example using spectrophotometer (V7100, Japanese light splitting company) measurement
Spectral transmission τ (λ) before vibration plate is placed 30 minutes under conditions of 105 DEG C and after placing, finds out just according to its result
Hand over spectral transmission spectrum, found out by following mathematical expressions 2 indicate it is heat-resisting after A700.
[mathematical expression 2]
A700=-Log after heat-resisting10{(TMD, 700×TTD, 700)/10000}
(in formula, TMD, 700It is that polarization plates produced after will be heat-resisting are configured to make the absorption axiss of the polarization plates and measurement
Transmissivity under the 700nm wavelength obtained when the orthogonal state of the rectilinearly polarized light of light, TTD, 700It is producing after will be heat-resisting
Polarization plates be configured to make the 700nm wave obtained when the absorption axiss of the polarization plates state parallel with the rectilinearly polarized light of light is measured
Transmissivity under long, unit %).
After above-mentioned Evaluation of Heat Tolerance, observes by visual observation and confirmed polarization plates and redden either with or without generation.
In the case where the A700 after heat-resisting is 2.3 situations below, can be observed to redden sometimes in visually observation polarization plates existing
As, it means that absorb the PVA-I in the region of the light of 600nm or more5The content of complex compound reduces.
5. the evaluation (H/S) of thermal shock test
After polarizing film manufactured by embodiment and comparative example is cut to 15.0cm (MD) × 11cm (TD) size, make
It is engaged in glass with the acrylic adhesive constituent of Dongwoo Fine-Chem company, has carried out autoclave (50
DEG C, 20 minutes, 5 air pressures) processing.After placing 24 hours, it is (alternately reciprocal that the sample produced is put into thermal shock oven
The condition that ground is set as 30 minutes at 30 minutes conditions at -40 DEG C and 70 DEG C is followed until the total ascent time reaches 6 hours as one
It is ring, reciprocal to carry out 200 circulations), and confirmed polarizing film either with or without cracking.
[table 2]
Referring to above-mentioned table 2, high degree of polarization and excellent is shown simultaneously using the polarization plates of the polarizing film of Examples 1 to 9
Heat resistance.
However, being reduced using the degree of polarization of the polarization plates of the polarizing film of comparative example 1~4, heat resistance is significantly reduced.
Claims (10)
1. a kind of polarizing film, which is characterized in that
Weight ratio, that is, potassium element/iodine of iodine and potassium element is 0.12~0.18, and the content of boron element is 3~4.5 weights
Measure %.
2. polarizing film according to claim 1, wherein
The weight ratio of iodine and potassium element is 0.14~0.16.
3. polarizing film according to claim 1 or 2, wherein
The content of boron element is 3.5~4.0 weight %.
4. polarizing film according to claim 1 or 2, wherein
Transmissivity is 43% or less.
5. a kind of polarization plates characterized by comprising
The polarizing film of any one of claims 1 to 4；And
Protective film is laminated in at least one side of the polarizing film.
6. a kind of image display device, which is characterized in that
Described image display device has polarization plates described in claim 5.
7. a kind of manufacturing method of polarizing film comprising be swollen to polarizing film formation with film, dye, be crosslinked, extending, complementary color
And dry step,
The manufacturing method of the polarizing film is characterized in that,
The content of the boronic acid compounds of the crosslinked fluid of the cross-linking step is 3~4.5 weight %, and the content of potassium iodide is 11~13
Weight %,
The content of the boronic acid compounds of the complementary color liquid of the complementary color step is 1.5~2.5 weight %, and the content of potassium iodide is 4~8
Weight %,
The transmissivity of the polarizing film is 43% or less.
8. the manufacturing method of polarizing film according to claim 7, wherein
The content of the boronic acid compounds of the dyeing liquor of the staining procedure is 0.3~5 weight %.
9. the manufacturing method of polarizing film according to claim 7 or 8, wherein
In the polarizing film, weight ratio, that is, potassium element/iodine of iodine and potassium element is 0.12~0.18, boron element
Content is 3~4.5 weight %.
