CN102707364B - Polarizing plate and image display - Google Patents
Polarizing plate and image display Download PDFInfo
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- CN102707364B CN102707364B CN201210189646.XA CN201210189646A CN102707364B CN 102707364 B CN102707364 B CN 102707364B CN 201210189646 A CN201210189646 A CN 201210189646A CN 102707364 B CN102707364 B CN 102707364B
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- film
- protection film
- methyl
- polarizer protection
- polarization plates
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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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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- G02B1/105—
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
- G02F2201/50—Protective arrangements
Abstract
Disclosed is a polarizer protection film which mainly contains a (meth)acrylic resin and has excellent adhesion to a polarizer. Also disclosed is a polarizing plate comprising such a polarizer protection film and a polarizer, wherein the polarizer protection film and the polarizer are hardly separated from each other. Further disclosed is a high-quality image display using such a polarizing plate. Specifically disclosed is a polarizer protection film which is obtained by coating one surface of a film mainly containing a (meth)acrylic resin with a solvent by which the film can be swelled or dissolved.
Description
The application be applicant in the international application no that on November 9th, 2006 submits to be PCT/JP2006/322376 (200680042524.0), denomination of invention is the divisional application of the PCT international application of " polarizer protection film, polarization plates and image display device ".
Technical field
The present invention relates to polarizer protection film, polarization plates and the image display device of liquid crystal indicator, organic EL display, PDP etc. at least containing 1 this polarization plates.
Background technology
In liquid crystal indicator, be required and indispensable by its image forming mode in the both sides configuration polarization plates of the glass substrate forming liquid crystal panel surface.Polarization plates, usually on the polaroid two sides be made up of the dichroic material of polyvinyl alcohol film and iodine etc., uses the component being employed the polarizer protection film of the cellulosic resin film of triacetyl cellulose etc. by the laminating of polyvinyl alcohol tackifier.
Because the humidity resistance of cellulosic resin film is insufficient, if used employing the polarization plates of cellulosic resin film as polarizer protection film under high temperature or high humidity, then there is the shortcoming that the polarization plates performance of degree of polarization and form and aspect etc. reduces.In addition, cellulosic resin film produces phase differential relative to tilted direction incident light.This phase differential is the progress along with liquid crystal display maximization in recent years, impacts significantly to angle of visibility characteristic.
As thermotolerance and the excellent resin material of optical transparence; know (methyl) acrylic resin having polymethylmethacrylate etc.; and have the report (for example, referring to patent documentation 1,2) of the use as polarizer protection film.But (methyl) acrylic resin, when through filming, easily fragile layer occurs near film surface, when being used as polarizer protection film, fully cannot show the tackiness with polaroid.Therefore, the problem easily peeled off between polarizer protection film and polaroid is had.
Compared to (methyl) in the past acrylic resin of polymethylmethacrylate etc., as the resin with more high-fire resistance, high transparent, high mechanical properties, there will be a known (methyl) acrylic resin (with reference to patent documentation 3) with lactonic ring structure.But this (methyl) acrylic resin with lactonic ring structure, when through filming, will have more in the past the easier problem that fragile layer occurs near film surface of (methyl) acrylic resin.
Patent documentation 1: Japanese Patent Laid-Open 2000-356714 publication
Patent documentation 2: Japanese Patent Laid-Open 2002-258051 publication
Patent documentation 3: Japanese Patent Laid-Open 2001-151814 publication
Summary of the invention
The present invention carries out to solve above-mentioned problem, its object is to provide: the tackiness of (1) and polaroid superior containing the polarizer protection film of (methyl) acrylic resin as major component; (2) containing this polarizer protection film and polaroid and polarizer protection film and polaroid are difficult to the polarization plates peeled off; And (3) use the high-quality image display device of this polarization plates.
Polarizer protection film of the present invention is containing in the one side of (methyl) acrylic resin as the film of major component, and coating can make the solvent of this films swell or dissolving.
In preferred example, above-mentioned (methyl) acrylic resin is (methyl) acrylic resin with lactonic ring.
According to a further aspect in the invention, a kind of polarization plates is provided.Polarization plates of the present invention the one side side of the solvent of this films swell or dissolving can be made to have polaroid being coated with of polarizer protection film of the present invention.
In preferred example, between above-mentioned polarizer protection film and polaroid, there is adhesive layer.
In preferred example, above-mentioned adhesive layer is the layer formed by polyvinyl alcohol tackifier.
In preferred example, there is adhesive phase further as outermost at least one party.
According to other aspects of the invention, a kind of image display device is provided.Image display device of the present invention contains at least 1 polarization plates of the present invention.
According to the present invention, can provide a kind of polarizer protection film, it is containing the polarizer protection film of (methyl) acrylic resin as major component, and excellent with the tackiness of polaroid.
Polymethylmethacrylate etc. in the past containing (methyl) acrylic resin as the polarizer protection film of major component; when through filming, easily near film surface, there is fragile layer, and fully cannot show the tackiness with polaroid.If according to the present invention, by processing using specific solvent containing the one side of (methyl) acrylic resin as the film of major component, then the polarizer protection film excellent with the tackiness of polaroid can be provided.
If according to the present invention, the polarization plates containing above-mentioned polarizer protection film and polaroid can be provided, and owing to using the polarizer protection film excellent with the tackiness of polaroid, therefore will be very difficult between polarizer protection film and polaroid peel off.Moreover, if according to the present invention, the high quality graphic display device employing above-mentioned polarization plates can be provided.
Accompanying drawing explanation
Fig. 1 is the sectional view of the example representing polarization plates of the present invention.
Fig. 2 is the summary section of the liquid crystal indicator of the preferred example of the present invention.
In figure,
10-liquid crystal cells, 11,11 '-glass substrate, 12-liquid crystal layer; 13-distance piece, 20,20 '-phase-contrast film, 30,30 '-polarization plates; 31-polaroid, 32-adhesive layer, the easy adhesive linkage of 33-; 34-polarizer protection film, 35-adhesive layer, 36-polarizer protection film; 40-light guide plate; 50-light source, 60-reverberator, 100-liquid crystal indicator.
Embodiment
Below, be described for preferred example of the present invention, but the present invention is not limited to this example.
[polarizer protection film]
Polarizer protection film of the present invention comprises containing the film of (methyl) acrylic resin as major component.
As above-mentioned (methyl) acrylic resin, preferred Tg (glass transition temperature) is more than 115 DEG C, be more preferably more than 120 DEG C so that be preferably more than 125 DEG C, be particularly preferably more than 130 DEG C.By containing Tg (glass transition temperature) be (methyl) acrylic resin of more than 115 DEG C as major component, then such as when being finally assembled to polarization plates, will easily be formed as excellent durability component.The higher limit of the Tg of above-mentioned (methyl) acrylic resin is not particularly limited, but by viewpoints such as formabilities, is preferably less than 170 DEG C.
As above-mentioned (methyl) acrylic resin, be not particularly limited, can illustrate as poly-(methyl) acrylate such as polymethylmethacrylates, methyl methacrylate-(methyl) acrylic copolymer, methyl methacrylate-(methyl) acrylate copolymer, methyl methacrylate-acrylate-(methyl) acrylic copolymer, (methyl) acrylate-styrene multipolymer (MS resin etc.), there is the polymkeric substance of alicyclic alkyl (such as, methyl methacrylate-cyclohexyl methacrylate multipolymer, methyl methacrylate-(methyl) acrylic acid norborneol ester copolymer etc.) etc.Be preferably poly-(methyl) acrylic acid C of poly-(methyl) methyl acrylate etc.
1-6arrcostab, is more preferably, and can illustrate as the Tri-n-butyltin methacrylate resin using methyl methacrylate as major component (50 ~ 100 % by weight, preferably 70 ~ 100 % by weight).
As the concrete example of above-mentioned (methyl) acrylic resin, can illustrate as the Acrypet VH of Rayon Inc. of Mitsubishi and Acrypet VRL20A; There is in the molecule that Japanese Patent Laid-Open 2004-70296 publication is recorded (methyl) acrylic resin of ring structure; By high Tg (methyl) acrylic resin of intramolecular crosslinking and intramolecular cyclization reaction gained.
