CN1375391A - Method for stretching polymer film, polarization diaphragm and method for making said polarization diaphragm, polarizer, double refraction diaphragm and liquid-crystal display device - Google Patents
Method for stretching polymer film, polarization diaphragm and method for making said polarization diaphragm, polarizer, double refraction diaphragm and liquid-crystal display device Download PDFInfo
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- CN1375391A CN1375391A CN 01136622 CN01136622A CN1375391A CN 1375391 A CN1375391 A CN 1375391A CN 01136622 CN01136622 CN 01136622 CN 01136622 A CN01136622 A CN 01136622A CN 1375391 A CN1375391 A CN 1375391A
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Images
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- Polarising Elements (AREA)
Abstract
A method for stretching an optical polymer film is described, which comprises allowing a locus L1 of the holding means from a substantial holding Initiation point to a substantial holding release point on one edge of the polymer film, a locus L2 of the holding means from a substantial holding initiation point to a substantial holding release point on the other edge of the polymer film, and a distance W between the two substantial holding release points to satisfy the following equation(1), maintaining the supporting property of the polymer film, stretching the film in the presence of a state in which the volatile content is 5% or more, and then, decreasing the volatile content while shrinking the film: |L2-L1|>0.4W (1).
Description
Invention field
The present invention relates to be orientated the method for optic polymer film by oblique stretching, manufacturing has the method for high yield polarizing coating, polarizing coating, polarizer, the birefringent film of the optic polymer film that use makes according to said method, and the liquid crystal indicator that uses described polarizer.
Background of invention
Along with the development of liquid crystal indicator (hereinafter referred to as LCD), the demand of polarizer is increasing.In polarizer, usually by a side or a bilateral superimposed layer diaphragm or a plurality of diaphragm of adhesive phase at polarization layer with polarizability.
The raw material of polarization layer mainly uses polyvinyl alcohol (PVA) (hereinafter referred to as PVA).The PVA film with the dyeing of iodine or dichroic dye, perhaps stretches after dyeing behind uniaxial tension again, carries out crosslinkedly then with boron compound, is formed for the polarizing coating of polarization layer thus.
For diaphragm, mainly use cellulose triacetate because its be optical transparence and also have a low birefringence.Generally, film all is a uniaxial tension, so that the absorption axes of polarizing coating almost is parallel in the vertical.
In the LCD of routine, the transmission axle of polarizer is arranged to longitudinal direction or horizontal direction inclination 45 degree with image.Therefore, in the stamping method of making the polarizer volume, longitudinal direction inclination 45 degree of stamping direction and polarizer volume carry out stamping thus.
But carrying out stamping in the miter angle direction can produce unsettled part near the end at volume.Particularly, large-sized polarizer has low yield value.And behind lamination, for polarizer, being difficult to reclaim its raw material, this has produced the problem that waste increases again.
Birefringent film is that they are sticked on the polarizer that is used to form LCD etc. in use, is used for optical compensation, as prevents painted and enlarge visible angle, and need set the axis of orientation of birefringent film in all angles of polarizer transmission axle.Generally, by the system that the film of the vertical or horizontal uniaxial tension of punching press cuts described film, its working method is: the axis of orientation of film and the specific angle of the edge tilt of film, but similar with polarizer still produce the problem of lower yield value.
For addressing this problem, certain methods has been proposed, wherein the axis of orientation of polymer film and the film shift direction desirable angle that tilts.JP-A-2000-9912 discloses in the right side of draw direction and left side with different mutually speed vertically or the cross directional stretch plastic foil, the described film of uniaxial tension on the horizontal or longitudinal direction different with above-mentioned draw direction makes the axis of orientation of film and above-mentioned uniaxial tension direction tilt thus simultaneously.But,, when for example using the expander system, need between the right side of draw direction and left side, produce different transporting velocities according to this method.Consequently produce the pleat that uneven pulling stress causes, and cause the local inhomogeneous of gauffer and thickness thus, make to be difficult to obtain desirable pitch angle (being 45 degree in the polarizer).When the speed difference that on purpose reduces between the right side and the left side, draw stage must prolong, and causes cost to increase greatly.
In addition, JP-A-3-182701 discloses a kind of method that is used to make film, the tensile axis of this film becomes arbitrarily angled θ with the moving direction of film, this method comprises with many bite that becomes the θ angle with the moving direction of the film right side and the continuous film of left hand edge clamping at film, then when film moves by each to the direction stretched film of bite with the θ angle.But this method also causes the generation of pleat and gauffer in film, and this is because film is right different with the translational speed in left side.For alleviating this problem, must prolong stretching time, increased equipment cost greatly.
Moreover, JP-A-2-113920 has proposed a kind of method of direction stretched film of intersecting at the longitudinal direction with film, it comprises moving film, arrange between the chuck that moves in the expander track two simultaneously and clamp described film, the following setting of described expander: the displacement of chuck is different mutually in the specific movable part on the film both sides.But this method also is disadvantageous for making blooming, because produce pleat and gauffer when crisscross stretched film.
Disclosure of the Invention
An object of the present invention is to provide the method that is stretched across polymer film, it can improve the yield value during stamping polarizer or the birefringent film.
Another object of the present invention provides the polarizer or the birefringent film of efficient cheapness, and it comprises the polymer film that is stretched across that makes by said method.
The present invention provides the liquid crystal indicator that uses polarizer in another purpose.
For achieving the above object, the present inventor has carried out deep research and has found a kind ofly obtaining the method for crossed orientation by regulating volatile quantity in drawing process and the contraction process, and this method does not produce the local unevenness of pleat, gauffer and thickness.
That is to say that according to the present invention, it provides the method for stretching polymer film, has polarizing coating, polarizer, birefringent film and a liquid crystal indicator of following composition respectively.
(1), a kind of method of the optic polymer film that stretches, two edges of the polymer film that provides continuously wherein are provided by clamping device, apply tension force then thereon, clamping device is advanced along the longitudinal direction of film, this method comprises makes track (locus) L1, track L2 and distance W satisfy following equation (1), wherein track L1 is the track that clamping device is decontroled point by essence clamping starting point to essence clamping on an edge of polymer film, track L2 is the track that clamping device is decontroled point by essence clamping starting point to essence clamping on another edge of polymer film, and W is two distances between the essence clampings relieving point, the support character that keeps polymer film, the performance amount be 5% or higher state under the described film that stretches, when film shrinks, reduce volatile quantity then:
|L2-L1|＞0.4W (1)
(2), as above-mentioned (1) described drawing process, wherein L1, L2 and W satisfy following equation (2):
0.9W＜|L2-L1|＜1.1W
(3), as above-mentioned (1) or (2) described drawing process, wherein the difference of clamping device between the vertical pace on two edges of polymer film is lower than 1%.
