KR20150052777A - Process for Preparing Polarizer - Google Patents
Process for Preparing Polarizer Download PDFInfo
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- KR20150052777A KR20150052777A KR1020140143578A KR20140143578A KR20150052777A KR 20150052777 A KR20150052777 A KR 20150052777A KR 1020140143578 A KR1020140143578 A KR 1020140143578A KR 20140143578 A KR20140143578 A KR 20140143578A KR 20150052777 A KR20150052777 A KR 20150052777A
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- polarizer
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- boronic acid
- acid derivative
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Abstract
The present invention relates to a process for producing a polarizer characterized in that a boronic acid derivative or a boronic acid derivative is introduced into at least one of a swelling step, a dyeing step, a crosslinking step and a water washing step. According to the production process of the present invention, it is possible to produce a polarizer having a low water permeability and a low shrinkage due to excellent water resistance and little change in transmittance and polarization degree even after being left under high temperature and high humidity conditions.
Description
The present invention relates to a method for producing a polarizer, and more particularly, to a method for producing a polarizer having excellent anti-wet heat stability.
Polarizing plates used in liquid crystal displays and the like are generally formed by attaching a protective film to one or both surfaces of a polarizer. The polarizer is a step of uniaxially stretching a polyvinyl alcohol-based (PVA) resin film, a step of staining a polyvinyl alcohol-based resin film with a dichroic dye to adsorb the dichroic dye, a step of staining the polyvinyl alcohol- A step of treating the resin film with an aqueous solution of boric acid and crosslinking the resin film, and a step of washing with water.
The polarizer using iodine as the dichroic dye in the dyeing process is referred to as iodine-based polarizer, and the polarizer using dichromatic dye is referred to as dye-based polarizer. The iodine polarizer is widely used because it has high transmittance and high polarization (high contrast) as compared with the dye-based polarizer.
However, the iodine polarizer has better optical characteristics than the dye-based polarizer, but has a lower optical durability. For example, when the iodine polarizer or the polarizing plate including the polarizer is left under dry heat, the transmittance is lowered or discolored.
In recent years, the field of use of liquid crystal display devices has widened and peripheral technologies have been advanced, and the demand for the performance of polarizing plates has become more severe. Specifically, a polarizing plate having high contrast (high transmittance and high polarization degree) as well as excellent optical durability such as heat resistance, heat resistance and humidity resistance is required.
Korean Patent Laid-Open Publication No. 2013-0030990 discloses a method for producing a polarizing film comprising a step of immersing a polyvinyl alcohol-based film in a crosslinked aqueous solution containing a metal nitrate salt and a step of immersing the polyvinyl alcohol film in a solution of a polarizer having excellent optical properties and preventing deterioration even after being left under dry heat, A manufacturing method is disclosed. However, the above patent does not disclose or mention the anti-wet heat stability of the polarizer.
It is an object of the present invention to provide a method for producing a polarizer excellent in anti-wet heat stability.
Another object of the present invention is to provide a polarizer produced by the above production method.
It is still another object of the present invention to provide a polarizing plate in which a protective film is laminated on at least one surface of the polarizer.
Meanwhile, the present invention provides a method for producing a polarizer, wherein the boronic acid derivative of the following formula (1) or the boronic acid derivative of the following formula (2) is added to at least one of the swelling step, the dyeing step, the crosslinking step and the water washing step .
[Chemical Formula 1]
(2)
In this formula,
R, R 1 and R 2 are each independently hydrogen, a C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl group, a C 3 -C 10 cycloalkyl group, or an aryl group.
In one embodiment of the present invention, the content of the boronic acid derivative of the formula (1) or the boronic acid derivative of the formula (2) is in the range of 0.005 to 5% based on 100% by weight of the swelling aqueous solution, the dyeing aqueous solution, By weight.
On the other hand, the present invention provides a polarizer produced by the above production method.
In one embodiment of the present invention, the polarizer may have a contact angle of water of 22 to 75 degrees.
In one embodiment of the present invention, the boronic acid derivative of Formula 1 or the boronic acid derivative of Formula 2 may be contained in the polarizer in an amount of 1 to 5000 ppm.
