CN102311552A - Method for preparing polarizer - Google Patents
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- CN102311552A CN102311552A CN2011101487016A CN201110148701A CN102311552A CN 102311552 A CN102311552 A CN 102311552A CN 2011101487016 A CN2011101487016 A CN 2011101487016A CN 201110148701 A CN201110148701 A CN 201110148701A CN 102311552 A CN102311552 A CN 102311552A
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Abstract
The invention discloses a polarizer preparing method, specifically, a method for preparing a polarizer. The method comprises the following steps of performing first crosslinking through an inorganic cross-linking agents; performing second crosslinking through organic cross-linking agents so as to effectively enhance the crosslinking reactions; and then preparing a polarizer having multiple advantages. The advantages include, for example, excellent optical performances, film rupture and wrinkling prevention, area increase and thickness decrease, and stability of height size in the longitudinal and the horizontal directions, etc. The method disclosed in the invention can achieve desired technique processability and production efficiency.
Description
Technical field
The application requires to enjoy korean patent application 10-2010-0054758 number submitted to Korea S Department of Intellectual Property on June 10th, 2010 and on December 22nd, 2010 right of priority to the korean patent application of Korea S Department of Intellectual Property submission 10-2010-0132164 number, and its disclosed full content is incorporated this paper in this mode by reference.
The present invention relates to a kind of polaroid and the method for making this polaroid; Said polaroid have excellent optical property and as prevent film rupture and wrinkling, enlarged areas and thickness reduces, other advantages such as dimensional stability of height, said method can be improved processes property and enhance productivity.
Background technology
In order to improve color rendition and the brightness like the image of the multiple image display device of LCD, electroluminescent (EL) indicating meter, plasma display (PDP), field-emission plane display (FED) etc., a large amount of researchs concentrate on the polaroid.Particularly, along with the quick increase of the purposes of this image display device in widespread use, recently, the area with expansion and the demand of the polaroid of the thickness that reduces are increased.In addition, because the varying environment of its use it is believed that the dimensional stability under different weather resistance conditions is guaranteeing that aspect the reliability of products also be very important.
Usually, polaroid be through the polymeric film like Z 150PH (PVA) film is carried out swelling, dyeing, crosslinked, stretch, clean and dry the preparation.About this point, use inorganic crosslinking agent to carry out crosslinked usually like boron cpd.Yet, only use this inorganic crosslinking agent can form short cross linked chain, cause the increase that causes neck-in owing to high elongation.Therefore, the thickness of polaroid increases and its narrowed width, thereby causes film rupture.In addition, aforementioned techniques is attended by other shortcoming, for example, relatively poor dimensional stability under high heat condition, production efficiency descends or the like.
In order to address the above problem, the someone proposes not only to use organic crosslinking agent but also use boron cpd.
Japanese patent application discloses H06-235815 number and discloses a kind of cross-linking method that uses the polyaldehyde compound.Yet, because aldehyde radical is reduced or oxidation in air easily, so be difficult for carrying out crosslinked and be difficult to guarantee dimensional stability in a lateral direction.In addition, because polyaldehyde compound distinctive (pungent) smell, above-mentioned technology is being had any problem aspect the manufacturing polaroid.
Summary of the invention
Therefore; An object of the present invention is to provide a kind of preparation method of polaroid; This polaroid has multiple advantage, like the optical property of excellence, prevent film rupture and wrinkling, enlarged areas and thickness reduces, the dimensional stability that on the vertical and horizontal direction, improves etc.
Another object of the present invention provides a kind of preparation method of polaroid, and this method has stability and the production efficiency that improves.
In addition, another purpose of the present invention provides a kind of polarization plates of the polaroid for preparing through preceding method and image display device that contains above-mentioned polarization plates of containing.
In order to solve the traditional problem of existence, for example: the thickness of polaroid is increased and its width is diminished as the boron cpd of typical linking agent, thereby with the problem of film rupture and dimensional stability deterioration; And organic crosslinking agent has as being difficult to guarantee that dimensional stability in a lateral direction, the pungent smell of organic crosslinking agent hinder shortcomings such as its use, and the inventor has carried out research extensively and profoundly.
About this point; Find; Thereby can in first cross-linking process, use the short cross linked chain of boron cpd performance wrinkling, improve its processibility thus and form the orientation of iodine, and can in second cross-linking process, use the stable crosslinking structure of line style polycarboxylic acid compound formation that contains at least two carboxyls with inflexible effect inhibition film; Thereby give film snappiness and stretchiness, therefore overcome foregoing problems.Thus, accomplished the present invention.
