Abstract:
The invention provides a way of using cellulose triacetate (CTA) made from softwood pulp to make films suitable for use in liquid crystal displays (LCDs). It has been surprisingly found that a combination of certain additives in the film casting dope and of metal and sulfur content of the CTA allow a softwood CTA to exhibit peeling characteristics from the casting substrate that are similar to those of lint-based CTA of similar sulfur content. The additives include a combination of acid scavengers and chelating agents.

Description:
CROSS REFERENCES TO RELATED APPLICATIONS 
       [0001]    This application claims the benefit of U.S. Provisional Application Ser. No. 61/303,810 filed Feb. 12, 2010. 
     
    
     FIELD OF THE INVENTION 
       [0002]    The present invention generally relates to using cellulose triacetate (CTA) made from sulfite-process softwood pulp to make films suitable for use in liquid crystal displays (LCDs). More particularly, the present invention relates to a dope for making a solvent-cast film containing the CTA, a method of preparing the dope, a film containing the CTA, a method of making a film containing the CTA, a polarizer plate for an LCD containing the film, and an optical lens containing the film. 
       BACKGROUND OF THE INVENTION 
       [0003]    Cellulose triacetate (CTA) is used in solvent-cast liquid crystal display (LCD) films for flat panel displays. CTA may be made from cotton linters (lint), hardwood, or softwood cellulose. Initially, only lint CTA was used for these applications, because it could be peeled more easily from the stainless steel casting substrate. 
         [0004]    As the LCD film market grew, the price of high-quality lint cellulose used to make CTA increased substantially relative to the price of hardwood and softwood pulps. LCD film growth was projected to exceed lint cellulose supply, so in 2004 a major LCD film caster implemented co-casting dies that allowed a core of hardwood CTA with thin outer layers of lint CTA to be cast. Other LCD film casters currently use only lint CTA in LCD films ranging from 22 to 80 microns thick. 
         [0005]    Thus, there is a continuing need in the art for LCD films to be made from cheaper sources of CTA such as from softwood pulp. The present invention is directed to addressing this need as well as others that will become apparent from the following description and claims. 
       SUMMARY OF THE INVENTION 
       [0006]    It has been surprisingly discovered that a combination of additives in the film casting dope plus control of metal and sulfur content of the CTA allow a softwood CTA having low sulfur content to exhibit peeling characteristics from the casting substrate that are similar to those of lint-based CTA of similar sulfur content. Additionally, it has been surprisingly discovered that the softwood CTA casting dope can provide a film with less haze, greater toughness, and comparable color to a film made from lint-based CTA. This film caster has recently extended this technology to allow films to be made using 90% hardwood CTA and 10% lint CTA and to use 100% hardwood CTA with the certain additives and film casting technology. 
         [0007]    Thus, in one aspect, the present invention provides a dope for making a solvent-cast film. The dope comprises:
       (a) cellulose triacetate made from sulfite-process softwood pulp and having less than 35 ppm of sulfur and less than 1 weight percent of xylose, both based on the weight of the cellulose triacetate, and a molar ratio of metals to sulfate of at least 3:1;   (b) an acid scavenger;   (c) a chelating agent; and   (d) a solvent.       
 
         [0012]    Thus, in one aspect, the present invention provides a dope for making a solvent-cast film. The dope comprises:
       (a) cellulose triacetate made from sulfite-process softwood pulp and having less than 35 ppm of sulfur and less than 2 weight percent of xylose, both based on the weight of the cellulose triacetate, and a molar ratio of metals to sulfate of at least 3:1;   (b) an acid scavenger;   (c) a chelating agent; and   (d) a solvent.       
 
         [0017]    In another aspect, the present invention provides a method of preparing the dope. The method comprises:
       (a) combining the cellulose triacetate, the acid scavenger, and the solvent together to form a solution; and   (b) adding the chelating agent to the solution from step (a) to form the dope.       
 
         [0020]    In another aspect, the present invention provides a film comprising:
       (a) cellulose triacetate made from sulfite-process softwood pulp and having less than 35 ppm of sulfur and less than 1 weight percent of xylose, both based on the weight of the cellulose triacetate, and a molar ratio of metals to sulfate of at least 3:1;   (b) an acid scavenger; and   (c) a chelating agent.       
 
         [0024]    In another aspect, the present invention provides a film comprising:
       (a) cellulose triacetate made from sulfite-process softwood pulp and having less than 35 ppm of sulfur and less than 2 weight percent of xylose, both based on the weight of the cellulose triacetate, and a molar ratio of metals to sulfate of at least 3:1;   (b) an acid scavenger; and   (c) a chelating agent.       
 
         [0028]    In another aspect, the present invention provides a method of making a film. The method comprises:
       (a) casting the dope according to the invention onto a continuously moving support to form a cast film on the support;   (b) partially drying the cast film;   (c) separating the cast film from the support; and   (d) drying the separated film.       
 
         [0033]    In another aspect, the present invention provides a polarizer plate for a liquid crystal display, wherein the polarizer plate comprises films according to the invention. 
         [0034]    In another aspect, the present invention provides an optical lens comprising films according to the invention. 
     
