CN101382616A - Polarized film, polaroid and its producing method - Google Patents
Polarized film, polaroid and its producing method Download PDFInfo
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- CN101382616A CN101382616A CNA2008102127482A CN200810212748A CN101382616A CN 101382616 A CN101382616 A CN 101382616A CN A2008102127482 A CNA2008102127482 A CN A2008102127482A CN 200810212748 A CN200810212748 A CN 200810212748A CN 101382616 A CN101382616 A CN 101382616A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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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
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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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
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- General Physics & Mathematics (AREA)
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Abstract
The invention relates to polaroid film, polaroid sheet and manufacturing method thereof. The invention provides polaroid film causing the black under the black display of liquid crystal display device into blacker and polaroid sheet using the same and the manufacturing method thereof. The invention provides polaroid film orientation adsorption with iodine on polyvinyl alcohol resin film and when entering with rectilinearly polarized light parallel to the absorbing shaft, the wavelength being 410 nm, 550 nm and 680 nm, the transmittivity being less than 0.01 %, and polaroid sheet using the same and the manufacturing method thereof.
Description
Technical field
The present invention relates to the polarizing coating of optical characteristics excellence and be pressed with the manufacture method of polaroid and these polarizing coatings and the polaroid of transparent protective film on the upper strata of single face at least of this polarizing coating.
Background technology
Polarizing coating has dichromatism pigment person to be widely used as absorption orientation on the polyvinyl alcohol resin film.And the known iodine that makes is that the iodine of dichromatism pigment is polarizing coating, to make the dichromatism direct dyes be that the dyestuff of dichromatism pigment is a polarizing coating etc.The bonding agent that common Jie of these polarizing coatings is contained the aqueous solution of polyvinyl alcohol resin sticks on transparent protective films such as tri acetyl cellulose on its single face or the two sides, makes polaroid.
Polaroid is extensively known as the liquid crystal display optical parts.Liquid crystal indicator is as display frames such as LCD TV, PC display, notebook computer, mobile phones, and its market enlarges to some extent, particularly sets foot in the market of slim big picture LCD TV significantly.During for LCD TV, image quality improves, particularly the improvement of color reproducibility requires very big.
For example, the spy opens and discloses in the 2007-59372 communique (patent documentation 1) in order to enlarge color reproducibility, is suitable for to have to have used emission wavelength backlight is widened to the liquid crystal indicator of the fluorescent tube unit of 4 wavelength pipes of long wavelength side.But, when the liquid crystal indicator of the fluorescent tube unit of having widened emission wavelength being arranged for patent documentation 1 disclosed use, the problem of the light leak of (quadrature of polaroid) when having the incident rectilinearly polarized light parallel with the polaroid absorption axes, the black pastiness under the black demonstration of LCD TV or rubescent, take place painted.
In addition, the spy opens 2002-169024 communique (patent documentation 2), and to have put down in writing the quadrature tone that makes polaroid be neutral gray, but its characteristic and insufficient.
In addition, manufacture method for polarizing coating has also proposed various improvement, and for example the spy opens flat 5-273412 communique (patent documentation 3) and put down in writing the washing after implementing iodine staining and boric acid under the temperature below 10 ℃ and handling or shorten the processing time when surpassing 10 ℃.In addition, the spy opens flat 8-304624 communique (patent documentation 4) and has proposed by the potassium iodide content in the minimizing boric acid processing bath, near the transmissivity the raising 420nm.
After Te Kaiping 10-153709 communique (patent documentation 5) has been put down in writing the polyvinyl alcohol resin film immersion made its swelling in water, dye with iodine, then stretch, and then, carry out dry method after the washing for grappling iodine carries out boric acid processing (in other words for utilizing crosslinked water-fastization processing).Utilize the swelling treatment of water to carry out: before dyeing, to make film swelling, the time of shortening dyeing, improvement dye unequal equably for following purpose.At this moment, from the unequal viewpoint that dyes, in bathing, swelling treatment contains boric acid in the patent documentation 5.In addition, after the dyeing film immersion is being stretched in the aqueous solution that contains boric acid in this patent documentation 5, further impregnated in the boric acid aqueous solution afterwards, utilizing crosslinked water-fastization processing (being called grappling or fixing in the patent documentation 5).
And the spy opens flat 6-281816 communique (patent documentation 6) and has put down in writing in order to make film swelling fully, adds chlorides such as lithium chloride, zinc chloride in swelling treatment is bathed.
Summary of the invention
The object of the present invention is to provide the black under the black demonstration that can make liquid crystal indicators such as LCD TV to be more black polarizing coating and polaroid that uses it and their manufacture method.
The inventor etc. further investigate in order to solve the problems of the technologies described above, found that the polaroid of having developed following polarizing coating and having used it, described polarizing coating is an absorption orientation of implementing iodine on the polyvinyl alcohol resin film continuously, boric acid is crosslinked, and carry out the polarizing coating of uniaxial tension by wantonly at least 1 operation of these treatment process or above-mentioned operation, transmissivity when the incident rectilinearly polarized light parallel with the polaroid absorption axes is at wavelength 410nm, be below 0.01% under 550nm and the 680nm, in the gamut of visible light, show extremely low absorption axes direction transmissivity.Also find to make the black of liquid crystal indicator be shown as darker black, and then finish the present invention by this polarizing coating or polaroid.
Polarizing coating of the present invention is characterized in that for absorption orientation on the polyvinyl alcohol resin film has the polarizing coating of iodine, and when the incident rectilinearly polarized light parallel with absorption axes, the transmissivity of wavelength 410nm, 550nm and 680nm is below 0.01%.
The present invention also provides a kind of polaroid; it is a polaroid of pasting transparent protective film on the single face at least of the polarizing coating of the invention described above; when the incident rectilinearly polarized light parallel with absorption axes, the transmissivity of wavelength 410nm, 550nm and 680nm is below 0.01%.
The present invention also provides a kind of manufacture method of polarizing coating, it makes its crosslinked crosslinked operation for using the iodine staining operation of iodine staining polyvinyl alcohol resin film successively and handling with boric acid aqueous solution, and by wantonly at least 1 operation before the crosslinked operation with polyvinyl alcohol resin film uniaxial tension, in crosslinked operation after by washing step and drying process, make the method for polarizing coating, crosslinked operation is carried out in the aqueous solution that contains 2～10 weight portion boric acid and 10～30 weight portion potassium iodides with respect to 100 weight parts waters, washing step carries out under 2～15 ℃ temperature, and during the incident rectilinearly polarized light parallel, according to making wavelength 410nm with the absorption axes of gained polarizing coating, the transmissivity of 550nm and 680nm is the condition of setting each operation below 0.01%.
Preferred iodine staining operation carried out for 10～600 seconds in the manufacture method of polarizing coating of the present invention in containing the aqueous solution that iodine and potassium iodide, iodine amount are 0.01～0.2 weight portion with respect to water 100 weight portions, crosslinked operation was carried out for 10～600 seconds under 50～70 ℃ temperature, and washing step carried out for 2～120 seconds.