Therefore, the invention provides a kind of preparation method of polaroid, this method may further comprise the steps: through polyvinyl alcohol film being immersed carry out in first crosslinker solution comprise boron cpd first crosslinked; With through said polyvinyl alcohol film being immersed carry out in second crosslinker solution that comprises the line style polycarboxylic acid compound that contains at least two carboxyls second crosslinked.
With respect to first crosslinker solution of 100 weight %, the content of said boron cpd can be 1 to 10 weight %.
The said line style polycarboxylic acid compound that contains at least two carboxyls can be and is selected from succsinic acid, pentanedioic acid, hexanodioic acid, oxalic acid, tartrate, Hydrocerol A, 1,2,3, at least a in 4-ethylene-dimalonic acid and the verivate thereof.
With respect to second crosslinker solution of 100 weight %, the said content that contains the line style polycarboxylic acid compound of at least two carboxyls can be 0.1 to 10 weight %.
With respect to the line style polycarboxylic acid compound of 1 weight part, said second crosslinker solution can further comprise the boron cpd below 10 weight parts.
Can carry out after crosslinked said second crosslinkedly said first, perhaps, different ground can carry out after crosslinked said first crosslinked said second.
The combination of said first crosslinked, said second crosslinked or said first cross-linking process and said second cross-linking process can repeat at least twice.
The invention provides a kind of composite polarizing plate, it is made through at least simultaneously the going up of polaroid that protective film is pressed in above-mentioned preparation.
Said polarization plates may further include at least a film in compensate film, compensation film for angular field of view and the brightness enhancement film that is selected from that is laminated on the said polaroid protective film.
The invention provides a kind of image display device that is arranged on the said polarization plates.
As stated; According to the present invention; Use inorganic crosslinking reaction of carrying out to be strengthened effectively, thereby improve pinning efficient (pinning efficiency), improve optical property thus and prevent film rupture as the iodine of dichroic polarizing material with organic crosslinking agent.Therefore, the present invention can provide a kind of polaroid, snappiness and stretchiness that it has excellent weather resistance and demonstrates improvement, thus prevent that film is wrinkling.
In addition, the present invention also can make the area of polaroid increase and the thickness of polaroid is reduced, and simultaneously, also can improve the dimensional stability on the vertical and horizontal direction.
In addition, the present invention also provides a kind of polaroid, and it is through stable prepared, thereby has improved processes property and improved production efficiency.
Embodiment
According to the present invention; A kind of preparation method of polaroid is provided; Said polaroid has the film rupture and the multiple advantage of corrugated of optical property, big area, the thickness that reduces, dimensional stability and minimizing like excellence, and this method can realize the production efficiency of improved processes property and raising.
Hereinafter, the present invention will be described in further detail.
Preparing method according to polaroid of the present invention can may further comprise the steps: through polyvinyl alcohol film being immersed carry out in first crosslinker solution comprise boron cpd first crosslinked; With through said polyvinyl alcohol film being immersed carry out in second crosslinker solution that comprises the line style polycarboxylic acid compound that contains at least two carboxyls second crosslinked.
According to the present invention, said polaroid refers to the conventional iodine polaroid that comprises polymeric film and in this polymeric film, adsorb and be orientated iodine.
The polymeric film that is used to prepare said polaroid can comprise, but is not limited to especially, can carry out painted any film by enough iodine.The specific examples of said polymeric film can comprise: polyvinyl alcohol film and/or partly-hydrolysed polyvinyl alcohol film; Hydrophilic polymer membrane is like polyethylene terephthalate film, Injecatable EVA Copolymer film, ethylene vinyl alcohol copolymer film, cellulose membrane and partly-hydrolysed film thereof; The polyenoid alignment films, the polyvinyl alcohol film that for example dewaters, dechlorination polyvinyl alcohol film etc.Wherein, preferred use can improve the consistence of degree of polarization effectively and show the polyvinyl alcohol film of excellent iodine staining affinity.
According to conventional art, the preparation method of polaroid comprises swelling, dyeing, crosslinked, stretching, cleaning and drying process.This preparation method is distinguished based on the kind of drawing process usually.For example, dried drawing process, wet drawing process or the combination of the two (that is, mixing drawing process) can be representational drawing process.Below explanation will make an explanation to the wet drawing process that uses among the preparation method according to the polaroid of an embodiment of the invention, but it is not limited to this especially.
Except that drying, other process can be carried out in water bath with thermostatic control, wherein packs into to be selected from least a polyvinyl alcohol film that immerses then in the different solutions.