    
     DETAILED DESCRIPTION OF THE INVENTION 
       [0035]    The dope for making a solvent-cast film according to the invention comprises four main components. The first main component is a cellulose triacetate made from sulfite-process softwood pulp and having less than 35 ppm of sulfur and less than 1 weight percent of xylose, both based on the weight of the cellulose triacetate, and a molar ratio of metals to sulfate of at least 3:1. Alternatively, the first main component is a cellulose triacetate made from sulfite-process softwood pulp and having less than 35 ppm of sulfur and less than 2 weight percent of xylose, both based on the weight of the cellulose triacetate, and a molar ratio of metals to sulfate of at least 3:1. 
         [0036]    By “sulfite-process softwood pulp,” it is meant wood pulp made from softwood trees such as spruce, pine, fir, larch, hemlock, and the like, using the sulfite process. The sulfite process produces wood pulp that is almost pure cellulose fibers by using various salts of sulfurous acid to extract the lignin from softwood chips in large pressurized vessels. The salts used are either sulfites or bisulfites, and the counter ions are typically sodium, calcium, potassium, or magnesium. The cellulose fibers are subsequently acetylated to yield cellulose triacetate (CTA). 
         [0037]    Without wishing to be bound by theory, it is believed that sulfite-process cellulose has branched xylan chains, which when acetylated, are more soluble in the film casting solvent than are the linear xylan chains of prehydrolyzed kraft (PHK) cellulose-based CTA. 
         [0038]    In another embodiment, the CTA has less than 25 ppm of sulfur. In another embodiment, the CTA has 8 to 15 ppm of sulfur. 
         [0039]    In another embodiment, the CTA has 0.8 weight percent or less of xylose. In another embodiment, the CTA has 0.5 to 0.6 weight percent of xylose. In other embodiments, the CTA may have a xylose content up to 1.5 or 2 weight percent. In other embodiments, the CTA may have a xylose content from 0.5 to 1.5 or from 0.5 to 2 weight percent. In other embodiments, the CTA may have a xylose content 0.5 to 0.8 weight percent. In these embodiments, the CTA may also have a mannose content ranging from 0.5 to 1.5 weight percent or from 0.5 to 1.2 weight percent or from 0 to 1.5 weight percent. 
         [0040]    In another embodiment, the CTA has at least 98 weight percent of a-cellulose, which is generally made from a high-purity grade cellulose. In another embodiment, the CTA has at least 96 weight percent of a-cellulose, which is generally made from a high-purity grade cellulose. 
         [0041]    In another embodiment, the CTA has a molar ratio of metals to sulfate ranging from 3:1 to 5:1, or 3:1 to 11:1, or 3:1 to 16:1. The metals, as noted above, typically include sodium, calcium, potassium, and/or magnesium, and can be in ionic form or bound as a salt. 
         [0042]    The CTA for use in the present invention can have any combination of sulfur content, xylose content, a-cellulose content, and molar ratio of metals to sulfate mentioned herein. The CTA having the properties described herein is commercially available from Eastman Chemical Company and may be made according to the process described in U.S. Pat. No. 6,924,010; the entire content of which is hereby incorporated by reference. 
         [0043]    The CTA is usually present in the dope in an amount ranging from 15 to 23 weight percent, based on the weight of the dope. 
         [0044]    The second main component of the dope according to the present invention is an acid scavenger such as epoxidized soybean oil (ESO) (CAS No. 8013-07-8). ESO is commercially available from various manufacturers such as from Chemtura Corporation under the name Drapex® 6.8. Epoxidized plant oils (EPO) which can be represented and exemplified by compositions of various epoxidized long chain fatty acid triglycerides (for example, epoxidized soybean oil and epoxidized linseed oil and other unsaturated natural oils (these are occasionally called epoxidized natural glycerides or unsaturated fatty acid and these fatty acid have 12-22 carbon atoms). These acid scavengers may be used in all embodiments of the dope and/or film of the present invention. 
         [0045]    Without wishing to be bound by theory, it is believed that the acid scavenger reacts with free acetic acid in the CTA to prevent the acid from causing odor, discoloration, and further hydrolysis of the CTA, which would change the optical and physical properties of the resulting film. 
         [0046]    The acid scavenger is typically present in the dope in an amount ranging from 0.1 to 1 weight percent, based on the total weight of the dope. 
         [0047]    The third main component of the dope according to the present invention is a chelating agent such as citric acid. The chelating agent is usually present in the dope in an amount ranging from 0.01 to 0.1 weight percent, based on the total weight of the dope. Other non-limiting examples of chelating agents include, but are not limited to, tartaric acid, oxalic acid, alkali metal (Group I of the Period Table) salts of the acids, alkaline earth metal (Group II of the Periodic Table) salts of the acids, or mixtures thereof. These chelating agents may be used in all embodiments of the dope and/or film of the present invention. 
         [0048]    Without wishing to be bound by theory, it is believed that the chelating agent complexes with the poorly soluble metal sulfate salts remaining in the CTA to inhibit their further precipitation onto the casting substrate. 
         [0049]    The fourth main component of the dope according to the invention is a solvent. The typical solvent for a casting dope includes methylene chloride and from 6 to 20 weight percent of methanol, ethanol, or both, based on the weight of the solvent. More typically, the solvent would be a 90/10 weight mixture of methylene chloride and methanol or ethanol. 
         [0050]    The dope usually contains from 65 to 75 weight percent of the solvent. 
         [0051]    The dope according to the invention may contain additional additives such as anti-solvents (e.g., n-butanol or isopropanol), hindered amine light stabilizers (HALS), dyes, plasticizers, UV-absorbers, flame retardants, matting agents, etc. 
         [0052]    The dope according to the invention can be prepared by first blending the CTA and the acid scavenger with the solvent in a suitable mixing device, such as a stirred container, to form a solution. The chelating agent is then added to the solution to form the dope. 
         [0053]    The dope according to the invention can be used to form solvent cast films using techniques known in the art. For example, the dope can be cast either by gravity or pressure onto a support such as a rotating belt or drum to form a cast film on the support. After casting, the cast film is partially dried to leave a residual solvent content of, for example, 12 to 17 weight percent or from 12 to 30 weight percent. The partially dried cast film is then separated from the support such as by a peeling roll. The separated film then undergoes additional drying to form the final film. 
         [0054]    The film according to the present invention comprises the CTA, acid scavenger, and chelating agent as its main components. In particular, the resulting film typically contains from 80 to 95 weight percent of the CTA, from 1 to 5 weight percent of the acid scavenger, and 0.1 to 0.5 weight percent of the chelating agent. The film may contain up to 10 weight percent of other additives. 
         [0055]    The film according to the invention can vary in thickness, depending on the end-use application. For example, the film can have a thickness ranging from 20 to 100 microns. Particularly preferred are films having a thickness in the range of 40 to 80 microns for use in LCDs. 
         [0056]    The film according to the invention is suitable for use in various applications, such as in a polarizer plate for an LCD. A polarizer plate in an LCD has a polarizer protective film attached to at least one side of a polarizer. Typically, a polarizer is obtained by dyeing a stretched polyvinyl alcohol (PVA) film with iodine or a dichroic dye. In most cases, a CTA film is used as the protective film for the PVA film and can be attached directly to it. The surface of the CTA film may be saponified with an alkaline solution to enhance adhesion in the polarizer assembly. 
         [0057]    The film according to the invention can also be used as a component of an optical lens, such as in a camera, telescope, or eyeglasses including sunglasses and 3-D glasses. The film may also be used in combination with a polarizer, as discussed above, in the lens of optical microscopes and sunglasses. 
         [0058]    This invention can be further illustrated by the following examples of preferred embodiments thereof, although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention. 
       EXAMPLES 
     Testing Methodology 
       [0059]    The intrinsic viscosity (IV) of the CTA was determined according to ASTM method D 871-91, “Standard Test Methods of Testing Cellulose Acetate” using a Viscotek Y501V viscometer. Intrinsic viscosity is defined to be the limit of the natural logarithm of the relative viscosity to the concentration as the concentration goes to zero. The solvent used was N-methylpyrrolidone. ASTM D 1343-91 was used to determine the viscosity of the CTA. 
         [0060]    ASTM D 882 was used to determine break strain, break stress, yield strain, yield stress, and Young&#39;s modulus of the film. 
         [0061]    ASTM D 1003 was used to determine film haze and transmittance. 
         [0062]    ASTM E 1164 was used to obtain spectrophotometric data for color evaluations, and ASTM E 308 was for color computation using the CIE system. 
         [0063]    For Examples 1-24, film thickness retardation (Rth) and planar retardation (Re) were determined using a Woollam ellipsometer. For Examples 25-28, Rth was determined using a COBRA-WR instrument. 
         [0064]    Qualitative Peel Strength Test—A screening test was used in which films were peeled by hand and assigned a qualitative rating of 1 to 3, with 1 reflecting easy peel with no sticking, 2 being moderate peel force needed but no residue remaining on the plate, and 3 representing strong force to peel, tearing of the film, or a residue left on the plate. 
         [0065]    Quantitative Peel Strength Test—In order to measure the peeling force of various films more precisely, an Instron tensile tester was employed. Actual film casting belt material from the manufacturer of commercial casting belts was obtained and used as the substrate for the peeling force testing. The films were cast to achieve a final thickness of 60 microns. They were cast 2 inches (5.08 cm) in width and approximately 10 inches (25.4 cm) in length. The metal plate was mounted horizontally in the Instron tensile tester and the film was pulled vertically. The plate was mounted on a sled allowing for it to move laterally to maintain a constant 90° angle during the measurement. The force required to peel the film from the plate was measured by a load cell as the film peeled at a rate of 100 inches/minute. This force was measured along the entire length of the plate. The peel strength was reported as the average force (grams) over the length of the film. 
       Laboratory Film Casting Device 
       [0066]    A laboratory film casting device was designed and constructed in order to prevent scratching of the mirror surface of the substrate, give a uniform width and length sample for testing, and reduce film thickness variation. 
         [0067]    The laboratory film casting apparatus had a metal support with Teflon guide bars attached. Four toggle clamps were used to secure a 5-inch wide by 10-inch long piece of stainless steel film casting belt. The Teflon guide bars were spaced to allow a 2-inch wide drawdown knife to move the length of the metal plate. The drawdown knife has adjustment knobs that can change the gap between the blade and the metal plate to allow casting of different thickness films. 
       Materials 
       [0068]    The cellulose triacetates, VM114 and VM149, are commercially available from Eastman Chemical Company and were made according to the procedures described in U.S. Pat. No. 6,924,010. VM114 was made of sulfite-process softwood pulp, and VM149 was made from cotton linters. The average properties of VM114 and VM149 are reported in Table 1. 
         [0000]    
       
