Patent Application
20220195149
This invention relates generally to optically clear panels, such as Human Machine Interface touch displays; in particular, it relates to certain plastic touch plate covers made from low hydroxyl cellulose esters.
Human Machine Interface (HMI) displays are becoming more prevalent in automobiles as they provide passengers with more control over the interior via a single interface. For example, the entertainment system, air conditioner, lighting, etc., can all be controlled by this single touch panel display via multiple selection options. HMI displays normally include an optical module of some sort (e.g., LCD panel, OLED, etc.) along with a protective, optically clear “touch plate” on the surface. The touch plate is required to be both scratch resistant (given the frequent physical contact), as well as having very low optical birefringence to minimize optical shadowing.
Glass meets these criteria and is the current material of choice but is still considered lacking because it adds extra weight and has poor impact resistance (which could lead to risk of injury during a crash). Automakers would also like to have greater design flexibility in the auto interior, including larger and more highly curved/contoured HMI panels. Such designs are simply not practical with glass, and so other options are needed.
There has been a desire to replace glass with plastic as it can be molded into different shapes more easily, while also offering better impact strength. However, molded plastics tend to have residual orientation and stress that leads to optical birefringence in the panel. This birefringence can in turn lead to undesirable optical defects, most noticeably “shadowing”. Shadowing occurs, for example, whenever a driver views the HMI display wearing polarized sunglasses. The polarized lenses impart additional gradations in color and/or brightness in the panel that can make the panel appear “mottled”. The only way to eliminate this shadowing currently is to use very low birefringence materials such as glass as the touch plate material.
It is also important that the low birefringence and optical clarity be maintained, without sacrificing impact strength. Some polymers such as acrylics, for example poly(methyl methacrylate) (PMMA) can be molded with sufficiently low birefringence, but such materials are inherently brittle and therefore not acceptable from a safety or reliability standpoint.
In one aspect, the invention is directed to an optically clear protective cover or cover plate for Human Machine Interface (HMI) touch panel displays wherein the cover plate is formed from melt processable cellulose ester having a low hydroxyl content. The total degree of substitution (DS) of the cellulose ester ranges from 2.85 to 3 wherein a DS of 0 represents no esters side groups (i.e. pure cellulose) and a DS of 3 represents the fully esterified cellulose ester. In embodiments, the DS is in the range of from 2.9 to 2.97. It has been discovered that cellulose esters having a DS as described herein can provide panels having essentially “zero birefringent” behavior. In embodiments, the acyl groups can be chosen from acetyl, propionyl and butyrl or combinations thereof. Cellulose esters substituted with such groups can maintain higher glass transition temperature. It is also contemplated that longer chain acyl groups can be included, particularly at lower levels.
In embodiments, the Human Machine Interface covers of the invention have a very low optical retardation wherein all parts of the optical panel within the viewable area have an in-plane optical retardation Re, ranging from −100 nm to 100 nm and a thickness retardation Rth that is also in the range of −100 nm to 100 nm. Such a low retardation panel does not require any additional compensation films.
In another embodiment, all parts of the optical panel within the viewable area have an in-plane optical retardation Re, ranging from −80 nm to 80 nm and a thickness retardation Rth that is in the range of −100 nm to 100 nm.
In another embodiment, all parts of the optical panel within the viewable area have an in-plane optical retardation Re, ranging from −50 nm to 50 nm and a thickness retardation Rth that is in the range of −100 nm to 100 nm.
In embodiments, the cover plate may further comprise one or more compensation layers to provide a cover plate assembly, where the compensation layer(s) can provide the cover plate assembly with a total optical retardation that falls within an acceptable range for an HMI cover application. In embodiments, the cover plate assembly exhibits a total optical retardation that is in a range chosen from: (i) from −100 to 100 nm, (ii) from 100 to 300 nm, or (iii) from −100 to −300 nm; or alternately, in terms of absolute value of retardation of from 0 to 100 or 100 to 300. In other embodiments, the cover plate assembly exhibits a total optical retardation in a range chosen from: (i) from −80 to 80 nm, (ii) from 100 to 260 nm, or (iii) from −100 to −260 nm; or alternately, in terms of absolute value of retardation of from 0 to 80 or 100 to 260. In another embodiment, the cover plate assembly exhibits a total optical retardation in a range chosen from: (i) from −50 to 50 nm, (ii) from 130 to 230 nm, or (iii) from −130 to −230 nm; or alternately, in terms of absolute value of retardation of from 0 to 50 or 130 to 230. In embodiments, the cover plate assembly exhibits a total optical retardation (discussed above) over at least the viewable portion of the HMI display.
Shadowing is an optical defect that occurs when a passenger views the HMI display while wearing polarized sunglasses. It produces variations in brightness from gray to white with the effect that the display appears distorted and/or mottled. This distortion is caused by localized variations in the birefringence. Birefringence, in turn, refers to differences in refractive index of a given transparent substrate, in different directions, which are brought on by stress and/or molecular orientation. Such shadowing usually consists of variations of gray coloring, but when the optical birefringence is large enough, it can even cause shifts in color in the display, starting at yellow, then orange, red, violet and on through the color spectrum. It is desirable that no variations in color occur and that the display remain a uniform color, for example black or gray, but white is also acceptable.
Birefringence of a substrate denoted as A, is defined as the difference in refractive index n, between any two mutually perpendicular directions. Typically, these directions will be associated with, for example, the machine direction (MD), transverse direction (TD) and thickness direction (thick). If one denotes these directions by the subscript a, b and c, then one can calculate three different values for the birefringence
Δab=na−nb
Δbc=nb−nc
Δac=na−nc (1)
Only two of the three are independent, and the choice of which best to use depends on the application. Birefringence is a parameter reflecting the amount of orientation by way of the refractive index. Refractive index, in turn is an inverse measure of the speed of light in the medium assuming the light wave is polarized in that particular direction. A higher value of n means lower velocity so if na>nb, this implies that the light wave polarized along the a direction will travel more slowly than the wave polarized in the b direction. So, given enough distance, the light wave along a will lag further behind b and become increasingly out of phase.