The not special restriction of the order of each technology and/or the multiplicity of technology.That is to say that each technology can be carried out simultaneously, perhaps can regularly carry out continuously.And, can omit some technologies.For example, stretching can be carried out before or after dyeing, perhaps side by side carried out with swelling or dyeing.
Before dyeing; Can through will be not the tensile polyvinyl alcohol film immerse in the swelling can that comprises swelling solution and carry out swell process; Thereby in the swelling polyvinyl alcohol film, remove the impurity (like anti or dust) that on the surface of this film, gathers; Therefore improved stretching efficient, avoided uneven dyeing, and finally strengthened the physical properties of polaroid.
Can be independent water (purify waste water, deionized water) at the swelling solution of this use, and further comprise a spot of glycerine or potassiumiodide alternatively, thereby can make the polymeric film swelling and improve its workability.In this case, with respect to the swelling solution of 100 weight %, the content of glycerine can be below the 5 weight %.Likewise, with respect to the swelling solution of 100 weight %, the content of potassiumiodide can be below the 10 weight %.
Temperature at the swelling can of this use can be 20～45 ℃, more preferably 25～40 ℃.
The swelling period (time of immersion in swelling can) can be below 180 seconds, more preferably below 90 seconds.If in above-mentioned scope, then can suppressing film, time of immersion soaked into the excessive swelling that causes by swelling solution.Therefore, can prevent polyvinyl alcohol film deliquescing or break.In addition, can adsorb iodine equably, thereby improve degree of polarization.
Can in swelling process, stretch, in this case, stretch ratio can be about 1.1 to 3.5 times.
Can omit swell process, perhaps, different ground carry out swelling and dyeing simultaneously.
Dyeing is to make iodine be adsorbed onto the process in the polyvinyl alcohol film through polyvinyl alcohol film being immersed in the dyeing pot that the dyeing solution that comprises dichroism material (for example, iodine) is housed.
Said dyeing solution can prepare through iodine being joined in water, water-containing organic solvent or its mixture.With respect to the dyeing solution of 100 weight %, the content of iodine can be 0.4 to 400mmol/L, and more preferably 0.8 to 275mmol/L, and most preferably 1 to 200mmol/L.In order to improve dyeing efficient, can further in dyeing solution, add iodide as solubility promoter.These iodide can comprise; For example; Potassiumiodide, lithium iodide, Soiodin, zinc iodide, aluminum iodide, lead iodide, cupric iodide, barium iodide, calcium iodide, Tin tetraiodide, titanium iodide, they can use separately or use with the mode of two kinds or more kinds of combinations.Wherein, more preferably use the potassiumiodide that in water, has high-dissolvability.With respect to the dyeing solution of 100 weight %, the content of iodide can be 0.01 to 10 weight %, more preferably 0.100 to 5 weight %.
The temperature of said dyeing pot can be 5～42 ℃, more preferably 10～35 ℃.The time of immersion that polyvinyl alcohol film is immersed dyeing pot can be 1 to 20 minute, and more preferably 2 to 10 minutes, to its not special restriction.
Can in dyeing course, stretch.In this case, the stretch ratio of accumulative total can be 1.1 to 4.0 times.Here " accumulative total stretch ratio " mentioned can be illustrated in the product of the stretch ratio in each technology and the value that obtains.
Crosslinked is through polyvinyl alcohol film being immersed the iodine molecule pinning that makes physical adsorption in the crosslinker solution technology to the painted polyvinyl alcohol film, thereby the dyeing property that prevents iodine molecule is because of the external environment deterioration.Although dichroic dye under the moisture-resistant condition seldom by wash-out, if crosslinked be unsettled, depend on environment, iodine molecule usually dissolved or the distillation.Therefore, must realize fully this crosslinked.In addition, thereby strengthen its optical property, in cross-linking process, must be stretched to maximal draw ratio for the iodine molecule that places between the Z 150PH molecule is orientated.That is to say that cross-linking process is very important.
The present invention can comprise the crosslinked of at least two stages.Particularly, can use first crosslinker solution comprise inorganic crosslinking agent in crosslinked first, and can second crosslinked in use comprise second crosslinker solution of organic crosslinking agent.
First crosslinked first crosslinker solution that comprises boron cpd that can use is as linking agent, and to give short cross-link bond and rigidity because of boron cpd, it is wrinkling to suppress film thus, thereby has improved processes property and can make the iodine orientation.
First crosslinker solution can comprise as the water of solvent with like the boron cpd of boric acid, Sodium Tetraborate etc.First crosslinker solution can further comprise the organic solvent with water compatible.