On the other hand, the present invention provides a polarizing plate in which a protective film is laminated on at least one surface of the polarizer.
According to the production process of the present invention, it is possible to produce a polarizer having a low water permeability and a low shrinkage due to excellent water resistance and little change in transmittance and polarization degree even after being left under high temperature and high humidity conditions.
Hereinafter, the present invention will be described in more detail.
One embodiment of the present invention is a process for producing a polarizer characterized by introducing a boronic acid derivative of the formula (1) or a boronic acid derivative of the formula (2) into at least one of a swelling step, a dyeing step, a crosslinking step and a washing step .
[Chemical Formula 1]
(2)
In this formula,
R, R 1 and R 2 are each independently hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl group, a cycloalkyl group or an aryl group of C 3 -C 10, preferably hydrogen, C 1 - C 6 alkyl group, C 2 -C 6 alkenyl group, C 3 -C 10 cycloalkyl group or phenyl.
As used herein, the C 1 -C 6 alkyl group means a linear or branched hydrocarbon group having 1 to 6 carbon atoms, for example, methyl, ethyl, n-propyl, i-propyl, Butyl, t-butyl, n-pentyl, n-hexyl, and the like.
As used herein, the C 2 -C 6 alkenyl group refers to straight or branched unsaturated hydrocarbons having from 2 to 6 carbon atoms having at least one carbon-carbon double bond and includes, for example, ethylene, propenyl, Tennessee, Penne Tenure, and the like.
C 3 -C 10 cycloalkyl group as used herein means a simple or fused ring hydrocarbon having 3 to 10 carbon atoms and includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like, It is not.
As used herein, an aryl group includes both an aromatic group and a heteroaromatic group and a partially reduced derivative thereof. The arometric group is a simple or fused ring group of 5 to 15-ary, and the heteroaromatic group means an arometric group containing at least one of oxygen, sulfur or nitrogen. Representative examples of aryl groups include, but are not limited to, phenyl, pyridine, indole, and the like.
The C 1 -C 6 alkyl group, the C 3 -C 10 cycloalkyl group, and the aryl group may be substituted by one or more hydrogen atoms of a C 1 -C 5 alkyl group, a C 2 -C 6 alkenyl group, a C 2 -C 6 An alkynyl group, a C 3 -C 10 cycloalkyl group, a C 3 -C 10 heterocycloalkyl group, a C 3 -C 10 heterocycloalkyloxy, a C 1 -C 5 haloalkyl group, a C 1 -C 5 alkoxy group C 1 -C 5 thioalkoxy, aryl, acyl, hydroxy, thio, halogen, amino, alkoxycarbonyl, carboxy, carbamoyl, cyano, nitro and the like.
The polarizer manufactured according to an embodiment of the present invention is prepared by dyeing and orienting a hydrophilic polymer film with iodine or a dichroic dye. Examples of the hydrophilic polymer film include a polyvinyl alcohol film, a partially saponified polyvinyl alcohol film, and the like Is used.
The polyvinyl alcohol film may have a degree of polymerization of usually 500 to 10,000, preferably 1,000 to 6,000, and more preferably 1,400 to 4,000. In the case of the saponified polyvinyl alcohol film, It is preferably 95.0 mol% or more, more preferably 99.0 mol% or more, and even more preferably 99.9 mol% or more.
The kind of the hydrophilic polymer film is not particularly limited as long as it is a film that can be dyed with iodine or a dichroic dye in addition to a polyvinyl alcohol film. For example, a hydrophilic polymer film such as a polyethylene terephthalate film, an ethylene-vinyl acetate copolymer film, an ethylene-vinyl alcohol copolymer film, a cellulose film and a partially saponified film thereof, and a hydrophilic polymer film such as a dehydrated polyvinyl alcohol film And polyene-oriented films such as dehydrochlorinated polyvinyl chloride and the like can be used.
The thickness of the polarizer is not particularly limited, but is, for example, in the range of 5 to 40 占 퐉, preferably in the range of 10 to 30 占 퐉, and more preferably in the range of 15 to 25 占 퐉.