For simplification, the incident light wave 3 can be vectorially decomposed into electric field components along the vertical and horizontal axes and which are normal to the propagation direction. Each of these components will then propagate through the sample at different velocities given the different refractive indices. Because of this speed difference, the exiting wave fronts 5 and 6 will be phase separated by a distance 8 (
When the two components 5 and 6 reach the second polarizer 30, the waves are effectively recombined to create the output wave 8 seen by the observer 90. If the retardation is zero, the waves remain in phase and add back to their original amplitude and direction. Since this combined wave is now oriented 90 degrees to the second polarizer it will be completely blocked, and a black or null state will exist where no light is transmitted. This is the same black state that would be observed if looking through two crossed polarizers with no sample present.
In contrast, if the two components are out of phase, then vectorial addition will result in a portion of the wave being aligned with the 2nd polarizer such that it will be transmitted through. This “light leakage” will vary with the level of retardation and will go through a maximum as retardation is increased, and eventually will return to near zero at integral multiples of the wavelength assuming monochromatic light. If the retardation is equal to A then this is denoted as the first order extinction point. Likewise, additional extinctions occur at 2A, 3A, etc. and are denoted as the 2nd and 3rd order extinction points, respectively.
For white or polychromatic light, each color corresponds to a different wavelength and each will undergo differing levels of extinction assuming a constant retardation in the part. For example, blues and violets are much shorter in wavelength than red, so they will undergo more relative phase shifting as retardation level is increased (e.g., a 100 nm retardation shift will be equivalent to a quarter wave shift if λ=400 nm but will only be λ/6 shift for a 600 nm wavelength). As the various colors undergo varying shifts in their intensity, the color of the light being transmitted changes. At zero retardation, no light is transmitted, and the color appears black. As retardation increases, this color shifts from black to dark gray, and then to white at about 100 nm. It stays white from roughly 100 nm to 300 nm where it begins to shift to yellow. From yellow it shifts to orange, then red and then violet at the 570 nm first order extinction point. Above 570 nm, the color cycling essentially repeats, albeit with some slightly different color shifts. However, for the purposes of HMI cover plates, retardation levels over 570 nm are unacceptably high from a shadowing perspective.
Retardation variation from about −100 nm to +100 nm generally exhibits a black to gray appearance with minimal shadowing. Likewise, retardation variation in the 100 to 300 nm (or −100 to −300) range provides a near uniform white appearance and shows minimal shadowing. In embodiments, both ranges are retardation targets for the present invention. In certain embodiments, the former range is a preferred target for the ultra-low retardation resins as discussed herein. It should be noted that within any given range, the lower the variability of retardation across the plaque is more preferred, but the above are considered the approximate maximum levels of variability that can occur within the band while still maintaining reasonable optical uniformity.
The retardation is easily calculated for any two directions (i, j) from the thickness of the part L, as
R
ij
=LΔ
ij (2)
As with birefringence, there are multiple values of retardation depending on which directions are chosen. For the purposes of shadowing, there are two values that are particularly important denoted as Re and Rth. These are defined as follows:
This assumes the a, b and c directions correspond to the MD, TD and thickness of the part accordingly. Re and Rth are important to shadowing for different reasons. Re represents the retardation and phase lag for light waves that are traveling normal to the surface as illustrated in
For off-axis or tilted viewing, however, nthick must be considered, hence the need for Rth. This is illustrated in
Refractive index is known to vary between the principal axes following an ellipsoidal shape. For normal incidence, the polarization direction will correspond to the horizontal/planar refractive index 61. But as the angle increases, the effective refractive index corresponds to the point on the ellipsoid where the polarization vector intersects. So as tilt angle increases, the effective refractive index approaches the thickness value 62. Note as mentioned below that if the thickness and planar refractive indices are identical, then 60 will take the shape of a sphere instead of an ellipsoid, and thus the effective refractive index will not change with tilt angle. Ideally, we want both Rth and Re to be small in the display cover to minimize all shadowing. It is also preferred that Rth be equal or close to Re in value so that no apparent shadowing occurs when viewing angle changes.
It is important to note that shadowing and retardation only matter in the presence of optical polarizers. In fact, shadowing can only occur if the retardation shift occurs between two polarizers such as 10 and 30 in
While the display module itself has a polarizer pair, the (HMI) touch plate is not between these polarizers so additional optical interference does not take place. The situation changes however, when sunglasses are worn, as now the touch plate is in between the 2nd polarizer of the LCD module and the polarized sunglasses. Sunglasses essentially introduce a third polarizer, and thus a second polarizer pair, and everything in between these polarizers must now be accounted for when trying to reduce shadowing. The following description of examples of HMI panels is provided for further illustration.
A typical structure of an LCD based HMI panel is illustrated in
An LCD module is very similar to the setup in
Polarizers also typically include protective or “compensation” films that sandwich the active polarizing element (13 and 33). These are denoted as 11 and 12 for the first polarizer and 31 and 32 for the second. Layers 11 and 32 are usually made from solvent cast cellulose triacetate film or a cyclo-olefin. Because they are “outside” of the polarizer pair, they do not normally affect retardation, so their retardation is usually not critical. In contrast, layers 12 and 31 are between the polarizers, and so their retardation can affect visual quality. For traditional LCD applications, these films are often designed to have a certain prescribed Re and Rth, so as to cancel out any residual retardation in the liquid crystal module. By properly designing these compensation films, the viewing angle and contrast of the display are increased significantly.