With respect to first crosslinker solution of 100 weight %, the content of said boron cpd can be 1 to 10 weight %, more preferably 2 to 6 weight %.If the content of said boron cpd is less than 1 weight %, then the crosslinked action meeting of boron cpd reduces, thereby causes difficulty aspect the rigidity giving.When said content surpassed 10 weight %, inorganic crosslinking agent can make crosslinking reaction excessive, thereby was carrying out effectively causing difficulty aspect crosslinked through organic crosslinking agent.
Second crosslinked second crosslinker solution that comprises the line style polycarboxylic acid compound that contains at least two carboxyls that can use is as linking agent, thereby gives film snappiness and stretchiness effectively and form stable crosslinking structure.
Second crosslinker solution can comprise the water and the line style polycarboxylic acid compound that contains at least two carboxyls as solvent.Second crosslinker solution can further comprise the organic solvent with water compatible.
The said line style polycarboxylic acid compound that contains at least two carboxyls can make polyvinyl alcohol film stablize crosslinked effectively and not have structure problem, gives its favourable snappiness and stretchiness simultaneously.Aforementioned polycarboxylic acid examples for compounds can comprise, but not be limited to especially: by succsinic acid, pentanedioic acid, hexanodioic acid, oxalic acid, tartrate, the Hydrocerol A, 1,2,3 of chemical formula 1 to 7 expression, 4-ethylene-dimalonic acid and verivate thereof.Wherein, more preferably use dicarboxylic acid compound and verivate thereof.Aforesaid compound can use separately perhaps with two kinds or the use of more kinds of array mode.
[Chemical formula 1]
[Chemical formula 2]
[chemical formula 3]
[chemical formula 4]
[chemical formula 5]
[chemical formula 6]
[chemical formula 7]
With respect to second crosslinker solution of 100 weight %, the said content that contains the line style polycarboxylic acid compound of at least two carboxyls can be 0.1 to 10 weight %.In view of economic benefit, easy technology controlling and process and/or dimensional stability, with respect to second crosslinker solution of 100 weight %, aforementioned content is preferably 0.5 to 6 weight %, more preferably 0.5 to 3 weight %.If said content is less than 0.1 weight %, then the crosslinked action meeting of organic crosslinking agent is very small, thereby causes difficulty giving flexibility.When said content surpassed 10 weight %, organic crosslinking agent can make crosslinking reaction excessive, thereby made dimensional stability and suppress film corrugated performance degradation.
The said line style polycarboxylic acid compound that contains at least two carboxyls can be united use with the boron cpd that uses then.With respect to the line style polycarboxylic acid compound that contains at least two carboxyls of 1 weight part, the content of said boron cpd can be below 10 weight parts, more preferably below 7 weight parts.If the content of said boron cpd surpasses 10 weight %, the effect meeting deterioration of organic crosslinking agent then, machining stress can increase simultaneously, thereby causes film rupture and/or wrinkling.
First and second crosslinker solutions can further comprise a spot of iodide separately, thereby guarantee the consistence of the polarisation in the polaroid, the desorption of the iodine that prevents simultaneously to catch.These iodide can with dyeing course in use identical, and with respect to first crosslinker solution or second crosslinker solution of 100 weight %, its content can be 0.05 to 15 weight %, more preferably 0.5 to 11 weight %.
Can make crosslinked bath remain on 20～70 ℃, the time of immersion that polyvinyl alcohol film is immersed crosslinked bath can be 1 second～and 15 minutes, more preferably 5 seconds～10 minutes.
This first crosslinked, second crosslinked or the said first crosslinked and said second crosslinked combination can repeat at least twice.The not special restriction of the sequencing of first cross-linking process and second cross-linking process.For example, can carry out after crosslinked second crosslinkedly, perhaps, on the contrary, can carry out after crosslinked first crosslinked second first.Further; The enforcement that repeats about aforementioned process; Can carry out crosslinked with any order; For example, first cross-linking process/second cross-linking process/first cross-linking process, second cross-linking process/first cross-linking process/second cross-linking process and/or first cross-linking process/second cross-linking process/first cross-linking process/second cross-linking process.
In cross-linking process, can stretch.In this case, can be stretched to the stretch ratio that adds up is 3.0 to 8.0 times.
As stated, can in swelling, dyeing and/or cross-linking process, stretch.Different ground use another jar that stretches that is filled with stretching solution, can after crosslinked, carry out another drawing process.
Cleaning is thereby that crosslinked fully and tensile polyvinyl alcohol film are immersed the process of removing undesirable residue (as adhering to the boric acid on the polyvinyl alcohol film) in the purge tank that comprises cleaning solution.