In the present invention, by the viewpoint with high-fire resistance, high transparent, high mechanical properties, as above-mentioned (methyl) acrylic resin, preferably there is (methyl) acrylic resin of lactonic ring structure.
As (methyl) acrylic resin with lactonic ring structure, (methyl) acrylic resin with lactonic ring structure as described in Japanese Patent Laid-Open 2000-230016 publication, JP 2001-151814 publication, JP 2005-146084 publication etc. of can illustrating.
(methyl) acrylic resin with lactonic ring structure preferably has the lactonic ring structure shown in following general formula (1).
[changing 1]
(in general formula (1), R
1, R
2and R
3independently represent the organic residue of hydrogen atom or carbon number 1 ~ 20.Again, organic residue also can contain oxygen atom.)
Have the lactonic ring structure represented with general formula (1) in the structure of (methyl) acrylic resin of lactonic ring structure containing proportional, be preferably 5 ~ 90 % by weight, be more preferably 10 ~ 70 % by weight and then be preferably 10 ~ 60 % by weight, be particularly preferably 10 ~ 50 % by weight.If what have the lactonic ring structure represented with general formula (1) in (methyl) acrylic resin of lactonic ring structure is less than 5 % by weight containing proportional, then there is the worry that thermotolerance, solvent resistance, skin hardness are inadequate.If have the lactonic ring structure represented with general formula (1) in (methyl) acrylic resin of lactonic ring structure containing proportional more than 90 % by weight, then have the worry lacking shaping processability.
There is the matter average molecular weight (sometimes also referred to as weight-average molecular weight) of (methyl) acrylic resin of lactonic ring structure, be preferably 1000 ~ 2000000, be more preferably 5000 ~ 1000000 and then preferably 10000 ~ 500000, be particularly preferably 50000 ~ 500000.If matter average molecular weight departs from above-mentioned scope, then there is the worry that cannot give full play to effect of the present invention.
With regard to (methyl) acrylic resin with lactonic ring structure, get over Gao Yuejia by the formed products of injection molded gained with total light transmittance of ASTM-D-1003 measured by the method for benchmark, be preferably more than 85%, be more preferably more than 88% and then be preferably more than 90%.If total light transmittance is less than 85%, then the transparency is had to reduce, cannot be used in the worry of the purposes of former object.
The content of (methyl) acrylic resin in polarizer protection film of the present invention, is preferably 50 ~ 99 % by weight, is more preferably 60 ~ 98 % by weight and then preferably 70 ~ 97 % by weight.The content of (methyl) acrylic resin in polarizer protection film less than 50 % by weight; the high-fire resistance that (methyl) acrylic resin will be had fully to reflect originally have, the worry of high transparent; when more than 99 % by weight, then there is the worry of mechanical strength deterioration.
In the present invention containing (methyl) acrylic resin as the film of major component, stretch preferably by longitudinal stretching and/or cross directional stretch formation.
Above-mentioned stretching can be the stretching (free end uniaxial tension) only carrying out longitudinal stretching, also can be the stretching (stiff end uniaxial tension) only carrying out cross directional stretch, but preferably longitudinal stretching multiplying power is 1.1 ~ 3.0 times, cross directional stretch multiplying power is the successively stretching or simultaneously biaxial stretch-formed of 1.1 ~ 3.0 times.Only carrying out the stretching (free end uniaxial tension) of longitudinal stretching and only carrying out in the stretching (stiff end uniaxial tension) of cross directional stretch, film strength is only made to improve in the stretching direction, do not increase relative to intensity in the right angle orientation of draw direction, and have the worry that cannot obtain abundant film strength with film integral.Above-mentioned longitudinal stretching multiplying power is more preferably 1.2 ~ 2.5 times and then preferably 1.3 ~ 2.0 times.Above-mentioned cross directional stretch multiplying power is more preferably 1.2 ~ 2.5 times and then preferably 1.4 ~ 2.5 times.When longitudinal stretching multiplying power, cross directional stretch multiplying power less than 1.1, stretching ratio by too low, and has the worry of almost tensionless winkler foundation effect.If longitudinal stretching multiplying power, cross directional stretch multiplying power are more than 3.0 times, then because of the flatness problem of film end face, and easily there is tensile fracture.
Above-mentioned draft temperature, Tg ~ (Tg+30 DEG C) of the film that is preferably stretched.If above-mentioned draft temperature is lower than Tg, then there is the worry of film breaks.If above-mentioned draft temperature exceedes (Tg+30 DEG C), then film is had to start melting and worry by becoming difficulty.
Polarizer protection film of the present invention forms by utilizing longitudinal stretching and/or cross directional stretch and being stretched, therefore has superior optical characteristics, and meanwhile, physical strength is also superior, and productivity and again property processed will improve.
Polarizer protection film of the present invention, be containing (methyl) acrylic resin as major component film-face, coating can by the solvent of this films swell or dissolving.
As above-mentioned solvent, be applicable to using: the ketone of acetone, MEK, methyl isobutyl ketone, methyl-n-amyl ketone, cyclohexanone, diacetone alcohol, diisobutyl ketone, methyl cyclohexanone etc.; The ester class of methyl acetate, ethyl acetate, ethyl lactate, butyl lactate, ethyl benzoate, methyl acetoacetate etc.; The ethers of Er Evil pentane, diox, methyl Cellosolve, methyl carbitol etc.; The polyol ester class of methyl Cellosolve acetic acid esters, Cellosolve acetic acid esters etc.; The furans of tetrahydrofuran, furfural etc.; The acids of glacial acetic acid etc.; The halogenated hydrocarbons of methylene chloride, ethylene dichloride, tetrachloroethane etc.; The nitrogen compound of nitromethane, nitroethane, pyridine, dimethyl formamide, nitrobenzene etc.; The sulphonic acids etc. of dimethyl sulfone etc.If consider the drying after coating, be then preferably volatile solvent, specifically, preferred boiling point is less than 200 DEG C.
In polarizer protection film of the present invention, as the example being coated with above-mentioned solvent in this film one side, can be the state having above-mentioned solvent on pellicular front, also can be the state that there is not above-mentioned solvent on pellicular front.Pellicular front does not exist the state of above-mentioned solvent, can illustrate as the situation making solvent volatilize by natural drying or force drying.
In polarizer protection film of the present invention, as the example being coated with above-mentioned solvent in this film one side, making at least partially after the dissolving at least partially of pellicular front again through the state of solidification as: above-mentioned the solvent be coated with more specifically can be illustrated; The state swelling at least partially making pellicular front at least partially of above-mentioned be coated with solvent; With and deposited the state etc. of above-mentioned two kinds of states.Again, also can the reacting at least partially of pellicular front and above-mentioned be coated with solvent, or solvent that also can be above-mentioned be coated with infiltrate into pellicular front at least partially.
In polarizer protection film of the present invention; by containing in the one side of (methyl) acrylic resin as the film of major component; coating can make the solvent of this films swell or dissolving; be present in thus and have an effect (dissolve, swelling etc.) as the fragile layer of the near surface of the film of major component and this solvent containing (methyl) acrylic resin, the tackiness that can to suppress with this fragile layer be reason reduces.
In polarizer protection film of the present invention; by at the film that can make the solvent of this films swell or dissolving containing (methyl) acrylic resin as coating in the one side of the film of major component, confirm by such as analyzing the near surface composition of polarizer protection film of the present invention.
In polarizer protection film of the present invention, the coating weight of above-mentioned solvent, in the scope not undermining effect of the present invention, can adopt the amount be applicable to arbitrarily.Preferably relative to be coated with pellicular front 1cm
2be 0.0001 ~ 1ml, be more preferably 0.001 ~ 0.1ml.
In polarizer protection film of the present invention, also can contain ultraviolet light absorber, common compounding ingredient, such as stabilizing agent, lubricant, processing aid, plastifier, shock-resistant auxiliary agent, phase differential lower agent, matting agent, antiseptic, mildewproof agent etc.