         
               
               
               
             
               
               
               
             
           
               
                   
                 TABLE 1 
               
               
                   
                   
               
               
                   
                 VM114 
                 VM 149 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                 Wt % Xylose 
                 0.48 
                 0.08 
               
               
                 Wt % Mannose 
                 0.58 
                 0.08 
               
               
                 Cellulose Type 
                 sulfite-process softwood pulp 
                 cotton linters 
               
               
                 Molecular Wt. Distribution 
               
               
                 Mn 
                 79,170 
                 82,807 
               
               
                 Mw 
                 282,358 
                 278,055 
               
               
                 Mz 
                 727,540 
                 703,604 
               
               
                 Polydispersity 
                 3.57 
                 3.39 
               
               
                 IV (dL/g) 
                 2.32 
                 2.40 
               
               
                 Viscosity (sec) 
                 71.8 
                 45.9 
               
               
                 Wt % Acetyl 
                 43.58 
                 43.51 
               
               
                 Color 
                 69 
                 33 
               
               
                 Haze (%) 
                 5.4 
                 4.0 
               
               
                 Elemental Analysis (ppm) 
               
               
                 sulfur 
                 13 
                 9 
               
               
                 magnesium 
                 52 
                 2 
               
               
                 iron 
                 1 
                 1 
               
               
                 calcium 
                 5 
                 33 
               
               
                 sodium 
                 5 
                 2 
               
               
                 potassium 
                 3 
                 1 
               
               
                 total metals 
                 66 
                 39 
               
               
                   
               
             
          
         
       
     
         [0069]    The chelating agent used was citric acid. 
         [0070]    The epoxidized soybean oil used was Drapex 6.8. 
         [0071]    Triphenyl phosphate and carboxymethyl ethylphthalate were used as plasticizers. 
         [0072]    Tinuvin 328 and Neo Heliopan 357 were used as typical UV inhibitors in the pressure casting trial (Examples 25-28). 
         [0073]    Methanol, methylene chloride, and n-butanol were used as the solvents in the statistically designed experiments (Examples 1-24), but only methanol and methylene chloride were used in the pressure casting trial. 
       Examples 1-24 
     Dope Preparation 
       [0074]    The CTA samples (VM114) were dried in a forced draft oven for 2 hours at 105° C., and then they were placed into a desiccator to cool. The solvents and additives were weighed and mixed in round bottles. The CTA was added slowly to the solvent in order to wet the individual particles and to reduce clumping. The bottle containing this mixture was placed into a paint shaker for 18 minutes. After this, the bottles were moved to a mechanical roller overnight to complete dissolution of the CTA. The bottles were removed from the roller and allowed to stand until the bubbles in the solutions dissipated. 
       Film Preparation 
       [0075]    60-micron thick films were hand cast on the laboratory film casting device and dried to 10-12 wt % residual solvent content. This level was chosen to simulate the low end of the 10 wt %-30 wt % typical residual solvent content range encountered when commercial LCD films are peeled from the casting belt. Experience has shown that the higher the residual solvent content, the less force that is needed to peel the film. However, if solvent content is too high, the films will distort when peeled and be useless. 
         [0076]    To cast the films, the solution was poured onto one end of the metal plate, then the drawdown blade was quickly pulled the length of the plate. The plate was then removed from the casting apparatus and placed into a film curing cabinet that was located inside a fume hood. The cabinet allowed evaporation of the solvents at a controlled rate. The necessary time to reach the 10-12 wt % residual solvent was determined by measuring the solvent content of films at 10 minute intervals of curing time in the cabinet. This time was determined to be approximately 1 hour. The curing time is well understood to be dependent on relative humidity, which must be monitored, because higher humidity retards solvent evaporation. 
         [0077]    The composition of each dope and film, and the film&#39;s properties are reported in Table 2. 
         [0000]    
       
         
               
               
             
               
               
               
               
               
               
               
             
               
               
             
               
               
               
               
               
               
               
             
               
               
             
               
               
               
               
               
               
               
             
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 2 
               
               
                   
                   
               
             
             
               
                   
                 EXAMPLE 
               
             
          
           
               
                   
                 1 
                 2 
                 3 
                 4 
                 5 
                 6 
               
               
                   
               
               
                 Wt % in Dope 
               
               
                 VM114 
                 15.00% 
                 15.00% 
                 15.00% 
                 15.00% 
                 15.00% 
                 15.00% 
               
               
                 Citric acid 
                 0.375% 
                 0.250% 
                 0.500% 
                 0.500% 
                 0.300% 
                 0.250% 
               