The retardation effects discussed previously with regard to
Upon exiting the second polarizer, the light will then pass through the display cover 70. In most applications, such as a traditional LCD television, the light will pass through the protective cover and on to the observer. Because there is no other polarizer after the cover, its retardation has no effect on the viewing quality.
This situation changes, however, if a 3rd polarizer is brought into the picture such as with an observer wearing polarized sunglasses. This is denoted as 80 in
In an automobile, these films (12 and 31) can also potentially influence shadowing and so one option is to modify the retardation of these films even further to reduce the perception of shadowing viewed by a passenger wearing polarized sunglasses. This option is less preferred however as tweaking the compensation films 12 and 31 would harm the visual performance under normal conditions when sunglasses are not being worn. Instead, it may be preferred to add an additional compensation layer 71 to the touch plate itself, or alternately in place of, or on top of layer 32. Films can be made to prescribed retardation levels much easier than molded products, so this offers an alternative way to shift retardation either higher or lower as needed. In embodiments, the film (shown on the touch surface) can also function as a protective layer having anti-scratch, hard coat, etc., properties applied to the surface. In embodiments, such films could also be applied on the underside of the panel if desired (not shown). Application could be by direct adhesion, in-mold labeling/decorating, etc.
In embodiments, the HMI touch panel can be bonded to a liquid crystal display component/assembly (e.g., the touch panel can be bonded to a polarizer layer, or a protective layer on the polarizer layer, that resides between the liquid crystal module and the touch panel) with a liquid optically clear adhesive (LOCA) or an optically clear adhesive (OCA) film (or tape). Such adhesives can also be used to bond a protective cover, such as a lens or hard coat layer to the touch panel. In embodiments, the adhesive is cured with ultraviolet light (UV), heat, moisture, or a combination, depending on the manufacturer and specifications for the LOCA or OCA.
In embodiments, the LOCA or OCA can improve the optical performance of the display, e.g., by eliminating air gaps between the layers being bonded. In embodiments, such optical bonding can improve the contrast ratio by reducing the amount of reflected light, thus improving viewability. Reflection from the touch panel screen or a protective cover layer, as well as the adhesive can degrade LCD viewability. Reflection can be caused by an impedance mismatch between air and one or more of the layers. The reflection can make the white brighter, but dilute black and other colors, which can decrease contrast. In certain embodiments, the LOCA is selected to match the refractive index of the HMI touch panel to minimize loss. In embodiments, the LCOA or OCA comprises acrylic-based and/or silicone-based chemistry.
In embodiments, the touch panel is molded with in mold decoration (IMD) or in mold labeling (IML) to provide indicia and/or passive haptic features. In embodiments, the IMD or IML are films that transfer decoration and/or UV curable hard coated surfaces to the plastic touch panel. IML films have the coating against the mold. The molten thermoplastic (e.g., cellulose ester thermoplastic) is injected such that it contacts the film surface facing the mold interior and has good adherence to the thermoplastic. Once the molded part drops out of the mold, the coating on the IML film is subjected to a UV curing step that hardens the surface and can impart scratch and chemical resistance. Other functionalities that can be imparted to the outward facing surface (of the molded part) include anti-fingerprint (oleophobic properties), antiglare and/or anti-reflective attributes. In embodiments, the indicia may be related to the control functions of the HMI unit. In embodiments, multi-color screen-printed and offset lithography printed graphics can be used to produce the indicia or graphics. In certain embodiments, second surface graphics are used, where the decoration is printed on the back side of a clear substrate film, e.g., polycarbonate, acrylic or cellulosic film and injection plastic is contacted on the ink side of the film (e.g., during injection molding). This encapsulates the decoration between the film layer and the injected plastic resulting in a decoration that can't be abraded during use. In embodiments, vision systems can be used to ensure accurate label positioning and can validate label correctness. In embodiments, printing can be performed by any known methods, such as digital printing (e.g., inkjet or xerography), spraying, transfer printing, flexography, gravure, etc.
In embodiments, the thickness of the touch panel module constructed using IMD or IML is comparatively thinner to a similar touch panel constructed using LOCA or OCA bonding for the printed layer. In embodiments, IMD techniques can be used to provide hard coats and/or ink transfer indicia.
In one embodiment, the HMI touch plate is prepared via injection molding or compression injection molding (CIM). Both techniques have been used for making optical discs. A third option is the use of thermoforming, particularly to make larger panels. Thermoforming requires the extrusion of sheet that is heated and formed into a mold. It has the advantage that larger size parts are possible, but disadvantages of high scrap rate, potentially higher stress levels and difficulty in molding in lugs and attachment points.
A key aspect with any production technique is the minimization of birefringence. There are two primary types of birefringence, namely orientation birefringence and “glassy” or stress related birefringence. The former arises from residual chain orientation left in the part after molding, whereas the latter results from thermal stresses that form during cooling of the part. Both components will change independently for each production method.
Conventional polymers used in automotive applications include polycarbonate (PC) and PMMA. Of these, PC is disadvantaged relative to PMMA with respect birefringence, in that a very small change in residual stress (or residual orientation) will cause a large change in birefringence. This sensitivity is often quantified via the stress optical coefficient (SOC) which is the change in birefringence that occurs for a unit change in stress.
Δij=SOC*(σi-σj) (5)
where σi is the stress in the i direction. There are two values of SOC for a given material, one for stressing above the glass transition temperature in the rubbery state (SOCR), and the other for stressing in the glassy state (SOCG). The former relates to orientational birefringence and the latter is a more traditional stress related birefringence. For PC, both SOC values are typically much higher than for acrylic, which makes low birefringence molding more difficult. In contrast, it has been found that cellulose esters according to embodiments herein can be modified to change the SOC values considerably, even to the point of being nearly zero. It has been discovered that this allows for much more fine tuning of birefringence during molding than either polycarbonate or acrylic.