The present invention also provide Jie by bonding agent behind sticking obedient transparent protective film on the single face at least of the polarizing coating of the present invention that obtains by the invention described above polarizing coating manufacture method, under 30～60 ℃ temperature, carry out the manufacture method of dry polaroid.
Can provide the black under the black demonstration that can make liquid crystal indicators such as LCD TV to be more black polarizing coating and polaroid that uses it and their manufacture method by the present invention.
Description of drawings
Fig. 1 is applicable to the figure of the device in the polarizing coating manufacture method of the present invention for the expression of pattern ground.
Fig. 2 is for polarizing coating of the present invention (embodiment 1) and uses the polaroid of the present invention (embodiment 2) of this polarizing coating and the curve map of the transmittance graph of the polarizing coating of comparative example 1 when showing the incident rectilinearly polarized light parallel with absorption axes that the longitudinal axis is that absorption axes direction transmissivity (%) (logarithmic scale), transverse axis are wavelength (nm).
Symbol description
1 former anti-film, 2 former anti-rollers, 3 swelling grooves, 4 water retting grooves, 5 staining troughs, 6 boric acid grooves, 7 rinsing bowls, 8 drying ovens, 9 polarizing coatings.
Embodiment
The manufacture method of＜polarizing coating 〉
Fig. 1 is applicable to the figure of the device in the manufacture method of polarizing coating of the present invention for pattern ground expression.The manufacture method of polarizing coating of the present invention is handled with the iodine staining operation of using iodine staining polyvinyl alcohol resin film successively with boric acid aqueous solution and is made its crosslinked crosslinked operation, and by the arbitrary at least operation before the crosslinked operation with polyvinyl alcohol resin film uniaxial tension, in crosslinked operation after the method for making polarizing coating by washing step and drying process is a prerequisite.Here, the uniaxial tension of polyvinyl alcohol resin film is undertaken by the arbitrary at least operation before the crosslinked operation, here the arbitrary at least operation before the said crosslinked operation comprises above-mentioned iodine staining operation and crosslinked operation certainly, also comprises the iodine staining operation stage before.The Production Example of this polarizing coating is as shown in Figure 1, provides the former anti-film 1 of polyvinyl alcohol resin to handle continuously and realize from former anti-(former anti-) roller 2 of roller shape.
In the example shown in Figure 1, from the former anti-film 1 of former anti-roller 2 spun polyvinyl alcohol resins successively the swelling groove 3 by being used to carry out swelling, be used to carry out water retting groove 4 that water retting handles, the staining trough 5 handled and be used to carry out the boric acid groove 6 that boric acid is handled is used to dye.In addition, in the example as shown in Figure 1, leave polyvinyl alcohol resin film behind the boric acid groove 6 in groove before, carry out drying by drying oven 8 afterwards, obtain polarizing coating 9 by the unreacted boric acid aqueous solution that rinsing bowl 7, flush away adsorb.
Illustrated that Fig. 1 has shown the example of swelling groove 3, water retting groove 4, staining trough 5, boric acid groove 6 and rinsing bowl 7 that 1 groove respectively is set respectively, can also to certain 1 processing a plurality of grooves be set as required.In addition, can also omit water retting groove 4, in swelling groove 3, implement swelling treatment after, directly move to following staining trough 5 processing of dyeing.But, the former anti-film 1 of polyvinyl alcohol resin is put under the state that does not stretch swelling groove 3 carry out swelling treatment, by after iodine staining operation and/or the crosslinked operation what is called of carrying out uniaxial tension adopt under the situation of wet type stretching, as described later, for suction state, the mechanical properties that improves film of putting the film Width in order, the optical characteristics homogeneity that improves the final polarizing coating that obtains, this water retting groove 4 is set preferably.On the other hand, under the situation about handling after after the former anti-film 1 of polyvinyl alcohol resin is implemented uniaxial tension in advance, carrying out swelling groove 3, water retting groove 4 is not set usually, directly moves to staining trough 5 from swelling groove 3.
The used polyvinyl alcohol resin of the present invention is by being that resin carries out saponification and obtains to polyvinyl acetate.Polyvinyl acetate be resin except polyvinyl acetate as leifa, can also enumerate vinyl acetate with can be with the multipolymer of the monomer of its copolymerization etc.Copolymerization for example can be enumerated unsaturated carboxylic acid class, unsaturated sulfonic acid class, olefines, ethene ethers, have the acrylic amide of ammonium etc. in other monomer of vinyl acetate.The saponification degree of polyvinyl alcohol resin is generally 85～100 moles of %, is preferably 98 moles more than the %.This polyvinyl alcohol resin can also for example can use by aldehydes modified polyethylene polymkeric substance, Pioloform, polyvinyl acetal etc. through modification.In addition, the average degree of polymerization of the polyvinyl alcohol resin of formation polarizing coating is generally 1000～10000, is preferably 1500～5000.
The thickness of the former anti-film 1 of polyvinyl alcohol resin is generally 20～100 μ m, is preferably 30～80 μ m.In addition, the width of former anti-film 1 has practicality about 1500～6000mm.Former anti-film 1 is provided by former anti-roller 2 under the state of unstretching film usually.Below illustrate the situation of using device shown in Figure 1, describe for each operation of the preferred example of polarizing coating of the present invention.
[1] swelling operation
In the example that uses device shown in Figure 1, at first the former anti-film 1 that is provided by former anti-roller 2 is carried out swelling treatment (swelling operation) in swelling groove 3.This swelling treatment is carried out for following purpose: except that the foreign matter on striping surface, except that the plastifier in the striping, the easy dyeing of giving the back operation, the plasticized of film etc.The condition of swelling treatment is by the scope that can reach these purposes and the scope decision of the problems such as extreme dissolving, devitrification of film can not take place.Enumerate following condition: the former anti-film 1 that will not stretch impregnated in the processing bath that is contained in for example temperature 10～50 ℃ (preferred 20～50 ℃) in the swelling groove 3 and carries out swelling treatment, carries out this swelling treatment 5～300 seconds (preferred 20～240 seconds).
In the swelling operation, since former anti-film on Width (perpendicular to direction) swelling as the length direction of throughput direction, be easy to produce the problem of gauffer etc., therefore preferably utilize known expanding device free of wrinkles such as spread rolls, propellers, crowned roll, guide, roller, stenter cloth gripper, carry former anti-film 1 simultaneously.In addition, for the conveying of the former anti-film 1 in the stabilization processes bath, the current during the shower control and treatment is bathed in the water, coupling EPC device (marginal position control device: detect the film end, prevent the device of film S shape bending) etc. are also useful.Illustrated that in the swelling operation, former anti-film 1 is also swelling expansion on throughput direction.Therefore, lax for the former anti-film 1 of eliminating throughput direction for example preferably takes to control the device of the speed etc. of the conveying roller that is in swelling groove 3 front and back.Specifically, preferably according to the temperature of handle bathing, the outlet side conveying roller linear velocity that makes swelling groove 3 is about 1.2～2 times with the ratio of entrance side conveying roller linear velocity.In addition, can also implement uniaxial tension by this operation if desired.