               
                 Drapex.6.8 
                 0.75% 
                 0.50% 
                 1.00% 
                 0.00% 
                 0.70% 
                 0.00% 
               
               
                 Triphenyl 
                 1.00% 
                 1.00% 
                 1.00% 
                 1.00% 
                 1.00% 
                 1.00% 
               
               
                 Phosphate 
               
               
                 Carboxymethyl 
                 0.34% 
                 0.34% 
                 0.34% 
                 0.34% 
                 0.34% 
                 0.34% 
               
               
                 ethylphthalate 
               
               
                 Methanol 
                 6.00% 
                 7.54% 
                 5.22% 
                 5.32% 
                 8.27% 
                 6.84% 
               
               
                 Methylene chloride 
                 74.28% 
                 74.62% 
                 73.94% 
                 74.84% 
                 74.39% 
                 75.07% 
               
               
                 n-butanol 
                 2.25% 
                 0.750% 
                 3.000% 
                 3.00% 
                 0.00% 
                 1.50% 
               
               
                 TOTAL 
                 100.00% 
                 100.00% 
                 100.00% 
                 100.00% 
                 100.00% 
                 100.00% 
               
               
                 Wt % in Film 
               
               
                 VM114 
                 85.89% 
                 87.77% 
                 84.08% 
                 89.07% 
                 86.51% 
                 90.42% 
               
               
                 Citric acid 
                 2.15% 
                 1.46% 
                 2.80% 
                 2.97% 
                 1.73% 
                 1.51% 
               
               
                 Drapex.6.8 
                 4.29% 
                 2.93% 
                 5.61% 
                 0.00% 
                 4.04% 
                 0.00% 
               
               
                 Triphenyl 
                 5.73% 
                 5.85% 
                 5.61% 
                 5.94% 
                 5.77% 
                 6.03% 
               
               
                 Phosphate 
               
               
                 Carboxymethyl 
                 1.95% 
                 1.99% 
                 1.91% 
                 2.02% 
                 1.96% 
                 2.05% 
               
               
                 ethylphthalate 
                   
                   
                   
                   
                   
                   
               
               
                 TOTAL 
                 100.00% 
                 100.00% 
                 100.00% 
                 100.00% 
                 100.00% 
                 100.00% 
               
               
                 Film Properties 
               
               
                 Break Strain (%) 
                 18.5 
                 19.7 
                 25.22 
                 26.46 
                 10.42 
                 23.18 
               
               
                 Break Stress (psi) 
                 12,639 
                 13,162 
                 13,222 
                 14,255 
                 12,444 
                 15,019 
               
               
                 Thickness 
                 62.1 
                 64.0 
                 66.9 
                 65.1 
                 85.7 
                 59.4 
               
               
                 (microns) 
               
               
                 Yield Strain (%) 
                 4.54 
                 4.14 
                 4.2 
                 4.12 
                 4.48 
                 4.26 
               
               
                 Yield Stress (psi) 
                 11,231 
                 11,294 
                 10,805 
                 11,086 
                 12,516 
                 11,882 
               
               
                 Young&#39;s Modulus 
                 440,826 
                 465,398 
                 429,309 
                 443,258 
                 480,146 
                 483,053 
               
               
                 (psi) 
               
               
                 Re @ 589 nm, 
                 0.0 
                 0.0 
                 0.1 
                 0.0 
                 0.2 
                 0.2 
               
               
                 normalized to 60 
               
               
                 micron 
               
               
                 Rth @ 589 nm, 
                 −33.6 
                 −25.6 
                 −14.9 
                 −23.2 
                 −31.4 
                 −35.9 
               
               
                 normalized to 60 
               
               
                 micron 
               
               
                 Haze (%) 
                 0.37 
                 0.12 
                 0.34 
                 0.14 
                 0.14 
                 0.11 
               
               
                 Total Transmittance 
                 92.76 
                 92.82 
                 92.81 
                 92.85 
                 92.84 
                 92.82 
               
               
                 (%) 
               
               
                 Peeling Strength 
                 1 
                 1 
                 1 
                 2 
                 1 
                 2 
               
               
                 Rating 
               
               
                   
               
             
          
           
               
                   
                 EXAMPLE 
               
             
          
           
               
                   
                 7 
                 8 
                 9 
                 10 
                 11 
                 12 
               
               
                   
               
               
                 Wt % in Dope 
               
               
                 VM114 
                 15.00% 
                 15.00% 
                 15.00% 
                 15.00% 
                 15.00% 
                 15.00% 
               
               
                 Citric acid 
                 0.500% 
                 0.500% 
                 0.500% 
                 0.000% 
                 0.500% 
                 0.125% 
               
               
                 Drapex.6.8 
                 0.00% 
                 1.00% 
                 0.00% 
                 0.00% 
                 0.50% 
                 0.25% 
               
               
                 Triphenyl 
                 1.00% 
                 1.00% 
                 1.00% 
                 1.00% 
                 1.00% 
                 1.00% 
               
               
                 Phosphate 
               
               
                 Carboxymethyl 
                 0.34% 
                 0.34% 
                 0.34% 
                 0.34% 
                 0.34% 
                 0.34% 
               
               
                 ethylphthalate 
               
               
                 Methanol 
                 5.32% 
                 8.22% 
                 8.32% 
                 8.37% 
                 6.77% 
                 6.08% 
               
               
                 Methylene chloride 
                 74.84% 
                 73.94% 
                 74.84% 
                 75.29% 
                 74.39% 
                 74.96% 
               
               
                 n-butanol 
                 3.00% 
                 0.00% 
                 0.00% 
                 0.00% 
                 1.50% 
                 2.25% 
               
               
                 TOTAL 
                 100.00% 
                 100.00% 
                 100.00% 
                 100.00% 
                 100.00% 
                 100.00% 
               
               
                 Wt % in Film 
               
               
                 VM114 
                 89.07% 
                 84.08% 
                 89.07% 
                 91.80% 
                 86.51% 
                 89.74% 
               
               
                 Citric acid 
                 2.97% 
                 2.80% 
                 2.97% 
                 0.00% 
                 2.88% 
                 0.75% 
               
               
                 Drapex.6.8 
                 0.00% 
                 5.61% 
                 0.00% 
                 0.00% 
                 2.88% 
                 1.50% 
               
               
                 Triphenyl 
                 5.94% 
                 5.61% 
                 5.94% 
                 6.12% 
                 5.77% 
                 5.98% 
               
               
                 Phosphate 
               
               
                 Carboxymethyl 
                 2.02% 
                 1.91% 
                 2.02% 
                 2.08% 
                 1.96% 
                 2.03% 
               
               
                 ethylphthalate 
                   
                   
                   
                   
                   
                   
               
               
                 TOTAL 
                 100.00% 
                 100.00% 
                 100.00% 
                 100.00% 
                 100.00% 
                 100.00% 
               