In the method for producing a polarizer according to an embodiment of the present invention, the polarizer produced through the swelling step, the dyeing step and the crosslinking step is washed with water and dried to prepare a polarizer.
The swelling step is carried out by immersing the unstretched polyvinyl alcohol film in a swelling tank filled with a swelling aqueous solution before dyeing to remove impurities such as dust and anti-blocking agent deposited on the surface of the polyvinyl alcohol film, Is a step for improving physical properties of the polarizer by swelling the alcoholic film to improve the stretching efficiency and preventing uneven dyeing.
Water (pure water, deionized water) can usually be used as a swelling aqueous solution, and when a small amount of glycerin or potassium iodide is added thereto, the swelling of the polyvinyl alcohol film can be improved and the processability can be improved. The content of glycerin is preferably 5% by weight or less based on 100% by weight of the aqueous swelling solution, and the content of potassium iodide is preferably 10% by weight or less.
The swelling bath temperature is preferably 20 to 45 캜, more preferably 25 to 40 캜. The execution time (swelling tank immersion time) of the swelling step is preferably 180 seconds or less, more preferably 90 seconds or less. When the immersion time is within the above range, it is possible to prevent the swelling from becoming excessive and saturation, to prevent breakage due to softening of the polyvinyl alcohol film and to improve the polarization degree by uniformly adsorbing iodine in the dyeing step have.
The stretching step may be carried out together with the swelling step, wherein the stretching ratio is preferably about 1.1 to 3.5 times.
The swelling step may be omitted and the swelling may be performed simultaneously in the staining step.
The dyeing step is a step of dipping the polyvinyl alcohol film in a dyeing bath filled with an aqueous dyeing solution containing a dichroic dye, for example, iodine, to adsorb iodine on the polyvinyl alcohol-based film.
The dyeing aqueous solution may comprise water, a water-soluble organic solvent or a mixed solvent thereof and iodine. The content of iodine is preferably 0.4 to 400 mmol / L, more preferably 0.8 to 275 mmol / L, even more preferably 1 to 200 mmol / L.
To further improve the dyeing efficiency, iodide may be further included as a dissolution aid. As the iodide, potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide and titanium iodide may be used alone or in combination of two or more. Of these, potassium iodide is preferable in view of high solubility in water. The content of iodide is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, based on 100% by weight of the dyeing aqueous solution.
The temperature of the dye bath is preferably 5 to 42 캜, more preferably 10 to 35 캜. The immersing time of the polyvinyl alcohol film in the dyeing tank is not particularly limited, and is preferably 1 to 20 minutes, and more preferably 2 to 10 minutes.
The dyeing step and the stretching step may be carried out. In this case, the cumulative stretching ratio is preferably 1.1 to 4.0 times. In the present specification, "cumulative stretching ratio" represents the value of the product of the stretching ratio at each step.
The crosslinking step is a step of immersing a dye-bound polyvinyl alcohol film in an aqueous crosslinking solution to immobilize the adsorbed iodine molecule or dye so that the dyeability due to the physically adsorbed iodine molecule or the dichroic dye is not lowered by the external environment . Although dichroic dyes are not often eluted in a humidity environment, iodine molecules often dissolve or sublimate depending on the environment when the crosslinking reaction is unstable, and sufficient crosslinking reaction is required. In addition, the crosslinking step is important because, in order to orient the iodine molecules positioned between all the polyvinyl alcohol molecules and the molecules and to improve the optical properties, the crosslinking step generally needs to be elongated to the largest stretching ratio.
The aqueous solution for crosslinking may further comprise water as a solvent, and boron compounds such as boric acid, sodium borate, and iodide, and may further comprise an organic solvent mutually soluble with water.
The boron compound imparts short crosslinking and rigidity to suppress wrinkling during processing, thereby improving handling properties and forming iodine alignment.