Said cleaning solution can be water and comprises the iodide that join wherein alternatively.
The temperature of said cleaning solution can be 10～60 ℃, more preferably 15～40 ℃.
Can omit cleaning, perhaps can work as in preceding technology (as stretching) and all clean when accomplishing at every turn.In addition, can repeated washing at least once, and restriction especially of the number of times of repeated washing.
Thereby drying is to make the orientation preparation dry and that improve the dyeing iodine molecule that contracts in dried of the polyvinyl alcohol film that cleaned have the technology of the polaroid of excellent optical property.
Drying can comprise, for example, and seasoning, dry air, heating, far infrared drying, microwave drying, hot-air dry etc.Although use hot-air dry usually, comprise the moisture that comprises in the activated membrane recently so that the use of its exsiccant microwave drying increases.For example, hot-air dry can carry out 1 to 10 minute at 20～90 ℃.Drying temperature can be relatively low to prevent the polaroid deterioration, more preferably below 80 ℃, and most preferably below 60 ℃.
As stated, the preparation method of polaroid of the present invention adopt use inorganic crosslinking agent first crosslinked with use organic crosslinking agent second crosslinked, thereby strengthen crosslinking reaction effectively, therefore increased pinning efficient as the iodine of dichroism material.Therefore, can realize multiple advantage, said advantage comprises, for example, excellent optical property prevents film rupture, and is wrinkling etc. thereby the snappiness of improving film and stretchiness suppress, so finally makes the polaroid of improved processes property.And prepared polaroid can have the area of expansion and the thickness that reduces, and shows dimensional stability favourable on the vertical and horizontal direction, has improved the production efficiency of manufacturing processed simultaneously.
The invention provides a kind of polaroid according to above-mentioned preparing method's preparation.
The present invention also provides a kind of polarization plates of protective membrane that has on polaroid and the one side at least that is laminated to said polaroid.
This protective membrane can comprise have favourable transparency, any film of physical strength, thermostability, moisture protective, isotropy etc.Particularly, can use thermoplastic resin to prepare said film, said thermoplastic resin comprises: for example, vibrin is like polyethylene terephthalate, polyethylene glycol isophthalate, polybutylene terephthalate etc.; Celluosic resin is like diacetyl cellulose, triacetyl cellulose etc.; Polycarbonate resin; Acrylate resin, as gather (methyl) methyl acrylate, gather (methyl) ethyl propenoate etc.; Styron is like PS, acrylonitritrile-styrene resin etc.; Polyolefin resin is like Vilaterm, Vestolen PP 7052, cyclic polyolefin or have polyolefine, ethylene-propylene copolymer of norbornylene structure etc.; Vinyl chloride resin; Polyimide resin is like nylon, aromatic polyimide; Imide resin; The polyether sulphur acid resin; Sulfonate resin; Polyether ketone resin; Polyphenylene sulfide; Vinyl alcohol resin; Vinylidene resin; The vinyl butyral resin; The allylation resin; Polyoxymethylene resin; Epoxy resin or the like.In addition, can use the film of mixture (or compsn) formation of adopting at least a above-mentioned thermoplastic resin.In addition, can also use employing based on the thermosetting resin of (methyl) propenoate, urethanum, epoxy compounds, silicone etc. or the film of UV curable resin formation.In aforementioned content, in view of polarity and/or weather resistance, the preferred especially cellulose membrane that has through basic material saponified surface that uses.And said protective membrane also can be used as optical layers.
Among the present invention, the structure of polarization plates is restriction especially not, but it can be made through the dissimilar optical layers that satisfies required optical property is laminated on the polaroid.The instance of this structure can comprise: comprise the rhythmo structure of the protective membrane on the one side at least that is laminated to polaroid, said protective membrane is used for protecting said polaroid; Comprise be laminated on the protective membrane or the one side at least of polaroid on the rhythmo structure of surface-treated layer (like hard coat, antireflection layer, tissue adhesion layer, barrier layer, antiglare layer etc.); Comprise the liquid crystal layer of the orientation that compensates the visual angle or be laminated on the protective membrane or the one side at least of polaroid on any other rhythmo structure of functional layer, or the like.In addition, at least a optical layers that comprises in the rhythmo structure is selected from: blooming, like the polarization conversion plate; Reflector; Half transmitting plate (transflector); Phase delay chip comprises, for example, wave plate (comprising the λ sheet) is like half-wave plate or quarter-wave plate; Compensation film for angular field of view; And brightness enhancement film, these optical layers are commonly used to make various image display devices.More particularly, the instance of polarization plates that has a rhythmo structure that comprises the protective membrane on the one side at least that is laminated to polaroid can comprise: comprise the reflector that is laminated on the lamination protective membrane or the reflection type polarizer or the translucent polarization plates of semitransparent reflector plate; The ellipse or the circular polarization plate that comprise lamination phase delay chip above that; Comprise the lamination viewing angle compensation layer above that or the wide visual angle type polarization plates of film; The polarization plates that comprises lamination brightness enhancement film above that, or the like.