               
                 Film Properties 
               
               
                 Break Strain (%) 
                 22.78 
                 28.18 
                 22.28 
                 19.7 
                 24.44 
                 26.62 
               
               
                 Break Stress (psi) 
                 14,167 
                 15,147 
                 15,364 
                 14,660 
                 13,584 
                 15,208 
               
               
                 Thickness 
                 63.3 
                 60.8 
                 55.1 
                 80.9 
                 65.1 
                 63.3 
               
               
                 (microns) 
               
               
                 Yield Strain (%) 
                 4.36 
                 4.32 
                 4.14 
                 4.8 
                 4.42 
                 4.22 
               
               
                 Yield Stress (psi) 
                 11,366 
                 11,310 
                 12,310 
                 12,347 
                 10,512 
                 11,498 
               
               
                 Young&#39;s Modulus 
                 459,301 
                 447,264 
                 499,629 
                 472,820 
                 416,145 
                 470,951 
               
               
                 (psi) 
               
               
                 Re @ 589 nm, 
                 0.2 
                 0.1 
                 0.1 
                 0.1 
                 0.1 
                 −0.1 
               
               
                 normalized to 60 
               
               
                 micron 
               
               
                 Rth @ 589 nm, 
                 −28.7 
                 −36.0 
                 −46.9 
                 −56.3 
                 −26.4 
                 −32.9 
               
               
                 normalized to 60 
               
               
                 micron 
               
               
                 Haze (%) 
                 0.25 
                 0.1 
                 0.11 
                 0.18 
                 0.16 
                 0.15 
               
               
                 Total Transmittance 
                 92.79 
                 92.78 
                 92.74 
                 92.72 
                 92.67 
                 92.87 
               
               
                 (%) 
               
               
                 Peeling Strength 
                 2 
                 1 
                 2 
                 3 
                 1 
                 1 
               
               
                 Rating 
               
               
                   
               
             
          
           
               
                   
                 EXAMPLE 
               
             
          
           
               
                   
                 13 
                 14 
                 15 
                 16 
                 17 
                 18 
               
               
                   
               
               
                 Wt % in Dope 
               
               
                 VM114 
                 15.00% 
                 15.00% 
                 15.00% 
                 15.00% 
                 15.00% 
                 15.00% 
               
               
                 Citric acid 
                 0.00% 
                 0.50% 
                 0.00% 
                 0.00% 
                 0.00% 
                 0.00% 
               
               
                 Drapex.6.8 
                 0.50% 
                 0.000% 
                 1.000% 
                 0.00% 
                 1.00% 
                 0.00% 
               
               
                 Triphenyl 
                 1.00% 
                 1.00% 
                 1.00% 
                 1.00% 
                 1.00% 
                 1.00% 
               
               
                 Phosphate 
               
               
                 Carboxymethyl 
                 0.34% 
                 0.34% 
                 0.34% 
                 0.34% 
                 0.34% 
                 0.34% 
               
               
                 ethylphthalate 
               
               
                 Methanol 
                 5.32% 
                 8.32% 
                 8.27% 
                 5.37% 
                 5.27% 
                 6.87% 
               
               
                 Methylene chloride 
                 74.84% 
                 74.84% 
                 74.39% 
                 75.29% 
                 74.39% 
                 75.29% 
               
               
                 n-butanol 
                 3.00% 
                 0.000% 
                 0.000% 
                 3.00% 
                 3.00% 
                 1.50% 
               
               
                 TOTAL 
                 100.00% 
                 100.00% 
                 100.00% 
                 100.00% 
                 100.00% 
                 100.00% 
               
               
                 Wt % in Film 
               
               
                 VM114 
                 89.07% 
                 89.07% 
                 86.51% 
                 91.80% 
                 86.51% 
                 91.80% 
               
               
                 Citric acid 
                 0.00% 
                 2.97% 
                 0.00% 
                 0.00% 
                 0.00% 
                 0.00% 
               
               
                 Drapex.6.8 
                 2.97% 
                 0.00% 
                 5.77% 
                 0.00% 
                 5.77% 
                 0.00% 
               
               
                 Triphenyl 
                 5.94% 
                 5.94% 
                 5.77% 
                 6.12% 
                 5.77% 
                 6.12% 
               
               
                 Phosphate 
               
               
                 Carboxymethyl 
                 2.02% 
                 2.02% 
                 1.96% 
                 2.08% 
                 1.96% 
                 2.08% 
               
               
                 ethylphthalate 
                   
                   
                   
                   
                   
                   
               
               
                 TOTAL 
                 100.00% 
                 100.00% 
                 100.00% 
                 100.00% 
                 100.00% 
                 100.00% 
               
               
                 Film Properties 
               
               
                 Break Strain (%) 
                 29.3 
                 13.42 
                 19.66 
                 18.54 
                 24.8 
                 28.84 
               
               
                 Break Stress (psi) 
                 15,762 
                 12,066 
                 13368 
                 13117 
                 13229 
                 15396 
               
               
                 Thickness, microns 
                 61.1 
                 89.8 
                 55.6 
                 77.6 
                 60.0 
                 55.7 
               
               
                 Yield Strain (%) 
                 4.5 
                 4.32 
                 4.02 
                 4.6 
                 4.34 
                 4.8 
               
               
                 Yield Stress (psi) 
                 11,246 
                 11,660 
                 11641 
                 11675 
                 10715 
                 11159 
               
               
                 Young&#39;s Modulus 
                 467,353 
                 459,754 
                 459025 
                 452609 
                 411880 
                 435193 
               
               
                 (psi) 
               
               
                 Re @ 589 nm, 
                 0.0 
                 0.1 
                 0.3 
                 0.1 
                 0.2 
                 0.1 
               
               
                 normalized to 60 
               
               
                 micron 
               
               
                 Rth @ 589 nm, 
                 −38.31 
                 −31.64 
                 −47.1 
                 −51.65 
                 −43.29 
                 −44.37 
               
               
                 normalized to 60 
               
               
                 micron 
               
               
                 Haze (%) 
                 0.24 
                 0.09 
                 0.26 
                 0.14 
                 0.18 
                 0.12 
               
               
                 Total Transmittance 
                 92.83 
                 92.74 
                 92.74 
                 92.84 
                 92.83 
                 92.71 
               
               
                 (%) 
               
               
                 Peeling Strength 
                 1 
                 2 
                 1 
                 3 
                 1 
                 3 
               
               
                 Rating 
               
               
                   
               
             
          
           
               
                   
                 EXAMPLE 
               
             
          
           
               
                   
                 19 
                 20 
                 21 
                 22 
                 23 
                 24 
               
               
                   
               
               
                 Wt % in Dope 
               
               
                 VM114 
                 15.00% 
                 15.00% 
                 15.00% 
                 15.00% 
                 15.00% 
                 15.00% 
               
               
                 Citric acid 
                 0.50% 
                 0.00% 
                 0.25% 
                 0.00% 
                 0.00% 
                 0.15% 
               