In polarizer protection film of the present invention, the film that in preferred high light transmission, face, phase difference nd and thickness direction phase differential Rth is lower.
The thickness of polarizer protection film of the present invention is preferably 20 ~ 200 μm, is more preferably 25 ~ 180 μm and then preferably 30 ~ 140 μm.If the thickness of polarizer protection film is more than 20 μm, then have suitable intensity, rigidity, the operability when secondary processing such as stacked and printings becomes good.Again, also can easily control because of the phase differential that occurs of stress during traction, Absorbable organic halogens and easily carry out thin film fabrication.If the thickness of polarizer protection film is less than 200 μm, then except easily carrying out except film batches, linear velocity, productivity, controlling also become easy.
YI in the thickness 80 μm of polarizer protection film of the present invention, is preferably less than 1.3, is more preferably less than 1.27 and then preferably less than 1.25, is more preferably less than 1.23, is particularly preferably less than 1.20.If the YI in thickness 80 μm more than 1.3, then has the worry that cannot play superior optical transparence.Again, YI such as uses high speed integrating sphere type spectral transmission measuring instrument (trade name DOT-3C: color technical institute system in village), by the tristimulus values (X, Y, Z) of the color of gained in the measurements, then can try to achieve with following formula.
YI＝[(1.28X-1.06Z)/Y]×100
B value (Yi Hante (Hunter) color specification system is the form and aspect yardstick of benchmark) in the thickness 80 μm of polarizer protection film of the present invention, is preferably less than 1.5, is more preferably less than 1.0.When b value is more than 1.5, painted due to film, will have the worry that cannot play superior optical transparence.Even b value is that such as polarizer protection film sample to be cut to 3cm square, uses high speed integrating sphere type spectral transmission measuring instrument (trade name DOT-3C: color technical institute system in village), then can measure form and aspect.Again, can be that benchmark utilizes b value to evaluate form and aspect with Chinese characteristic.
In polarizer protection film of the present invention, in face, phase difference nd is preferably below 3.0nm, is more preferably below 1.0nm.If above-mentioned interior phase difference nd is more than 3.0nm, then there is the worry that cannot play effect of the present invention, especially superior optical characteristics.Thickness direction phase differential Rth is preferably below 5.0nm, is more preferably below 3.0nm.If above-mentioned thickness direction phase differential Rth more than 5.0nm, then has the worry that cannot play effect of the present invention, especially superior optical characteristics.
In polarizer protection film of the present invention, moisture permeability is preferably 100g/m
2below 24hr, be more preferably 60g/m
2below 24hr.If above-mentioned moisture permeability is more than 100g/m
224hr, then have the worry of moisture-proof difference.
In polarizer protection film of the present invention, preferably there is superior physical strength.Pulling strengrth in the MD direction, is preferably 65N/mm
2above, 70N/mm is more preferably
2above so be preferably 75N/mm
2above, 80N/mm is particularly preferably
2above; On TD direction, be preferably 45N/mm
2above, 50N/mm is more preferably
2above so be preferably 55N/mm
2above, 60N/mm is particularly preferably
2above.Tensile elongation in the MD direction, is preferably more than 6.5%, is more preferably more than 7.0% and then preferably more than 7.5%, is particularly preferably more than 8.0%; On TD direction, be preferably more than 5.0%, be more preferably more than 5.5% and then preferably more than 6.0%, be particularly preferably more than 6.5%.If when pulling strengrth or tensile elongation depart from above-mentioned scope, then there is the worry that cannot play superior physical strength.
In polarizer protection film of the present invention, represent that the turbidity value of optical transparence is more low better, be preferably less than 5%, be more preferably less than 3% and then preferably less than 1.5%, be particularly preferably less than 1%.If turbidity value is less than 5%, then visually can give good clear sense to film, moreover, if be set to less than 1.5%, even if then when being used as the daylighting structure material of window etc., identification and daylighting can be obtained, again simultaneously.Even if when being used as the front panel of display device, can identification displaying contents well, therefore industrialness value is high.
In polarizer protection film of the present invention; also can manufacture by any method; preferably can illustrate as: will be formed containing (methyl) acrylic resin as the raw material (resin combination) of the film of major component; be supplied to extrusion molding (extrusion by melting of T die head and blow moulding etc.), casting forming (melting the tape casting etc.), calendaring molding; manufacture film thus; thereafter; preferably after making this film stretch as described above; in the one side of gained film, coating can by the method for the solvent of this films swell or dissolving.
As the method for the above-mentioned solvent of coating, the method be applicable to arbitrarily can be adopted.Can illustrate as with stick coating method, scrape the coating process such as the skill in using a kitchen knife in cookery, dip coating and be coated with, thereafter, make its nature or method dry forcibly.
Extrusion molding is as dry type layered manner, do not need to make to add solvent (organic solvent in the tackifier that such as dry type is stacked) in tackifier used in man-hour dry, disperse, and do not need solvent seasoning operation, highly productive.Specifically can illustrating as the resin combination becoming raw material being supplied to the extruder being attached at T die head, after melting is mixed, extruding, take out after giving water-cooled, by film shaped method.The screw rod pattern of extruder can be single shaft or twin shaft, also can add the adjuvant of plastifier or antioxidant etc.
Extrusion molding temperature can suitably set, when the glass transition temperature of the resin combination becoming raw material is set to Tg (DEG C), preferably (Tg+80) DEG C ~ (Tg+180) DEG C, more preferably (Tg+100) DEG C ~ (Tg+150) DEG C.If extrusion molding temperature is too low, then resin without mobility, then have the worry that cannot be shaped.If extrusion molding temperature is too high, then resin viscosity step-down, then have in the molding worry waiting generation problem in production stability in uneven thickness.
In the resin combination forming polarizer protection film of the present invention; also can contain ultraviolet light absorber and common compounding ingredient, such as stabilizing agent, lubricant, processing aid, plastifier, shock-resistant auxiliary agent, phase differential lower agent, matting agent, antiseptic, mildewproof agent etc.
As the optical characteristics of polarizer protection film, the phase place extent of front and thickness direction will become problem.Therefore, in the resin combination forming polarizer protection film of the present invention, also agent can be lowered containing phase differential.Lower agent as phase differential, be preferably such as acrylonitrile-styrene analog copolymer etc. and contain cinnamic polymkeric substance.Lower the addition of agent as phase differential, relative to (methyl) acrylic resin, be preferably less than 30 % by weight, be more preferably less than 25 % by weight and then preferably less than 20 % by weight.If exceed this scope when being added, owing to making luminous ray scattering or undermining the transparency, therefore be weak as the worry of the characteristic of polarizer protection film.
Polarizer protection film of the present invention, can be layered on other base material and use.Such as can for glass, polyolefin resin, become the base material of the ethene vinylidene copolymer, polyester etc. of high barrier, the shaping or multi-layer blow molding by the multilayer extrusion containing tackiness resin bed, and carry out cascading into shape.When hot glue viscosity is higher, also adhesive layer can be omitted.
In polarizer protection film in the present invention; except the purposes of polaroid protection; also such as can be layered in the display structure material of the agricultural daylighting structure material of the vehicle daylighting structure material, greenhouse etc. of the daylighting structure material for building, window etc. of window and bicycle shed roof material etc., illumination structure material, above light filter etc. etc. and use; again, also can be layered in is the household electrical appliances framework, vehicle in-built structure material, in-built building materials, wallpaper, decorative panel, entry Door and window frame, skirting board etc. of capped (methyl) acrylic resin film and use in the past.
[polarization plates]
Polarization plates of the present invention is the polarization plates containing polarizer protection film of the present invention and polaroid, and the one side side of the solvent of this films swell or dissolving can be made to have polaroid in being coated with of polarizer protection film of the present invention.One preferred example of polarization plates of the present invention as shown in Figure 1; for following form: the one side of polaroid 31 is via adhesive layer 32 and easy adhesive linkage 33 and be bonded on the above-mentioned solvent coated face side of polarizer protection film 34 of the present invention, and the another side of polaroid 31 is bonded in polarizer protection film 36 via adhesive layer 35.Polarizer protection film 36 can be polarizer protection film of the present invention, also can be the polarizer protection film that other is applicable to arbitrarily.