(4), as one of above-mentioned (1)-(3) described drawing process, the angle that forms between the center line of polymer film when sending into next procedure after wherein polymer film center line of introducing during clamping and clamping are decontroled is in 3 degree.
(5), as one of above-mentioned (1)-(4) described drawing process, wherein the draw ratio of polymer film is 1.2-10.
(6), as one of above-mentioned (1)-(5) described drawing process, wherein polymer film volatile quantity be 7% or higher state under stretch.
(7), as one of above-mentioned (1)-(5) described drawing process, wherein polymer film volatile quantity be 10% or higher state under stretch.
(8), as one of above-mentioned (1)-(5) described drawing process, wherein polymer film volatile quantity be 10% or higher state under stretch with the draw ratio of 2-10, shrink 10% or more then, make direction of orientation and its longitudinal direction inclination 40-50 degree of polymer film thus.
(9), a kind of method of the optic polymer film that provides continuously of stretching, wherein clamping two edges of described film by clamping device when, apply tension force thereon, this method comprises:
(i) at least on its Width with the draw ratio of the 1.1-20.0 described film that stretches,
(ii) the difference between vertical pace of the clamping device on two edges of film is adjusted to 1% or lower,
The (iii) working direction of bending film under the state at two edges of clamping film makes angle at the essence draw direction inclination 20-70 degree of the working direction of the exit film of the step at two edges of clamping film and film, and
The support character that (iv) keeps polymer film, the performance amount be 5% or higher state under the described film that stretches, when film shrinks, reduce volatile quantity then.
(10), as one of above-mentioned (1)-(9) described drawing process, wherein said polymkeric substance is polyvinyl alcohol (PVA), acylated cellulose, polycarbonate or polysulfones.
(11), as one of above-mentioned (1)-(9) described drawing process, wherein said polymkeric substance is the vinyl alcohol based polyalcohol.
(12), a kind of method of making polarizing coating, it comprises according to one of above-mentioned (1)-(9) described method stretching vinyl alcohol based polyalcohol, and before stretching or the back absorption polarization element that stretches.
(13) polarizing coating that makes according to the method for above-mentioned (12), the wherein angle of the longitudinal direction of film and transmission axle direction inclination 20-70 degree.
(14) as above-mentioned (13) described polarizing coating, the angle of the longitudinal direction of film and transmission axle direction inclination 40-50 degree wherein.
(15) polarizer is wherein protected with hyaline membrane as at least one side of above-mentioned (13) or (14) described polarizing coating.
(16) as above-mentioned (15) described polarizer, wherein the retardance of the diaphragm at least one side at the 632.8nm place is 10nm or lower.
(17) a kind of liquid crystal indicator, wherein use as above-mentioned (16) described polarizer as in two polarizers that are arranged on the LCD panel both sides at least one.
(18) birefringent film that stretches and make according to the described method in one of above-mentioned (1)-(9), the wherein longitudinal direction of film and direction of orientation thereof the 20-70 degree that tilts mutually.
The accompanying drawing summary
Fig. 1 is the schematic plan view that shows an embodiment of the inventive method that is stretched across polymer film;
Fig. 2 is the schematic plan view that shows another embodiment of the inventive method that is stretched across polymer film;
Fig. 3 is the schematic plan view that shows another embodiment of the inventive method that is stretched across polymer film;
Fig. 4 is the schematic plan view that shows another embodiment of the inventive method that is stretched across polymer film;
Fig. 5 is the schematic plan view that shows another embodiment of the inventive method that is stretched across polymer film;
Fig. 6 is the schematic plan view that shows another embodiment of the inventive method that is stretched across polymer film;
Fig. 7 shows the schematic plan view that forms the method for conventional polarizer by punching press;
Fig. 8 shows the schematic plan view that forms the method for polarizer of the present invention by punching press; And
Fig. 9 is the schematic plan view of layer structure that shows the liquid crystal indicator of embodiment 5.
： （A）： （B） （a） （b） （c）A1： （：）B1： （） （）C1： （：）Cx： （：）Ay： （：）|L1-L2|：W：θ：11：12：13： （）14： （）15：16：17； 17 ＇: right and left side film clamping starting point 18; 18 ＇: by the relieving point 21 of right and left side film clamping device:the center line 22 of film on the introducing side:the center line 23 of film when sending into later step:the track 24 of film clamping device (left side): the track 25 of film clamping device (right side): the film 26 on the introducing side:the film 27 of sending into later step; 27 ＇: right and left side film clamping starting point 28; 28 ＇: by the relieving point 33 of right and left side film clamping device; 43; 53; 63:the track 34 of film clamping device (left side); 44; 54; 64:the track 35 of film clamping device (right side); 45; 55; 65:at the film 36 of introducing on the side; 46; 56; 66:the film 71 of sending into later step:absorption axes (tensile axis) 72:longitudinal direction 81:absorption axes (tensile axis) 82:longitudinal direction 91; 91 ＇: iodine type of polarization device (polarization layer) 92:lower polarizer 93:upper polarizer 94; 94 ＇: optical compensation films 95:anti-dazzle anti-reflection film 96:diaphragm (Fujitac) 97:liquid crystal board 98:bias light.
The detailed description of invention
Below will describe the present invention in detail.
Fig. 1 and Fig. 2 are respectively the typical case who shows the inventive method that is stretched across polymer film and implement The schematic plan view of example.
Drawing process of the present invention comprises: (a) introduce raw material according to the direction shown in the arrow (A) Film (b) along its width stretched film, and (c) is transferred to stretched film subsequently step In, that is to say along the direction shown in the arrow (B). " stretching step " is at this used term The institute of fingering row the present invention's drawing process comprises these steps (a)-(c) in steps.
Introduce continuously film according to the direction shown in the arrow (A), and shown in upstream side, in the left side At first clamp at a B1 place with clamping device. At this moment, another edge of film is not held, because of This does not have tension force at width. That is to say that some B1 is not corresponding to essence folder of the present invention Hold starting point.
In the present invention, essence clamping starting point is defined as, when two edges of film are at first clamped The point. Essence clamping starting point is with the clamping starting point A1 on the downstream and put these two points of C1 Expression, wherein for a C1 be, by A1 to the center line 11 (Fig. 1) or 21 of introducing film on the side (Fig. 2) draw the straight line of approximate vertical and track 13 (Fig. 1) or 23 (Fig. 2) of clamping device The point that intersects.