               
                 Drapex.6.8 
                 1.00% 
                 0.50% 
                 1.00% 
                 1.00% 
                 0.00% 
                 1.00% 
               
               
                 Triphenyl 
                 1.00% 
                 1.00% 
                 1.00% 
                 1.00% 
                 1.00% 
                 1.00% 
               
               
                 Phosphate 
               
               
                 Carboxymethyl 
                 0.34% 
                 0.34% 
                 0.34% 
                 0.34% 
                 0.34% 
                 0.34% 
               
               
                 ethylphthalate 
               
               
                 Methanol 
                 8.22% 
                 6.82% 
                 6.74% 
                 8.27% 
                 8.37% 
                 7.25% 
               
               
                 Methylene chloride 
                 73.94% 
                 74.84% 
                 74.17% 
                 74.39% 
                 75.29% 
                 74.26% 
               
               
                 n-butanol 
                 0.00% 
                 1.50% 
                 1.50% 
                 0.00% 
                 0.00% 
                 1.00% 
               
               
                 TOTAL 
                 100.00% 
                 100.00% 
                 100.00% 
                 100.00% 
                 100.00% 
                 100.00% 
               
               
                 Wt % in Film 
               
               
                 VM114 
                 84.08% 
                 89.07% 
                 85.28% 
                 86.51% 
                 91.80% 
                 85.76% 
               
               
                 Citric acid 
                 2.80% 
                 0.00% 
                 1.42% 
                 0.00% 
                 0.00% 
                 0.86% 
               
               
                 Drapex.6.8 
                 5.61% 
                 2.97% 
                 5.69% 
                 5.77% 
                 0.00% 
                 5.72% 
               
               
                 Triphenyl 
                 5.61% 
                 5.94% 
                 5.69% 
                 5.77% 
                 6.12% 
                 5.72% 
               
               
                 Phosphate 
               
               
                 Carboxymethyl 
                 1.91% 
                 2.02% 
                 1.93% 
                 1.96% 
                 2.08% 
                 1.94% 
               
               
                 ethylphthalate 
                   
                   
                   
                   
                   
                   
               
               
                 TOTAL 
                 100.00% 
                 100.00% 
                 100.00% 
                 100.00% 
                 100.00% 
                 100.00% 
               
               
                 Film Properties 
               
               
                 Break Strain (%) 
                 21.86 
                 24.8 
                 25.14 
                 21.86 
                 19.1 
                 21.76 
               
               
                 Break Stress (psi) 
                 12710 
                 14342 
                 14167 
                 13789 
                 14130 
                 14335 
               
               
                 Thickness 
                 91.1 
                 81.5 
                 83.8 
                 62.0 
                 86.5 
                 61.0 
               
               
                 (microns) 
               
               
                 Yield Strain (%) 
                 5.04 
                 5.1 
                 4.2 
                 4.78 
                 5.04 
                 4.44 
               
               
                 Yield Stress (psi) 
                 10955 
                 11431 
                 11637 
                 11488 
                 12196 
                 12276 
               
               
                 Young&#39;s Modulus 
                 391756 
                 430277 
                 435333 
                 426376.5 
                 442305 
                 460021 
               
               
                 (psi) 
               
               
                 Re @ 589 nm, 
                 0.1 
                 0.4 
                 0.2 
                 −0.1 
                 −0.2 
                 −0.1 
               
               
                 normalized to 60 
               
               
                 micron 
               
               
                 Rth @ 589 nm, 
                 −31.06 
                 −40.97 
                 −31.88 
                 −36.78 
                 −44.38 
                 −38.1 
               
               
                 normalized to 60 
               
               
                 micron 
               
               
                 Haze (%) 
                 0.1 
                 0.18 
                 0.18 
                 0.12 
                 0.1 
                 0.1 
               
               
                 Total Transmittance 
                 92.8 
                 92.83 
                 92.81 
                 92.76 
                 92.81 
                 92.82 
               
               
                 (%) 
               
               
                 Peeling Strength 
                 1 
                 1 
                 1 
                 1 
                 3 
                 1 
               
               
                 Rating 
               
               
                   
               
             
          
         
       
     
         [0078]    Examples 1-24 showed that there were no significant changes for planar retardation (Re), break strain, break stress, yield strain, Young&#39;s Modulus, haze, or total transmission, based on changes in the amount of the citric acid, ESO, and n-butanol. Yield stress showed slight decrease as the ESO level increased, and the thickness retardation (Rth) showed a decrease with increasing citric acid content. 
       Examples 25-28 
       [0079]    Three batches of dope were made and formed into films on a commercial pressure casting line. The batches of dope were prepared by adding a mixture of methylene chloride and methanol to a mixing vessel having a rotating stirrer. The VM114 and all other ingredients except citric acid were then added to the stirred vessel. Once a solution was obtained that was free of undissolved material, the citric acid was added to the solution. Stirring was continued for one hour. The film casting solution was then passed through filtration devices, and film was cast at the target thickness. The composition of the dopes and films, and the films&#39; properties are reported in Table 3. 
         [0080]    Peeling force in Table 3 was measured continuously by pressure transducers in the takeoff roll that peels the film from the casting belt. 
         [0081]    Knurling pressure ratio in Table 3 is the ratio of force required to impart the knurling pattern of each experimental film to that typically seen for 100% lint-based CTA film. 
         [0000]    
       
         
               
               
             
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                 TABLE 3 
               
             
             
               
                   
                   
               
               
                   
                 EXAMPLE 
               
             
          
           
               
                   
                 25 
                 26 
                 27 
                 28 
               
               
                   
                 Batch 1 
                 Batch 2 
                 Batch 3 
                 Batch 3 
               
               
                   
                   
               
             
          
           
               
                 Wt % in Dope 
                   
                   
                   
                   
               
               
                 VM114 
                 8.625% 
                 12.75% 
                 16.75% 
               
               
                 VM149 
                 8.625% 
                 4.25% 
                 0.00% 
               
               
                 Citric acid 
                 0.057% 
                 0.056% 
                 0.055% 
               
               
                 Drapex. 6.8 
                 0.57% 
                 0.56% 
                 0.56% 
               
               
                 Triphenyl Phosphate 
                 1.09% 
                 1.07% 
                 1.05% 
               
               
                 Carboxymethyl 
                 0.25% 
                 0.24% 
                 0.24% 
               
               
                 ethylphthalate 
               
               
                 Tinuvin 328 
                 0.08% 
                 0.08% 
                 0.08% 
               
               
                 Neo Heliopan 357 
                 0.05% 
                 0.05% 
                 0.04% 
               
               
                 Methanol 
                 8.07% 
                 8.10% 
                 8.12% 
               
               
                 Methylene chloride 
                 72.59% 
                 72.85% 
                 73.10% 
               
