CN104412138B - Preparation method including the polarization plates being irradiated the operation adjusting polaroid color by ultraviolet light - Google Patents
Preparation method including the polarization plates being irradiated the operation adjusting polaroid color by ultraviolet light Download PDFInfo
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- CN104412138B CN104412138B CN201480000909.5A CN201480000909A CN104412138B CN 104412138 B CN104412138 B CN 104412138B CN 201480000909 A CN201480000909 A CN 201480000909A CN 104412138 B CN104412138 B CN 104412138B
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- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/12—Optical coatings produced by application to, or surface treatment of, optical elements by surface treatment, e.g. by irradiation
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- 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
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Abstract
The present invention provides the preparation method of a kind of polaroid, contaminates, including spare iodine processed or dichroic dye, the film based on polyvinyl alcohol then stretched, and adjusts the color of described polaroid by irradiating polarized ultraviolet on the film based on polyvinyl alcohol of described stretching, extension.
Description
Technical field
The present invention relates to the preparation method of a kind of polaroid and polarization plates, and, especially, relate to one can be used in as
The preparation of the polarization plates of the image display device of liquid crystal indicator, organic light-emitting display device and plasma display panel (PDPs)
Method.
Background technology
Generally, in liquid crystal indicator, polaroid is arranged in the both sides of liquid crystal panel to provide that become clear and having
There is the image of good color re-production capabilities.Polaroid is typically prepared by the following method: contaminate with dichroic material such as iodine
(exhausting) film based on polyvinyl alcohol, then uses its product of cross-linking agents, and uses single shaft stretching, extension method such as to take
To this product.Described polaroid is easily shunk because of being prepared by stretching, extension, and especially, described film based on polyvinyl alcohol
It is easily deformed under wet heat condition because using hydrophilic polymer.Additionally, because the mechanical strength of described film self is relative
Weak, it may occur that the tear of film.Accordingly, used by supplementing partially in the both sides of polaroid or side adhering protective film
The intensity of vibration plate.
Meanwhile, the application of liquid crystal indicator is expanded, and liquid crystal indicator is widely used for from mobile electricity
Words are to the device of family's large screen television, and the development of technology has been advanced, in order to ensure in various liquid crystal indicators
Outstanding display quality.The color of polaroid is important as the degree of polarization in the display quality of liquid crystal indicator.
In described correlation technique, for adjusting the color of described polaroid, use in contaminating operation as adjusted's
Dip-dye amount, adjusts the time period that film based on polyvinyl alcohol immerses in processing pond, or the method adjusting temperature etc..
But,It is relatively difficult to produce, unless the orientation levels of film based on polyvinyl alcohol is higher than certain level, and i.e.
Make production,Amount the most relatively fewer, therefore, by adjust described in described polaroidDip-dye amount adjust described partially
The color of sheet of shaking is difficult.
Additionally, for adjusting color, cross-linking procedure can adjust the time period immersed in crosslinking pond；But, at this
In method, when the condition that stretches in stretching operation changes, need to adjust the immersion time period in crosslinking pond, therefore, color
Adjustment be relative difficulty.
As it has been described above, existing methodical the haveing a problem in that of color adjusting polaroid is difficult to control to, and, because color with
Described dip-dye, cross-link and stretch the change of condition of operation and change so that the adjustment of color needs individual processing.
Summary of the invention
Technical problem
In view of the foregoing, it is made that one aspect of the present invention, it is an object of the invention to provide a kind of than existing system
The simpler method preparing polaroid of method of standby polaroid, and owing to the temperature increase of described polaroid adjusts described
The color of polaroid and colour-fast.
Technical scheme
According to an aspect of the present invention, it is provided that the preparation method of a kind of polaroid, including spare iodine processed or dichroic dye
Contaminate the film based on polyvinyl alcohol then stretched, and by irradiating polarization on the film based on polyvinyl alcohol of described stretching, extension
Ultraviolet light adjusts the color of described polaroid.
The operation of color of described adjustment polaroid can be carried out so that the value of described equation 1 below is from 0.05 to 0.2
Scope.
[equation 1]
Furthermore, it is possible to carry out the color of described adjustment polaroid operation in case the value of described equation 2 below from 0.4 to
The scope of 1.2.
[equation 2]
Further, the operation of color of described adjustment polaroid can be carried out so that the value of described equation 3 below exists
From the scope of 0.004 to 0.028.
[equation 3]
Meanwhile, it is possible to use wire grid polarizer forms described polarized ultraviolet.
Here, the polarization direction of described polarized ultraviolet preferably forms the suction relative to described film based on polyvinyl alcohol
Receive the angle from 0 to 1.0 degree scopes of axle, and it is possible to more preferably with the absorption relative to described film based on polyvinyl alcohol
Axle be arranged in parallel.
Additionally, described polarized ultraviolet can have scope from 0.5 to 3J/cm2Intensity.
Further, after by the operation irradiating the color adjusting described polaroid of described polarized ultraviolet, institute
The temperature range stating polaroid can include from 20 DEG C to 70 DEG C.
Meanwhile, the described method preparing polaroid can include the cooling reducing the temperature of described polaroid further
Operation.
Here, described cooling down operation can use has 10 DEG C of chill rolls to the temperature of 30 DEG C of scopes.
Meanwhile, according to a further aspect in the invention, it is provided that the preparation method of a kind of polarization plates, including, with iodine or two
Color dyestuff is contaminated and is then stretched the film based on polyvinyl alcohol prepared, by the film based on polyvinyl alcohol in described stretching, extension
Upper irradiation polarized ultraviolet adjusts the color of described polaroid, and adheres to protection at least one side surface of described polaroid
Film.
Beneficial effect
The preparation method of the polaroid of the present invention has following benefit, and the method can be irradiated at described use ultraviolet light
After stretching operation, by adjusting the color of described polaroid, independent of dip-dye operation, cross-linking procedure and the stretching, extension of described polaroid
Operation, and individually adjust the color change of described polaroid.