When the clamping device on two edges is carried with identical speed basically, open at these some places Begin, corresponding each chronomere of A1 move to A2, A3 ... An, and C1 moves to similarly C2, C3 ... Cn. That is to say that the draw direction of this moment uses the connection standard clamping device in phase The point An that passes through with the time and the line of Cn represent.
In the present invention, as illustrated in fig. 1 and 2, An postpones gradually with respect to Cn, makes Getting draw direction is begun to tilt by the direction perpendicular to throughput direction lentamente. Essence folder of the present invention Hold decontrol point be defined as the some Cx in downstream when film is decontroled in by clamping device and some Ay this two Individual point represents, wherein for an Ay is, by the center line 12 of Cx to the film that is delivered to later step (Fig. 1) or 22 (Fig. 2) draw the track 14 of clamping device on the straight line of approximate vertical and the opposition side (Fig. 1) or the point that intersects of 24 (Fig. 2).
The angle of the final draw direction of film is by essence terminal point (the essence clamping relieving of stretching step Point) locate between the right side and the left side clamping device displacement difference Ay-Ax (namely, | L1-L2 |) and the essence clamping decontrol the ratio of the distance W (distance between Cx and the Ay) between the point Determine. Therefore, by draw direction and be transferred to and form between the shift direction of later step Tiltangleθ satisfies following equation:
Tan θ=W/ (Ay-Ax), namely, Tan θ=W/|L1-L2|
Although the top edge of film is retained to 18 (Fig. 1) or the 28 (figure behind the Ay among Fig. 1 and 2 2), but other edges be not held. Therefore, do not have new stretching development at width, make Get 18 and 28 and be not equivalent to essence clamping relieving point of the present invention.
As mentioned above, in the present invention, essence clamping starting point is not on two edges of film Simple bite at right and left side clamping device. If more strictly describe above-mentioned definition, this Two bright essence clamping starting points are respectively to connect one of right and left bite and another bite Straight line intersecting with the center line of the angle at about right angle and the film of in the step of clamping film, introducing Point, and be defined as the point that is positioned at upstream.
Similarly, in the present invention, two essence clampings decontrol point be respectively the straight line that connects one of right and left bite and another bite with the angle at about right angle and the crosspoint of the center line of the film when sending into later step, and be defined as the point that is positioned at downstream
The center line that refers to film at this used term " about right angle " be connected right and left essence clamping rises The straight line institute angulation that point is decontroled in initial point or essence clamping is 90 ± 0.5 degree.
Make between right and the left clamping device at the stretching-machine that is similar to the present invention and uses the expander system Motion produces difference, between the bite of clamping device and the essence clamping starting point, perhaps by clamping It is owing to mechanical constraint such as rail sometimes that gap big between the point is decontroled in the point that device is decontroled and essence clamping Road length produces. But, as long as defined above essence clamping starting point and essence clamping relieving Track between the point satisfies the relation of equation (1), just can realize purpose of the present invention.
In the above description, the angle of inclination of axis of orientation can be according to right and left clamping in the gained stretched film Track difference between the device | the ratio between the exit width W of L1-L2| and step (c) is come Control and adjusting.
In polarizer and birefringent film, common with the film of miter angle orientation with respect to longitudinal direction Desirable. In the case, for obtaining the angle of orientation near 45 degree, preferred satisfied Following equation (2):
0.9W＜|L1-L2|＜1.1W (2)
More preferably satisfy following equation (3):
0.97W＜|L1-L2|＜1.03W (3)
The implementation of the structure of stretching step for example shown in Fig. 1-6, wherein is stretched across polymerization The thing film also satisfies equation (1), and these can design arbitrarily, as long as consider equipment cost and life Productive rate gets final product.
Direction (B) when the direction when film is sent into stretching step (A) is transferred to later step with film Formed angle can be the angle of any number. Comprise establishing of stretch front and the rear step that stretches from making The minimized angle of standby erection space sees that preferred above-mentioned angle is as much as possible little. This angle is preferred In 3 degree, and more preferably in 0.5 degree. For example, the structure shown in Fig. 1 and 4 can be real The existing angle of this numerical value.
At the moving direction of film as mentioned above basically in the constant method, only by increasing the clamping dress Distance between putting is difficult to obtain the angle of orientation with respect to longitudinal direction 45 degree, and this is at polarizer Be preferred in the birefringent film. | L1-L2| can be by carrying out after stretching as shown in Figure 1 Collapse step increases.
Draw ratio is preferably 1.1-10.0, and 2-10 more preferably. Shrinkage ratio is subsequently wished 10% or higher. In addition, also preferably carry out as shown in Figure 42 times or more times stretching and contraction, Because can increase | L1-L2|.
Moreover from the minimized angle of the equipment cost that makes stretching step, clamping device still less Crooked circle and littler angle of bend are preferred. Therefore, preferably, such as Fig. 2,3 and 5 Shown in, the bending when moving direction of film is held at two edges of film is so that at two of clamping film The moving direction of the step exit film at individual edge is with respect to the essence draw direction inclination 20-70 of film The angle of degree.
As among the present invention when two edges of clamping film the equipment of stretched film, the preferred use as figure Expander shown in one of 1-5. Except the plane expander of routine, as shown in Figure 6, also can Use the mobile stretching step that produces difference that makes spirally two clamping devices on the edge.
In the stretching-machine of expander type, be fixed with in many cases the chain edge of clip on it Orbital motion. Horizontal uneven pulling method such as the present invention makes this step entrance and exit place track Terminal point produce deviation, as illustrated in fig. 1 and 2, this causes film not to be held sometimes, and simultaneously Decontroled at right and left hand edge place film. In the case, actual path length L1 and L2 are also The distance between bite and the relieving point remarkablely, but as mentioned above, two ends of film That part of movement length when being held the device clamping.
If the right side and the displacement between the left hand edge at the exit of stretching step film are variant, Exit in stretching step produces gauffer and inhomogeneous thickness. It is therefore preferable that right and The film clamping device in left side is mutually identical basically aspect translational speed. On the translational speed Difference is preferably 1% or lower, more preferably less than 0.5%, and most preferably is lower than 0.05%. This used term " speed " refers to the length right and track that left clamping device per minute moves. In the stretching-machines of common expander type etc., the inhomogeneities of speed is the several seconds or lower, this Depend on cycle of sprocket of chain drive-belt and the frequency of CD-ROM drive motor, and often produce number Percentage point inhomogeneities. But the inhomogeneities of this speed is not equivalent to described in the present invention Speed difference.
Because the movement difference between right and the left clamping device produces gauffer and local inhomogeneous film Thick. For addressing this problem, the present invention includes following steps: keep the support character of polymer film, The performance amount be 5% or higher state under the described film that stretches, when film shrinks, reduce then Volatile quantity. Refer in sandwich institute at this used term " the support character that keeps polymer film " State film, but do not damage film character.