The polaroid formed by above-mentioned polyvinyl alcohol resin uses and polyvinyl alcohol resin film dichroic substance (representative is iodine, dichroic dye) is carried out dyeing and the film of uniaxial tension.Form the degree of polymerization of the polyvinyl alcohol resin of polyvinyl alcohol resin film, be preferably 100 ~ 5000, be more preferably 1400 ~ 4000.The polyvinyl alcohol resin film forming polaroid can be shaped with any appropriate methodology (such as, making resin dissolves carry out at the solution of water or organic solvent the tape casting, casting method, the extrusion molding of casting film-forming).The object of the LCD that the thickness of polaroid can coordinate polarization plates to use or purposes and suitably set, but representative be 5 ~ 80 μm.
As the manufacture method of polaroid, object can be coordinated, use material and condition etc. and adopt the method be applicable to arbitrarily.Representative, adopt by above-mentioned polyvinyl alcohol resin membrane supplying to by swelling, dyeing, crosslinked, stretch, the method for a succession of manufacturing process that washing and drying process are formed.In each processing step except drying process, by processing in the bath of thin film dipped for the polyvinyl alcohol resin solution used in containing each operation.Swelling, dyeing, crosslinked, stretch, the order of each process of washing and drying, number of times and with or without enforcement, object can be coordinated, use material and condition etc. and suitably set.Such as, in an operation, several process can be carried out simultaneously, also can omit particular procedure.More specifically, such as stretch processing can be carried out after dyeing process, also can carry out before dyeing process, also can with swelling treatment, dyeing processes and crosslinking Treatment is carried out simultaneously.In addition, such as the method for carrying out crosslinking Treatment before and after stretch processing can suitably be adopted.Again, such as washing process can carry out after all process, also can only carry out after particular procedure.
In swelling operation, representative has, by carrying out thin film dipped for above-mentioned polyvinyl alcohol resin in water-filled process bath (swelling bath).By this process, the dirty of polyvinyl alcohol resin film surface and antiblocking agent can be cleaned, and the unequal unevenness of dyeing that causes because making polyvinyl alcohol resin films swell can be prevented.Suitably glycerine and potassium iodide etc. can be added in swelling bath.What the temperature of swelling bath was representative is about 20 ~ 60 DEG C, and what the dip time of swelling bath was representative is about 0.1 ~ 10 minute.
Representative dyeing process is, is undertaken in thin film dipped for above-mentioned polyvinyl alcohol resin bath such as the process in the dichroic substance containing iodine etc. (dye bath).The solvent used in the solution of dye bath, normally water, but also can add organic solvent having a miscibility with water in right amount.Dichroic substance, relative to solvent 100 weight portion, is used with the ratio of 0.1 ~ 1.0 weight portion typically.When using iodine as dichroic substance, the auxiliary agent of solution preferably again containing iodide etc. of dye bath.This is to improve staining efficiency.Relative to solvent 100 weight portion, auxiliary agent is preferably with 0.02 ~ 20 weight portion, more preferably used with the ratio of 2 ~ 10 weight portions.As the concrete example of iodide, can illustrate as potassium iodide, lithium iodide, sodium iodide, zinc iodide, silver iodide, lead iodide, cupric iodide, barium iodide, calcium iodide, stannic iodide, titanium iodide.What the temperature of dye bath was representative is about 20 ~ 70 DEG C, and what the dip time of dye bath was representative is about 1 ~ 20 minute.
In cross-linking process step, representative is, by thin film dipped for the polyvinyl alcohol resin processed through above-mentioned dyeing bath in (crosslinked bath) in the process containing crosslinking chemical being carried out.As crosslinking chemical, the crosslinking chemical be applicable to arbitrarily can be adopted.The concrete example of crosslinking chemical can be illustrated as the boron compound of boric acid, borax etc., with glyoxal, glutaraldehyde etc.These can be used alone or combinationally use.The solvent used in the solution of crosslinked bath, usually uses water, but also can add organic solvent having a miscibility with water in right amount.Crosslinking chemical, relative to solvent 100 weight portion, is used with the ratio of 1 ~ 10 weight portion typically.When the concentration of crosslinking chemical is less than 1 weight portion, then the situation that cannot obtain abundant optical characteristics is more.When crosslinker concentration is more than 10 weight portion, then the tensile force occurred at film when stretching becomes large, and the situation that rewarding polarization plates is shunk.The solution of crosslinked bath is preferably again containing auxiliary agents such as iodide.This is because easily obtain uniform characteristic in face.The concentration of auxiliary agent is preferably 0.05 ~ 15 % by weight, is more preferably 0.5 ~ 8 % by weight.The concrete example of iodide is identical with the situation of dyeing process.What crosslinked temperature of bathing was representative is about 20 ~ 70 DEG C, is preferably 40 ~ 60 DEG C.What crosslinked dip time of bathing was representative is 1 second ~ about 15 minutes, is preferably 5 seconds ~ 10 minutes.
Stretching process as above, can carry out in any stage.Specifically, can carry out after dyeing process, also can carry out before dyeing process, also can with swelling treatment, dyeing processes and crosslinking Treatment is carried out simultaneously, also can carry out after crosslinking Treatment.The accumulation stretching ratio of polyvinyl alcohol resin film is necessary for more than 5 times, is preferably 5 ~ 7 times, is more preferably 5 ~ 6.5 times.When accumulation stretching ratio is less than 5 times, the situation being difficult to the polarization plates obtaining high degree of polarization will be had.When accumulation stretching ratio is more than 7 times, then polyvinyl alcohol resin film (polaroid) is had to become the situation of easily fracture.As the concrete grammar stretched, method suitable arbitrarily can be adopted.Such as, when adopting wet type pulling method, polyvinyl alcohol resin film is stretched as regulation multiplying power in process bath (stretch bath).As the solution of stretch bath, suitably can be used in the solvent of water or organic solvent (such as ethanol) etc., with the addition of the solution of the compound of various slaine, iodine, boron or zinc.
Representatively in washing step be, by carrying out in process bath (water washing bath) through the polyvinyl alcohol resin of above-mentioned various process is thin film dipped.By washing step, what can wash away polyvinyl alcohol resin film does not need residue.Water washing bath can be pure water, also can be the aqueous solution of iodide (such as potassium iodide, sodium iodide).The concentration of iodide aqueous solution is preferably 0.1 ~ 10 quality %.In the aqueous solution of iodide, also can add the auxiliary agent of zinc sulfate, zinc chloride etc.The temperature of water washing bath is preferably 10 ~ 60 DEG C, is more preferably 30 ~ 40 DEG C.What dip time was representative is 1 second ~ 1 minute.Washing step only can carry out 1 time, optionally also can carry out repeatedly.When implementing repeatedly, additive types contained in water washing bath used in each process or concentration suitably can be adjusted.Such as, washing step comprises: thin polymer film be impregnated in potassium iodide aqueous solution (0.1 ~ 10 quality %, 10 ~ 60 DEG C) operation of 1 second ~ 1 minute, and with the operation of pure water rinsing.
As drying process, the drying means (such as, natural drying, air-supply drying, heat drying) be applicable to arbitrarily can be adopted.Such as, when heat drying, what baking temperature was representative is 20 ~ 80 DEG C, and what drying time was representative is 1 ~ 10 minute.As previously discussed, then obtain polaroid.
In polarization plates of the present invention, though containing above-mentioned polaroid and polarizer protection film of the present invention, preferably there is adhesive layer between polarizer protection film and polaroid.
The layer that above-mentioned adhesive layer is preferably formed by polyvinyl alcohol tackifier.Polyvinyl alcohol tackifier contains polyvinyl alcohol resin and crosslinking chemical.