Here, according to the intensity of described ultraviolet light it is anticipated that the degree of described polaroid color change, therefore, outstanding
Effect is that the color of described polaroid can easily and accurately adjust, and only changes the color not shadow of described polaroid
Ring degree of polarization.
Additionally, by hitting use polarized ultraviolet at described ultraviolet lighting, can suppress owing to described ultraviolet light irradiates
The temperature of the described polaroid caused increases, and therefore, it can the variable color preventing to produce owing to the temperature of described polaroid increases,
And predictable color can be obtained adjust.
Accompanying drawing explanation
Fig. 1 is the embodiment representing and irradiating polarized ultraviolet on film based on polyvinyl alcohol.
Fig. 2 is the figure of the change representing intensity list transmittance and absorption value according to polarized ultraviolet.
Fig. 3 is to represent changing of intensity monochromatic degree b value (single body color b value) according to polarized ultraviolet
The figure become.
Fig. 4 is the photo on the surface representing the described polaroid according to embodiment 1 preparation.
Fig. 5 is the photo on the surface representing the described polaroid according to comparing embodiment 2 preparation.
Detailed description of the invention
The illustrative embodiments of the present invention be will now be described.However, it is possible in many different forms example this
Bright, and it is not limited in said specific embodiment analysis.Certainly, it is provided that these embodiments will be so that the present invention will be
Completely with complete, and the scope of the present invention will be passed on fully to those skilled in the art.
The present inventor repeats research in the preparation method of polaroid, develops no matter one stretches operation
And the method that the color of polaroid can be adjusted, inventor finds that this target can be by irradiating polarized UV after stretching operation
Light completes, and completes the present invention.
The preparation method of polaroid according to an illustrative embodiment of the invention includes spare iodine processed or dichroic dye
Contaminate the operation of the film based on polyvinyl alcohol then stretched, and can be shone by the film based on polyvinyl alcohol in described stretching, extension
Penetrate polarized ultraviolet and adjust the color of described polaroid.
Below, each operation of described preparation method will be described according to an illustrative embodiment of the invention in detail.
First, spare iodine processed or dichroic dye contaminate the film based on polyvinyl alcohol then stretched.Here, described preparation
The operation contaminating the film based on polyvinyl alcohol then stretched with iodine or dichroic dye can be by known in the related
The method preparing polaroid based on polyvinyl alcohol, or use film described in commercially available film preparation.
Meanwhile, by contaminating with iodine or dichroic dye described in the dip-dye operation of film based on polyvinyl alcohol, crosslinking
Film based on polyvinyl alcohol and described iodine or the cross-linking procedure of dichroic dye and stretch described film based on polyvinyl alcohol
Stretch operation, the preparation method of polaroid based on polyvinyl alcohol can be carried out.
First, described dip-dye operates for contaminating iodine molecule on film based on polyvinyl alcohol or having dichromatic two colors
Property dye molecule, and, described iodine molecule or dichroic dye molecules can be by absorbing the direction of extension in described polarization plates
The light of upper vibration and obtain through the light of vibration in the vertical direction of described polarization plates there is the inclined of certain vibration direction
Shake the operation of light.Here, it is generally described based on poly-by immersing in equipped with the process pond of the solution containing iodine or dichroic dye
The film of vinyl alcohol realizes contaminating.
Here, generally use water as the solvent used in the described solution contaminating operation, however, it is possible to add appropriate
And water there is the organic solvent of the compatibility.Meanwhile, relative to solvent described in 100 weight portions, it is possible to use proportion
From described iodine or the dichroic dye of 0.06 weight portion to 0.25 weight portion.When described iodine and dichroic dye are in above-mentioned scope
In, single transmittance of the described polaroid prepared after stretching, extension meets the scope of 42.0% to 47.0%.
Meanwhile, when using iodine as described dichroic material, can include auxiliary extraly for improving dip-dye efficiency
Help thing such as iodide, and relative to solvent described in 100 weight portions, it is possible to use proportion from 0.3 weight portion to 2.5 weight
The described adminicle of part.Here, because iodine has low solubility in water, the dissolubility of water is added described for increasing described iodine
Adminicle such as iodide.Meanwhile, the mixed proportion scope of described iodine and iodide can comprise about from 1:5 to 1:10.
Here, the object lesson of the described iodide included in an exemplary embodiment of the present invention embodiment includes: potassium iodide,
Lithium iodide, sodium iodide, zinc iodide, silver iodide, lead iodide, Copper diiodide, barium iodide, calcium iodide, Tin tetraiodide., titanium iodide, its mixing
Thing or the like, but, present embodiment is not limited to this.
Meanwhile, the temperature in described process pond may remain in about 25 DEG C to 40 DEG C, low due to less than 25 DEG C
Temperature is lower contaminates the situation that efficiency can reduce, and owing to the distillation of iodine described under the high temperature higher than 40 DEG C aggravates, therefore can increase
Add the amount of the iodine of described use.Additionally, in described process pond the time of the immersion of film based on polyvinyl alcohol can be about
30 seconds to 120 seconds, due to when the described immersion time is less than 30 seconds, it is impossible to obtain the uniform leaching on film based on polyvinyl alcohol
Dye, and when the described time is more than 120 seconds, be no longer necessary to immerse because contaminating the most saturated.
Meanwhile, generally film based on polyvinyl alcohol is immersed the immersion method carried out in aqueous boric acid solution etc. to commonly use
In cross-linking procedure；But it is also possible to use solution spraying coating process on film or spraying process.