In addition, term " the performance amount be 5% or higher state under the described film that stretches " not complete Full representative volatile quantity in whole drawing process all remains 5% or higher, and refers to draw in part Extend through that volatile quantity can be lower than 5% in the journey, if 5% or the stretching during higher volatile quantity can realize Effect of the present invention. The method that comprises volatile materials in these modes comprises following methods: casting Film comprises volatile materials such as water and nonaqueous solvents thus; Before stretching, film is immersed in volatilization In property material such as water or the nonaqueous solvents, use the above-mentioned substance coated film, perhaps above-mentioned substance is sprayed at On the film; And during stretching with volatile materials such as water or nonaqueous solvents coated film. Hydrophily is poly-Therefore the film of compound such as polyvinyl alcohol comprises water in the environment of high temperature and high humility, in high humility Carry out moisture in the environment and regulate after-drawing, perhaps under high humidity, stretch, it can be wrapped Contain volatile materials. Except these methods, if can make the volatile quantity of polymer film be 5% or Higher, also can use any other means.
Preferred volatile quantity changes according to the kind of polymer film.The maximal value of volatile quantity can be an arbitrary value, is kept as long as the supportive mass-energy of polymer film is enough.Volatile quantity is preferably 10-100% for polyvinyl alcohol (PVA), and is preferably 10-200% for acylated cellulose.
Stretched film can be shunk during stretching or after stretching.The method that film is shunk comprises: remove volatile matter by the rising temperature.But,, also can use any other method as long as film is shunk.Dried volatile quantity is preferably 3% or lower, and more preferably 2% or lower, and most preferably be 1.5% or lower.
As mentioned above, the preferred embodiments of the invention are following drawing process, and it comprises:
(i) at least on its Width with the draw ratio of the 1.1-20.0 described film that stretches,
(ii) the difference between vertical pace of the clamping device on two edges of film is adjusted to 1% or lower,
The (iii) working direction of bending film under the state at two edges of clamping film makes angle at the essence draw direction inclination 20-70 degree of the working direction of the exit film of the step at two edges of clamping film and film, and
The support character that (iv) keeps polymer film, the performance amount be 5% or higher state under the described film that stretches, when film shrinks, reduce volatile quantity then.
The track that is used for limiting in the present invention the track of clamping device often need have big bending curvature.Concentrate for the phase mutual interference of avoiding the film clamping device or by the track stress that the bending of point causes, the track of preferred clamping device be the circular arc of bending.
There is not concrete restriction for polymer film to be stretched among the present invention.Can use the film that is dissolved in the suitable polymers in the volatile solvent.The example of this polymkeric substance comprises PVA, polycarbonate, acylated cellulose and polysulfones.
Though the thickness before stretching is not had concrete restriction, and from film clamping stability and stretching homogeneity, this thickness is preferably 1 μ m-1mm, and preferred especially 20 μ m-200 μ m.
Though stretched film of the present invention can be used for various uses, because axis of orientation and longitudinal direction tilt, it is suitable as polarizing coating or birefringent film.Particularly, wherein axis of orientation with respect to longitudinal direction inclination 40-50 degree, more preferably the polarizing coating of 44-46 degree is preferably used as the polarizer of LCD.
When using the present invention to make polarizing coating, preferably use PVA as polymkeric substance.The product that PVA normally obtains by the saponified polyvinyl acetic acid esters.But, its can comprise can with the composition of vinyl acetate copolymerization, as unsaturated carboxylic acid, unsaturated sulfonic acid, alkene and vinyl ether.The modified PVA that comprises acetoacetyl, sulfonic group, carboxyl and/or oxyalkylene group also is operable.
Though the saponification degree to PVA has no particular limits, from stable aspect, it is preferably 80-100mol%, and is preferably 90-100mol% especially.In addition, though the degree of polymerization of PVA is had no particular limits, be preferably 1000-10000, and be preferably 1500-5000 especially.
PVA obtains polarizing coating by dyeing, and this dyeing course can be undertaken by gas phase or liquid phase adsorption.When using iodine as the example of liquid phase adsorption, the PVA film is immersed in the aqueous solution of IKI.The amount of iodine is preferably 0.1-20g/l, and the amount of potassium iodide is preferably 1-100g/l water, and the weight ratio of iodine and potassium iodide is 1-100.Dyeing time is preferably 30-5000 second, and solution temperature is preferably 5-50 ℃.Can use any means as colouring method, not only can use immersion method, but also can use the method for coating or spraying iodine or dye solution.Staining procedure can carry out before stretching step of the present invention or afterwards.But, particularly preferably being, film is dyeing in liquid phase before the stretching step, because the suitable swelling of film makes to be easy to stretch.
Also preferably dye with dichroic dye and iodine.The object lesson of dichroic dye comprises dye composition, as azo group dyestuff, talan radical dye, pyrazoles woods quinoline ketone group dyestuff, triphenyl methane radical dye, quinolyl dyestuff, oxazines radical dye, thiazinyl dyestuff and anthraquinone-based dyes.Dyestuff is preferably water miscible, but is not limited only to these dyestuffs.In addition further preferably, in these dichroic dye molecules, introduce the water wettability substituting group, as sulfonic group, amino and hydroxyl.The object lesson of dichroic dye molecule comprises C.I.Direct Yellow 12, C.I.Direct Orange39, C.I.Direct Orange 72, C.I.Direct Red 39, C.I.Direct Red 79, C.I.Direct Red 81, C.I.Direct Red 83, C.I.Direct Red 89, C.I.Direct Violet48, C.I.Direct Blue 67, C.I.Direct Blue 90, C.I.Direct Green 59, with C.I.Acid Red 37, and further be included in the dyestuff of describing in the following document: JP-A-1-161202, JP-A-1-172906, JP-A-1-172907, JP-A-1-183602, JP-A-1-248105, JP-A-1-265205 and JP-A-7-261024.These dichroic molecules can free acid, the form of alkali metal salt, ammonium salt or amine salt is used.Polarizer with various tones can prepare by compound two or more above-mentioned dichroic molecules.The polarizer or the polarizer of the compound (dyestuff) of performance black when being included in place, right angle cross polarization axle perhaps comprise polarizer or the polarizer of various dichroic molecules with performance black, are being excellent especially aspect veneer transmission and the polarizability.