The processing that are contained in the swelling groove 3 are bathed except pure water, can also use the aqueous solution of the boric acid that is added with above-mentioned patent documentation 5 (spy opens flat 10-153709 communique) and put down in writing in the scope of 0.01～10 weight %, chloride that patent documentation 6 (spy opens flat 6-281816 communique) is put down in writing, other mineral acid, other inorganic salts, water-miscible organic solvent, alcohols etc. etc.But,, preferably use the pure water that does not dissolve composition substantially in bathing handling from the complicacy that reduces the liquid waste processing that the used processing of swelling groove 3 bathe, the viewpoint that suppresses treatment cost of waste liquor as far as possible.
[2] water retting operation
Then, after the polyvinyl alcohol resin film after the swelling treatment dewatered, in water retting groove 4, carry out water retting and handle (water retting operation).As mentioned above, can also omit this water retting operation.This water retting is handled and is carried out for following purpose: the optical characteristics homogeneity of the suction state of arrangement film Width, the mechanical properties that improves film, the final polarizing coating that obtains of raising.In this operation, preferably film is handled making and to reach the stretching ratio more than 1 times, below 1.05 times with respect to operating direction (MD, be the film throughput direction).Stretching ratio is 1 times and is meant that film neither stretches with respect to operating direction and does not also shorten.When the stretching ratio when water retting is handled surpasses 1.05 times, the tendency of homogeneity variation of the optical characteristics of gained polarizing coating is arranged.Illustrated that in the polarizing coating manufacture method of the present invention, because former anti-film 1 is the tension force that applies relax level not on throughput direction, carries out a series of operation, so the stretching ratio under this water retting operation can not be lower than 1 times usually.
The temperature that is contained in the processing bath in the water retting groove 4 is preferably 10～50 ℃.The temperature of handle bathing is during less than 10 ℃, and temperature control is because essential large-scale cooling device is therefore uneconomical; When the opposite temperature of handling bath surpasses 50 ℃, there is film that the misgivings of dissolving take place.In addition, this water retting is handled used processing and is bathed the pure water that does not preferably dissolve composition substantially.Its reason is when medicaments such as containing boric acid is bathed in this processing, the impaired misgivings of homogeneity of film are arranged.
[3] iodine staining operation
Then, in staining trough 5, implement with the processing (iodine staining operation) of iodine the dyeing of polyvinyl alcohol resin film.This iodine staining operation is carried out as the purposes such as iodine of dichromatism pigment in order to adsorb on film.The scope decision of problems such as extreme dissolving or devitrification can not taken place in treatment conditions by the scope that can reach this purpose and film.
The iodine staining operation for example can be enumerated being contained in the staining trough 5 with the temperature of 10～50 ℃ (preferred 20～40 ℃) and with respect to the aqueous solution that 100 weight parts waters contain 0.01～0.2 weight portion iodine and 0.1～10 weight portion potassium iodide, with the polyvinyl alcohol resin film immersion situation in 10～600 seconds (preferred 30～200 seconds) in this aqueous solution.Can also replace potassium iodide to use other iodide, zinc iodide etc. for example, in addition, can also be with other iodide and potassium iodide coupling.And, the compound beyond the iodide that can also coexist, for example boric acid, zinc chloride, cobalt chloride etc.Illustrated that even if when adding boric acid in handle bathing, this respect that contains iodine during used processing is bathed in the iodine staining operation is different with the crosslinked operation of aftermentioned boric acid groove 6.When bathing, can regard the used processing of this iodine staining operation as and bathe for the processing that contains the above iodine of 0.003 weight portion with respect to 100 weight parts waters.
In the iodine staining operation, identical with above-mentioned swelling operation, can and/or bathe the place, gateway in handling bath spread rolls, propellers, crowned roll, guide, roller etc. suitably are set.In addition, in the time of in the iodine staining operation, the processing of polyvinyl alcohol resin film immersion in being contained in staining trough 5 being bathed, can on operating direction, implement uniaxial tension to film simultaneously.
[4] crosslinked operation
Then, in the boric acid aqueous solution (handle bathe) of the polyvinyl alcohol resin film immersion after the dyeing processing in being loaded on boric acid groove 6, handle, make its crosslinked (crosslinked operation) thereby implement boric acid.One of feature of the manufacture method of polarizing coating of the present invention is, in this crosslinked operation, use the boric acid aqueous solution that contains the potassium iodide of the boric acid of 2～10 weight portions (preferred 3～5 weight portions) and 10～30 weight portions (preferred 11～20 weight portions) with respect to 100 weight parts waters.When the boric acid in the boric acid aqueous solution is less than 2 weight portions with respect to 100 weight parts waters, can't obtain crosslinked water tolerance that produces of sufficient boric acid and humidity resistance, and when surpassing 10 weight portions, the crystallization of boric acid is separated out on film, bad order.In addition, when the potassium iodide in the boric acid aqueous solution is less than 10 weight portions with respect to the water of 100 weight portions, can't obtain the transmission characteristics of target, and when surpassing 30 weight portions, variety of issues such as the bad order that can hinder crystallization on boric acid cross-linking reaction, the film to separate out to cause, manufacturing cost increase.
In the crosslinked operation of the present invention, except boric acid and potassium iodide, can also use the boric acid aqueous solution that contains at least 1 other composition that is selected from zinc iodide, zinc chloride, cobalt chloride, zirconium chloride, sodium thiosulfate, potassium sulfite, sodium sulphite, glazier's salt, sodium sulphate.
It is to carry out for crosslinked water-fastization that produces, tone adjustment (preventing to turn blue) etc. that the boric acid of crosslinked operation is handled.With crosslinked produced water-fast when turning to purpose, can be as required with boric acid use glyoxal, crosslinking chemical such as glutaraldehyde.Illustrated that the boric acid processing that is used for water-fastization can also be called water-fastization processing, crosslinking Treatment, immobilization processing etc.In addition, carry out boric acid for the tone adjustment and handle, can also be called complementary color processing, toning processing etc.Boric acid is handled and can suitably be changed the concentration of boric acid and potassium iodide, the temperature that processing is bathed according to its purpose.
In the polarizing coating manufacture method of the present invention, be necessary to carry out the water-fast crosslinking Treatment that turns to purpose that produced with crosslinked, boric acid and the potassium iodide that contains concentration in the above-mentioned scope bathed in processing for this reason.The temperature of crosslinking Treatment is generally 50～70 ℃, is preferably 53～65 ℃, and its processing time was generally for 10～600 seconds, was preferably for 20～300 seconds, 20～100 seconds more preferably.The crosslinked operation of polarizing coating manufacture method of the present invention is meant so with water-fast and turns to the operation that purpose is carried out crosslinking Treatment.