Here, as an embodiment of described cross-linking procedure, contaminate operation iodine molecule or dichroic dye when using
When molecule contaminates film based on polyvinyl alcohol, immersion method is carried out as follows: by using cross-linking agent to have described based on poly-
The iodine molecule absorbed on the polymeric matrices of the film of vinyl alcohol or dichroic dye molecules, and molten equipped with containing described cross-linking agent
Described film based on polyvinyl alcohol is immersed in the crosslinking pond of liquid.Owing to not having suitably when described iodine molecule or dichroic dye molecules
When ground absorbs on described polymeric matrices, the situation that described degree of polarization declines, and therefore, polarization plates can not suitably play it
Effect.
Here, generally use water as the solvent used in the solution in described crosslinking pond, however, it is possible to add appropriate
Water is had the organic solvent of dissolubility, and relative to the described solvent of 100 weight portions, can be with additional proportion scope from 0.5
Weight portion is to the described cross-linking agent of 5.0 weight portions.Here, when the described cross-linking agent included is less than 0.5 weight portion, due in institute
Stating and lack crosslinking in film based on polyvinyl alcohol, described in water, film strength based on polyvinyl alcohol may decline, and,
When the described cross-linking agent included is more than 5.0 weight portion, due to the formation of excessively crosslinking, stretching of described film based on polyvinyl alcohol
Malleability matter reduces.
Additionally, the object lesson of described cross-linking agent includes boride (such as boric acid and Borax), Biformyl, glutaraldehyde etc., and
And it can be used alone or in combination.
Meanwhile, the temperature in described crosslinking pond is different with described percentage of elongation according to the amount of described cross-linking agent, and not office
Being limited to this, it can have the scope of 45 DEG C to 60 DEG C.Normally, along with the amount of described cross-linking agent increases, the temperature in described crosslinking pond
Degree is adjusted to high temperature to improve the mobility of the chain of described film based on polyvinyl alcohol, and, when the amount of described cross-linking agent
Time few, the temperature in described crosslinking pond is adjusted to relative low temperature.But, in an exemplary embodiment of the present invention embodiment, because wanting
Obtaining the stretching, extension of more than 5 times, for improving the stretch property of described film based on polyvinyl alcohol, the temperature in described crosslinking pond needs to protect
Hold at 45 DEG C or higher.
Meanwhile, described in crosslinking pond, the immersion time of film based on polyvinyl alcohol can be about 30 seconds to 120
Second, due to when the described immersion time is less than 30 seconds, it is impossible to obtain the uniform dip-dye on film based on polyvinyl alcohol, and work as
When the described time period was more than 120 seconds, it is no longer necessary to immerse because of contaminating saturated.
Meanwhile, single shaft ground stretched film is referred in the described stretching, extension stretched in operation to stretch described in a certain direction
The polymer of film.Described stretching, extension method is segmented into wet stretching, extension method and dry stretching, extension method, and described dry stretching, extension method can be separated into rolling
Stretch method between Tong, hot cylinder stretches method, compressing and stretching method, tentering stretching, extension method etc., and described wet stretching, extension method can be separated into drawing
Width stretches stretching, extension method etc. between method, cylinder.
In an exemplary embodiment of the present invention embodiment, described stretching, extension method is not particularly limited, and, both can use described
Wet stretching, extension method can also use described dry stretching, extension method, and the need to, it is also possible to use a combination of both.
Here, at a temperature of the stretching, extension of 45 DEG C to 60 DEG C, described stretching, extension operates extensible described film based on polyvinyl alcohol
To the stretching, extension of 4 times to 7 times.In order to provide polarizability to film based on polyvinyl alcohol, the chain of described film based on polyvinyl alcohol needs
Stretch, and when being less than the stretching, extension of 4 times, the orientation of the most described chain can not fully occur, and when being more than the stretching, extension of 7 times, then
The chain of described film based on polyvinyl alcohol may be able to be cut off.Additionally, described stretching, extension temperature according to described cross-linking agent amount and not
With.Because the mobility of the chain of film based on polyvinyl alcohol reduces, stretching efficiency at a temperature of less than 45 DEG C may decline,
Further, when described temperature is higher than 60 DEG C, and due to the softening of described film, described film strength based on polyvinyl alcohol may become
Weak.
Meanwhile, described stretching, extension operation is carried out at the same time or separately with described dip-dye operation or described cross-linking procedure.Work as institute
State stretching, extension operation when carrying out with described dip-dye operation simultaneously, can carry out described contaminating operation in iodine solution, and, when with institute
State cross-linking procedure when carrying out simultaneously, can carry out described contaminating operation in aqueous boric acid solution.
Meanwhile, in an exemplary embodiment of the present invention embodiment, the preparation of the film based on polyvinyl alcohol of described stretching, extension
Operation can further include at the operation of drying layer stack after described stretching, extension operates.Here, in view of the optics of described polaroid
Character, described be dried can from about 20 DEG C to 100 DEG C, more preferably from about 40 DEG C to 90 DEG C within the temperature range of carry out, but
It is not limited to this, and described drying time is preferably 1 to 10 minutes.The effect of described drying process is, prevents by removing
It is described based on polyvinyl alcohol that moisture in the polaroid preparation section of the surface of described polyvinyl alcohol and internal moisture causes
Polaroid character reduce, with by smoothly causing the contraction of the width of the film based on polyvinyl alcohol of described stretching, extension to improve
The orientation of the complex formed by polyvinyl alcohol and iodine, thus improve the polarization degree of polaroid.Here, at dip-dye, crosslinking, color
Described drying process is carried out after color compensation deals.
When being prepared the film based on polyvinyl alcohol of described stretching, extension by said method, by described prepared based on
Irradiate polarized ultraviolet on the film of polyvinyl alcohol, be adjusted the operation of the color of described polaroid.