When making polarizing coating, preferably be used for the adjuvant of crosslinked PVA by stretching PVA.Particularly, of the present invention when being stretched across method when using, the not adequately hardened PVA film in the stretching step exit because the tension force that produces in this step, causes the direction of orientation deviation of PVA film.Therefore, film is preferably before stretching or be immersed in the crosslinking chemical in stretching step or with the crosslinking chemical coating, make thus to comprise crosslinking chemical in the film.As crosslinking chemical, can use the material of describing in the United States Patent (USP) of authorizing again for No. 232897, and boronic acid compounds most preferably.
Drawing process of the present invention also is preferred for making so-called polyvinyl polarizing coating, and wherein PVA dehydration or Polyvinylchloride dechlorination can form polyene structure thus, and obtains the polarization by the conjugated double bond generation.
The one or both sides adhering protective film of the polarizing coating that makes in the present invention, described polarizing coating can be used as polarizer thus.Kind for diaphragm has no particular limits.The example that can be used for the diaphragm among the present invention comprises cellulose esters, as cellulose acetate, cellulose butyrate and cellulose propionate, and polycarbonate, polyolefin, polystyrene and polyester.But when the hysteresis value of diaphragm equaled or exceeded particular value, the polarization axle of diaphragm and axis of orientation were intersected mutually and are departed from, and made linear polarization be changed to oval polarization unfriendly.Therefore, preferred low diaphragm hysteresis value.
For example, hysteresis value is preferably 10nm or lower at the 632.8nm place, and 5nm or lower more preferably.For obtaining so low hysteresis value, the polymkeric substance that especially preferably uses cellulose triacetate to use as diaphragm.In addition, also preferred polyolefin such as Zeonex and Zeonor (all be by Nippon Zeon Co., Ltd. makes) and the ARTON (making) of using by JSR Corp..Moreover, also can use the non-birefringent optical resin material of in JP-A-8-110402 or JP-A-11-293116, describing.
Have no particular limits for used bonding agent when sticking to protective seam on the polarizing coating.The example of bonding agent comprises the aqueous solution of PVA base resin (comprising the modified PVA that comprises acetoacetyl, sulfonic group, carboxyl and/or oxyalkylene group) and boron compound.In them, PVA base resin is preferred.The thickness of adhesive phase is preferably 0.01-10 μ m after drying, and preferred especially 0.05-5 μ m.
Fig. 7 has shown the example of a conventional polarizer of stamping, and Fig. 8 has then shown the example of stamping the present invention's polarizer.In conventional polarizer, as shown in Figure 7, the absorption axes 71 of polarization, promptly, tensile axis, with longitudinal direction 72 is consistent, and in polarizer of the present invention, as shown in Figure 8, the absorption axes 81 of polarization, promptly, tensile axis, with respect to longitudinal direction 82 45 degree that tilt.This angle be stacked in LCD in the absorption axes of polarizer on the liquid crystal board and the vertical or horizontal formed angle of liquid crystal board itself be consistent, this makes that need not to carry out crossed module in the stamping step dashes.In addition, as shown in Figure 8, polarizer of the present invention is straight cuts along the longitudinal direction, also can make by section along the longitudinal direction thus, and need not to carry out stamping.Therefore, polarizer of the present invention also is very excellent aspect throughput rate.
From increasing the angle of contrast of LCD degree, preferred polarizer of the present invention has higher transmissivity and the degree of polarization of Geng Gao.Transmissivity is preferably 30% or higher at the 550nm place, and more preferably 40% or higher.Degree of polarization is preferably 95.0% or higher at the 550nm place, and more preferably 99.0% or higher, and be preferably 99.9% or higher especially.
Stretched film according to the present invention has the feature with the longitudinal direction crossed orientation, therefore also is suitable as birefringent plate.When this film is used as birefringent plate, preferably by being stretching in the film that the very excellent material in transparent aspect makes, for example polycarbonate, polysulfones or acylated cellulose such as cellulose acetate.In the middle of them, preferred especially acylated cellulose.Though the thickness to film has no particular limits, be preferably 5-300 μ m usually.
Below with reference to embodiment the present invention is described in more detail, but the present invention is not limited in these embodiment.
Embodiment 1
Under 25 ℃, the PVA film is immersed in the aqueous solution of 5.0g/l iodine and 10.0g/l potassium iodide 90 seconds, further submergence 60 seconds again under 25 ℃ in the 10g/l boric acid aqueous solution then.Then this film is introduced in the drawing machine of expander type, this drawing machine has the form of Fig. 1, and the draw ratio with 7.0 stretches in the environment of 60 ℃ and 90%RH.Make film shrink 5.3 times then, and dry under 70 ℃, the width of film is remained unchanged.From expander, take out film.Before beginning stretching, the volatile quantity of PVA film is 31%, and is 1.5% after drying.
Translational speed difference between the right and left expander folder is 0.05%, and the formed angle of center line of film is 0 degree when introducing the center membrane line and sending into later step.At this, | L1-L2| is 0.7m, and W is 0.7m, and satisfies | the L1-L2|=W relation.Do not observe the local unevenness of gauffer and thickness in the exit of expander.
In addition, (PVA-117H is by Kuraray Co. to use the 3%PVA aqueous solution, Ltd. make) as bonding agent, (by Fuji Photo FilmCo., Ltd. makes with above-mentioned stretched film and through the Fujitac of saponification film, cellulose triacetate, hysteresis value are 3.0nm) be stacked in together.The laminate of gained is dry under 80 ℃, to obtain having the polarizer of 650mm effective width.The direction of the absorption axes of gained polarizer and the longitudinal direction of this polarizer inclination 45 degree.The transmissivity of this polarizer is 43.3% at the 550nm place, and its degree of polarization is 99.98%.
Then, as shown in Figure 8, this polarizer is cut into 310 * 233mm size.Consequently, the absorption axes of gained polarizer and side inclination 45 degree, its area efficiency is 91.5%.
Embodiment 2
Under 25 ℃, the PVA film is immersed in the aqueous solution of 2.0g/l iodine and 4.0g/l potassium iodide 240 seconds, further submergence 60 seconds again under 25 ℃ in the 10g/l boric acid aqueous solution then.Then this film is introduced in the drawing machine of expander type, this drawing machine has the form of Fig. 2, and stretches with 5.3 draw ratio.Expander bends to draw direction as shown in Figure 2.Dry under 80 ℃ then, the width of film is remained unchanged, film is shunk.From expander, take out film.Before beginning stretching, the volatile quantity of PVA film is 31%, and is 1.5% after drying.
Translational speed difference between the right and left expander folder is 0.05%, and the center line of introducing film formed angle of center line of film when sending into later step is 46 degree.At this, | L1-L2| is 0.7m, and W is 0.7m, and satisfies | the L1-L2|=W relation.At the center line 22 of the exit of expander essence draw direction Ax-Cx film when being delivered to later step 45 degree that tilt.Do not observe the local unevenness of gauffer and thickness in the exit of expander.