10. a kind of manufacturing method of polarizing film comprising be swollen to polarizing film formation with film, dye, be crosslinked, extending, mending
Color and the step of drying,
The manufacturing method of the polarizing film is characterized in that,
The content of the boronic acid compounds of the crosslinked fluid of the cross-linking step is 3~4.5 weight %, and the content of potassium iodide is 11~13
Weight %,
The content of the boronic acid compounds of the complementary color liquid of the complementary color step is 1.5~2.5 weight %, and the content of potassium iodide is 4~8
Weight %,
The second extension is carried out with film to polarizing film formation with 1.01~1.1 times of ratio of elongation in the complementary color step.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2014-0138382 | 2014-10-14 | ||
| KR1020140138382A KR20160043765A (en) | 2014-10-14 | 2014-10-14 | Polarizer and preparing method thereof |
| PCT/JP2015/078800 WO2016060087A1 (en) | 2014-10-14 | 2015-10-09 | Polarizer and method for producing polarizer |
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| CN106796321A CN106796321A (en) | 2017-05-31 |
| CN106796321B true CN106796321B (en) | 2019-09-27 |
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| JP (1) | JP6685915B2 (en) |
| KR (2) | KR20160043765A (en) |
| CN (1) | CN106796321B (en) |
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| JP6735541B2 (en) * | 2015-07-31 | 2020-08-05 | 株式会社クラレ | Polarizing film |
| KR102535102B1 (en) * | 2016-08-18 | 2023-05-19 | 스미또모 가가꾸 가부시키가이샤 | Process for producing polarizing film and apparatus for producing polarizing film |
| JP2018091980A (en) * | 2016-12-02 | 2018-06-14 | 住友化学株式会社 | Polarizing film and manufacturing method of polarized laminate film |
| WO2018235461A1 (en) * | 2017-06-23 | 2018-12-27 | 日東電工株式会社 | Polarizing film, polarizing plate including said polarizing film, and vehicle on-board image display device including said polarizing plate |
| TWI640555B (en) * | 2017-08-16 | 2018-11-11 | 住友化學股份有限公司 | Method and system for manufacturing a polarizer film |
| TW201917197A (en) | 2017-08-31 | 2019-05-01 | 日商日本合成化學工業股份有限公司 | Polarizing plate, liquid crystal display device, method for producing liquid crystal display device, and polyvinyl alcohol-based polarizing film |
| WO2019188779A1 (en) * | 2018-03-28 | 2019-10-03 | 日東電工株式会社 | Polarizer, polarizing film, multilayer polarizing film, image display panel and image display device |
| JP2020126226A (en) * | 2019-02-04 | 2020-08-20 | 住友化学株式会社 | Polarizing plate and display device |
| JP2022526109A (en) * | 2019-03-29 | 2022-05-23 | エルジー・ケム・リミテッド | Display device |
| WO2020204335A1 (en) * | 2019-03-29 | 2020-10-08 | 주식회사 엘지화학 | Optical laminate |
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| CN101371173A (en) * | 2006-06-15 | 2009-02-18 | 日东电工株式会社 | Polarizing plate, image display, and method for producing polarizing plate |
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| JP3960520B2 (en) * | 2002-02-05 | 2007-08-15 | 日東電工株式会社 | Polarizer, polarizing plate and image display device |
| JP2004133242A (en) * | 2002-10-11 | 2004-04-30 | Nitto Denko Corp | Polarizing plate, optical film, and image display device |
| JP2005266326A (en) * | 2004-03-18 | 2005-09-29 | Nitto Denko Corp | Method for manufacturing polarizing film, polarizing film, optical film using the same and image display device |
| 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 |
| KR100947939B1 (en) | 2007-12-26 | 2010-03-15 | 주식회사 에이스 디지텍 | Method for manufacturing polarizer |
| JP5438581B2 (en) * | 2010-03-31 | 2014-03-12 | 住友化学株式会社 | Manufacturing method of polarizing film |
| JP6191197B2 (en) * | 2013-03-29 | 2017-09-06 | 住友化学株式会社 | Manufacturing method of polarizing film |
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| JPWO2016060087A1 (en) | 2017-07-27 |
| CN106796321A (en) | 2017-05-31 |
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| TWI702421B (en) | 2020-08-21 |
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