The content of the boron compound is preferably 1 to 10% by weight, more preferably 2 to 6% by weight, based on 100% by weight of the aqueous crosslinking solution. When the content is less than 1% by weight, the crosslinking effect of the boron compound is reduced and it is difficult to impart rigidity. When the content is more than 10% by weight, the crosslinking reaction of the inorganic crosslinking agent is excessively activated and the crosslinking reaction of the organic crosslinking agent is difficult to proceed effectively.
Iodide is used to prevent the uniformity of the degree of polarization in the plane of polarizers and the desorption of dyed iodine. The iodide may be the same as that used in the dyeing step, and its content may be 0.05 to 15% by weight, preferably 0.5 to 11% by weight, based on 100% by weight of the aqueous crosslinking solution. If the content is less than 0.05% by weight, the iodide ion in the film may escape to increase the transmittance and the color value of the polarizer may be changed. Further, if the content exceeds 15% by weight, There is a problem that the transmittance is reduced due to penetration into the film.
The temperature of the crosslinking bath is 20 to 70 ° C, and the immersion time of the polyvinyl alcohol film in the crosslinking bath may be 1 second to 15 minutes, preferably 5 seconds to 10 minutes.
The stretching step may be performed together with the crosslinking step, and in this case, it is preferable that the total stretching ratio is 3.0 to 8.0 times.
As described above, the stretching step may be performed in conjunction with the swelling step, the dyeing step and the crosslinking step, and may be carried out as an independent stretching step using a separate stretching tank filled with the eluting aqueous solution after the crosslinking step.
The washing step is a step of immersing the crosslinked and stretched polyvinyl alcohol film in a water bath filled with water for washing to remove unnecessary residues such as boric acid attached to the polyvinyl alcohol film in the previous steps.
The aqueous solution for washing may be water, and iodide may be further added thereto.
The temperature of the water bath is preferably 10 to 60 ° C, more preferably 10 to 40 ° C. The running time of the washing step is usually 1 to 60 seconds, preferably 3 to 30 seconds, and more preferably 5 to 20 seconds.
The wash step may be performed each time previous steps such as dyeing step, crosslinking step or stretching step are completed. It may also be repeated one or more times, and the number of repetition is not particularly limited.
The drying step is a step of drying the washed polyvinyl alcohol-based film and further improving the orientation of the iodine molecules dyed by the necking by drying, thereby obtaining a polarizer excellent in optical characteristics.
As the drying method, natural drying, air drying, heating and drying, far infrared ray drying, microwave drying, hot air drying and the like can be used. Recently, microwave drying in which only water in the film is activated and dried is newly used, Drying is mainly used. For example, it may be hot air dried at 20 to 90 DEG C for 1 to 10 minutes. The drying temperature is preferably low in order to prevent deterioration of the polarizer, more preferably 80 deg. C or lower, still more preferably 70 deg. C or lower.
In the method for producing a polarizer according to one embodiment of the present invention, the boronic acid derivative of the formula (1) or the boronic acid derivative of the formula (2) is introduced into at least one of the swelling step, the dyeing step, the crosslinking step and the washing step, It is preferable to add it to the step.
The boronic acid derivative of Formula 1 or the boronic acid derivative of Formula 2 may be added to an aqueous solution prepared in each step (that is, an aqueous solution for swelling, an aqueous solution for dyeing, an aqueous solution for bridging, a solution for aqueous solution) Can be put together when making. The content thereof may be 0.005 to 5% by weight based on 100% by weight of each aqueous solution. If the content is less than 0.005% by weight, the effect of improving the heat and humidity resistance is insignificant. If the content is more than 5% by weight, the polarizer light characteristics are affected and adverse effects may occur.
One embodiment of the present invention relates to a polarizer produced by the above production method.
In one embodiment of the present invention, the polarizer may have a contact angle of water of 40 to 75 DEG, preferably 55 to 75 DEG.
The polarizer according to one embodiment of the present invention is hydrophobicized by the boronic acid derivative of the formula 1 or the boronic acid derivative of the formula 2 to increase the contact angle of water droplets and reduce the moisture content to suppress shrinkage.