In addition, (PVA-117H is by Kuraray Co. to use the 3%PVA aqueous solution, Ltd. make) as bonding agent, (by Fuji Photo FilmCo., Ltd. makes with above-mentioned stretched film and through the Fujitac of saponification film, cellulose triacetate, hysteresis value are 3.0nm) be stacked in together.The laminate of gained is dry under 80 ℃, to obtain having the polarizer of 650mm effective width.
The direction of the absorption axes of gained polarizer and the longitudinal direction of this polarizer inclination 45 degree.The transmissivity of this polarizer is 43.7% at the 550nm place, and its degree of polarization is 99.97%.Then, as shown in Figure 8, this polarizer is cut into 310 * 233mm size.Consequently, the absorption axes of gained polarizer and side inclination 45 degree, its area efficiency is 91.5%.
Embodiment 3
Following solid constituent is dissolved in the mixed solvent of being made up of 92 weight portion methylene chloride and 8 weight portion methyl alcohol, with the preparation concentrated solution.
Cellulose triacetate: 89 weight portions
Triphenyl: 7.39 weight portions
Xenyl diphenyl phosphoester: 3.60 weight portions
Silicon dioxide: 0.01 weight portion
The solid concentration of concentrated solution is 18.2%.This concentrated solution casts in continuously to be with, and is dried to it and has self-supporting, peels off with form membrane then.
With volatile quantity is that this film of 32% is introduced in the expander of Fig. 3 form, stretches 20% then on its Width.As shown in Figure 3, with respect to the film incoming direction expander crooked 30 is spent.By being blown into 145 ℃ hot-air thereon, make this film drying then, and simultaneously its width is kept constant, then make its contraction.From expander, take out described film.Dry back volatile quantity is 0.5%.
Translational speed difference between the right and left expander folder is 0.05%, and the center line of introducing film formed angle of center line of film when sending into later step is 30 degree.At this, | L1-L2| is 0.29m, and W is 0.5m, and satisfies | the L1-L2|=0.58W relation.Do not observe the local unevenness of gauffer and thickness in the exit of expander, and the volatile quantity in exit is 8%.Essence draw direction in the expander exit is spent with respect to the center line inclination 60 of the film that is delivered to later step.This film further is dried to volatile quantity and is reduced to 1%.The hysteresis value of gained film is 23nm, and slow axis is with respect to longitudinal direction inclination 60 degree of film.
Embodiment 4
Under 25 ℃, the PVA film is immersed in the aqueous solution of 1.0g/l iodine and 60.0g/l potassium iodide 30 seconds, then in the aqueous solution of 40g/l boric acid and 30g/l potassium iodide in 25 ℃ of further submergences 120 seconds again.Then this film is introduced in the drawing machine of expander type, this drawing machine has the form of Fig. 4, and the draw ratio with 2 stretches in the environment of 60 ℃ and 90%RH.Expander bends to draw direction as shown in Figure 3, and repeats to shrink.Dry in 80 ℃ atmosphere then, from expander, take out film.Before beginning stretching, the volatile quantity of PVA film is 31%, and is 1.5% after drying.
Translational speed difference between the right and left expander folder is 0.05%, and the center line of introducing film formed angle of center line of film when sending into later step is 0 degree.At this, | L1-L2| is 0.7m, and W is 0.7m, and satisfies | the L1-L2|=W relation.At the center line of the exit of expander essence draw direction Ax-Cx film when being delivered to later step 45 degree that tilt.Do not observe the local unevenness of gauffer and thickness in the exit of expander.
In addition, (PVA-117H is by Kuraray Co. to use the 3%PVA aqueous solution, Ltd. make) as bonding agent, (by Fuji Photo FilmCo., Ltd. makes with above-mentioned stretched film and through the Fujitac of saponification film, cellulose triacetate, hysteresis value are 3.0nm) be stacked in together.The laminate of gained is dry under 80 ℃, to obtain having the polarizer of 650mm effective width.
The direction of the absorption axes of gained polarizer and the longitudinal direction of this polarizer inclination 45 degree.The transmissivity of this polarizer is 43.7% at the 550nm place, and its degree of polarization is 99.97%.Then, as shown in Figure 8, this polarizer is cut into 310 * 233mm size.Consequently, the absorption axes of gained polarizer and side inclination 45 degree, its area efficiency is 91.5%.
Embodiment 5
Under 25 ℃, the PVA film is immersed in the aqueous solution of 1.0g/l iodine and 60.0g/l potassium iodide 30 seconds, then in the aqueous solution of 40g/l boric acid and 30g/l potassium iodide in 25 ℃ of further submergences 120 seconds again, the PVA film being dried to volatile quantity subsequently is 2%.Then this film is introduced in the drawing machine of expander type, this drawing machine has the form of Fig. 2, and the draw ratio with 5.3 stretches in the environment of 60 ℃ and 90%RH.Expander bends to draw direction as shown in Figure 2.Desciccator diaphragm in 80 ℃ atmosphere makes the width of film remain unchanged simultaneously then, and film is shunk.From expander, take out film.During stretching in 60 ℃ and 90%RH atmosphere, the volatile quantity of PVA film is 19%, and is 1.0% after drying.
Translational speed difference between the right and left expander folder is 0.05%, and the center line of introducing film formed angle of center line of film when sending into later step is 46 degree.At this, | L1-L2| is 0.7m, and W is 0.7m, and satisfies | the L1-L2|=W relation.At the center line 22 of the exit of expander essence draw direction Ax-Cx film when being delivered to later step 45 degree that tilt.Do not observe the local unevenness of gauffer and thickness in the exit of expander.
In addition, (PVA-117H is by Kuraray Co. to use the 3%PVA aqueous solution, Ltd. make) as bonding agent, (by Fuji Photo FilmCo., Ltd. makes with above-mentioned stretched film and through the Fujitac of saponification film, cellulose triacetate, hysteresis value are 3.0nm) be stacked in-rise.The laminate of gained is dry under 80 ℃, to obtain having the polarizer of 650mm effective width.