The result of study carried out according to the present inventor, it is seen then that described when carrying out on the polaroid in described stretching, extension
During the operation that ultraviolet light irradiates, according to described ultraviolet light intensity can colourity b adjusting polaroid as scheduled value and single thoroughly
Penetrate ratio.More specifically, when contaminating irradiating ultraviolet light on the film based on polyvinyl alcohol then stretched with iodine and dichroic dye
Time, due to oscillating movement or excite to excited electronic state, described iodine and dichroic dye molecules become active and unstable, and
In this operation, the color of described polaroid can change or polarize complete stability.Here, work as with the ultraviolet light with suitable energy
During irradiation, the color of described polaroid can be adjusted to any desired color.But, when on polaroid as above
When irradiating unpolarized ultraviolet light, the temperature in some regions of described polaroid increases, and this is counted as in described polaroid
Cause variable color or stain.
In order to prevent the such variable color on polaroid or stain, the present inventor be repeated research and
Discovery can solve such problem by irradiating the polarized ultraviolet as described ultraviolet light.Specifically, when using polarization purple
Outer smooth time because the amount of the energy absorbed by the per unit area of polaroid is few, in irradiating operation, suppress described polaroid
Temperature increase, and prevent uncertain variable color and the appearance of stain of described polaroid.Accordingly, the present invention's is exemplary
The preparation method of the polaroid of embodiment is very simple operation, and, no matter contaminating, cross-linking and stretch in operation
Process conditions, it is allowed to preparation has the polaroid of color of object, therefore, there is no need to be different from the complicated color of Existing methods and adjusts
Method.
Meanwhile, described polarized ultraviolet is used in correlation technique the ultraviolet light of known method polarization, and not
It is confined to this, it is contemplated that efficiency and operation are convenient, it is possible to use wire grid polarizer.
Specifically, in an exemplary embodiment of the present invention embodiment, by using ultra-violet lamp and ultraviolet light polaroid (wiregrating
Polaroid) on the surface of described film based on polyvinyl alcohol, irradiation polarized ultraviolet carries out the preparation method of described polaroid.
Here, as shown in the schematic diagram in Fig. 1, by adjusting polarization direction (such as, the ultraviolet light polaroid of the ultraviolet light of described irradiation
Rotation etc.), can adjust described ultraviolet light relative to described polaroid absorb axle arbitrarily angled (θ) irradiate.
Here, the polarization direction of described polarized ultraviolet relative to described polaroid absorption axle can forming range from 0 to
The angle of 1.0.Specifically, preferred irradiation is the polarization direction the making described polarized ultraviolet absorption axle relative to described film
Parallel (θ=0 °).It is useful for meeting above-mentioned scope in terms of the illumination efficiency and heat generation of the polarized ultraviolet of described irradiation
's.
Meanwhile, the operation of the color of described adjustment polaroid can be carried out, and be not limited to this, in order to below described
The value of equation 1 is in the range of 0.05 to 0.2, and for example, it is preferable to carries out this operation so that the value of described equation 1 below exists
In the range of 0.1 to 0.2.When before and after irradiation polarized ultraviolet, the rate of change of degree of monochromaticity b value within the above range, can
Only to adjust described degree of monochromaticity b value, and do not affect the polarization degree of described polaroid.
[equation 1]
Here, degree of monochromaticity represents the single polaroid color using color difference meter to measure in degree of monochromaticity b value, colourity b value refers to
CIE coordinate system represents the value of color, and by b=200 [(Y/Yn)1/3-(Z/Zn)1/3] calculate described colourity b value, and+b
Refer to yellow and-b refers to blueness.(here, Yn with Zn is consistent with reference white Y and Z.) i.e., described degree of monochromaticity b value refers to use color difference meter
Colourity b value in the CIE coordinate system of the single polaroid color measured.
In an exemplary embodiment of the present invention embodiment, V-7000-UV-VIS-NIR spectrophotometer is used by JASCO
(optical measuring apparatus) measures described degree of monochromaticity b value, and by optical measuring apparatus measure described degree of monochromaticity b value and
Described degree of monochromaticity b value is as value display.Here, the height in the value of degree of monochromaticity b described in polaroid refers to the suction in short wavelength
The height of luminosity, and more specifically, when absorbance height in short wavelength, described degree of monochromaticity b value is high, and when short wavelength
In absorbance low time, described degree of monochromaticity b value is low.
Simultaneously, in an exemplary embodiment of the present invention embodiment, the degree of monochromaticity b of described polaroid after irradiating ultraviolet light
Value meets the scope of 3.5 to 4.0.When polarization plates orthogonal arrangement, when described degree of monochromaticity b value is less than 3.5, blue cast is obvious, and works as
When described degree of monochromaticity b value is more than 4.0, yellow hue is obvious, therefore, it is difficult to obtain nature black, and described CR value can reduce.When
When the described degree of monochromaticity b value of the polaroid stretched is unsatisfactory for above-mentioned scope, described list can be changed by irradiating polarized ultraviolet
Colourity b value, and, here, described degree of monochromaticity b can be adjusted within the above range by the intensity adjusting described polarized ultraviolet
Value.
Furthermore, it is possible to carry out the operation of the color of described adjustment polaroid, but it is not limited to this, in order to described below equation
The value of 2 is in the range of 0.4 to 1.2, and for example, it is preferable to the value of the most described equation 2 below is 0.5 to 1.0
In the range of.Before or after irradiating ultraviolet light, the rate of change of the value of orthogonal colourity b is within the above range, can only adjust described
The value of orthogonal colourity b, does not affect the polarization degree of described polaroid.
[equation 2]
Here, orthogonal colourity represents in the value of described orthogonal colourity b, its absorption axle measured with color difference meter is orthogonal
The color of a pair of polaroid arranged, and colourity b value refers to expression value of color described in CIE coordinate system, and pass through b
=200 [(Y/Yn)1/3-(Z/Zn)1/3] calculating the value of described colourity b ,+b refers to that yellow and-b refer to blueness.(here, Yn and Zn and base
Quasi-white Y with Z is consistent.) i.e., the value of described orthogonal colourity b refers to measure the face of its a pair of polaroid absorbing axle orthogonal arrangement
The value of colourity b in the CIE coordinate system of color.