               
                 TOTAL 
                 100.00% 
                 100.00% 
                 100.00% 
               
               
                 Wt % in Film 
               
               
                 VM114 
                 44.59% 
                 66.90% 
                 89.19% 
               
               
                 VM149 
                 44.59% 
                 22.30% 
                 0.00% 
               
               
                 Citric acid 
                 0.29% 
                 0.30% 
                 0.30% 
               
               
                 Drapex. 6.8 
                 2.97% 
                 2.96% 
                 2.96% 
               
               
                 Triphenyl Phosphate 
                 5.62% 
                 5.61% 
                 5.61% 
               
               
                 Carboxymethyl 
                 1.28% 
                 1.28% 
                 1.28% 
               
               
                 ethylphthalate 
               
               
                 Tinuvin 328 
                 0.42% 
                 0.42% 
                 0.42% 
               
               
                 Neo Heliopan 357 
                 0.24% 
                 0.24% 
                 0.24% 
               
               
                 TOTAL 
                 100.00% 
                 100.00% 
                 100.00% 
               
               
                 Film Properties 
               
               
                 Wt % of Sulfite 
                 50 
                 75 
                 100 
                 100 
               
               
                 Softwood CTA 
               
               
                 Wt % of Cotton 
                 50 
                 25 
                 0 
                 0 
               
               
                 Lint CTA 
               
               
                 Film Thickness (microns) 
                 60 
                 60 
                 60 
                 40 
               
               
                 Transmission (%) 
                 93.2 
                 93.3 
                 93.3 
                 93.2 
               
               
                 Haze (%) 
                 0.19 
                 0.15 
                 0.09 
                 0.09 
               
               
                 b* color 
                 0.40 
                 0.33 
                 0.35 
                 0.40 
               
               
                 Rth @ 589 nm 
                 36.45 
                 37.63 
                 40.50 
                 31.30 
               
               
                 Peeling Force 
                 110 
                 109 
                 110 
                 109 
               
               
                 from Casting Belt (N) 
               
               
                 Knurling Pressure Ratio 
                 1.00 
                 1.00 
                 1.06 
                 1.13 
               
               
                   
               
             
          
         
       
     
       Examples 29-34 
       [0082]    Dopes and films were made following the procedures of Examples 1-24 with CTA derived from sulfite softwood, cotton lint, and hardwood having varying levels of sulfur to determine the peeling force required to separate the film from the casting substrate. These compositions were made to test the effect of sulfur on peeling force in the absence of the chelating agent and acid scavenger. The results indicate that the higher the sulfur level, the higher the peeling force. 
         [0083]    The composition of the dopes and films, and the peeling force results are shown in Table 4. 
         [0000]    
       
         
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                   
                 TABLE 4 
               
             
             
               
                   
                   
               
               
                   
                 EXAMPLE 
               
             
          
           
               
                   
                 29 
                 30 
                 31 
                 32 
                 33 
                 34 
               
               
                   
                   
               
             
          
           
               
                 Wt % in Dope 
                   
                   
                   
                   
                   
                   
               
               
                 VM114, sulfite softwood, 
                 13.65% 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 11 ppm S 
               
               
                 VM149, lint, 9 ppm S 
                 — 
                 13.65% 
                 — 
                 — 
                 — 
                 — 
               
               
                 PHK Hardwood CTA, 70 ppm S 
                 — 
                 — 
                 13.65% 
                 — 
                 — 
                 — 
               
               
                 Lint CTA, 37 ppm S 
                 — 
                 — 
                 — 
                 13.65% 
                 — 
                 — 
               
               
                 Lint CTA, 16 ppm S 
                 — 
                 — 
                 — 
                 — 
                 13.65% 
                 — 
               
               
                 Lint CTA, 25 ppm S 
                 — 
                 — 
                 — 
                 — 
                 — 
                 13.65% 
               
               
                 Triphenyl phosphate 
                 1.35% 
                 1.35% 
                 1.35% 
                 1.35% 
                 1.35% 
                 1.35% 
               
               
                 Methylene chloride 
                 76.50% 
                 76.50% 
                 76.50% 
                 76.50% 
                 76.50% 
                 76.50% 
               
               
                 Methanol 
                 8.50% 
                 8.50% 
                 8.50% 
                 8.50% 
                 8.50% 
                 8.50% 
               
               
                 Wt % in Film 
               
               
                 VM114, sulfite softwood, 
                 91.00% 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 11 ppm S 
               
               
                 VM149, lint, 9 ppm S 
                 — 
                 91.00% 
                 — 
                 — 
                 — 
                 — 
               
               
                 PHK Hardwood CTA, 70 ppm S 
                 — 
                 — 
                 91.00% 
                 — 
                 — 
                 — 
               
               
                 Lint CTA, 37 ppm S 
                 — 
                 — 
                 — 
                 91.00% 
                 — 
                 — 
               
               
                 Lint CTA, 16 ppm S 
                 — 
                 — 
                 — 
                 — 
                 91.00% 
                 — 
               
               
                 Lint CTA, 25 ppm S 
                 — 
                 — 
                 — 
                 — 
                 — 
                 91.00% 
               
               
                 Triphenyl phosphate 
                 9.00% 
                 9.00% 
                 9.00% 
                 9.00% 
                 9.00% 
                 9.00% 
               
               
                 Sulfur in CTA (ppm) 
                 11 
                 9 
                 70 
                 37 
                 16 
                 25 
               
               
                 Average Peeling Force (g) 
                 85 
                 64 
                 152 
                 98 
                 81 
                 104 
               
               
                   
               
             
          
         
       
     
         [0084]    Samples of CTA having a range of sulfur content were made using sulfite softwood pulp as shown in Table 5. Above about 35 ppm sulfur content, increased peeling force from the casting substrate is observed when using the target amounts of additives. 
         [0000]    
       
         
               
               
               
               
               
             
               
               
               
               
               
             
           
               
                 TABLE 5 
               
               
                   
               
               
                 % in Film 
                 1 
                 2 
                 3 
                 4 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Sulfite Softwood 0.80% Xylose, 
                 89.82% 
                 — 
                 — 
                 — 
               
               
                 0.97% Mannose (24.5 ppm S) 
               
               
                 Sulfite Softwood 0.80% Xylose, 
                 — 
                 89.82% 
                 — 
                 — 
               
               
                 0.97% Mannose (33.5 ppm S) 
               
               
                 Sulfite Softwood 0.80% Xylose, 
                 — 
                 — 
                 89.82% 
                 — 
               
               
                 0.97% Mannose (40.1 ppm S) 
               
               
                 Sulfite Softwood 0.80% Xylose, 
                 — 
                 — 
                 — 
                 89.82% 
               
               
                 0.97% Mannose (48.9 ppm S) 
               
               
                 Citric acid 
                 0.15% 
                 0.15% 
                 0.15% 
                 0.15% 
               