Above-mentioned polyvinyl alcohol resin is not particularly limited, can illustrate as: by the polyvinyl alcohol (PVA) of polyvinyl acetate (PVA) saponification gained, its derivant, and then there is the saponified of the multipolymer of the monomer of copolymerization with vinyl acetate; By the modified polyvinylalcohol of polyvinyl alcohol (PVA) through acetalation, urethane, etherificate, grafting, Phosphation etc.; Deng.As above-mentioned monomer, can illustrate as the unsaturated carboxylic acid of maleic acid (acid anhydride), fumaric acid, crotonic acid, itaconic acid, (methyl) acrylic acid etc. and ester class thereof; The alpha-olefin of ethene, propylene etc.; (methyl) allyl sulphonic acid (sodium), sodium sulfonate (monoalkyl malate), sodium disulfonate alkyl malate, N hydroxymethyl acrylamide, acrylamide alkyl sulfonic acid alkali salt, NVP, NVP derivant etc.These polyvinyl alcohol resins can only use a kind, also can and use two or more.
By the viewpoint of tackiness, the average degree of polymerization of above-mentioned polyvinyl alcohol resin is preferably 100 ~ 3000, is more preferably 500 ~ 3000, and mean saponification degree is preferably 85 ~ 100 % by mole, is more preferably 90 ~ 100 % by mole.
As above-mentioned polyvinyl alcohol resin, the polyvinyl alcohol resin with acetoacetyl can be used.The polyvinyl alcohol resin with acetoacetyl is the polyvinyl alcohol tackifier of the functional group with high response, from the view point of raising polarization plates permanance, preferably.
Polyvinyl alcohol resin containing acetoacetyl, can make polyvinyl alcohol resin and dicthenone known method carry out reacting and obtaining.Can illustrate as: polyvinyl alcohol resin is dispersed in the solvent of acetic acid etc., then adds the method for dicthenone wherein; Polyvinyl alcohol resin is dissolved in the solvent of dimethyl formamide Huo diox etc. in advance, then adds the method etc. of dicthenone wherein.Again, can illustrate as the method making polyvinyl alcohol (PVA) directly contact with dicthenone gas or aqueous dicthenone.
If have the acetoacetyl modified degree more than 0.1 % by mole of the polyvinyl alcohol resin of acetoacetyl, be then not particularly limited.When less than 0.1 % by mole, the water tolerance of adhesive layer is not enough and inappropriate.Acetoacetyl modified degree is preferably 0.1 ~ 40 % by mole, is more preferably 1 ~ 20 % by mole.If acetoacetyl modified degree is more than 40 % by mole, then tail off with the reflecting point of crosslinking chemical, and the raising effect of water tolerance is less.Acetoacetyl modified degree is by the value measured by NMR.
As above-mentioned crosslinking chemical, the crosslinking chemical used in polyvinyl alcohol tackifier can be used with no particular limitation.Crosslinking chemical can use at least to be had 2 and has the compound of reactive functional group with polyvinyl alcohol resin.Can illustrate as: ethylene diamine, triethylene amine, hexamethylene diamine etc. there is 2 alkylidenes and amino Alkylenediamine class (wherein, preferred hexamethylene diamine); The isocyanates of tolylene diisocyanate, hydrogenation tolylene diisocyanate, trimethylene propane tolylene diisocyanate addition product, triphenylmethane triisocyanate, di-2-ethylhexylphosphine oxide (4-phenylmethane triisocyanate), isophorone diisocyanate and their ketoxime block thing or phenol block thing etc.; The epoxies of ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, glycerine two (or three) glycidol ether, 1,6-hexanediol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, 2-glycidyl aniline, 2-glycidyl amine etc.; Single aldehydes of formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde etc.; Glyoxal, the twain-aldehyde compound of MDA, butanedial, glutaraldehyde, malealdehyde, o-phthalaldehyde(OPA) etc.; The amino-formaldehyde resins of the condensation product of methylol methylol melamine, alkylated methylol groups urea, alkylated methylol groups melamine, acetylguanamine, benzoguanamine and formaldehyde etc.; Moreover, the divalent metal of sodium, potassium, magnesium, calcium, aluminium, iron, nickel etc. or the salt of trivalent metal and oxide thereof; Deng.As crosslinking chemical, preferred sweet amine cross-linking agent, particularly preferably methylol melamine.
The use level of above-mentioned crosslinking chemical, relative to polyvinyl alcohol resin 100 weight portion, is preferably 0.1 ~ 35 weight portion, is more preferably 10 ~ 25 weight portions.On the other hand, when making permanance improve further, can relative to polyvinyl alcohol resin 100 weight portion, with more than the range fit crosslinking chemical below 30 weight portions, 46 weight portions.Especially when using the polyvinyl alcohol resin containing acetoacetyl, preferably use the crosslinking chemical more than 30 weight portions.By with more than the range fit crosslinking chemical below 30 weight portions, 46 weight portions, water tolerance can be made to improve.
Even, in above-mentioned polyvinyl alcohol tackifier, also can coordinate the coupling agent of silane coupling agent, titanium coupling agent etc. again, the stabilizing agent etc. of various bonding imparting agent, ultraviolet light absorber, antioxidant, heat-resisting stabilizing agent, stabilizer against hydrolysis etc.
In polarizer protection film of the present invention, in order to make tackiness improve, easy bonding process can be implemented in the face contacted with polaroid.As easy bonding process, can illustrate as the surface treatment of corona treatment, plasma treatment, low pressure UV process, saponification process etc.
In polarizer protection film of the present invention, in order to make tackiness improve, preferably form easy adhesive linkage (fixed bed) in the face contacted with polaroid.
As above-mentioned easy adhesive linkage, the silicone layer can illustrated as having reactive functional group.There is no particular restriction to have the material of the silicone layer of reactive functional group, but can illustrate as the alkoxyl silicone alkanols containing isocyanate group, containing amino alkoxyl silicone alkanols, the alkoxyl silicone alkanols containing sulfydryl, the alkoxyl silicone alkanols containing carboxyl, the alkoxyl silicone alkanols containing epoxy radicals, the alkoxyl silicone alkanols containing ethylene type unsaturated group, the alkoxyl silicone alkanols containing halogen radical, the alkoxyl silicone alkanols containing isocyanate group, wherein preferred amino silanol.Moreover, by adding for the titanium class catalyzer that makes above-mentioned silanol efficiency more preferably react or tin class catalyzer, then bonding force can be made to become firm.Again, also can above-mentioned have in the organosilicon of reactive functional group add other adjuvant.Specifically, the bonding imparting agent of terpene resin, phenolics, Terpene-phenolic resin, abietic resin, xylene resin etc. can be used further, the stabilizing agent etc. of ultraviolet light absorber, antioxidant, heat-resisting stabilizing agent etc.
The above-mentioned silicone layer with reactive functional group is undertaken being coated with by known technology, dry and formed.The thickness of silicone layer after the drying, is preferably 1 ~ 100nm, is more preferably 10 ~ 80nm.During coating, also useable solvents dilution has the organosilicon of reactive functional group.There is no particular restriction for diluting solvent, can illustrate as alcohols.There is no particular restriction for dilute concentration, but be preferably 1 ~ 5 % by weight, be more preferably 1 ~ 3 % by weight.
The formation of above-mentioned adhesive layer be either side by above-mentioned tackifier being applied to polarizer protection film or both sides, with the either side of polaroid or both sides on and carry out.After polarizer protection film and polaroid are fitted, implement drying process, form the adhesive layer formed by coating drying layer.It can be made to fit after formation adhesive layer.The laminating of polaroid and polarizer protection film is folded machine etc. by layer of rolls and carries out.Heat drying temperature, drying time coordinate the kind of tackifier and suitably determine.
The thickness of adhesive layer is the tackiness from the view point of polarizer protection film, if dried thickness is blocked up, not good, therefore is preferably 0.01 ~ 10 μm, is more preferably 0.03 ~ 5 μm.
Polarizer protection film, for the laminating of polaroid, can, on the two sides of polaroid, carry out bonding with the side of above-mentioned polarizer protection film.