In one embodiment of the present invention, the boronic acid derivative of Formula 1 or the boronic acid derivative of Formula 2 may be contained in the polarizer in an amount of 1 to 5000 ppm, preferably 200 to 1600 ppm.
If the content is less than 1 ppm, the effect of improving wet heat stability and water resistance is insignificant. If the content is more than 5000 ppm, the polarizer light characteristics may be adversely affected and adverse effects may occur.
An embodiment of the present invention provides a polarizing plate in which a protective film is laminated on at least one surface of the polarizer.
The protective film is not particularly limited as long as it is a film excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, and the like. Specifically, polyester resins such as polyethylene terephthalate, polyethylene isophthalate and polybutylene terephthalate; Cellulose-based resins such as diacetylcellulose and triacetylcellulose; Polycarbonate resin; Acrylic resins such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; Styrene resins such as polystyrene and acrylonitrile-styrene copolymer; Polyolefin-based resins such as polyethylene, polypropylene, cyclo-based or norbornene-structured polyolefin, and ethylene propylene copolymer; Vinyl chloride resin; Polyamide resins such as nylon and aromatic polyamide; Imide resin; Polyether sulfone type resin; Sulfone based resin; Polyether ketone resin: a polyphenylene sulfide resin; Vinyl alcohol-based resin; Vinylidene chloride resins; Vinyl butyral resin; Allylate series resin; Polyoxymethylene type resin; Epoxy resin, and the like, and a film composed of the blend of the thermoplastic resin may also be used. Further, a film made of a thermosetting resin such as (meth) acrylic, urethane, epoxy, or silicone or a film made of an ultraviolet curable resin may be used. Among them, a cellulose-based film or an acrylic-based film having a surface saponified (saponified) by alkali or the like is preferable in view of polarization characteristics or durability. Further, the protective film may have the function of the optical layer described below.
In the present invention, the structure of the polarizing plate is not particularly limited, and various kinds of optical layers capable of satisfying the required optical characteristics may be laminated on the polarizer. For example, a structure in which a protective film for protecting a polarizer is laminated on at least one side of a polarizer; A structure in which a surface treatment layer such as a hard coating layer, an antireflection layer, an anti-adhesion layer, a diffusion prevention layer, and an anti-glare layer is laminated on at least one surface of a polarizer or on a protective film; Or a structure in which an alignment liquid crystal layer or another functional film is laminated on at least one surface of the polarizer or on the protective film to compensate for the viewing angle. Further, it is also possible to use an optical film such as a polarization conversion device used for forming various image display devices, a retarder including a wave plate (including a? Plate) such as a reflector, a transflector plate, a half-wave plate or a quarter- , A viewing angle compensating film, and a luminance improving film may be laminated with an optical layer. More specifically, the present invention relates to a polarizing plate having a structure in which a protective film is laminated on one surface of a polarizer, which comprises a reflective polarizing plate or a transflective polarizing plate in which a reflector or a transflective reflector is laminated on a laminated protective film; An elliptic or circular polarizer in which a retarder is stacked; A wide viewing angle polarizer in which a viewing angle compensation layer or a viewing angle compensation film is laminated; Or a polarizing plate in which a brightness enhancement film is laminated.
Such a polarizing plate is applicable not only to a general liquid crystal display but also to various image display devices such as an electroluminescent display device, a plasma display device, and a field emission display device.
Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are for illustrative purpose only and that the scope of the present invention is not limited to these embodiments.
Example 1: Preparation of a polarizer using aqueous solution for washing containing methylboronic acid
A transparent unstretched polyvinyl alcohol film (VF-PS, KURARAY Co.) having a degree of saponification of 99.9% or more was immersed in water (deionized water) at 30 ° C for 2 minutes and swelled. Then, 3.5 mM of iodine and 2 wt% of potassium iodide Was immersed in an aqueous solution for dyeing at 30 DEG C for 4 minutes to be dyed. At this time, stretching was performed at 1.3 times and 1.4 times at the swelling and dyeing stages, respectively. Subsequently, it was immersed in an aqueous solution for crosslinking at 50 DEG C containing 10 wt% of potassium iodide and 3.7 wt% of boric acid for 2 minutes to crosslink. At this time, the crosslinking step was such that the total cumulative stretching ratio was 5.8 times. After completion of the crosslinking, the resultant was washed with a water bath aqueous solution containing 1% by weight of methylboronic acid for 20 seconds. The washed polyvinyl alcohol film was dried in an oven at 70 DEG C for 4 minutes to prepare a polarizer.