Meanwhile, V-7000-UV-VIS-NIR spectrophotometer (optical measuring apparatus) is used to survey by JASCO
Measure described orthogonal colourity b value.Here, be not limited to this, in an exemplary embodiment of the present invention embodiment, because nature can be obtained
Black, after irradiating ultraviolet light, the value of orthogonal colourity b of described polaroid can be preferably close to 0 in about scope from-1 to 1
Value.
As the embodiment of the value adjusting described orthogonal colourity b of the present invention, described after contaminating, cross-link and stretch operation
When the value of orthogonal colourity b occurs less than 0, can increase and adjust the value of described orthogonal colourity b close to 0.
Meanwhile, the result of study carried out according to the present inventor, show when irradiating partially on described polaroid
Shake ultraviolet light time can the single transmittance that adjust polaroid the same with the color of described polaroid.That is, when contaminating, cross-linking and stretch
When operation rear polarizer does not have target list transmittance, only can change described single transmittance by irradiation polarized ultraviolet.This
Outward, according to an illustrative embodiment of the invention, described single transmittance of intensity according to described polarized ultraviolet can be predicted
Change, therefore, advantage is the ultraviolet light being had by irradiation and changing just desirable strength, can in the scope of desired value letter
Singly adjust described single transmittance.
For example, it is possible to be adjusted the operation of the color of polaroid, in order to the value of equation 3 below is from 0.004 to 0.028
In the range of, and, the most preferably carry out this operation so that the value of described equation 3 below is in the range of 0.01 to 0.028.
Irradiate before or after polarized ultraviolet when single transmittance in the above range, can only adjust described single transmittance, and not
Affect the degree of polarization of described polaroid.
[equation 3]
Here, described single transmittance refers to the transmittance of single polaroid, and lead in an exemplary embodiment of the present invention embodiment
Crossing JASCO uses V-7000-UV-VIS-NIR spectrophotometer (optical measuring apparatus) to measure described single transmittance.
Single transmittance of polaroid prepared by described use method according to an illustrative embodiment of the invention can meet
The scope of the value of 42.0% to 47%, and, such as, described value can be the scope from 42.5% to 43%.When described polarization
When the transmittance of sheet is less than 42%, because the high-selenium corn of described light, described screen can be dark, and when described transmittance is more than
When 47%, described degree of polarization reduces and cannot suitably obtain black.
Meanwhile, more preferably can be with 0.5 to 3.0J/cm2Polarized ultraviolet described in the intensity illumination of scope includes, with
And, for example, it is possible to irradiate 0.8J/cm2To 1.5J/cm2Intensity.When described polarized UV light intensity meets above-mentioned scope, occur
Sufficiently color change, and the solidification of the polaroid risen due to ultraviolet light can be prevented, therefore, it can be readily available face
The adjustment of color.In addition, as it has been described above, the irradiation of ultraviolet light can activate iodine or dichroic dye molecules energetically thus solve
Polarization, thus, when the intensity of described ultraviolet light meets above-mentioned scope, it is possible to obtain the adjustment of color, and do not reduce described partially
Degree of shaking.
According to Fig. 2, the intensity of described ultraviolet light represents the figure of the change of absorbance by orthogonal transmittance values.Here,
The x-axis of described Fig. 2 represents the intensity (J/cm of ultraviolet light2), represent absorbance according to orthogonal transmittance values (Tc) described y-axis
(Ac), and, when described orthogonal transmittance is Tc, and described absorbance is calculated as-log (Tc).Meanwhile, due to favourable iodine
Orientation, has big absorbance and refers to have little orthogonal transmittance values (Tc), and has little orthogonal transmittance values (Tc) and refer to have
Big degree of polarization.
As shown in figure in fig. 2, when the intensity of described polarized ultraviolet is more than 3J/cm2Time, described absorbance (Ac)
Promptly reduce.When absorbance described above (Ac) reduces, described orthogonal transmittance (Tc) value increases, and described polarization
Degree reduces.That is, because the intensity of described polarized ultraviolet is more than 3J/cm2, due in the orientation of described film based on polyvinyl alcohol
Adverse effect, the phenomenon that orthogonal transmittance (Tc) value increases occurs.
Additionally, the figure of the change that figure 3 below is the degree of monochromaticity b value representing the intensity according to described polarized ultraviolet.Here,
The x-axis of described Fig. 3 represents the intensity (J/cm of polarized ultraviolet2), and, the b value of described y-axis refers to degree of monochromaticity b value.Pass through Fig. 3
The visible intensity when described polarized ultraviolet is less than 0.5J/cm2Low-yield time, color described in polaroid change not
Significantly, furthermore, it is desirable to have minimum 0.5J/cm2The polarized ultraviolet of intensity to adjust the color of described polaroid.
Meanwhile, after the operation of the color by irradiating the polarized ultraviolet described polaroid of adjustment, described polarization
The temperature of sheet is preferably about in the range of 20 DEG C to 70 DEG C, and in the range of more preferably at about 25 DEG C to 60 DEG C.As
On, when irradiating ultraviolet light, the described stretching, extension film experience temperature contaminated with iodine or dichroic dye increases, and, as based on
The film of polyvinyl alcohol, when the temperature on described film surface is more than more than 80 DEG C, absorbs the visible ray of long wavelength rangeDecompose, because of
And, however, a problem that described film variable color and finally have and run through the stain of described polaroid and experience deformation.But, when according to this
When the illustrative embodiments of invention irradiates described polarized UV light, after irradiating described ultraviolet light, the temperature of described polaroid is full
The above-mentioned scope of foot, and in the case, variable color and the stain of polaroid substantially reduce.