Again, the laminating of the polarizer protection film of polaroid, can, at the one side of polaroid, carry out bonding with the side of above-mentioned polarizer protection film, at another single-sided lamination cellulosic resin film.
There is no particular restriction for above-mentioned cellulosic resin film, but from the view point of the transparency, tackiness, then preferred triacetyl cellulose.The thickness of cellulosic resin film is preferably 30 ~ 100 μm, is more preferably 40 ~ 80 μm.If Thickness Ratio 30 μm is thin, then film strength reduce and workability is poor, if thicker than 100 μm, then in permanance, the reduction of light transmission will become remarkable.
Polarization plates of the present invention also can have adhesive phase as outermost at least one party (sometimes also this polarization plates being called adhesion type polarizing plate).As particularly preferred form, in the side of the polaroid of not bonding above-mentioned polarizer protection film, the adhesive phase being used for bonding other structure material such as other optical thin film or liquid crystal cells etc. can be set.
There is no particular restriction to form the bonding agent of above-mentioned adhesive phase, suitably can select the bonding agent of such as polymkeric substance based on the polymkeric substance of acrylic polymers, silicone-based polymers, polyester, polyurethane, polyamide, polyethers, fluorine class or rubber-like etc.Particularly preferably use the optical transparence as acrylic adhesives superior, show the adhesion characteristic of suitable wettability and compendency and tackiness, and the bonding agent that weatherability and thermotolerance etc. are excellent.The acrylic adhesives particularly preferably formed by the acrylic polymers of carbon number 4 ~ 12.
Again, in addition to that mentioned above, by the foamed phenomenon prevented because moisture absorption causes or peeling, prevent the optical characteristics caused because of thermal expansion difference etc. from reducing or the viewpoint such as liquid crystal cells warpage, even high-quality and the formative of the liquid crystal indicator of excellent durability, be preferably the low and adhesive phase of superior for heat resistance of hydroscopicity.
In above-mentioned adhesive phase, also can containing the resene of such as natural goods or complex, especially cohesive gives the adjuvant added within the adhesive layer of filling agent that resin, glass fibre, beaded glass, metal powder, other inorganic powder etc. form or pigment, colorant, antioxidant etc.
In addition, also can be diffusible adhesive phase of display light etc. containing particulate.
The available appropriate ways of setting up of above-mentioned adhesive phase carries out.As its example, the method of stating can be exemplified below: in the solvent that independent thing or the potpourri of the appropriate solvent of toluene or ethyl acetate etc. are formed, make base polymer or its composition dissolves or dispersion, and modulate the binder solution of 10 ~ 40 about % by weight, it is directly attached in polarization plates or the mode of optical thin film with the suitable expansion mode of curtain coating mode or coating process etc.; Or more state as benchmark forms adhesive phase on distance piece, moved the mode etc. being attached to polarizer protection film face.
Adhesive phase can be made for the overlayer of the adhesive phase of different composition or kind and be located in the one or two sides of polarization plates.Again, when being located at two sides, the table back side of polarization plates also can be made to become the adhesive phase of different composition, kind and thickness etc.
The thickness of adhesive phase suitably can determine with the use of object or bonding force etc., is preferably 1 ~ 40 μm, is more preferably 5 ~ 30 μm, is particularly preferably 10 ~ 25 μm.If thinner than 1 μm, then permanance be deteriorated, again, if thick than 40 μm, then easily occur foam grade cause float and peel off, make bad order.
In order to improve the adhesiveness between above-mentioned polarizer protection film and above-mentioned adhesive phase, also can ask at this layer and fixed bed is set.
As above-mentioned fixed bed, preferably use by polyurethane, polyester, in the molecule containing the fixed bed selected in amino polymer class, particularly preferably contain amino polymer class in the molecule.Containing the reaction of amino polymer class due to the amino display in molecule and the carboxyl in bonding agent or the polar group in electric conductive polymer in molecule, or, the interaction of ionic interaction etc., therefore good adhesiveness can be guaranteed.
As in the molecule containing amino polymer class, can illustrate as the polymkeric substance etc. of the emulsion stability of polyethyleneimine, PAH, polyvinylamine, polyvinylpyridine, polyvinylpyrrolidone, the dimethylamino ethyl acrylate that represents with the copolymerization monomer of above-mentioned acrylic adhesives etc.
In order to give antistatic behaviour at above-mentioned fixed bed, also antistatic agent can be added.As the antistatic agent for giving antistatic behaviour, can illustrate as the conducting polymer class of ionic surfactant, polyaniline, polythiophene, polypyrrole, polyquinoxaline etc.; The metal oxide-type etc. of tin oxide, antimony oxide, indium oxide etc., especially from the view point of during optical characteristics, outward appearance, antistatic effect and antistatic effect hot and humidification time stability, preferably use electric conductive polymer class.Wherein, particularly preferably use the water-soluble conducting polymkeric substance of polyaniline, polythiophene etc., or aqueous-dispersible conductive polymkeric substance.This is because when using water-soluble conducting polymkeric substance or aqueous-dispersible conductive polymkeric substance forms material as antistatic layer, in painting process, the optical thin film substrate deterioration that organic solvent causes can be suppressed.
Even; in the present invention; in each layer of the polaroid or polarizer protection film etc. or adhesive phase etc. of above-mentioned formation polarization plates; can utilize and such as use the ultraviolet light absorber such as salicylate compounds or phenol (benzophenol) compounds, benzotriazole compound or acrylic acid cyano group ester type compound, nickel coordination compound compounds to carry out the modes such as the mode processed, make it that there is ultraviolet absorption ability etc.
Polarization plates of the present invention can be located at liquid crystal cells depending on recognize side, backlight side arbitrary one-sided, also can be located at both sides, and indefinite.
Secondly, be described for image display device of the present invention, image display device of the present invention contains at least a slice polarization plates of the present invention.Be described for liquid crystal indicator at this, but all display device that the present invention is applicable to needs polarization plates are self-evident.As the concrete example of polarization plates of the present invention image display device applicatory, can illustrate as electroluminescence EL display, plasma display (PD), field-emitter display (FED; Field Emission Display) as self-luminous display device.Fig. 2 is the summary section of the liquid crystal indicator of the preferred example of the present invention.Be described for transmissive liquid crystal display device by icon example, but the present invention is also applicable to reflection-type liquid-crystal display device etc. certainly.
Liquid crystal indicator 100 possesses: liquid crystal cells 10; Clamp the phase-contrast film 20,20 ' of liquid crystal cells 10 and configuration; Be configured in the polarization plates 30,30 ' in phase-contrast film 20,20 ' outside; Light guide plate 40; Light source 50; With reverberator 60.It is mutually orthogonal that polarization plates 30,30 ' is configured to its polarizing axis.Liquid crystal cells 10 has a pair glass substrate 11,11 ' and the liquid crystal layer 12 as display medium that is configured between this substrate.On the substrate 11 of side, be provided with the on-off element (representative is TFT) of the electro-optic properties controlling liquid crystal and give the sweep trace of gate signal to this on-off element and give the signal wire (all non-icon) of source signal.On the glass substrate 11 ' of opposite side, be provided with the color layer and light shield layer (black matrix layer) (all not shown) that form color filter.The interval (cell gap) of substrate 11,11 ' is controlled by distance piece 13.In liquid crystal indicator of the present invention, as at least one of polarization plates 30,30 ', adopt the polarization plates of the present invention of above-mentioned record.
Such as when TN mode, this liquid crystal indicator 100 is when without applying voltage, and the liquid crystal molecule of liquid crystal layer 12 carries out assortment to make the state of polarizing axis skew 90 degree.In this state, only penetrated the incident light of single direction by polarization plates, will be turned round by liquid crystal molecule and turn 90 degrees.As above-mentioned, due to polarization plates, to be configured to its polarizing axis mutually orthogonal, therefore the light (polarized light) arriving opposite side polarization plates will penetrate this polarization plates.Thus when without applying voltage, liquid crystal indicator 100 carries out white display (normal white mode).On the other hand, if apply voltage at this liquid crystal indicator 100, then the liquid crystal molecule assortment in liquid crystal layer 12 will change.As a result, the light (polarized light) arriving opposite side polarization plates cannot penetrate this polarization plates, and become black display.The switching of this display is by using active component to carry out for each pixel, and forms image.