During injection molding, the geometry and gating of the mold are very important with respect to the effect on stress and birefringence.
In the case of this small tab gate, a radially progressing type flow takes place that is analogous to inflation of a balloon. The polymer is being stretched radially as well as circumferentially which results in primary stresses σr and σ⊖ in the radial and hoop directions (108). As shown in formula (5) above, the birefringence increases as the relative stress difference increases and the stress difference tends to be very high closer to the gate. Because of this radial stress pattern, the orientation and birefringence profiles will have a similar radial geometry which serves to amplify shadowing as there will be more angular dependence. Therefore, in embodiments, it is preferred to go with a wider fan or film type gate that provides for a more uniform flow front through the part. This is illustrated in
Compression injection molding is an alternative to standard injection molding in that the mold is initially kept partially open during filling to reduce flow stresses, but then closed to produce the final part. For thinner items like optical discs, this can reduce birefringence more than traditional injection molding alone.
Thermoforming is another alternative for producing the display cover and it allows for larger panels than traditional injection molding.
Thermoforming offers the additional advantage that multilayer structures can be easily produced. For example, the cellulose ester of the present invention can be coextruded between cap layers of PMMA to produce a hard coat surface. The three-layer sheet can then be thermoformed into the final part as long as sheet and mold temperatures are set up appropriate for the materials involved.
Multilayer thermoforming offers other advantages in that the upper use temperature for the part can be adjusted by using layers having appropriate glass transition temperatures. Likewise, the cap layer can help serve as a protective layer to keep moisture out of the inside of the sheet, and to keep volatile compounds (e.g. plasticizers) inside the structure. This may allow for the use of highly plasticized cellulose esters as core layers with a stiffer cap layer (e.g. PMMA, PC) to seal in the plasticizer and offset the lower Tg.
Any combination of layers can be envisioned for the current invention as it is only critical that the overall structure meet the birefringence requirements and that at least one layer contain the low hydroxyl cellulose ester of the present invention. Because the protective cap layers can be kept thin, even more highly birefringent layers can be used as the total retardation produced can be kept to a minimum.
In one embodiment, part thickness for HMI displays will range from about 1 mm up to about 10 mm, or 1 mm to 8 mm, or 1 mm to 5 mm, or about 2 mm to about 10 mm, or 2 mm to 8 mm, or 2 mm to 5 mm, or from greater than 2 mm to 5 mm, or from 2 mm to 4 mm, or from 2 mm to 3 mm. The thickness has an important effect on birefringence and retardation since, as already mentioned, the retardation is equal to the birefringence multiplied by the thickness. So, all things being equal, a thicker part will have higher retardation. However, it has been discovered that thicker parts may have reduced filling pressures and thus a reduced level of orientational birefringence. So even though the thickness is higher, the average birefringence across the part may be lower and so sometimes the overall retardation will decrease. Thicker parts are otherwise preferred from an impact and crashworthiness standpoint, although not too thick as this adds extra weight. In embodiments, the thickness is about 2 to 3 mm.
It has been discovered that molding with hotter polymer melt temperatures can also help reduce birefringence by lowering viscosity and reducing overall stress and orientation formation. There is usually a practical upper limit on molding for most materials before excessive degradation and/or flashing becomes a problem.
Mold temperatures can also be increased to reduced stressing although this can make cycle times longer (due to a longer cooling cycle). Mold temperature has a particularly strong influence on residual stress and the resulting stress induced birefringence brought about by cooling. To help reduce this further, parts can also be annealed after molding at a temperature close to the glass transition temperature Tg. This can minimize the stress component of birefringence but usually does not impact the orientational birefringence. Also, it is less desirable in that it adds significantly to cycle time and cost.
Other processing parameters such as the injection rate/pressure can influence the birefringence formation and fill rates can be profiled to optimize birefringence. It has been discovered that birefringence can be reduced, particularly in the gate area, by running at higher injection fill rates and/or mold filling pressures, particularly at the end of filling. Likewise hold pressures should also be kept high, but low enough to prevent flashing. If fill rates are too low, it is believed that cooling effects would be too strong during filling which drives up orientational birefringence as the material must flow past a more viscous skin layer.
It is also observed that birefringence can be minimized, particularly in the gate region, by profiling the pressure profile during filling. It was found that a high initial filling rate and packing pressure, followed by a slight reduction in the pack and hold pressures, will lower gate birefringence compared with a constant pressure profile.
Lowering the molecular weight of polymers can reduce the viscosity as well as the orientation that results during molding. However, lower molecular weight is typically a trade off with toughness and impact strength.