Meanwhile, according to an illustrative embodiment of the invention, the preparation method of described polaroid can farther include
Reduce the cooling down operation of the temperature of described polaroid.As it appears from the above, when irradiating ultraviolet light on described polaroid, due to described
The temperature increase of polaroid may occur in which the problem of stain and variable color, and in order to prevent this phenomenon, described cooling down operation is additional
Operation.Here, described cooling down operation can be carried out before or after adjusting the operation of color of polaroid, but, due to
The temperature that the suppression of described cooling down operation is irradiated, by ultraviolet light, the described polaroid caused increases, preferably after polarized ultraviolet irradiates
Carry out.
More specifically, described cooling down operation can be carried out while the operation of described irradiating ultraviolet light or bending operation, or
As separate operation before/after the operation of irradiating ultraviolet light.Described cooling down operation, is not limited to the greatest extent this, such as, can make
With chilling roll, and use the stretching, extension operation carried out before/after the operation of described irradiating ultraviolet light or described bending behaviour
The cylinder used in work can carry out described cooling down operation as sub-cooled cylinder.In particular, it is contemplated that described irradiation polarizes
The operation of ultraviolet light, described cooling down operation is preferably between operation and the operation of described bending of the polarization mirror of described dry stretching, extension
Carry out.
Meanwhile, described cooling down operation preferably has the temperature from 10 DEG C to 20 DEG C scopes, and more preferably makes apparatus
There are about 10 DEG C to 30 DEG C or the chilling roll of the temperature of 10 DEG C to 20 DEG C.When the temperature of described chilling roll meets above-mentioned scope
Time, the temperature of described film itself reduces, and does not has film to damage and deformation.
Meanwhile, as it has been described above, use prepared by described preparation method according to an illustrative embodiment of the invention is inclined
The sheet degree of polarization between the irradiation front and rear of ultraviolet light that shakes does not has difference.In the method that existing color adjusts, problem exists
Adjust in being difficult to single color, because degree of polarization can change when adjusting the color of described polaroid, but according to this
The preparation method of the polaroid inventing exemplary embodiment has good effect, and described method can only change polaroid
Color, and not polarisation-affecting degree.The preparation method advantage of polaroid exists i.e., according to an illustrative embodiment of the invention
In, by irradiating ultraviolet light, only simple and regulate the color property of described polaroid fine, it is possible to prepare have fabulous partially
The polaroid of degree of shaking.
Further, in the conventional method, normally, degree (DOP) is polarized when single transmittance (Ts) increases usual
Reduce.Accordingly, problematically, work as by changing described dip-dye in the conventional method, cross-linking and stretch the condition increase list of operation
During transmittance, polarization degree reduces, but, when by contaminating, cross-linking as in an exemplary embodiment of the present invention embodiment
With when irradiating, after stretching, extension operation, single transmittance that polarized ultraviolet adjusts polaroid, advantage is when single transmittance increase permissible
Keep degree of polarization on certain level.
Additionally, the polaroid using described preparation method to prepare according to an illustrative embodiment of the invention can have
99.995% or higher degree of polarization, and, for example, it is preferable to have 99.996% or higher, or 99.997% or higher
Degree of polarization.When degree of polarization height, the polarization plates with fabulous contrast ratio (CR) can be prepared, and, when according to the present invention's
During the color that the preparation method of illustrative embodiments adjusts described polaroid by irradiating polarized ultraviolet, advantage is, can
There is the polaroid of 99.995% or higher fabulous degree of polarization with preparation.
Meanwhile, degree of polarization is defined as √ { (Ts-Tc)/(Ts+Tc) }, and here, Ts refers to single transmittance, and Tc
Make a comment or criticism friendship transmittance.Additionally, described orthogonal transmittance refer to when arrangement a couple polaroid in case they absorb orthogonal saturating of axle
Penetrate ratio.
Secondly, according to another aspect of the present invention, it is provided that a kind of method preparing polarization plates, including spare iodine processed or two
The film based on polyvinyl alcohol then stretched contaminated by color dyestuff, by irradiating on the film based on polyvinyl alcohol of described stretching, extension
Polarized ultraviolet adjusts the color of described polaroid, and adhering protective film at least one side surface of described polaroid.
Described spare iodine processed or dichroic dye contaminate the operation of the film based on polyvinyl alcohol then stretched, and pass through
The film based on polyvinyl alcohol of described stretching, extension irradiates the operation of color of the polarized ultraviolet described polaroid of adjustment with above-mentioned
Those are identical, therefore, will not be repeated again and illustrate.
When preparation adjusts the polaroid of color by said method, by carrying out at least side of described polaroid
Polarization plates is prepared in the operation of adhering protective film.Here, can be entered by the preparation method of known polarization plates in the related
The operation of the described adhering protective film of row, and, described method is limited to the most especially.It is, for example possible to use at the one of polaroid
Side or both sides coating adhesive, then adhering protective film, and the method for this result of dried.As the method for described coating,
Known method in the related can be used, such as mixing method, mayer rod (mayer bar) method, air knife method, intaglio printing
Method, spurt method, doctor blade method, die coating method, casting, spin-coating method, reverse roll method and kiss roller method；But, described method is not limited to
This.Such as hot blast can be used at about 40 DEG C to 100 DEG C, and preferably carry out described under the baking temperature of 60 DEG C to 100 DEG C
Dried 20 seconds to 1,200 seconds.
Here, described protecting film can include the various hyaline membranes being attached to polaroid both sides for protecting described polaroid,
And its example that can use can include resin molding based on acetate, such as triacetyl cellulose (TAC), tree based on polyester
Adipose membrane, resin molding based on polyether sulfone, resin molding based on Merlon, resin molding based on polyamide, based on polyimides
Resin molding, based on polyolefinic resin molding, based on acrylic acid resin molding etc.；But, described protecting film is not limited to this.