(embodiment)
Below, illustrate the present invention by embodiment, but the present invention is not limited to these embodiments.Again, when without special instruction, the part in embodiment and number percent are weight basis.
< matter average molecular weight >
The Shodex GPC system-21H using Showa electrician (stock) to make, measures by polystyrene conversion.
<Tg (glass transition temperature, sometimes also referred to as TG) >
Polymkeric substance is temporarily dissolved in tetrahydrofuran, drop into excessive hexane or toluene and precipitate again, to filter carrying out and the sediment taken out carries out drying under reduced pressure (1mmHg (1.33hPa), more than 3 hours), remove volatile ingredient thus, resin for gained uses DSC device (Rigaku (stock) makes, DSC8230) to measure.
< dealcoholization rate (lactonic ring rate) >
When dealcoholization rate is dealcoholysis during the polymkeric substance obtained by polymerization using whole hydroxyl as methyl alcohol forms, caused weight reduction is benchmark, in dynamic TG measures, start 150 DEG C before reducing by weight and rise and start to polymkeric substance the weight minimizing that the dealcoholization of 300 DEG C before decomposing causes and tried to achieve.
That is, in the dynamic TG of the polymkeric substance with lactonic ring structure measures, carry out the measurement of the weight reduction rates between 150 DEG C to 300 DEG C, the actual measurement weight reduction rates of gained is set to (X).On the other hand, forming by this polymkeric substance, the formation and supposing participating in lactonic rings because of all hydroxyls contained in this polymkeric substance composition become alcohol and dealcoholysis time theoretical weight slip (that is, this composition supposes generation 100% dealcoholization and calculate weight reduction rates) be set to (Y).Again, theoretical weight slip (Y), more specifically, can by the mol ratio of the starting monomer of the structure (hydroxyl) of the dealcoholization had in participation polymkeric substance, that is, the containing ratio of the above-mentioned raw materials monomer in being made up of this polymkeric substance is calculated.These values (X, Y) substituted into following dealcoholysis calculating formula and tries to achieve this value, if represent with %, then obtaining dealcoholization rate (lactonic ring rate).
1-(actual measurement weight reduction rates (X)/theoretical weight slip (Y))
< melt flow rate >
Melt flow rate is according to JIS-K6874, measures with test temperature 240 DEG C, load 10kg.
< makes test > again
The one side of polarization plates is implemented bonding processing, is pasted to glass plate and is made test specimen.By an angle diagonal, peel off to 90 degree of directions with the speed of 1mm/sec, carry out the confirmation of peeling off position.Judge to carry out as follows.
Zero: the stripping of the interface of bonding agent and glass plate
×: the stripping of the interface of polarizer protection film and polaroid
< flex test >
The polarization plates of gained is bent up and down to bend footpath 3mm, confirms with or without stripping.Judge to carry out as follows.
Zero: the interface of polarizer protection film and polaroid is without stripping
×: there is stripping the interface of polarizer protection film and polaroid
[Production Example 1: the manufacture of polaroid]
The polyvinyl alcohol film of thickness 80 μm is dyeed in the iodine aqueous solution of 5 % by weight (weight ratios: iodine/potassium iodide=1/10).Secondly, impregnated in the aqueous solution containing 3 % by weight boric acid and 2 % by weight potassium iodides, and then carry out being stretched to 6.0 times in the aqueous solution containing 4 % by weight boric acid and 3 % by weight potassium iodides after, impregnated in the potassium iodide aqueous solution of 5 % by weight.Thereafter, at the oven drying 3 minutes of 40 DEG C, the polaroid of thickness 30 μm is obtained.
[Production Example 2: the manufacture of the acrylic resin containing lactonic ring]
Possessing stirring apparatus, temperature inductor, cooling tube, in the 30L reactor of nitrogen ingress pipe, add the methyl methacrylate (MMA) of 8000g, 2-(methylol) methyl acrylate (MHMA) of 2000g, the toluene of 10000g, to its circulation nitrogen be warming up to 105 DEG C, after backflow, adding the different n-nonanoic acid tert-pentyl ester of 10.0g peroxidating (the lucky rich system of Atofina as initiating agent, trade name: Lupasol 570) while, while last the solution dripping for 4 hours and be made up of the initiating agent of 20.0g and the toluene of 100g, (about 105 ~ 110 DEG C) carry out solution polymerization under reflux on one side, last 4 hours again and carry out slaking.
In the polymer solution of gained, add the two octadecane ester admixture of 10g phosphoric acid octadecane ester/phosphoric acid (Sakai chemistry system, trade name: PhoslexA-18), (about 90 ~ 110 DEG C) carry out cyclized condensation reaction 5 hours under reflux.Secondly, by the polymer solution of gained in above-mentioned cyclized condensation reaction, the processing speed of 2.0kg/ hour is scaled with amount of resin, import the vented twin-screw extruder (Φ=29.75mm at bowl temperature 260 DEG C, revolution 100rpm, degree of decompression 13.3 ~ 400hPa (10 ~ 300mmHg), final vacuum pipe number 1, front exhaust pipe number 4, L/D=30) in, in this extruder, carrying out cyclized condensation reaction and devolatilization, obtaining the transparent acrylic resin particle containing lactonic ring by extruding.
The lactonic ring rate of the acrylic resin particle containing lactonic ring is 97.0%, and matter average molecular weight is 147700, and melt flow rate is 11.0g/10 minute, Tg (glass transition temperature) is 130 DEG C.
[Production Example 3: the modulation of polyvinyl alcohol tackifier aqueous solution]
By relative to through acetoacetyl modified polyvinyl alcohol resin 100 weight portion (the acetylating degree 13%) aqueous solution containing methylol melamine 20 weight portion, be modulated to the polyvinyl alcohol tackifier aqueous solution being adjusted to concentration 0.5 % by weight.
[embodiment 1]
The acrylic resin (lactonic ring rate is 20%) containing lactonic ring of above-mentioned gained is supplied to extruder, after melting is mixed at 250 DEG C, is extruded by T die head, carry out water-cooled with chill roll and take out, obtain the film of thickness 100 μm.After this, utilize successively biaxial extruder to be longitudinally stretched to 1.8 times (heating-up temperatures 140 DEG C), then cross directional stretch to 2.4 times (heating-up temperature 140 DEG C), obtains the biaxially oriented film of thickness 30 μm.
In the biaxially oriented film one side of gained, use line rod coating methylene chloride, at room temperature make it air-dry.
Then, relative to silane coupling agent (Dong Lidao Co., Ltd. system, trade name: APZ-6661) 100 parts, add isopropyl alcohol 66.7 parts, be modulated into solution thus, utilized by this solution line rod #5 to be coated with, drying 2 minutes at 90 DEG C.The thickness of the fixed bed after evaporation is 50nm.
The polyvinyl alcohol tackifier aqueous solution of above-mentioned gained is flowed into supreme stating between the fixed bed side of film and polaroid, and crimps simultaneously, drying 10 minutes at 70 DEG C, and make polarization plates (1).
The recasting test of polarization plates (1) and the result of flex test are shown in table 1.
[embodiment 2]
Except using ethyl acetate to replace except methylene chloride, all the other carry out similarly to Example 1, make polarization plates (2).
The recasting test of polarization plates (2) and the result of flex test are shown in table 1.
[embodiment 3]
Except using MEK to replace except methylene chloride, all the other carry out similarly to Example 1, make polarization plates (3).
The recasting test of polarization plates (3) and the result of flex test are shown in table 1.
[embodiment 4]
Except using methyl isobutyl ketone to replace except methylene chloride, all the other carry out similarly to Example 1, make polarization plates (4).
The recasting test of polarization plates (4) and the result of flex test are shown in table 1.