Except typical LCD, aforementioned polarization plates also can be applicable to multiple image display device, comprise, for example, EL indicating meter, PDP, FED.
Hereinafter, in order more specifically to understand the present invention, will describe preferred embodiment with reference to embodiment and comparing embodiment.Yet; It will be apparent for a person skilled in the art that; It is for purpose of explanation that these embodiments are provided; And under the situation that does not depart from scope of the present invention and essence, can carry out multiple modification and change, and these modifications and change are included in certainly and like enclosed among the present invention that claim limits.
Embodiment
Embodiment 1
At 30 ℃ is that transparent not tensile polyvinyl alcohol film (VF-PS, Kuraray Chemical Co.Ltd.) more than 99.9% immerses in the water (deionized water) and to make its swelling in 2 minutes with saponification deg.After above-mentioned immersion and swelling, immerse in the dyeing solution of potassiumiodide of the iodine that comprises 3.5mmol/L and 2 weight % at the 30 ℃ of films that will handle and to dye in 4 minutes.At this moment, in swelling and dyeing course, respectively this film is stretched to 1.3 times and 1.4 times.Then; In first crosslinker solution of 50 ℃ of boric acid that painted film immersed the potassiumiodide that comprises 10 weight % and 3.5 weight % 2 minutes (first cross-linking step); Then; In second crosslinker solution of the pentanedioic acid of the boric acid of 50 ℃ of potassiumiodides that comprising 10 weight %, 3.5 weight % and 1 weight % 1 minute (second cross-linking step), thereby carry out crosslinking reaction.At this moment, in first and second cross-linking step, the film that will handle respectively is stretched to 2.5 times and 1.5 times.Therefore, the total drawing ratio of accumulative total reaches 6.8 times.Accomplish crosslinked after, with the film that forms in 70 ℃ of baking ovens dry 4 minutes, thereby make polaroid.
Through with triacetyl cellulose (TAC) film lamination on the two sides of polaroid of preparation, make polarization plates.
Embodiment 2
Except second crosslinker solution comprises the pentanedioic acid of 3 weight %, repeat the identical step of describing among the embodiment 1.
Embodiment 3
Except second crosslinker solution comprises the pentanedioic acid of 6 weight %, repeat the identical step of describing among the embodiment 1.
Embodiment 4
Except second crosslinker solution comprises the pentanedioic acid of 9 weight %, repeat the identical step of describing among the embodiment 1.
Embodiment 5
Except second crosslinker solution comprises hexanodioic acid but not the pentanedioic acid, repeat the identical step of describing among the embodiment 1.
Embodiment 6
Except second crosslinker solution comprises Hydrocerol A but not the pentanedioic acid, repeat the identical step of describing among the embodiment 1.
Embodiment 7
Except second crosslinker solution comprises 1,2,3,4-ethylene-dimalonic acid but not beyond the pentanedioic acid repeats the identical step of describing among the embodiment 1.
Embodiment 8
Except in first and second cross-linking step, respectively film being stretched to 1.5 times and 2.5 times, repeat the identical step of describing among the embodiment 1.
Embodiment 9
Except second carry out after crosslinked first crosslinked, repeat the identical step of describing among the embodiment 1.
Embodiment 10
Except second crosslinker solution of the pentanedioic acid that in second crosslinked (second cross-linking step) process, uses the potassiumiodide that comprises 10 weight % be in 50 ℃ and 3 weight % and in first and second cross-linking step, respectively film is stretched to 2.5 times and 1.5 times, repeat the identical step of description among the embodiment 1
Comparing embodiment 1
Except second crosslinker solution comprises oxalic dialdehyde but not the pentanedioic acid, repeat the identical step of describing among the embodiment 1.
Comparing embodiment 2
First crosslinked and not carry out the second crosslinked and stretch ratio be 4.0 times except only carrying out, repeat the identical step of describing among the embodiment 1.
Comparing embodiment 3
Second crosslinked and not carry out the first crosslinked and stretch ratio be 4.0 times except only carrying out, repeat the identical step of describing among the embodiment 1.