               
                 Drapex. 6.8 
                 1.50% 
                 1.50% 
                 1.50% 
                 1.50% 
               
               
                 Triphenyl Phosphate 
                 7.49% 
                 7.49% 
                 7.49% 
                 7.49% 
               
               
                 Carboxymethyl ethylphthalate 
                 1.05% 
                 1.05% 
                 1.05% 
                 1.05% 
               
               
                 Qualitative Peel Rating 
                 1 
                 1.5 
                 2 
                 3 
               
               
                   
               
             
          
         
       
     
         [0085]    Additional sulfite softwood pulps having higher levels of the hemicelluloses impurities, xylan and mannan, were used to make CTA. Table 6 shows such pulps containing that up to 2% xylose and 1% mannose produce CTA having good peeling characteristics from casting belt substrate. 
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
             
           
               
                 TABLE 6 
               
               
                   
               
               
                 % in Film 
                 1 
                 2 
                 3 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Softwood Sulfite Pulp 0.80% Xylose, 
                 89.82% 
                 — 
                 — 
               
               
                 0.97% Mannose 
               
               
                 Softwood Sulfite Pulp 1.68% Xylose, 
                 — 
                 89.82% 
                 — 
               
               
                 1.10% Mannose 
               
               
                 Softwood Sulfite Pulp 1.94% Xylose, 
                 — 
                 — 
                 89.82% 
               
               
                 1.19% Mannose 
               
               
                 Citric acid 
                 0.15% 
                 0.15% 
                 0.15% 
               
               
                 Drapex. 6.8 
                 1.50% 
                 1.50% 
                 1.50% 
               
               
                 Triphenyl Phosphate 
                 7.49% 
                 7.49% 
                 7.49% 
               
               
                 Carboxymethyl ethylphthalate 
                 1.05% 
                 1.05% 
                 1.05% 
               
               
                 Total 
                 100.00% 
                 100.00% 
                 100.00% 
               
               
                 Qualitative Peel Rating 
                 1 
                 1 
                 1 
               
               
                 CIE b* Color 
                 0.184 
                 0.215 
                 0.263 
               
               
                   
               
             
          
         
       
     
         [0086]    Stability of optical properties is very important in LCD films. Durability testing was carried out for 1000 hours at 60° C. and 95% relative humidity on the films shown in Table 7. 
         [0000]    
       
         
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 7 
               
               
                   
               
               
                 % in Film 
                 1 
                 2 
                 3 
                 4 
                 5 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 VM149 
                 89.72% 
                 89.85% 
                 — 
                 — 
                 — 
               
               
                 VM114 
                 — 
                 — 
                 89.72% 
                 89.85% 
                 89.99% 
               
               
                 Citric acid 
                 0.30% 
                 0.15% 
                 0.30% 
                 0.15% 
                 0.00% 
               
               
                 Drapex. 6.8 
                 2.99% 
                 1.50% 
                 2.99% 
                 1.50% 
                 0.00% 
               
               
                 Triphenyl Phosphate 
                 6.99% 
                 8.50% 
                 6.99% 
                 8.50% 
                 10.01% 
               
               
                 CIE L* 
               
               
                 0 Hours @ 60° C., 95% RH 
                 97.16 
                 97.14 
                 97.16 
                 97.17 
                 97.14 
               
               
                 500 Hours @ 60° C., 95% RH 
                 97.08 
                 97.13 
                 97.13 
                 97.14 
                 97.14 
               
               
                 1000 Hours @ 60° C., 95% RH 
                 97.06 
                 97.08 
                 97.12 
                 97.14 
                 97.11 
               
               
                 CIE a* 
               
               
                 0 Hours @ 60° C., 95% RH 
                 0.000 
                 0.000 
                 0.000 
                 0.000 
                 0.000 
               
               
                 500 Hours @ 60° C., 95% RH 
                 0.150 
                 0.100 
                 0.035 
                 0.100 
                 0.010 
               
               
                 1000 Hours @ 60° C., 95% RH 
                 0.050 
                 0.100 
                 0.010 
                 0.100 
                 0.015 
               
               
                 CIE b* 
               
               
                 0 Hours @ 60° C., 95% RH 
                 0.2 
                 0.2 
                 0.2 
                 0.1 
                 0.2 
               
               
                 500 Hours @ 60° C., 95% RH 
                 0.3 
                 0.2 
                 0.2 
                 0.2 
                 0.2 
               
               
                 1000 Hours @ 60° C., 95% RH 
                 0.3 
                 0.2 
                 0.2 
                 0.2 
                 0.1 
               
               
                 Haze 
               
               
                 0 Hours @ 60° C., 95% RH 
                 0.31 
                 0.49 
                 0.30 
                 0.26 
                 0.39 
               
               
                 500 Hours @ 60° C., 95% RH 
                 0.91 
                 0.33 
                 0.40 
                 0.30 
                 0.40 
               
               
                 1000 Hours @ 60° C., 95% RH 
                 0.94 
                 0.50 
                 0.43 
                 0.30 
                 0.39 
               
               
                 Planar Retardation Of 60 
               
               
                 micron films @ 589 nm 
               
               
                 0 Hours @ 60° C., 95% RH 
                 0.47 
                 0.05 
                 1.42 
                 0.74 
                 1.59 
               
               
                 500 Hours @ 60° C., 95% RH 
                 0.73 
                 0.78 
                 0.84 
                 0.40 
                 0.70 
               
               
                 1000 Hours @ 60° C., 95% RH 
                 0.52 
                 0.83 
                 0.66 
                 0.52 
                 0.42 
               
               
                 Thickness Retardation Of 60 
               
               
                 micron films @ 589 nm 
               
               
                 0 Hours @ 60° C., 95% RH 
                 −42.3 
                 −45.4 
                 −39.3 
                 −43.5 
                 −46.1 
               
               
                 500 Hours @ 60° C., 95% RH 
                 −38.5 
                 −42.7 
                 −39.6 
                 −39.8 
                 −44.5 
               
               
                 1000 Hours @ 60° C., 95% RH 
                 −38.5 
                 −44.3 
                 −41.9 
                 −45.7 
                 −44.7 
               
               
                   
               
             
          
         
       
     
         [0087]    The data shows the sulfite softwood CTA (VM114) to have very stable optical properties at the target levels of 1.5% acid scavenger and 0.15% citric acid. These stable optical properties are very important for use in LCD applications. 
         [0088]    Belt deposits cause very tiny indentations in the film surface, which manifests itself as haze when the film is viewed at an angle. Such haze makes the films unacceptable, and the belt has to be cleaned. This down time reduces production and increases cost. In order to measure the effectiveness of the chelating agent in preventing deposits of salts on the film casting belt, an additional 30 day trial was made on the commercial film casting line using the target levels of 1.5% acid scavenger and 0.15% citric acid. No belt deposits occurred. 
         [0089]    The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.