Example 2: Preparation of a polarizer using aqueous solution for washing containing ethylboronic acid
Polarizers were prepared in the same manner as in Example 1, except that an aqueous solution for washing containing 1% by weight of ethyl boronic acid was used.
Example 3: Preparation of a polarizer using aqueous solution for washing containing phenylboronic acid
A polarizer was prepared in the same manner as in Example 1, except that an aqueous solution for washing containing 1% by weight of phenylboronic acid was used.
Example 4: Preparation of a polarizer using aqueous solution for washing containing n-propylboronic acid
Polarizers were prepared in the same manner as in Example 1 except that an aqueous solution for washing containing 1% by weight of n-propylboronic acid was used.
Example 5: Preparation of a polarizer using aqueous solution for washing containing n-butylboronic acid
Polarizers were prepared in the same manner as in Example 1, except that an aqueous solution for washing containing 1% by weight of n-butylboronic acid was used.
Example 6: Preparation of a polarizer using aqueous solution for washing containing cyclohexylboronic acid
A polarizer was prepared in the same manner as in Example 1, except that an aqueous solution for washing containing 1% by weight of cyclohexylboronic acid was used.
Example 7: Preparation of a polarizer using aqueous solution for washing containing cis-1-propen-1-ylboronic acid (cis-1-propen-
Polarizers were prepared in the same manner as in Example 1, except that an aqueous solution for washing containing 1% by weight of cis-1-propene-1-ylboronic acid was used.
Example 8: Preparation of a polarizer using aqueous solution for washing containing trans-1-propen-1-ylboronic acid
Polarizers were prepared in the same manner as in Example 1, except that a water-containing aqueous solution containing 1% by weight of trans-1-propen-1-ylboronic acid was used.
Example 9: Preparation of a polarizer using aqueous solution for washing containing 1-pentene-1-ylboronic acid
Polarizers were prepared in the same manner as in Example 1, except that an aqueous solution for washing containing 1% by weight of 1-penten-1-ylboronic acid was used.
Example 10: Preparation of a polarizer using aqueous solution for water containing borinic acid
A polarizer was prepared in the same manner as in Example 1, except that an aqueous solution for washing containing 1% by weight of boric acid was used.
Example 11: Preparation of a polarizer using a swelling aqueous solution containing methylboronic acid
A polarizer was prepared in the same manner as in Example 1, except that a swelling aqueous solution containing 0.2% by weight of methyl boronic acid was used and an aqueous solution for washing, which did not contain methyl boronic acid, was used.
Example 12: Preparation of polarizer using aqueous solution for dyeing containing methylboronic acid
A polarizer was prepared in the same manner as in Example 1, except that an aqueous solution for dyeing containing 0.2% by weight of methylboronic acid was used and an aqueous solution for aqueous solution containing no methylboronic acid was used.
Example 13: Preparation of polarizer using aqueous crosslinking solution containing methylboronic acid
A polarizer was prepared in the same manner as in Example 1 except that an aqueous solution for crosslinking containing 0.2% by weight of methylboronic acid was used and an aqueous solution for aqueous solution containing no methylboronic acid was used.
Example 14: Preparation of a polarizer using a swelling aqueous solution containing phenylboronic acid
A polarizer was prepared in the same manner as in Example 3, except that a swelling aqueous solution containing 0.2% by weight of phenylboronic acid was used and an aqueous solution for washing without phenylboronic acid was used.
Example 15: Preparation of a polarizer using a dyeing aqueous solution containing phenylboronic acid
A polarizer was prepared in the same manner as in Example 3, except that an aqueous solution for dyeing containing 0.2% by weight of phenylboronic acid was used and an aqueous solution for aqueous solution containing no phenylboronic acid was used.