Simultaneously, such as binding agent, it is possible to use aqueous binder or Photocurable pressure-sensitive adhesive.The type of described sticker
Limit to the most especially, if its effectively bond polaroid to protecting film, there is fabulous optical clarity and do not suffer from
Such as the change of yellow in time, but, such as can use containing resin based on polyvinyl alcohol and the aqueous binder of cross-linking agent
Agent compositions.Additionally, for extra performance improvement, described polarization plates can comprise additionally in functional membrane, except as described in protecting film it
Outer wide viewing angle compensates film or brightness improving film.
Below, will be described in the preferred illustrative embodiment of the present invention to help to understand the present invention.However, it is desirable to
Understand that explanation set forth herein is only the exemplary and illustrative illustrative embodiments describing the purpose of the present invention, and
It is not intended to limit to the present invention.
Preparation embodiment
Prepare polaroid as follows: by film based on polyvinyl alcohol (by Nippon Synthetic Chemical
Industry Co.Ltd. manufactures, degree of polarization: 2600) by flushed channel and expansion tank, including I2Aqueous solution with KI
Its result of middle dip-dye, then extends to 6 times in including the aqueous solution of boric acid and KI.
Embodiment 1
Measure according to described preparation embodiment prepare described in single transmittance of polaroid based on polyvinyl alcohol, degree of monochromaticity
After b value and orthogonal colourity b value, the polaroid of described preparation irradiates 0.5J/cm2The polarization direction of energy is relative to absorbing axle
Parallel polarized ultraviolet (merges UV system, Inc., UV16B), then measures single transmittance, degree of monochromaticity b value and orthogonal
Colourity b value.
Embodiment 2
Measure according to described preparation embodiment prepare described in single transmittance of polaroid based on polyvinyl alcohol, degree of monochromaticity
After b value and orthogonal colourity b value, the polaroid of described preparation irradiates 1.0J/cm2The polarization direction of energy is relative to absorbing axle
Parallel polarized ultraviolet (merges UV system, Inc., UV16B), then measures single transmittance, degree of monochromaticity b value and orthogonal
Colourity b value.
Embodiment 3
Measure according to described preparation embodiment prepare described in single transmittance of polaroid based on polyvinyl alcohol, degree of monochromaticity
After b value and orthogonal colourity b value, the polaroid of described preparation irradiates 1.5J/cm2The polarization direction of energy is relative to absorbing axle
Parallel polarized ultraviolet (merges UV system, Inc., UV16B), then measures single transmittance, degree of monochromaticity b value and orthogonal
Colourity b value.
Embodiment 4
Measure according to described preparation embodiment prepare described in single transmittance of polaroid based on polyvinyl alcohol, degree of monochromaticity
After b value and orthogonal colourity b value, the polaroid of described preparation irradiates 2.0J/cm2The polarization direction of energy is relative to absorbing axle
Parallel polarized ultraviolet (merges UV system, Inc., UV16B), then measures single transmittance, degree of monochromaticity b value and orthogonal
Colourity b value.
Embodiment 5
Measure according to described preparation embodiment prepare described in single transmittance of polaroid based on polyvinyl alcohol, degree of monochromaticity
After b value and orthogonal colourity b value, the polaroid of described preparation irradiates 2.5J/cm2The polarization direction of energy is relative to absorbing axle
Parallel polarized ultraviolet (merges UV system, Inc., UV16B), then measures single transmittance, degree of monochromaticity b value and orthogonal
Colourity b value.
Comparative example 1
Measure according to described preparation embodiment prepare described in single transmittance of polaroid based on polyvinyl alcohol, monochrome
After degree b value and orthogonal colourity b value, the polaroid of described preparation irradiates 2.5J/cm2The polarization direction of energy is relative to absorption
The parallel unpolarized ultraviolet light of axle (merges UV system, Inc., UV16B), then measure single transmittance, degree of monochromaticity b value and
Orthogonal colourity b value.
Comparative example 2
Measure according to described preparation embodiment prepare described in single transmittance of polaroid based on polyvinyl alcohol, degree of monochromaticity
After b value and orthogonal colourity b value, the polaroid of described preparation irradiates 5.0J/cm2The polarization direction of energy is relative to absorbing axle
Parallel polarized ultraviolet (merges UV system, Inc., UV16B), then measures single transmittance, degree of monochromaticity b value and orthogonal
Colourity b value.
Concrete intensity in embodiment 1 to 5 and comparative example 1 to 2 is at each value of irradiating ultraviolet light pre-test and photograph
The each value measured after penetrating ultraviolet light is converted to knots modification with following equation 4, and represent in table 1 below described knots modification and
The temperature of described polaroid after irradiating ultraviolet light.
[equation 4]
[table 1]
Result based on table 1, it is seen that when irradiating ultraviolet light, described single transmittance, degree of monochromaticity b value and orthogonal colourity b value
Increasing, and increase with the intensity of ultraviolet light, the knots modification of described each value increases.Additionally, according to the intensity of described ultraviolet light,
The knots modification of the measurable each value of illustrative embodiments of the present invention, therefore, only by after contaminating, cross-linking and stretch operation
The ultraviolet light irradiating concrete intensity can adjust each chromatic value, transmittance etc..Further, advantage is: no matter in leaching
Contaminate, cross-link and stretch the change of condition described in operation, the adjustment of polaroid color described above can be carried out.
Additionally, when contrasting comparing embodiment 5 and comparative example 1, when the unpolarized ultraviolet light of irradiation identical energy, institute
State the surface temperature of polaroid more than 80 DEG C, cause described polaroid variable color.Further, institute in such as comparative example 2
State the energy of irradiation more than 3J/cm3Time, the surface temperature of described polaroid is more than 100 DEG C, therefore as verified in Figure 5, and institute
State its colour changed into yellow of polaroid.