The direction of the absorption axes of gained polarizer and the longitudinal direction of this polarizer inclination 45 degree.The transmissivity of this polarizer is 43.7% at the 550nm place, and its degree of polarization is 99.97%.Then, as shown in Figure 8, this polarizer is cut into 310 * 233mm size.Consequently, the absorption axes of gained polarizer and side inclination 45 degree, its area efficiency is 91.5%.Comparative Examples 1
Use commercially available iodine polarizer (HLC 2-5618, width: 650nm are made by SanritzCorporation) 1 polarizer as a comparison case.Cut this polarizer as shown in Figure 7, so that the absorption axes of spending with side inclination 45 to be provided, area efficiency is 64.7%.Comparative Examples 2
Under 25 ℃, the PVA film is immersed in the aqueous solution of 2.0g/l iodine and 4.0g/l potassium iodide 240 seconds, then in the 10g/l boric acid aqueous solution in 25 ℃ of further submergences 60 seconds again, according to the mode identical with embodiment 2, then 80 ℃ dry 10 minutes down.The volatile quantity of PVA film is 1%.Then desciccator diaphragm is introduced in the drawing machine of expander type, this drawing machine has the form of Fig. 2, and stretches with 5.3 draw ratio.Expander bends to draw direction as shown in Figure 2.Film is dry in 80 ℃ atmosphere then, and the width of film is remained unchanged.From expander, take out film.On whole film, there is gauffer, makes and to use this film as optical thin film.
Embodiment 6 makes optical compensation films
Water (130g) and 40g methyl alcohol being added among the PVA (MP-203, by Kuraray Co., Ltd. makes) of 30g straight chained alkyl modification, with its dissolving, is to filter in the polypropylene filter of 30 μ m by the aperture with under agitation then.Make the coating solution that is used for oriented layer thus.
The thick tri acetyl cellulose film of 100 μ m (by Fuji Photo Co., Ltd. make) that with excellent applicator with undercoat is dawn glued membrane (0.1 μ m) is with the above-mentioned coating solution coating that is used for oriented layer, then 60 ℃ of dryings down.With machine direction processings of swiping on the directions of 45 degree of tilting, be the oriented layer of 0.5 μ m with formation thickness.
1.6g had the compound L C-1 of following structure as liquid crystal discotic compound, 0.4g phenoxy group diethylene glycol acrylate (M-101, by Toagosei Chemical Industry Co., Ltd. make), 0.05g cellulose acetate-butyrate (CAB 531-1, make by Eastman ChemicalCo.) and the Photoepolymerizationinitiater initiater of 0.01g (Irugacure 907, make by Ciba SpecialtyChemicals Inc.) be dissolved in the 3.65g methyl ethyl ketone, gained solution is to filter in the polypropylene filter of 1 μ m by the aperture, is used for the solution of optical anisotropic layer with preparation.
With excellent applicator the above-mentioned coating solution that is used for optical anisotropic layer is coated in above-mentioned oriented layer, dry down at 120 ℃ then.Proceed to heat 3 minutes, so that liquid crystal aging makes discotic compound orientation thus.Use 160W air cool metal Halogen lamp LED (by EyeGraphics Co., Ltd. makes) to use 400mW/cm
2Ultraviolet ray irradiation overlay under the exposure intensity keeps 120 ℃, simultaneously so that irradiation energy is 300mJ/cm
2, the sclerosis overlay, forming thickness is the optical anisotropic layer of 1.8 μ m, prepares optical compensation films thus.
Then as shown in Figure 9, optical compensation films 94 ＇ are arranged on the side of two iodine polarizing coatings 91 making among the embodiment 2 and polarizing coating 91 ＇ among 91 ＇, then at its opposite side superimposed layer through the Fujitac of saponification film 96 (by Fuji Photo Film Co., Ltd. make, cellulose triacetate, hysteresis value: 3.0nm), to make polarizer 92.Optical compensation films 94 is arranged on the side of another polarizing coating 91, and commercially available anti-dazzle anti-reflection film (being made by SabritzCorporation) 95 is set on its opposite side, to make polarizer 93.At this moment, the stacked system of optical compensation films is, oriented layer to scrape wiping direction consistent with the draw direction of polarizing coating.
Use polarizer 92 as the polarizer on bias light 98 1 sides in two polarizers, between above-mentioned two polarizers, place liquid crystal board 97, and polarizer 93 is the polarizers that show on the side, they all are stacked on the optical anisotropic layer side of optical compensation films 94 and 94 ＇ by bonding agent and liquid crystal board 97, to make LCD.
The LCD that makes thus has excellent luminance, angle of visibility characteristic and visibility, even and under the condition of 40 ℃ and 30%RH, used 1 month, still do not have the sign of display quality deterioration.Measure the degree of polarization at transmissivity and 550nm place
Measure transmissivity with Shimazu recording spectrophotometer UV2100.In addition, the transmissivity of measuring when overlapped and absorption axes is consistent with each other at two polarizers is as H0 (%), and two polarizers are overlapped and the transmissivity measured during absorption axes crossing at right angle as H1 (%), then use following equation mensuration degree of polarization P (%):
P=((H0-H1)/(H0+H1))
1/2The measurement of * 100 hysteresis value
With Oji Keisoku Kiki Co., the KOBRA 21DH that Ltd. makes measures hysteresis value at the 632.8nm place.
Polarizing coating, polarizer and the birefringent film that the polymer film that is stretched across by drawing process according to the present invention makes has high yield value when the stamping step, and obtains easily.Therefore, their low cost of manufacture.Also can low-cost obtain having the liquid crystal indicator of excellent display quality simultaneously.
Though with reference to specific embodiment the present invention is described in detail, it will be apparent for a person skilled in the art that under situation without departing from the spirit and scope of the present invention and also can carry out various changes and improvements.
Claims (22)
1, a kind of method of the optic polymer film that stretches, two edges of the polymer film that provides continuously wherein are provided by clamping device, apply tension force then thereon, clamping device is advanced along the longitudinal direction of film, this method comprises makes track L1, track L2 and distance W satisfy following equation (1), wherein track L1 is the track that clamping device is decontroled point by essence clamping starting point to essence clamping on an edge of polymer film, track L2 is the track that clamping device is decontroled point by essence clamping starting point to essence clamping on another edge of polymer film, and W is two distances between the essence clampings relieving point, and the support character of maintenance polymer film, the performance amount be 5% or higher state under the described film that stretches, when film shrinks, reduce volatile quantity then:
|L2-L1|＞0.4W (1)
2, drawing process as claimed in claim, wherein L1, L2 and W satisfy following equation (2):
0.9W＜|L2-L1|＜1.1W
3, drawing process as claimed in claim 1, wherein the difference of clamping device between the vertical pace on two edges of polymer film is lower than 1%.
4, drawing process as claimed in claim 1, the angle that forms between the center line of polymer film when sending into next procedure after wherein polymer film center line of introducing during clamping and clamping are decontroled is in 3 degree.
5, drawing process as claimed in claim 1, wherein the draw ratio of polymer film is 1.2-10.
6, drawing process as claimed in claim 1, wherein polymer film volatile quantity be 7% or higher state under stretch.