Carry out thisly, can also further be used for the boric acid that tone adjusts and handle with after the water-fast crosslinking Treatment that turns to purpose.Carry out this when being used for boric acid that tone adjusts and handling after the above-mentioned crosslinked operation, handle bath as this, the preferred aqueous solution (being illustrated that each concentration itself can be bathed different with crosslinking Treatment) of using used processing to bathe the boric acid and the potassium iodide that contain concentration in the above-mentioned scope as crosslinked operation.Its temperature is generally 10～45 ℃ scope, and its time was generally for 1～300 second, was preferably for 2～100 seconds.The boric acid processing that is used for the tone adjustment is compared with the crosslinked operation that is used for water-fastization, carries out at low temperatures usually.
The boric acid processing that comprises crosslinking Treatment can be used a plurality of boric acid grooves, and polygamy is put 1～5 boric acid groove (Fig. 1 represents to use the situation of 1 boric acid groove 6) usually.When disposing a plurality of boric acid groove, make film, implement boric acid continuously and handle successively by each boric acid groove.At this moment, be contained in the composition, temperature of the boric acid aqueous solution in a plurality of boric acid grooves can be identical mutually also can difference.In addition, can also use a plurality of boric acid grooves to carry out the above-mentioned boric acid that is used for water-fastization respectively and handle, be used for the boric acid processing that tone is adjusted.Illustrated, identical with above-mentioned dyeing process in crosslinked operation, can on operating direction, implement uniaxial tension to film.
[5] washing step
Then, in rinsing bowl 7, the polyvinyl alcohol resin film after the boric acid processing is implemented washing and handle (washing step).Washing is for example handled by with crosslinking Treatment or carried out method in water of film immersion that boric acid handles, water is carried out as the method for shower spray or the method for coupling dipping and spraying etc. in order to adjust tone as required.One of feature of polarizing coating manufacture method of the present invention is, from the viewpoint of the polarizing coating that obtains required optical characteristics, the temperature of the water when washing is handled is 2～15 ℃, is preferably 2～10 ℃.The temperature of the water when washing is handled is during less than 2 ℃, and temperature control is very difficult substantially, and when surpassing 15 ℃, can't obtain the polarizing coating of object penetrating rate characteristic.In addition, washing processing time of handling was 2～120 seconds, was preferably for 2～60 seconds.
[6] drying process
At last, the film by after the washing of drying oven 8 inner dryings obtains polarizing coating 9 (drying process).Dry preferably taking under the film condition in 30～600 seconds in the drying oven 8 that remains in 40～90 ℃ of temperature carried out.
[7] uniaxial tension operation
As mentioned above, in the polarizing coating manufacture method of the present invention, implement uniaxial tension by at least 1 before the crosslinked operation of boric acid groove 6 operation.This uniaxial tension can be undertaken by an operation, can also be undertaken by a plurality of operations, preferably carries out uniaxial tension by a plurality of operations, for example dyeing process and crosslinked operation etc.For example stretch can be by making the groove entrance side conveying roller and the conveying roller of the groove outlet side method that has linear differential etc. carry out.
In addition, when the roll that is contacted with heating can suitably be chosen in, give method that tension force stretches etc. in the wings.Final accumulative total stretching ratio is preferably 4.5～10 times, more preferably 5～7 times.Here said accumulative total stretching ratio is meant in the film of length direction standard length after all stretch processings finish of former anti-film to become which kind of length, when all being stretched in swelling operation, water retting treatment process, for also comprising the value of these stretchings.For example, if be that the accumulative total stretching ratio of this moment becomes 5 times when becoming 5m in the film of part after all stretch processings finish of 1m in former anti-film Central Plains.
In addition, can also carry out uniaxial tension, for example can enumerate in the method that in air, stretches before the swelling treatment of swelling groove 3, be contacted with method that stretches in the roll of heating etc. with dry type.When adopting this dry type stretching, as mentioned above, preferably after stretching by swelling groove 3, water retting groove 4 afterwards omits, and it is directly moved to iodine staining groove 5 from swelling groove 3.
Particularly importantly set the condition of each operation in the polarizing coating manufacture method of the present invention, make the potassium iodide concentration in the used boric acid aqueous solution when concentration of potassium iodide of the boric acid aqueous solution that uses in the above-mentioned crosslinked operation is higher than common crosslinked operation, but the water with respect to 100 weight portions is the scope of 10～30 weight portions, under 2～15 ℃ scope of the temperature that is lower than common washing step, carry out washing step, and when the incident rectilinearly polarized light parallel with the absorption axes of the polarizing coating that obtains by this method, wavelength 410nm, the transmissivity of 550nm and 680nm is below 0.01%.
The amount that above-mentioned patent documentation 2 (spy opens the 2002-169024 communique) has been put down in writing the potassium iodide in the used boric acid aqueous solution of boric acid processing (crosslinking Treatment) is preferably about 5～20 weight portions with respect to the water of 100 weight portions, washing after boric acid is handled is carried out under the temperature more than 20 ℃, among the embodiment, boric acid is handled to bathe and is used per 100 weight parts waters to contain the aqueous solution of 9.5 weight portion boric acid and 8 weight portion potassium iodides, and the washing after boric acid is handled is carried out under 35 ℃.In addition, above-mentioned patent documentation 8 (spy opens flat 5-273412 communique) has been put down in writing in the washing of carrying out below 10 ℃ or below 20 ℃ after boric acid is handled, make concentration that boric acid handles the boric acid in the used aqueous solution with respect to the water of 100 weight portions be 2～15 weight portions, the concentration that makes potassium iodide is 2～20 weight portions, preferred 5～12 weight portions with respect to the water of 100 weight portions, and the embodiment mesoboric acid is handled to bathe and is used the aqueous solution that contains 6 weight portion potassium iodides and 7.5 weight portion boric acid with respect to the water of 100 weight portions.And, above-mentioned patent documentation 4 (spy opens flat 8-304624 communique) is different with the present invention, be provided near the wavelength 420nm, i.e. near blue high polarizing coating or the polaroid of transmissivity, quadrature transmittance (with the value of representing with Tc in the document) as the polaroid shown in its comparative example is low, is nonetheless also reading transmissivity about 0.1% near the wavelength 410nm, also reads the transmissivity about 0.4% near wavelength 680nm.
Relative therewith, the present invention finds for the used boric acid aqueous solution of the crosslinked operation of utilizing boric acid aqueous solution behind the iodine staining, when the water with respect to 100 weight portions contains 2～10 weight portion boric acid, the what is called that contains 10～30 weight portions (preferred 11～20 weight portions) potassium iodide is more set potassium iodide concentration in the highland, temperature with washing step afterwards is set at 2～15 ℃ than the lowland simultaneously, by making up these conditions, when the incident rectilinearly polarized light parallel with absorption axes, at wavelength 410nm, the transmissivity of 550nm and 680nm is the transmissivity when very reducing the incident rectilinearly polarized light parallel with absorption axes under the visible light total size below 0.01%, obtains the polarizing coating that did not in the past have.