Comparing embodiment 4
Second crosslinked and do not carry out first crosslinkedly and to use second crosslinker solution and the stretch ratio of the pentanedioic acid of the potassiumiodide comprise 10 weight % and 3 weight % be 4.0 times except only carrying out, repeat the identical step of describing among the embodiment 1.
Table 1
EXPERIMENTAL EXAMPLE
For the polaroid for preparing in previous embodiment and the comparing embodiment, according to following method physical properties, and its measuring result is shown in the following table 2.
1. optical property (degree of polarization, transparence)
The polaroid of each preparation is cut into the size of 4cm * 4cm, then uses UV-visible spectrometer (V-7100, JASCO Co.) to measure optical property.Can calculate transparence through following formula 1.
(formula 1)
Wherein, T
1Be illustrated in the parallel transmitted light degree that obtains when a pair of polaroid arranged with the parallel mode of its absorption axes; And T
2The vertical light transmission degree that obtains when being illustrated in the mode that a pair of polaroid is perpendicular to one another with its absorption axes and arranging.
2. thickness (μ m)
(MS-5C Nikon), measures the thickness of each polaroid for preparing and obtains measuring average thickness value on 10 points on the width to use the film thickness surveying instrument.
3. interior shrinkage (%)
This factor is represented with the ratio of the initial disc width of polyvinyl alcohol film by the width of the polaroid of preparation, shrinkage in then calculating according to following formula 2.
(formula 2)
Wherein, L
1Represent the not initial disc width and the L of tensile polyvinyl alcohol film
2The width of the polaroid of expression preparation.
4. dimensional stability
The polaroid with each preparation be cut into longitudinal direction (width: TD) and horizontal direction (length: MD) go up to after the size of 1cm * 3cm, under heat-resisting condition with cutting sample place 80 ℃ 24 hours.Use the two-dimensional measurement apparatus measures make sample experience this heat-resisting condition before with afterwards size, then, change (sometimes, being called ' dimensional stability ') (%) according to following formula 3 calculated sizes.
(formula 3)
Wherein, P
1The initial length of expression polaroid, and P
2Length for this polaroid after polaroid being placed under the heat-resisting condition.
5. tensile strength (MPa)
Use the roller that load cell has been installed on it, be polyvinyl alcohol film to be stretched after the stretch ratio that reaches final accumulative total and before drying, measures and be applied to the tensile strength on the polyvinyl alcohol film in crosslinked jar.If tensile strength is more than the 10MPa, then need consider the disruptive excessive risk that film has
6. corrugated evaluation
After crosslinked and just before drying, it is wrinkling whether the polyvinyl alcohol film that visual observation was handled has.
7. crosslinked affirmation
Whether crosslinked for the polaroid that verification process is crossed, use spectrograph (FT-IR) that the polaroid that is dissolved in the hot water is analyzed with inspection at 1700～1720cm
-1Near the appearance at C=O peak.
Table 2
Shown in above table 2; Can confirm; Compare with the polaroid of preparation in the comparing embodiment 1 to 4; According to the polaroid of preparation among the embodiment 1 to 10 that comprises first crosslinked and the second crosslinked method of using the line style polycarboxylic acid compound that contains at least two carboxyls of using boron cpd by crosslinked effectively, thereby have excellent optical property.And these polaroids do not have film rupture and wrinkling, have therefore realized excellent processes property and on the vertical and horizontal direction, have had excellent size stability.
Although described the present invention with reference to preferred implementation, those skilled in the relevant art will be appreciated that not breaking away under the situation of liking the scope of the present invention that claim limits enclosed can make various modifications and change.
Claims (10)
1. the preparation method of a polaroid, this method may further comprise the steps:
Through polyvinyl alcohol film being immersed carry out in first crosslinker solution comprise boron cpd first crosslinked; With
Through said polyvinyl alcohol film being immersed carry out in second crosslinker solution that comprises the line style polycarboxylic acid compound that contains at least two carboxyls second crosslinked.
2. method according to claim 1, wherein, with respect to first crosslinker solution of 100 weight %, the content of said boron cpd is 1 to 10 weight %.
3. method according to claim 1; Wherein, the said line style polycarboxylic acid compound that contains at least two carboxyls is for being selected from succsinic acid, pentanedioic acid, hexanodioic acid, oxalic acid, tartrate, Hydrocerol A, 1,2; 3, at least a in 4-ethylene-dimalonic acid and the verivate thereof.
4. method according to claim 1, wherein, with respect to second crosslinker solution of 100 weight %, the said content that contains the line style polycarboxylic acid compound of at least two carboxyls is 0.1 to 10 weight %.