In embodiments, the cellulose ester utilized in this invention can be any cellulose ester having a sufficient content of salt or ester moieties of 03 to OW acids, preferably propionate and/or butyrate moieties. Cellulose esters that can be used for the present invention generally comprise repeating units of the structure:
wherein R1, R2, and R3 are selected independently from the group consisting of hydrogen or straight chain alkanoyl having from 2 to 10 carbon atoms. For cellulose esters, the substitution level is usually expressed in terms of degree of substitution (DS), which is the average number of non-OH substituents per anhydroglucose unit (AGU). Generally, conventional cellulose contains three hydroxyl groups in each AGU unit that can be substituted; therefore, DS can have a value between zero and three. However, low molecular weight cellulose mixed esters can have a total degree of substitution slightly above 3, as a result of end group contributions. Native cellulose is a large polysaccharide with a degree of polymerization from 250-5,000 even after pulping and purification, and thus the assumption that the maximum DS is 3.0 is approximately correct. However, as the degree of polymerization is lowered, as in low molecular weight cellulose mixed esters, the end groups of the polysaccharide backbone become relatively more significant, thereby resulting in a DS that can range in excess of 3.0. Because DS is a statistical mean value, a value of 1 does not assure that every AGU has a single substituent. In some cases, there can be unsubstituted anhydroglucose units, some with two and some with three substituents, and typically the value will be a non-integer. Total DS is defined as the average number of all of substituents per anhydroglucose unit. The degree of substitution per AGU can also refer to a particular substituent, such as, for example, hydroxyl, acetyl, butyryl, or propionyl. In embodiments, the degree of polymerization for the cellulose ester is lower than that of the native cellulose. In embodiments, n is an integer in a range from 25 to 250, or 25 to 200, or 25 to 150, or 25 to 100, or 25 to 75.
In one aspect of the invention, a Human Machine Interface (HMI) cover is provided in the form of a sheet, having a thickness of about 2 mm to about 5 mm, comprising a melt processable cellulose ester having a total degree of substitution (DS) of 2.85 to 3. In embodiments, the DS is in a range from 2.9 to 2.97 and more closely represents “zero birefringent” behavior. Alternately, DS can be expressed in terms of the number of hydroxyl groups DSOH. In embodiments, the cellulose ester has a DSOH in the range from 0 to 0.15, or from 0.03 to 0.1. In embodiments, the acyl groups preferably consist of acetyl, propionyl and butyrl.
By having a total DS in the ranges discussed herein, it has been found that the refractive index perpendicular to the chain backbone, is approximately equal to the refractive index parallel to the chain backbone. Thus, the birefringence for the monomer is close to zero, and the value of SOCR is also very close to zero. Consequently, any orientation that takes place during molding/forming will have negligible effect on birefringence and/or retardation. In contrast, when total DS is below about 2.85, it has been found that there are sufficient hydroxyl groups present such that the refractive index is noticeably higher along the chain axis relative to the perpendicular direction and SOCR is no longer negligible.
In embodiments, the cellulose ester composition can also contain up to 20 wt % of a plasticizer, although automotive restrictions on volatile organic compounds (VOCs) suggest that plasticizer level should ideally be zero, or very close to zero, unless the cellulose ester is sealed with a varnish or coating. Alternately, if a multilayer thermoforming method is used, the cellulose ester can be sandwiched between layers that help to prevent plasticizer migration. In embodiments, higher molecular weight plasticizers that are less volatile can be used.
Likewise, in embodiments, up to about 20 wt % of a miscible polymer can be blended in with the cellulose esters. Examples include certain ethyl vinyl acetate (EVAc) copolymers, certain aliphatic polyesters, e.g., poly(butylene succinate) and/or poly(ethylene succinate), PVDF, epoxies, polyvinylpyrrolidone, etc.
In embodiments, the cellulose ester composition can also contain typical additives including impact modifiers, processing aids, stabilizers, UV protectants, colorants, and the like.
Because of fitness for use and processability requirements, in embodiments, the Tg of the cellulose ester plus any plasticizers/modifiers is in the range from 105° C. to 160° C., 105° C. to 150° C., 110° C. to 160° C., or 120° C. to 150° C. In embodiments, the lower Tg limit can be determined by requirements associated with high temperatures that can occur in an automobile interior, particularly in hotter climates. In such embodiments, the display cover must not warp, creep or otherwise deform under these conditions. In embodiments, the higher Tg temperature requirement can be determined by requirements associated with melt processability restrictions. As Tg increases, the processing temperature needed to adequately melt and plasticate the resin also increases, and higher melt temperatures can lead to increased yellowing and degradation. It is noted that in the case of multilayer thermoformed HMI covers, the Tg restriction not be as limited, as long as the additional layers provide the necessary high temperature stiffness to support the panel.
As mentioned previously, molecular weight is also important as it impacts both strength and birefringence. In embodiments, the number average molecular weight (polystyrene equivalent) should ideally be between about 40,000 g/mole and 80,000 g/mole in order to maintain adequate toughness. Higher MW materials have better toughness, but flow orientation and birefringence tend to increase. Fortunately, with the low hydroxyl resin according to embodiments herein, it has been discovered that the material is relatively insensitive to flow orientation and so higher molecular weights can be used. The only limit is in processability in that very high molecular weights are more viscous, and thus more difficult to inject into intricate molds.
Alternately the molecular weight can be defined indirectly in terms of the falling ball viscosity (FBV), as described in ASTM D817 and D1343. In embodiments, cellulosics of the current invention can have an FBV ranging between 5 and 30 seconds. Below this range, the material tends to be too brittle, whereas above this the viscosity is too high.
In embodiments, preferred cellulose esters for the present invention include cellulose acetate propionates, cellulose propionates (or cellulose tripropionate, CTP), and cellulose acetate butyrates. In embodiments, because of Tg limitations, the degree of substitution for acetyl groups DS(Ac), should be below about 2.1, more preferably below about 1.7. It has been found that high acetyl levels tend to push the Tg too high and therefore limit processability. In contrast, materials like cellulose triacetate (CTA) and cellulose acetate (CA) are not preferred as they are difficult to melt process, e.g., without a significant level of plasticizer present (although they can be used as a protective or compensating layer).
In certain embodiments, the Human Machine Interface covers of the invention have a very low optical retardation, wherein all parts of the optical panel within the viewable area have an in-plane optical retardation Re, ranging from −100 nm to 100 nm and a thickness retardation Rth that is also in the range of −100 nm to 100 nm. Such a low retardation panel does not require any additional compensation films.