Certainly, if be defined as above the temperature of boric acid concentration and the potassium iodide concentration and the washing step of the used boric acid aqueous solution of crosslinked operation, because and the polarizing coating of the above-mentioned demonstration low transmissivity of nonessential acquisition, therefore comprise that other condition also will set the condition of each operation, obtain above-mentioned transmissivity when making the incident rectilinearly polarized light parallel with the absorption axes of gained polarizing coating.Other condition that is used for obtaining having the polarizing coating of above-mentioned transmissivity comprises processing time of the temperature of the various conditions (for example iodine concentration of dye bath, treatment temperature, processing time etc.) of iodine staining operation, crosslinked operation and processing time, washing step etc.Wherein, the processing time of the temperature of the iodine concentration of the dye bath of iodine staining operation and processing time, the crosslinked operation of boric acid and processing time and washing step is important.
Thereby, except the temperature of the boric acid concentration of the used boric acid aqueous solution of above-mentioned crosslinked operation and potassium iodide concentration and washing step, preferably carry out condition enactment make satisfy (1) shown below～(5) any one or a plurality of, preferably especially satisfy all.
(1) aqueous solution of using in the iodine staining operation (dye bath) with respect to 100 weight parts waters contain 0.01～0.2 weight portion iodine,
(2) make processing time (dyeing time) of iodine staining operation be 10～600 seconds,
(3) make the treatment temperature (temperature of boric acid aqueous solution) of the crosslinked operation of boric acid be 50～70 ℃,
(4) make processing time of the crosslinked operation of boric acid be 10～600 seconds (preferred 20～300 seconds, more preferably 20～100 seconds) scope,
(5) making the processing time of washing step is the scope in 2～120 seconds (preferred 2～60 seconds).
And then, adopt other condition that shows as optimum condition in above-mentioned swelling operation, water retting operation (when carrying out this operation), iodine staining operation, crosslinked operation, washing step, drying process and uniaxial tension operation, also be effective certainly.
＜polarizing coating 〉
The present invention also provides a kind of polarizing coating, it has the polarizing coating of iodine for absorption orientation on the polyvinyl alcohol resin film, when incident (that is, be in absorption axes direction) rectilinearly polarized light parallel with absorption axes, the transmissivity of wavelength 410nm, 550nm and 680nm is below 0.01%.If this polarizing coating of the present invention has above-mentioned transmissivity, then be not particularly limited for its manufacture method, can preferably make by the polarizing coating manufacture method of the invention described above.
Here, the curve map of the transmittance graph of Fig. 2 for for the polarizing coating (dotted line among the figure) of polarizing coating of the present invention (thick line of solid line among aftermentioned embodiment 1, the figure), the polaroid of the present invention (fine rule of solid line among aftermentioned embodiment 2, the figure) that uses this polarizing coating and the aftermentioned comparative example 1 demonstration incident rectilinearly polarized light parallel with absorption axes the time, the longitudinal axis represents that with logarithmic scale absorption axes direction transmissivity (%), transverse axis are wavelength (nm).As shown in Figure 2, polarizing coating of the present invention (embodiment 1) is when the incident rectilinearly polarized light parallel with absorption axes, and the transmissivity of wavelength 410nm, 550nm and 680nm is below 0.01%.Here, the absorption axes direction transmissivity TD (λ) of certain wavelength X is meant that the rectilinearly polarized light of illumination wavelength lambda makes transmissivity when being in absorption axes equidirectional with polarizing coating.Illustrated that the transmissivity during the incident rectilinearly polarized light parallel with above-mentioned absorption axes for example can use V7100 (Japanese beam split (strain) system) to measure.By the polarizing coating of the present invention that use has this transmissivity, can make the black under the black demonstration of liquid crystal indicators such as LCD TV become darker black.Illustrated that the thickness of polarizing coating of the present invention is not particularly limited, be generally 1～50 μ m, be preferably 10～35 μ m.
＜polaroid 〉
The present invention also provides the polaroid that uses the invention described above polarizing coating.Polaroid of the present invention is characterised in that, pastes transparent protective film on the single face at least of the invention described above polarizing coating, and during the incident rectilinearly polarized light parallel with absorption axes, the transmissivity of wavelength 410nm, 550nm and 680nm is below 0.01%.As mentioned above; Fig. 2 also shows the transmittance graph (embodiment 2) of polaroid of the present invention; irrelevant with the state that whether possesses transparent protective film as can be known; same with polarizing coating of the present invention; when the incident rectilinearly polarized light parallel with absorption axes, the transmissivity of wavelength 410nm, 550nm and 680nm is below 0.01%.By the polaroid of the present invention that use has this transmissivity, can make the black under the black demonstration of liquid crystal indicators such as LCD TV is darker black.
By inventor's etc. investigation, this wavelength 410nm, 550nm and the transmissivity of the 680nm polaroid that is the demonstration utmost point low value below 0.01% when the incident rectilinearly polarized light parallel with absorption axes do not exist on the existing market.Here said polaroid is to paste the transparent protective film person on the single face at least of the polarizing coating that contains polyvinyl alcohol resin; by pasting transparent protective film; how many transmissivities when the incident rectilinearly polarized light parallel with above-mentioned absorption axes has the tendency of raising; therefore as mentioned above, the transmissivity when the incident rectilinearly polarized light parallel with absorption axes shows all that under wavelength 410nm, 550nm and 680nm the polarizing coating of utmost point low value does not exist yet on the existing market.
In the polaroid of the present invention, transparent protective film is situated between and is sticked on the single face at least of polarizing coating of the invention described above by bonding agent.Transparent protective film can only stick on the single face of polarizing coating, also can stick on the two sides.As transparent protective film, for example can be not particularly limited to use by for example acetate fiber prime system resin, cyclic olefine resin, polyolefin-based resins, acrylic resin, polyimide is always as the film that the widely used suitable material of material constitutes that forms of diaphragm in this areas such as resin, polycarbonate-based resin, polyester based resin.From production, fusible viewpoint, preferably possesses the transparent protective film that constitutes by acetate fiber prime system resin or cyclic olefine resin in above-mentioned.In addition; from the easiness that surface-treated layer is set and the viewpoint of optical characteristics, the structure of the transparent protective film that polaroid of the present invention can be formed in lamination is made of acetate fiber prime system resin on the side single face of polarizing coating transparent protective film, lamination is made of the cyclic olefine resin on the opposite side single face of polarizing coating.