Although the most having described embodiments of the invention in detail, the scope of the present invention is not limited to this, and to this area
It is obvious to the skilled person that in the case of the essence without departing from the present invention being defined by the appended claims, can
To carry out various modifications and variations.
(bibliography numbering)
1:Polarized Ultraviolet Light
2:Polyvinyl Alcohol-Based Film
3:Absorption Axis of Polyvinyl Alcohol-Based Film
Claims (12)
1. a preparation method for polaroid, comprises:
Spare iodine processed or dichroic dye contaminate the film based on polyvinyl alcohol then stretched, and
The color of described polaroid is adjusted by irradiating polarized ultraviolet on the film based on polyvinyl alcohol of described stretching, extension,
Wherein, carry out the operation of the color of described adjustment polaroid so as the value of equation 1 below from 0.05 to 0.2 scope
In,
[equation 1]
2. the preparation method of polaroid as claimed in claim 1, wherein, carry out described adjustment polaroid color operation with
Just the value of equation 2 below is in the range of 0.4 to 1.2,
[equation 2]
3. the preparation method of polaroid as claimed in claim 1, wherein, carry out described adjustment polaroid color operation with
Just the value of equation 3 below is in the range of 0.004 to 0.028,
[equation 3]
4. the preparation method of polaroid as claimed in claim 1, wherein, uses wire grid polarizer to form described polarized UV
Light.
5. the preparation method of polaroid as claimed in claim 1, wherein, the polarization direction of described polarized ultraviolet is relative to institute
The axle that absorbs stating film based on polyvinyl alcohol forms the angle from 0 to 1.0 degree scopes.
6. the preparation method of polaroid as claimed in claim 1, wherein, the polarization direction of described polarized ultraviolet is relative to institute
The absorption axle stating film based on polyvinyl alcohol is parallel.
7. the preparation method of polaroid as claimed in claim 1, wherein, described polarized ultraviolet has from 0.5 to 3J/cm2Model
The intensity enclosed.
8. the preparation method of polaroid as claimed in claim 1, wherein, through by irradiating the polarized ultraviolet described polarization of adjustment
After the operation of the color of sheet, the temperature of described polaroid is in the range of 20 DEG C to 70 DEG C.
9. the preparation method of polaroid as claimed in claim 1, further comprises temperature cold reducing described polaroid
But operate.
10. the preparation method of polaroid as claimed in claim 9, wherein, described cooling down operation uses to be had from 10 DEG C to 30
DEG C the chilling roll of temperature range.
The preparation method of 11. 1 kinds of polarization plates, comprises:
Spare iodine processed or dichroic dye contaminate the film based on polyvinyl alcohol then stretched；
The color of described polaroid is adjusted by irradiating polarized ultraviolet on the film based on polyvinyl alcohol of described stretching, extension；And
Adhering protective film at least one side surface of described polaroid,
Wherein, carry out the operation of the color of described adjustment polaroid so as the value of equation 1 below from 0.05 to 0.2 scope
In,
[equation 1]
The preparation method of 12. polarization plates as claimed in claim 11, wherein, described polarized ultraviolet has from 0.5 to 3J/cm2
The intensity of scope.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20130067396 | 2013-06-12 | ||
| KR10-2013-0067396 | 2013-06-12 | ||
| KR1020140070108A KR101584442B1 (en) | 2013-06-12 | 2014-06-10 | Method for polarizer comprising a step for adjusting color of polarizing element by uv irradiation |
| KR10-2014-0070108 | 2014-06-10 | ||
| PCT/KR2014/005183 WO2014200296A1 (en) | 2013-06-12 | 2014-06-12 | Method for manufacturing polarizing plate comprising step of controlling polarizer color by uv irradiation |
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| CN104412138A CN104412138A (en) | 2015-03-11 |
| CN104412138B true CN104412138B (en) | 2016-12-07 |
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| JP3925413B2 (en) * | 2003-01-16 | 2007-06-06 | 住友化学株式会社 | Iodine polarizing film, method for producing the same, and polarizing plate using the same |
| JPWO2005085918A1 (en) * | 2004-03-09 | 2008-01-24 | 株式会社クラレ | Optical element |
| KR20080000877A (en) * | 2006-06-28 | 2008-01-03 | 주식회사 코오롱 | Polarizing film and manufacturing method for the same |
| JP5448024B2 (en) * | 2007-03-15 | 2014-03-19 | 住友化学株式会社 | Photocurable adhesive, polarizing plate using the photocurable adhesive, method for producing the same, optical member, and liquid crystal display device |
| KR20100015898A (en) * | 2007-04-26 | 2010-02-12 | 니폰 제온 가부시키가이샤 | Display screen protection film and polarization plate |
| KR100950503B1 (en) * | 2008-01-21 | 2010-03-31 | 삼성정밀화학 주식회사 | Polarizing plate with improved dichroic ratio and liquid crystal display having the same |
| JP2009237124A (en) * | 2008-03-26 | 2009-10-15 | Sumitomo Chemical Co Ltd | Method of manufacturing polarizing film and its use |
| JP4928529B2 (en) * | 2008-11-12 | 2012-05-09 | 日東電工株式会社 | Manufacturing method of polarizing plate, polarizing plate, optical film, and image display device |
| CN102576107A (en) * | 2009-09-22 | 2012-07-11 | Lg化学株式会社 | High ultraviolet transmitting double-layer wire grid polarizer for fabricating photo-alignment layer and fabrication method thereof |
| JP2011215264A (en) * | 2010-03-31 | 2011-10-27 | Sumitomo Chemical Co Ltd | Polarizing plate and method for manufacturing the same |
| JP2012018383A (en) * | 2010-06-08 | 2012-01-26 | Sumitomo Chemical Co Ltd | Optical film, anti-glare film, and polarizing plate |
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