7, drawing process as claimed in claim 1, wherein polymer film volatile quantity be 10% or higher state under stretch.
8, drawing process as claimed in claim 1, wherein polymer film volatile quantity be 10% or higher state under stretch with the draw ratio of 2-10, shrink 10% or more then, make direction of orientation and its longitudinal direction inclination 40-50 degree of polymer film thus.
9, a kind of method of the optic polymer film that provides continuously of stretching wherein applies tension force thereon clamping two edges of described film by clamping device when, and this method comprises:
(i) at least on its Width with the draw ratio of the 1.1-20.0 described film that stretches,
(ii) the difference between vertical pace of the clamping device on two edges of film is adjusted to 1% or lower,
The (iii) working direction of bending film under the state at two edges of clamping film makes angle at the essence draw direction inclination 20-70 degree of the working direction of the exit film of the step at two edges of clamping film and film, and
The support character that (iv) keeps polymer film, the performance amount be 5% or higher state under the described film that stretches, when film shrinks, reduce volatile quantity then.
10, drawing process as claimed in claim 1, wherein said polymkeric substance are polyvinyl alcohol (PVA), acylated cellulose, polycarbonate or polysulfones.
11, drawing process as claimed in claim 9, wherein said polymkeric substance are polyvinyl alcohol (PVA), acylated cellulose, polycarbonate or polysulfones.
12, the method for claim 1, wherein said polymkeric substance are the vinyl alcohol based polyalcohols.
13, method as claimed in claim 9, wherein said polymkeric substance are the vinyl alcohol based polyalcohols.
14, a kind of method of making polarizing coating, it comprises method stretching vinyl alcohol based polyalcohol according to claim 1, and absorbs the polarization element before stretching or after stretching.
15, a kind of method of making polarizing coating, it comprises method stretching vinyl alcohol based polyalcohol according to claim 9, and absorbs the polarization element before stretching or after stretching.
16, the polarizing coating that makes of method according to claim 14, the wherein angle of the longitudinal direction of film and transmission axle direction inclination 20-70 degree.
17, polarizing coating as claimed in claim 16, the wherein angle of the longitudinal direction of film and transmission axle direction inclination 40-50 degree.
18, a kind of polarizer, wherein at least one side of polarizing coating as claimed in claim 16 is protected with hyaline membrane.
19, polarizer as claimed in claim 18, wherein the retardance of the diaphragm at least one side at the 632.8nm place is 10nm or lower.
20, a kind of liquid crystal indicator wherein uses polarizer as claimed in claim 19 as in two polarizers that are arranged on the LCD panel both sides at least one.
21, method according to claim 1 stretches and the birefringent film that makes, wherein the longitudinal direction of film and direction of orientation thereof the 20-70 degree that tilts mutually.
22, method according to claim 9 stretches and the birefringent film that makes, wherein the longitudinal direction of film and direction of orientation thereof the 20-70 degree that tilts mutually.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP080744/2001 | 2001-03-21 | ||
| JP2001080744A JP2002086554A (en) | 2000-07-10 | 2001-03-21 | Method of orienting polymer film, method of manufacturing polarizing film, polarizing plate and phase difference film, and liquid crystal display device |
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| Publication Number | Publication Date |
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| CN1375391A true CN1375391A (en) | 2002-10-23 |
| CN1212918C CN1212918C (en) | 2005-08-03 |
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| CN 01136622 Expired - Lifetime CN1212918C (en) | 2001-03-21 | 2001-10-22 | Method for stretching polymer film, polarization diaphragm and method for making said polarization diaphragm, polarizer, double refraction diaphragm and liquid-crystal display device |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100360301C (en) * | 2002-11-27 | 2008-01-09 | 3M创新有限公司 | Methods and devices for processing polymer films |
| CN100369738C (en) * | 2002-11-27 | 2008-02-20 | 3M创新有限公司 | Methods and devices for stretching polymer films |
| CN102033258B (en) * | 2005-11-28 | 2013-02-06 | 日本瑞翁株式会社 | Process for producing long obliquely drawn film |
| CN102947735A (en) * | 2010-06-22 | 2013-02-27 | 住友化学株式会社 | Method for manufacturing polarizing film |
| CN103009615A (en) * | 2012-12-27 | 2013-04-03 | 曾立敏 | Equipment of bidirectional tension film |
| CN103442871A (en) * | 2011-03-29 | 2013-12-11 | 可乐丽股份有限公司 | Polyvinyl alcohol polymer film and process for producing same |
| CN104416898A (en) * | 2013-08-26 | 2015-03-18 | 谢书伟 | New drawing process for making broad width polaroid |
| CN117048031A (en) * | 2023-10-10 | 2023-11-14 | 龙华相位新材料(绵阳)股份有限公司 | Optical film stretching device and stretching method |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8305547B2 (en) | 2006-12-28 | 2012-11-06 | Nitto Denko Corporation | Method of manufacturing polarizer, polarizer, polarizing plate, optical film, method of manufacturing composite polarizing plate, composite polarizing plate and image display |
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2001
- 2001-10-22 CN CN 01136622 patent/CN1212918C/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100360301C (en) * | 2002-11-27 | 2008-01-09 | 3M创新有限公司 | Methods and devices for processing polymer films |
| CN100369738C (en) * | 2002-11-27 | 2008-02-20 | 3M创新有限公司 | Methods and devices for stretching polymer films |
| CN102033258B (en) * | 2005-11-28 | 2013-02-06 | 日本瑞翁株式会社 | Process for producing long obliquely drawn film |
| CN102947735A (en) * | 2010-06-22 | 2013-02-27 | 住友化学株式会社 | Method for manufacturing polarizing film |
| CN102947735B (en) * | 2010-06-22 | 2015-04-29 | 住友化学株式会社 | Method for manufacturing polarizing film |
| CN103442871A (en) * | 2011-03-29 | 2013-12-11 | 可乐丽股份有限公司 | Polyvinyl alcohol polymer film and process for producing same |
| CN103009615A (en) * | 2012-12-27 | 2013-04-03 | 曾立敏 | Equipment of bidirectional tension film |
| CN104416898A (en) * | 2013-08-26 | 2015-03-18 | 谢书伟 | New drawing process for making broad width polaroid |
| CN117048031A (en) * | 2023-10-10 | 2023-11-14 | 龙华相位新材料(绵阳)股份有限公司 | Optical film stretching device and stretching method |
| CN117048031B (en) * | 2023-10-10 | 2023-12-19 | 龙华相位新材料(绵阳)股份有限公司 | Optical film stretching device and stretching method |
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| CN1212918C (en) | 2005-08-03 |
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