The cyclic olefine resin that can preferably use in the transparent protective film of the present invention for example is meant the thermoplastic resin (being also referred to as thermoplasticity cyclic olefine resin) of the unit with the monomer that contains norborene, encircles cyclic olefins (cycloolefin) such as norborneol alkene monomer more.The ring-opening polymerization polymer that this cyclic olefine resin can be above-mentioned cycloolefin, use the hydrogenation thing of the ring opening copolymer thing of cycloolefin more than 2 kinds, can also be cycloolefin and chain alkene, have an addition polymer of the aromatics etc. of vinyl etc.In addition, importing has the compound of polar group also effective.
Use cycloolefin and chain alkene, when having the multipolymer formation transparent protective film of aromatics etc. of vinyl etc.; chain alkene can be enumerated ethene, propylene etc., and the aromatics with vinyl can be enumerated styrene, α-Jia Jibenyixi, nuclear alkyl-substituted styrene etc.In this multipolymer, comprise that the unit of the monomer of cycloolefin can be 50 moles (preferred 15～50 moles of %) below the %.Particularly, when using the terpolymer formation transparent protective film of cycloolefin and chain alkene and aromatics, comprise that the unit of the monomer of cycloolefin can be less amount as mentioned above with vinyl etc.In this terpolymer, comprise that the unit of the monomer of chain cycloolefin is generally 5～80 moles of %, comprise that the unit of the monomer of the aromatics with vinyl is generally 5～80 moles of %.
The cyclic olefine resin can preferably use suitable commercially available product, for example Topas (Ticona society system), ア-ト Application (JSR (strain) system), ZEONOR (Japanese ゼ オ Application (strain) system), ZEONEX (Japanese ゼ オ Application (strain) system), ア ペ Le (Mitsui Chemicals (strain) system) etc.When this cyclic olefine resin system film is made film, suitably use known method such as solvent casting method, extrusion by melting.In addition, for example use エ ス シ-Na (ponding chemical industry (strain) system), SCA40 (ponding chemical industry (strain) system), ゼ オ ノ ア Off イ Le system ((strain) ア プ テ ス system) etc. to make the commercially available product of cyclic olefine resin system film of film in advance as transparent protective film.
Can be by the transparent protective film that the cyclic olefine resin constitutes through uniaxial tension or biaxial stretch-formed.The stretching ratio of this moment is generally 1.1～5 times, is preferably 1.1～3 times.
In addition, the preferred acetate fiber prime system resin that uses is cellulosic partially or completely acid esterification thing in the transparent protective film of the present invention, for example can enumerate tri acetyl cellulose film, diacetyl cellulose film etc.
This acetate fiber prime system resin can preferably use suitable commercially available product, for example Off ジ Star Network TD80 (Fuji Photo film (strain) system), Off ジ Star Network TD80UF (Fuji Photo film (strain) system), Off ジ Star Network TD80UZ (Fuji Photo film (strain) system), KC8UX2M (コ ニ カ ミ ノ Le オ プ ト (strain) system), KC8UY acetate fiber prime system resin system films such as (コ ニ カ ミ ノ Le オ プ ト (strain) systems).
The thickness of the transparent protective film of polaroid of the present invention is preferably thin, thinly takes place then that intensity reduces, the problem of poor in processability but cross, and blocked uply takes place then that the transparency reduces, necessary problems such as service time prolongation behind the lamination.Therefore, transparency protected film thickness of the present invention be generally 5～200 μ m, be preferably 10～150 μ m, 10～100 μ m more preferably.Illustrated; polaroid of the present invention can also be implemented surface treatments such as corona treatment, flame treatment, Cement Composite Treated by Plasma, ultraviolet ray irradiation, plasma coating processing, saponification processing to polarizing coating and/or transparent protective film in order to improve the cohesive of bonding agent and polarizing coating and/or transparent protective film.
In addition, transparent protective film can also be implemented non-glare treated respectively alone or in combination more than 2 kinds, surface treatments such as processing, electrostatic prevention processing, antifouling processing are handled, are coated with firmly to antireflection.In addition, transparent protective film and/or transparent protective film sealer can have plastifier such as ultraviolet light absorbers such as benzophenone based compound, 124 Triazole based compound, phenyl phosphate based compound, phthalic acid ester compounds.
It is that bonding agent, organic solvent are that bonding agent, heat fusing are the sticking cards of bonding agents such as bonding agent, non-solvent adhesive that polarizing coating and transparent protective film are situated between by hydrosolvent.Hydrosolvent is that bonding agent for example can be enumerated the polyvinyl alcohol resin aqueous solution, water-based two-liquid type ammonia ester is an emulsion binder etc., and it is that bonding agent, epoxy are bonding agent etc. that non-solvent adhesive for example can be enumerated a liquid type ammonia ester.
Use with the adhesive surface of polarizing coating by saponification processing etc. through the acetyl group cellulose mesentery of hydrophilicity-imparting treatment during as transparent protective film, the polyvinyl alcohol resin aqueous solution is preferably used as bonding agent.The polyvinyl alcohol resin that uses as bonding agent be except handling and the alcotex that obtains as the polyvinyl acetate saponification of leifa, also have ethenol system copolymer that vinyl acetate is obtained with handling with the multipolymer saponification of the monomer of its copolymerization, with their the modified polyvinylalcohol based polymer etc. of hydroxylic moiety modification.Can also cooperate polyaldehyde, soluble epoxide compound, melamine compound etc. as crosslinking chemical in this bonding agent.
Polaroid of the present invention can also make in addition transparent protective film have function as phase retardation film, as brightness improve the function of film, as the function of reflectance coating, as the function of Transflective film, as the optical functions such as function of optical compensation films.At this moment; for example improve optically functional films such as film, reflectance coating, Transflective film, diffusion barrier, optical compensation films by lamination phase retardation film on the surface of transparent protective film, brightness; thereby not only can make it have this function, but also can give transparent protective film itself this function.In addition, can also as have the diffusion barrier of brightness raising film function etc., make transparent protective film itself have a plurality of functions.
For example by implement the stretch processing of records such as No. the 2841377th, patent, No. the 3094113rd, patent at above-mentioned transparent protective film, patent waits the processing of record for No. 3168850, can give the function as phase retardation film.The phase difference characteristics of phase retardation film for example can suitably be selected the scope of front phase difference value 5～100nm, thickness direction phase difference value 40～300nm etc.In addition; open the method for records such as 2003-29030 communique and on above-mentioned transparent protective film, form minute aperture by utilizing the spy to open 2002-169025 communique, spy; the different cholesteric more than 2 layers of centre wavelength of perhaps overlapping selection reflection can be given the function that improves film as brightness.