In another embodiment, all parts of the optical panel within the viewable area have an in-plane optical retardation Re, ranging from −80 nm to 80 nm and a thickness retardation Rth that is in the range of −100 nm to 100 nm.
In another embodiment, all parts of the optical panel within the viewable area have an in-plane optical retardation Re, ranging from −50 nm to 50 nm and a thickness retardation Rth that is in the range of −100 nm to 100 nm.
In certain embodiments, the Human Machine Interface cover of the invention further comprises one or more compensation layers and possess a total optical retardation that is either in the range of
(i) −100 to 100 nm,
(ii) 100 to 300 nm, or
(iii) −100 to −300 nm.
In other embodiments, the Human Interface cover of the invention further comprising one or more compensation layers possess a total optical retardation that is either in the range of −80 to 80 nm, 100 nm to 260 nm, or −100 nm to −260 nm.
In another embodiment, the Human Interface covers of the invention further comprising one or more compensation layers possess a total optical retardation that is either in the range of (i) −50 to 50 nm or (ii) 150 to 250 nm or (iii) −250 to −150 nm.
Traditional stabilizers, catalysts, impact modifiers, flame retardant agents, reinforcing agents and the like which are well known in the plastic arts may be used to the extent such additives are of a type and/or in an amount that does not cause the cover to have unacceptable optical or strength properties, as described herein. Examples of additives that are contemplated for use include Irgafor® and Irganox® antioxidants, available from BASF and Tinuvin® and Uvinil® light stabilizers, available from BASF.
As mentioned herein, the use of plasticizers is also an option although the part typically must meet certain limits related to volatile organic compounds and so a plasticized cellulose ester will preferably be sealed in, via the use of a cap layer (e.g. multilayer coextrusion and thermoforming), by co-injection, or using a varnish or sealing type layer.
In embodiments, in addition to having a Tg (as discussed herein), the display panel must also meet certain impact requirements. In embodiments, a cover panel made from the cellulose ester composition having a thickness of 1 mm to 10 mm, or 1 mm to 8 mm, or 1 mm to 5 mm, or 2 mm to 10 mm, or 2 mm to 8 mm, or 2 mm to 5 mm will survive impact of a 1.05 kg steel ball from a height of 20″ (50.8 cm) at both room temperature and −30° C. without breaking. This height represents an impact energy of 5.2 Joules. Because of the variety of panel geometries available, the panel is supported on a 4″ (10.2 cm) diameter tube with impact at the center of the panel or plaque.
In order to have an HMI display panel without shadowing, it is important for the total retardation of all “optically active layers” to fall within one of two ranges, as follows:
The reason for targeting one of these two areas, is that the color changes very little with a given change in retardation. In contrast, for retardations above 260 nm, or above 300 nm (or below −260 nm, or below −300 nm) range, the effective color is changing rapidly through non-grayscale values (yellow initially) as retardation is increased. Consequently, even small variations in retardation will produce noticeable shifts in color. It should also be noted that if a portion of the panel is in the gray region, but another portion is in the “white” region, there will be an unacceptable level of apparent shadowing. The entire viewing area (or in one embodiment, the entire panel) should be in one or the other, but not both. Likewise, these ranges listed are the minimum considered to be acceptable but even lower variation ranges around 0 nm or around 180 nm (or −180 nm) are preferred.
Insofar as the above acceptable ranges roughly span 200 nm, or 160 nm of retardation, it is desirable that the difference between the maximum and minimum retardation of the part (at least over the viewable area of the HMI cover) be less than or equal to about 200 nm, or 160 nm. In embodiments, the maximum variability in retardation that a part can have over the entire viewable area and still be acceptable is 160 nm. However, if the mean retardation from the part does not fall within the target range, it can be shifted via the addition of an optically active compensation layer to the cover plate.
As an example, a part having a mean retardation of 100 nm, with the maximum value being 150 nm, and the minimum being 50 nm, would have unacceptable shadowing if used by itself, because part of the retardation is in the gray region, and part in the white region. However, since the retardation range (max-min) is only 100 nm, the mean value can be shifted downwards using a −100 nm optically active compensation layer. This shifts the mean to 0 nm, the min value shifts to −50 nm and the max value shifts to 50 nm. Now all points are within the −80 to +80 nm gray region and so shadowing is minimized. Alternately, the mean value could have been shifted upwards so that the entire range falls in the white region.
It should be noted that a 200 nm range is essentially the minimum needed to stay within the gray or white bands. In embodiments, the difference between the maximum and minimum retardation Re of the cellulose ester part within the viewable area, will be less than or equal to about 160 nm, or preferably less than or equal to 100 nm. The narrower the range of retardation values encountered across the part, the lower the shadowing.
To minimize distortions when viewed off angle, it is important that both the in plane Re and thickness retardation Rth be kept low. Ideally if both Re and Rth are kept near zero, the display will appear the same from all viewing angles. As Re increases, there is more optical distortion, and this will vary depending on how the refractive indices vary in the plane of the film relative to the refractive index in the thickness direction. Likewise, for higher values of Re, it is more difficult to define a precise Rth target that will fully eliminate off axis distortion.
The “optically active layers” constitute all layers between the second polarizer of the display 33, and the polarized sunglasses 80. Therefore, the outer protective layer 32 of the second polarizer, the HMI display 70, and any protective/compensation layer(s) applied to the display 71 (or alternately applied in between 32 and 70) can be considered optically active layers. The sum of the in-plane retardation should be substantially in one of the two ranges described above. It is accepted that areas around the gate or on the edges may be outside of the acceptable range if these areas are hidden (e.g., outside the viewable area of the HMI cover) and/or removed as part of the installation.