Example 16: Preparation of polarizer using aqueous solution for crosslinking containing phenylboronic acid
A polarizer was prepared in the same manner as in Example 3, except that an aqueous solution for crosslinking containing 0.2% by weight of phenylboronic acid was used and an aqueous solution for aqueous solution containing no phenylboronic acid was used.
Example 17: Preparation of a polarizer using a swelling aqueous solution containing boric acid
A polarizer was prepared in the same manner as in Example 10, except that a swelling aqueous solution containing 0.2% by weight of boric acid was used and an aqueous solution for aqueous solution containing no boric acid was used.
Example 18: Preparation of polarizer using aqueous solution for dyeing containing boric acid
A polarizer was prepared in the same manner as in Example 10 except that an aqueous solution for dyeing containing 0.2% by weight of boric acid was used and an aqueous solution for aqueous solution containing no boric acid was used.
Example 19: Preparation of polarizer using aqueous crosslinking solution containing boric acid
A polarizer was prepared in the same manner as in Example 10, except that an aqueous solution for crosslinking containing 0.2% by weight of boric acid was used and an aqueous solution for aqueous solution containing no boric acid was used.
Comparative Example 1: Preparation of a polarizer using a conventional aqueous solution for washing
A polarizer was prepared in the same manner as in Example 1, except that an aqueous solution for aqueous solution containing no boronic acid derivative was used.
Experimental Example 1: Evaluation of anti-wet heat stability
The polarizers prepared in Examples 1 to 19 and Comparative Example 1 were cut into a size of 4 cm x 4 cm and then the transmittance was measured using an ultraviolet ray spectrophotometer (V-7100, manufactured by JASCO). At this time, the degree of polarization is calculated by the following equation (1).
[Equation 1]
The degree of polarization (P) = [(T 1 - T 2 ) / (T 1 + T 2 )] 1/2
T 1 is a parallel transmittance obtained when the pair of polarizers are arranged in parallel with the absorption axis, and T 2 is the orthogonal transmittance obtained when the pair of polarizers are arranged in a state in which the absorption axes are perpendicular to each other.
The polarizer was allowed to stand for 240 hours at a relative humidity of 60% and a temperature of 90 ° C, and the transmittance and the degree of polarization were measured. The results are shown in Table 1 below.
As shown in Table 1, in the case of the polarizers of Examples 1 to 19 prepared using a boronic acid or a boronic acid derivative according to the production method of the present invention, the change in transmittance (Δ transmittance) was 0.69 to 1.53, It was confirmed that the transmittance change was smaller than that of Comparative Example 1 in which no acid or boric acid derivative was used. In particular, in Examples 1 to 10 in which a boronic acid or a boronic acid derivative was added to an aqueous solution for washing, the change in the transmittance was remarkably small.
Experimental Example 2: Contact angle and content analysis
(1) Contact angle
After dropping water droplets onto the surface of the polarizer at room temperature (25 캜), the contact angle with respect to water drops was measured using a contact angle meter (KSV, CAM100) after 1 minute. The contact angles of the droplets were measured three times with the same sample, and the average values thereof are shown in Table 2 below.
(2) Content of boronic acid and boric acid derivatives
The contents (ppm) of boronic acid and boric acid derivatives present in 1 g of the polarizer were measured using liquid chromatography (LC) (Agilent 1100) and are shown in Table 2 below.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention. Do. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Accordingly, the actual scope of the invention is defined by the appended claims and their equivalents.
Claims (11)
[Chemical Formula 1]
(2)
In this formula,
R, R 1 and R 2 are each independently hydrogen, a C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl group, a C 3 -C 10 cycloalkyl group, or an aryl group.
R, R 1 and R 2 are each independently hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 3 -C 10 cycloalkyl or phenyl.
R is methyl, ethyl, n-propyl, n-butyl, cyclohexyl, propenyl,
Wherein R < 1 > and R < 2 > are hydrogen.
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| KR20130134070 | 2013-11-06 | ||
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