In addition, when utilizing evaporation, sputter etc. on transparent protective film, to form metallic film, can give function as reflectance coating or Transflective film.Contain atomic resin solution by coating on transparent protective film, can give function as diffusion barrier.In addition, make its orientation, can give function as optical compensation films by liquid crystal compounds such as coating collar plate shape liquid-crystal compoundss on above-mentioned transparent protective film.And, can also use suitable adhesive that various optical functional films are directly sticked on the polarizing coating.As the commercially available product of optical functional film, for example can enumerate DBEF (3M society system, obtain from Sumitomo ス リ-エ system (strain)) and wait that brightness improves film, WV film angle of visibilities such as (Fuji Photo film (strain) systems) is improved film, ス ミ カ ラ イ ト (Sumitomo Chemical (strain) system) equiphase difference film etc. in Japan.
The manufacture method of＜polaroid 〉
The present invention also provides the method for preferred manufacturing the invention described above polaroid in addition.Polaroid manufacture method of the present invention is characterised in that, be situated between transparent protective film is sticked on the single face at least of the polarizing coating that obtains by the invention described above polarizing coating manufacture method by bonding agent after, under 30～60 ℃ temperature, carry out drying.By this polaroid manufacture method of the present invention; as mentioned above, can preferably make irrelevant with the state that whether possesses transparent protective film, the transmissivity of wavelength 410nm, 550nm and 680nm is the polaroid of the present invention below 0.01% during with the polarizing coating of the present invention incident similarly rectilinearly polarized light parallel with absorption axes.
In the polaroid manufacture method of the present invention; the method of pasting polarizing coating and transparent protective film is not particularly limited; for example can enumerate on the surface of polarizing coating or transparent protective film coating adhesive equably; overlapping another film on coated face utilizes that roll etc. is pasted, dry method etc.
Bonding agent is coated with under 15～40 ℃ temperature usually, and sticking temperature is generally 15～30 ℃ scope.Carries out dried after the stickup, water equal solvent contained in the bonding agent is removed, but polaroid manufacture method of the present invention is characterised in that making baking temperature after this stickup is to be lower than 30～60 ℃ of common baking temperature, to be preferably 40～55 ℃.Baking temperature can't be dry fully during less than 30 ℃, in addition, when baking temperature surpasses 60 ℃, can't obtain the polaroid of object penetrating rate characteristic.Be more than 20 seconds, be preferably more than 60 seconds the drying time of utilizing this baking temperature.
After can drying under these conditions in the polaroid manufacture method of the present invention, surpassing 60 ℃ temperature, for example carrying out drying under the temperature more than 70 ℃.Afterwards, can also bonding agent be solidified 15～85 ℃, preferred 20～50 ℃, more preferably maintenance about 1～90 day usually under 35～45 ℃ the temperature environment.When diaphragm is the cellulose-based resin of acetyl group; can not show sufficient bond strength even if do not implement this maintenance yet; but when using the transparent protective film that constitutes by other resin and be situated between, preferably implement above-mentioned maintenance by hydrosolvent bonding agent and polarizing coating stickup.Long more between this curing period, then productivity is poor more, thus be preferably about 1～14 day between curing period, more preferably about 1～7 day.
Embodiment
Below enumerate embodiment and comparative example the present invention is described in further detail, but the present invention is not limited to these embodiment.
＜embodiment 1 〉
The continuous conveying device that niproll and free roller arranged with combination is delivered to the long film of polyvinyl alcohol resin in the device that disposes swelling groove 3, water retting groove 4, staining trough 5, boric acid groove 6, rinsing bowl 7 and drying oven 8 successively shown in Figure 1, carries out various processing simultaneously.Use the polyvinyl alcohol film (Network ラ レ PVC ニ ロ Application VF-PS#7500, (strain) Network ラ レ system) of average degree of polymerization 2400, saponification degree more than 99.9% mole, thickness 75 μ m, width 3000mm as former anti-film 1.Make driving niproll before and after each groove have linear differential and stretch.
At first make under its unflagging situation, be immersed in 80 seconds in the swelling groove 3 that 30 ℃ of pure water are housed, make film swelling (swelling operation) fully in the tense situation that keeps former anti-film 1.The speed of rolls ratio of the entrance and exit of following swelling in the swelling groove 3 is 1.2.After utilizing niproll to dewater, be immersed in 160 seconds (water retting operation) in the water retting groove 4 that 30 ℃ of pure water are housed.Operating direction stretching ratio in this groove is 1.04 times.Then, impregnated in to be equipped with and contain in the staining trough 5 that the processing of 0.02 weight portion iodine and 2.0 weight portion potassium iodides bathes, carry out uniaxial tension (iodine staining operation) with 2 times of stretching ratios simultaneously with respect to 100 weight parts waters.Afterwards, in the boric acid groove 6 that the boric acid aqueous solution that contains 5 weight portion boric acid and 12 weight portion potassium iodides with respect to 100 weight parts waters is housed,, carry out uniaxial tension simultaneously and make and reach 5.3 times (crosslinked operations) by former anti-accumulative total stretching ratio 56.5 ℃ of following 130 seconds of dipping.Pure water with 8 ℃ washs 16 seconds (washing step) in rinsing bowl 7 at last, afterwards 60 ℃ of following dry 160 seconds (drying process) in drying oven 8, obtains polarizing coating 9.
For gained polarizing coating 9, measure absorption axes direction transmissivity, it be the results are shown in Fig. 2 (thick line of solid line among the figure).Illustrated, absorption axes direction transmissivity is meant the transmissivity the when absorption axes with 1 polarizing coating or polaroid shines the rectilinearly polarized light that obtains by polarizing prism abreast, transmissivity when therefore, the absorption axes direction transmissivity TD (λ) of certain wavelength X is meant rectilinearly polarized light with the same direction of polarizing coating absorption axes ground illumination wavelength lambda.This absorption axes direction transmissivity uses V7100 (Japanese beam split (strain) system) to measure.The absorption axes direction transmissivity of wavelength 410nm is 0.0033%, the absorption axes direction transmissivity of wavelength 550nm is 0.0002%, the absorption axes direction transmissivity of wavelength 680nm is 0.0014%.
＜embodiment 2 〉
Be situated between respectively by the bonding agent phase retardation film that stickup contains the diaphragm of tri acetyl cellulose on the single face of the polarizing coating that embodiment 1 obtains, stickup contains norbornene resin on another face of the aqueous solution that contains polyvinyl alcohol resin; after the stickup immediately in 50 ℃ of following dry 60 seconds of kiln temperatures; dry under 70 ℃ afterwards, the polaroid of acquisition monomer transmissivity 41.88%, degree of polarization 99.997%.For the gained polaroid, measure absorption axes direction transmissivity similarly to Example 1, its result is shown in Fig. 2 (fine rule of solid line among the figure) with the result of embodiment 1.
The absorption axes direction transmissivity of wavelength 410nm is 0.0062%, the absorption axes direction transmissivity of wavelength 550nm is 0.0010%, the absorption axes direction transmissivity of wavelength 680nm is 0.0024%.This polaroid is configured in the two sides of LCD TV, when observing black the demonstration, is aterrimus.