In embodiments, the display panel is 2 to 5 mm, or 2 to 4 mm, or 2 to 3 mm, thick and will survive impact at room temperature and −30° C. using a 1.05 kg steel ball dropped from a height of 20″ (50.8 cm) without breaking. In embodiments, the HMI display covers are larger than typical molded optical discs and are non-symmetric in geometry, both of which make it much harder to meet the low birefringence requirements (as discussed herein).
In embodiments, the HMI cover panel is produced by injection molding, compression injection molding, or thermoforming and can optionally be annealed to further reduce birefringence. In embodiments, the cover is injection molded and the gate is at least 50% or greater, or at least 60%, or at least 70%, or at least 80%, of the width of the cover on the entry side of the mold, in order to reduce angular dependence of retardation.
In an aspect, a method for making the Human Machine Interface cover is provided that includes the steps of:
In embodiments, the gate opening has a width that is at least 60% of the mold width. In embodiments, the barrel temperature is at least the thermoplastic polymer Tg (in ° C.)+80° C.
The optically active layers can be produced by various means including solvent casting, extrusion, stretching and so forth. In embodiments, compensating layers can be made from one or more cellulose esters. In another embodiment, compensating layers can be made from oriented polycarbonate, e.g., in the case of common quarter wave plate films. Additional layers can also be incorporated to improve scratch resistance, glare etc. These “hard coat” layers might be applied to a compensating film, for example, which is then adhered to the display panel using in-mold labeling techniques, direct adhesion, coating, or other methods known in the art. In embodiments, the hard coat is chosen from a silicone based hard coat, (poly)siloxane based hard coat, urethane based hard coat, or acrylic based hard coat.
It has also been discovered that molded articles made from cellulose esters having a low hydroxyl content or higher DS(Total) (as discussed herein) maintain optical clarity (i.e., have less haze increase) better than cellulose esters having a higher hydroxyl content or lower DS, when exposed to heat and humidity. Thus, in another aspect, molded articles having improved resistance to moisture induced haze are provided. In embodiments, such molded articles are made from cellulose ester having a total degree of substitution (DS) in the range from 2.85 to 3. In embodiments, the DS is in the range of from 2.9 to 2.97. In embodiments, high heat and/or humidity exposure refers to higher temperature and humidity environmental conditions experienced by typical consumer products, e.g., products that may be put in a dish washer or reside in an automotive interior. In embodiments, the temperature range can be from 27° C. to 100° C., or 38° C. to 95° C., or 38° C. to 78° C. In embodiments, the humidity can be in the range from RH of 80 to 100%, or 90 to 100%.
The cellulose ester compositions having low hydroxyl content (as discussed herein) are useful for providing molded articles that have a requirement of high optical clarity and that will be exposed to high heat and/or humidity in the use of the articles. For example, articles that are put in a dish washer, or articles that are otherwise subjected to heat and humidity (e.g., certain vehicle components) can benefit from using the cellulose ester compositions having low hydroxyl content (as discussed herein). As such, in one aspect, the invention is directed to use of a cellulose ester having low hydroxyl content (as discussed herein) for molded articles requiring high optical quality that may be exposed to high heat and/or humidity during use. In one aspect, the invention is directed to use of a cellulose ester having low hydroxyl content (as discussed herein) for molded articles having reduced haze increase when exposed to high heat and/or humidity during use, compared to similar articles made from cellulose ester having higher hydroxyl content.
This invention can be further illustrated by the following examples of certain 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 unless otherwise specifically indicated.
The following experimental methods were used to characterize molded articles of the present invention.
The melt flow rate, or melt flow index (MFI), is measured following ASTM D-1238 at 300° C. and with a 1.2 kg load.
Optical birefringence in the plane (Re) was characterized by one of two means. First is by using a Strainoptics™ PS-100SF polarimeter. Testing was conducted in “plane polarization” mode with optimization quantified either with the rotating analyzer method, or with the Strainoptics™ LWC-100 wedge compensator. Measures were made at multiple points across the part and the max and min points also noted.
When both Re and Rth values are needed, testing was performed with a Woolam™ ellipsometer. The ellipsometer performs a series of measurements at different tilt angles, and then extrapolates retardation results to a full 90 degree tilt in order to determine Rth.
Impact strength is determined at room temperature and −30° C. Impact is performed with a 1.05 kg steel ball dropped from a height of 4″ (10 cm) and 20″ (50.8 cm). The panel is supported on a 4″ (10.2 cm) diameter tube. This height represents a maximum impact energy of 5.2 Joules and the sample must survive impact with no cracks or breaks in order to pass the test.
The degree of substitution of the cellulose esters reported in the examples below was determined by 1H NMR using a JEOL Model 600 NMR spectrometer operated at 600 MHz. The sample tube size was 5 mm and the sample temperature was 80° C. using dimethysulfoxide-d6 with a couple of drops of deuterated trifluroacetic acid as the solvent. The pulse delay was 5 seconds and 64 scans were acquired for each experiment.
Unless otherwise specified, the glass transition temperature Tg, was determined using a TA DSC 2920 instrument from Thermal Analyst Instruments on non-plasticized samples using DSC with a ramp rate of 20° C./minute according to ASTM D3418. Tg values were extracted from 2nd heating cycle measurements to ensure a clearly denoted transition and the removal of any residual water. The melting point was also measured using DSC according to ASTM D3418. Falling ball viscosity was measured using ASTM Method D1343-91 in ASTM A solvent.
Percent Haze and Light Transmission were measured on 102 mm×102 mm×2 mm injection molded plaques using a Hunterlab Ultrascan VIS Dual-Beam spectrophotometer according to ASTM D1003, Sect. 8, Proc. B.