[comparative example 1]
Except replacing being coated with methylene chloride on the biaxially oriented film of gained, and with discharge capacity 133wmin/m
2implement beyond corona treatment, all the other carry out similarly to Example 1, make polarization plates (C1).
The recasting test of polarization plates (C1) and the result of flex test are shown in table 1.
[table 1]
| Polarization plates | Recasting test | Flex test | |
| Embodiment 1 | (1) | ○ | ○ |
| Embodiment 2 | (2) | ○ | ○ |
| Embodiment 3 | (3) | ○ | ○ |
| Embodiment 4 | (4) | ○ | ○ |
| Comparative example 1 | (C1) | × | × |
As shown in the result of embodiment 1 ~ 4; by processing containing the one side of (methyl) acrylic resin as the film of major component with specific solvent; the polarizer protection film superior with the tackiness of polarisation then can be provided; in the polarization plates containing this polarizer protection film and polaroid; the tackiness of polarizer protection film and polaroid is superior, known for being very difficult to stripping.
(utilizability in industry)
Polarizer protection film of the present invention is applicable to various image display device (liquid crystal indicator, organic EL display, PDP etc.).
Claims (3)
1. a polarization plates, it can make the one side side of the solvent of this films swell or dissolving have polaroid in being coated with of following polarizer protection film,
Between described polarizer protection film and polaroid, there is adhesive layer,
Described adhesive layer is the layer formed by polyvinyl alcohol tackifier,
Described polarizer protection film is containing the one side of (methyl) acrylic resin as the film of major component with the lactonic ring structure shown in general formula (1); coating can make the solvent of this films swell or dissolving; in the structure of described (methyl) acrylic resin with the lactonic ring structure shown in general formula (1); this lactonic ring structure containing proportional be 5 ~ 90 % by weight
In general formula (1), R
1represent hydrogen atom, R
2represent methyl, R
3represent methyl.
2. polarization plates according to claim 1, wherein,
There is adhesive phase further as outermost at least one party.
3. an image display device, it is at least containing the polarization plates described in 1 claim 1 or 2.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005333583A JP4849665B2 (en) | 2005-11-18 | 2005-11-18 | Polarizer protective film, polarizing plate, and image display device |
| JP2005-333583 | 2005-11-18 | ||
| CNA2006800425240A CN101310200A (en) | 2005-11-18 | 2006-11-09 | Polarizer protection film, polarizing plate and image display |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800425240A Division CN101310200A (en) | 2005-11-18 | 2006-11-09 | Polarizer protection film, polarizing plate and image display |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102707364A CN102707364A (en) | 2012-10-03 |
| CN102707364B true CN102707364B (en) | 2015-07-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210189646.XA Active CN102707364B (en) | 2005-11-18 | 2006-11-09 | Polarizing plate and image display |
| CNA2006800425240A Pending CN101310200A (en) | 2005-11-18 | 2006-11-09 | Polarizer protection film, polarizing plate and image display |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800425240A Pending CN101310200A (en) | 2005-11-18 | 2006-11-09 | Polarizer protection film, polarizing plate and image display |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP4849665B2 (en) |
| KR (1) | KR100973454B1 (en) |
| CN (2) | CN102707364B (en) |
| TW (1) | TW200736678A (en) |
| WO (1) | WO2007058115A1 (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009042457A (en) * | 2007-08-08 | 2009-02-26 | Nitto Denko Corp | Polarizing plate, method for producing the same, optical film, and image display apparatus |
| JP2009098653A (en) | 2007-09-27 | 2009-05-07 | Nitto Denko Corp | Polarizing plate, optical film and image display device |
| JP5204608B2 (en) * | 2007-10-10 | 2013-06-05 | 日東電工株式会社 | Polarizing plate, optical film and image display device |
| JP5231157B2 (en) * | 2007-10-22 | 2013-07-10 | 日東電工株式会社 | Polarizing plate, manufacturing method thereof, optical film, and image display device |
| WO2009054376A1 (en) * | 2007-10-24 | 2009-04-30 | Nitto Denko Corporation | Polarizing plate, optical film and image display device |
| JP5204616B2 (en) * | 2007-10-24 | 2013-06-05 | 日東電工株式会社 | Polarizing plate, optical film and image display device |
| JP5204629B2 (en) * | 2007-11-29 | 2013-06-05 | 日東電工株式会社 | Polarizing plate, optical film and image display device |
| JP5231181B2 (en) | 2007-11-30 | 2013-07-10 | 日東電工株式会社 | Polarizing plate, manufacturing method thereof, optical film, and image display device |
| JP5588626B2 (en) | 2008-08-04 | 2014-09-10 | 富士フイルム株式会社 | Optical film, polarizing plate, optical compensation film, antireflection film, and liquid crystal display device |
| KR101243714B1 (en) * | 2009-02-12 | 2013-03-13 | 주식회사 엘지화학 | A Method for Treatment of Protective Film of Polarizing Plate and A Method for Preparing Polarizing Plate |
| CN102325852B (en) | 2009-02-20 | 2014-03-26 | Lg化学株式会社 | Modified polyvinyl alcohol resins and adhesive, polarizer, and display device containing same |
| TWI592452B (en) | 2011-08-25 | 2017-07-21 | 東洋油墨Ｓｃ控股股份有限公司 | Photopolimerabe composition and photopolimerable coating agent and fuel cell stack and polarizer |
| JP6342791B2 (en) | 2013-12-27 | 2018-06-13 | 住友化学株式会社 | Protective film for polarizing plate and polarizing plate using the same |
| JP2016021034A (en) * | 2014-04-08 | 2016-02-04 | 株式会社巴川製紙所 | Protective film, film laminate, and polarizing plate |
| KR20160093885A (en) * | 2015-01-30 | 2016-08-09 | 동우 화인켐 주식회사 | Polarizing plate and image display device comprising the same |
| JP6201025B1 (en) * | 2016-10-14 | 2017-09-20 | 住友化学株式会社 | Polarizer, polarizing plate and image display device |
| KR102027568B1 (en) * | 2017-02-01 | 2019-11-14 | 삼성에스디아이 주식회사 | Polarizing plate, method for preparing polarizing plate and optical display apparatus comprising the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1399148A (en) * | 2001-07-19 | 2003-02-26 | 日东电工株式会社 | Polaroid and its prepn, protecting film, optical diaphragm and visual display |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09272169A (en) * | 1996-04-04 | 1997-10-21 | Nippon Synthetic Chem Ind Co Ltd:The | Optical laminated body |
| JP4158498B2 (en) * | 2002-11-20 | 2008-10-01 | 東レ株式会社 | Copolymer and process for producing the same |
| JP2005070744A (en) * | 2003-08-05 | 2005-03-17 | Konica Minolta Opto Inc | Optical film, method for manufacturing optical film, polarizing plate, and display apparatus |
-
2005
- 2005-11-18 JP JP2005333583A patent/JP4849665B2/en active Active
-
2006
- 2006-11-09 CN CN201210189646.XA patent/CN102707364B/en active Active
- 2006-11-09 KR KR1020087010201A patent/KR100973454B1/en active IP Right Grant
- 2006-11-09 CN CNA2006800425240A patent/CN101310200A/en active Pending
- 2006-11-09 WO PCT/JP2006/322376 patent/WO2007058115A1/en active Application Filing
- 2006-11-16 TW TW095142389A patent/TW200736678A/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1399148A (en) * | 2001-07-19 | 2003-02-26 | 日东电工株式会社 | Polaroid and its prepn, protecting film, optical diaphragm and visual display |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200736678A (en) | 2007-10-01 |
| KR20080066732A (en) | 2008-07-16 |
| KR100973454B1 (en) | 2010-08-02 |
| JP2007140092A (en) | 2007-06-07 |
| JP4849665B2 (en) | 2012-01-11 |
| CN101310200A (en) | 2008-11-19 |
| WO2007058115A1 (en) | 2007-05-24 |
| CN102707364A (en) | 2012-10-03 |
| TWI327651B (en) | 2010-07-21 |
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