5. method according to claim 1, wherein, with respect to the line style polycarboxylic acid compound that contains at least two carboxyls of 1 weight part, said second crosslinker solution further comprises the boron cpd below 10 weight parts.
6. method according to claim 1 wherein, is carried out after crosslinked said second crosslinkedly said first, perhaps carry out after crosslinked said first crosslinked said second.
7. method according to claim 1, wherein, the combination of said first crosslinked, said second crosslinked or said first cross-linking process and said second cross-linking process repeats at least twice.
8. polarization plates, it is gone up through the one side at least that protective film is pressed in the polaroid through each described preparing method's preparation in the claim 1 to 7 and makes.
9. polarization plates according to claim 8, it further comprises at least a film in phase retardation film, compensation film for angular field of view and the brightness enhancement film that is selected from that is laminated on said polaroid or the polaroid protective film.
10. image display device, it comprises the described polarization plates of claim 8.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20100054758 | 2010-06-10 | ||
| KR10-2010-0054758 | 2010-06-10 | ||
| KR10-2010-0132164 | 2010-12-22 | ||
| KR1020100132164A KR20110135321A (en) | 2010-06-10 | 2010-12-22 | Method for preparing polarizer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102311552A true CN102311552A (en) | 2012-01-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011101487016A Pending CN102311552A (en) | 2010-06-10 | 2011-05-27 | Method for preparing polarizer |
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| Country | Link |
|---|---|
| JP (1) | JP2011257756A (en) |
| CN (1) | CN102311552A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107667305A (en) * | 2015-06-03 | 2018-02-06 | 株式会社Lg化学 | For the method for manufacturing polarizer and the polarizer being produced from it |
| CN110221376A (en) * | 2019-06-28 | 2019-09-10 | 昆山工研院新型平板显示技术中心有限公司 | A kind of preparation method of polaroid, display panel and polaroid |
| US11314006B2 (en) * | 2015-01-27 | 2022-04-26 | Lg Chem, Ltd. | Method for manufacturing polarizer and polarizer manufactured by the same |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5420519B2 (en) * | 2010-11-15 | 2014-02-19 | 日東電工株式会社 | Manufacturing method of polarizer, polarizer, polarizing plate, optical film, and image display device |
| JP6073566B2 (en) * | 2012-03-30 | 2017-02-01 | 日東電工株式会社 | Manufacturing method of polarizer, polarizer, polarizing plate, optical film, and image display device |
| JP6076609B2 (en) * | 2012-04-09 | 2017-02-08 | 日東電工株式会社 | Polarizer, production method thereof, polarizing plate, optical film, and image display device |
| JP6232921B2 (en) * | 2013-03-18 | 2017-11-22 | 住友化学株式会社 | Production method of polarizing laminated film and polarizing plate |
| JP6366712B2 (en) * | 2014-03-26 | 2018-08-01 | エルジー・ケム・リミテッド | Method for manufacturing a polarizer having a locally depolarized region |
| JP6610020B2 (en) * | 2014-06-23 | 2019-11-27 | 三菱ケミカル株式会社 | Manufacturing method of polarizing film and manufacturing method of polarizing plate |
| KR102327242B1 (en) | 2016-07-26 | 2021-11-16 | 주식회사 쿠라레 | Polarizing film and its manufacturing method |
| JP6729199B2 (en) * | 2016-09-01 | 2020-07-22 | 三菱ケミカル株式会社 | Method for producing iodine-based polarizing film |
| KR20220007091A (en) | 2019-05-09 | 2022-01-18 | 주식회사 쿠라레 | Polarizing film and its manufacturing method |
-
2011
- 2011-05-27 CN CN2011101487016A patent/CN102311552A/en active Pending
- 2011-06-08 JP JP2011128309A patent/JP2011257756A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11314006B2 (en) * | 2015-01-27 | 2022-04-26 | Lg Chem, Ltd. | Method for manufacturing polarizer and polarizer manufactured by the same |
| CN107667305A (en) * | 2015-06-03 | 2018-02-06 | 株式会社Lg化学 | For the method for manufacturing polarizer and the polarizer being produced from it |
| CN107667305B (en) * | 2015-06-03 | 2020-06-30 | 株式会社Lg化学 | Method for manufacturing polarizer and polarizer manufactured thereby |
| CN110221376A (en) * | 2019-06-28 | 2019-09-10 | 昆山工研院新型平板显示技术中心有限公司 | A kind of preparation method of polaroid, display panel and polaroid |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2011257756A (en) | 2011-12-22 |
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Application publication date: 20120111 |