＜comparative example 1 〉
To the film of the thickness 80 μ m that contain polyvinyl alcohol (PVA),, make the polarisation base material at the uniaxial tension of implementing 5 times more than 100 ℃.This polarisation base material is being remained under the situation of tense situation, after 60 ℃ of 60 seconds of water treatment, impregnated in respect to 100 weight parts waters and contain 60 seconds in the aqueous solution of 0.05 weight portion iodine and 5 weight portion potassium iodides, obtain the monadic stretching membrane that the absorption orientation has the polyvinyl alcohol resin of iodine.With this film immersion 160 seconds in 67 ℃ the aqueous solution that contains 6 weight portion potassium iodides and 7.5 weight portion boric acid with respect to 100 weight parts waters.Afterwards, washed for 36 seconds with 15 ℃ pure water after, 60 ℃ dry down, obtain the polarizing coating of the optical property of monomer transmissivity 43.0%, degree of polarization 99.9%.The absorption axes direction transmissivity of gained polarizing coating is shown in Fig. 2 (dotted line of solid line among the figure) with the result of embodiment 1,2.
The absorption axes direction transmissivity of wavelength 410nm is 0.36%, the absorption axes direction transmissivity of wavelength 550nm is 0.03%, the absorption axes direction transmissivity of wavelength 680nm is 0.33%.The polarizing coating that uses this comparative example 1 to obtain is made polaroid similarly to Example 2, is configured in the two sides of LCD TV, when observing black the demonstration, is the black that turns blue.
This disclosed embodiment and embodiment should think that all aspects are for giving an example, being not that limitation is arranged.The scope of the invention is not by above-mentioned explanation but is represented by the scope of claim, comprise with claims be equal to claims in whole changes.
Claims (5)
1. polarizing coating, it has the polarizing coating of iodine for absorption orientation on the polyvinyl alcohol resin film, and when the incident rectilinearly polarized light parallel with absorption axes, the transmissivity of wavelength 410nm, 550nm and 680nm is below 0.01%.
2. polaroid, it is a polaroid of pasting transparent protective film on the single face at least of the described polarizing coating of claim 1, when the incident rectilinearly polarized light parallel with absorption axes, the transmissivity of wavelength 410nm, 550nm and 680nm is below 0.01%.
3. the manufacture method of polarizing coating, it makes its crosslinked crosslinked operation for using the iodine staining operation of iodine staining polyvinyl alcohol resin film successively and handling with boric acid aqueous solution, and by the arbitrary at least operation before the crosslinked operation with polyvinyl alcohol resin film uniaxial tension, in crosslinked operation after by washing step and drying process, make the method for polarizing coating
Crosslinked operation is carried out in the aqueous solution that contains 2～10 weight portion boric acid and 10～30 weight portion potassium iodides with respect to 100 weight parts waters,
Washing step carries out under 2～15 ℃ temperature, and
During the incident rectilinearly polarized light parallel, be the condition of setting each operation below 0.01% according to the transmissivity that makes wavelength 410nm, 550nm and 680nm with the absorption axes of gained polarizing coating.
4. the manufacture method of polarizing coating according to claim 3, wherein the iodine staining operation carried out for 10～600 seconds in containing the aqueous solution that iodine and potassium iodide, iodine amount are 0.01～0.2 weight portion with respect to water 100 weight portions, crosslinked operation was carried out for 10～600 seconds under 50～70 ℃ temperature, and washing step carried out for 2～120 seconds.
5. the manufacture method of polaroid wherein, is situated between by bonding agent behind the sticking obedient transparent protective film on the single face at least of the polarizing coating that obtains by claim 3 or 4 described methods, carries out drying under 30～60 ℃ temperature.
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| JP2007-231594 | 2007-09-06 | ||
| JP2007231594A JP2009063829A (en) | 2007-09-06 | 2007-09-06 | Polarizing film, polarizing plate and those manufacturing method |
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| CN101382616A true CN101382616A (en) | 2009-03-11 |
| CN101382616B CN101382616B (en) | 2013-10-30 |
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| CN107200977A (en) * | 2017-05-27 | 2017-09-26 | 中国石油化工集团公司 | A kind of polyvinyl alcohol mesentery and preparation method thereof and by its obtained light polarizing film |
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| CN2289251Y (en) * | 1997-01-09 | 1998-08-26 | 张钢虎 | Colour polarizing diaphragm |
| JP2002258042A (en) * | 2001-03-02 | 2002-09-11 | Nitto Denko Corp | Polarizing plate and liquid crystal display device using the same |
| CN1453598A (en) * | 2002-04-24 | 2003-11-05 | 日东电工株式会社 | Polarized film and its producing method, polaroid and optical structural parts |
| JP4594804B2 (en) * | 2005-06-17 | 2010-12-08 | 大倉工業株式会社 | Manufacturing method of polarizing film |
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2007
- 2007-09-06 JP JP2007231594A patent/JP2009063829A/en active Pending
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2008
- 2008-09-03 TW TW097133755A patent/TWI463196B/en active
- 2008-09-03 KR KR1020080086806A patent/KR101553411B1/en active IP Right Grant
- 2008-09-04 CN CN2008102127482A patent/CN101382616B/en active Active
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| CN105103013A (en) * | 2013-03-29 | 2015-11-25 | 住友化学株式会社 | Process for producing polarizing film |
| CN107003464A (en) * | 2014-12-12 | 2017-08-01 | 住友化学株式会社 | The manufacture method and polarizing coating of polarizing coating |
| CN107003464B (en) * | 2014-12-12 | 2020-05-19 | 住友化学株式会社 | Polarizing film manufacturing method and polarizing film |
| CN106873066A (en) * | 2015-11-04 | 2017-06-20 | 日东电工株式会社 | The method of polarizer, polarizer and manufacture polarizer |
| US10578786B2 (en) | 2015-11-04 | 2020-03-03 | Nitto Denko Corporation | Polarizer, polarizing plate, and method of producing polarizer |
| CN106873066B (en) * | 2015-11-04 | 2020-12-25 | 日东电工株式会社 | Polarizer, polarizing plate and method for manufacturing polarizer |
| CN107111043A (en) * | 2015-11-05 | 2017-08-29 | 住友化学株式会社 | Polarizer and its manufacture method |
| CN107200977A (en) * | 2017-05-27 | 2017-09-26 | 中国石油化工集团公司 | A kind of polyvinyl alcohol mesentery and preparation method thereof and by its obtained light polarizing film |
| CN107200977B (en) * | 2017-05-27 | 2020-06-05 | 中国石油化工集团公司 | Polyvinyl alcohol film, manufacturing method thereof and polarizing film prepared from polyvinyl alcohol film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2009063829A (en) | 2009-03-26 |
| TWI463196B (en) | 2014-12-01 |
| KR20090026067A (en) | 2009-03-11 |
| KR101553411B1 (en) | 2015-09-15 |
| CN101382616B (en) | 2013-10-30 |
| TW200931081A (en) | 2009-07-16 |
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