Moisture content of test plaques was measured by a TGA method as follows: a sample of approximately 2 mgs was cut from the edge of a 2 mm thick injection molded plaque and loaded into a TA Instruments Q5000SA vapor sorption analyzer. The sample was dried at 60° C. and 0% relative humidity for 240 minutes (4 hours). Once the drying step was completed, the sample was equilibrated at 30° C. and 90% relative humidity for 300 minutes (5 hours). Percent weight gain (of water) was measured during this timeframe as well as at the end of the 300 minutes. The final % weight gain is the reported moisture absorption value.
Rectangular plaques were injection molded on a Toyo Plastar TM-200G2 molding machine having a 50 mm screw and 397 cc shot capacity. A designed experiment was conducted using a variety of processing conditions and resins. Rectangular plaques with dimensions of 10.2 cm by 15.2 cm and a thickness of 2.5 mm were produced. The mold was filled with a film type gate along the entire 10.2 cm short side of the plaque.
Three polycarbonate resins were molded including Makrolon™ 2458 (19 MVR or 20 MFR), Makrolon™ 2207 (35 MVR or 38 MFR) and Tarflon™ LC1500 (65 MVR or 70 MFR). The Makrolon resins were supplied by Bayer (Covestro) and the Tarflon resin by Idemitsu Kosan Company. In addition to the polycarbonate samples, a PMMA polymer Acrylite™ H12 (Evonik Industries) was also tested as a control as well as a commercial cellulose acetate propionate (CAP), Eastman Treva GC6021 (Eastman Chemical Company) having a total DS of 2.68.
Mold temperature was fixed at 82° C. for the PMMA and CAP samples and 88 C. for the polycarbonate samples. Barrel temperature, and injection speed were all varied to determine optimal conditions. Retardation values (Re) were then measured 1 cm from the gate, at the center of the plaque, and 1 cm from the non-gated end of the plaque. Maximum and minimum values were also noted over the entire part, but excluding the 2 cm region near the gate. It is known that retardation levels will be higher near the gate region, but it is assumed that this high retardation could be incorporated into a larger gate area that would be removed and/or hidden from view upon final assembly of the panel. The molding conditions and test results are listed in Table 1.
A review of Table 1 reveals that, for the polycarbonate samples, only Sample CE18 fell within the desirable target retardation range (−100 to 100 nm) and/or had a retardation variability less than the more preferred 100 nm range. This was produced using the 65 MVR sample running at hotter barrel temperature and fast injection rate. For this part to be acceptable, the gate region would have to be excluded from the viewing area of the panel as already noted, but it could potentially be used without additional compensating layers.
Samples CE14 was within the 200 nm broader range, but the mean would need to be shifted via a compensation film for an HMI application. Performance would not be as good as CE18, but might still be acceptable for some applications. Sample CE17 was of intermediate performance and had a retardation range falling within an intermediate 160 nm range. If the gate region was excluded from the viewable area, this part would be acceptable without a compensating layer and would fall in between the shadowing performance of CE14 and CE18.
For the other PC samples, the processing conditions did not produce sufficiently low variability in retardation and would have produced unacceptable shadowing. Likewise, the lower MVR samples were not even close to the required retardation targets.
The acrylic samples (CE19 through CE24) had low retardation profiles but were not useful because of their low impact strength (impact data not shown). If impact strength had been acceptable, these could have been used without a compensation layer although CE19 and CE21 would need to exclude the gate region from the viewable area.
The CAP samples (CE25 through CE30) had higher retardation than the cellulosics of the present invention. As discussed herein, the DS for these CAP samples was lower than the cellulosics according to the invention. Only CE26 and CE30 had acceptably low variability in retardation. CE26 could be used in the “white” region without a compensator if a small part of the gate area was excluded from the viewable area. CE30 would require a compensator film to shift the mean retardation downward into the gray region, or upward into the white region. The gate region of CE30 would also need to be excluded from the viewable area.
Values of SOC for both the glassy (SOCg) and rubbery (SOCr) were determined for a series of materials. SOCg was estimated by loading a tensile bar in an Instron tensile testing rig and stressing the part incrementally while measuring changes in the retardation. Stresses were maintained in the linear regime below the yield point. Retardation values were then converted to birefringence via the part thickness, and the birefringence plotted vs. stress. The slope of this plot was the SOCg value.
SOCr values were determined by stretching film samples at different stretch ratios using a Brueckner laboratory film stretcher. Initial film samples were 100 mm×100 mm and typically 200 to 250 um thick. Samples were stretched nominally at a temperature about 10° C. above the Tg, to different stretch ratios. After stretching, the retardation was measured and compared with the stresses in the film at the end of stretching (determined from force gauges built into the film stretcher. SOCr could then be estimated from a plot of the birefringences at the different stretch ratios plotted versus the stress difference in the film at each given stretch ratio.
Actual SOC values are listed in Table 2. Note that the PC and PMMA values were obtained from the literature (Wimberger-Friedl, R. (1991) Orientation, stress and density distributions in injection-moulded amorphous polymers determined by optical techniques, Eindhoven: Technische Universiteit Eindhoven DOI:10.6100/IR364279). Values for CTA were estimated from the data in Cellulose (2015) 22: 3003-3012.
The values for SOCg are all comparable with the exception that PMMA is slightly negative, and PC has a much higher value. SOCr values, on the other hand, change over a much wider range. PMMA for example is known to change significantly with orientation temperature, hence the range listed. For cellulose esters, it can be observed that SOCr values are a strong function of the total DS. As DS approaches 3, the SOCr value decreases, and as with the case of cellulose triacetate, actually crosses through zero and becomes negative. Consequently, for low birefringence molding, it is desirable to have a composition where the SOCr is close to zero. This shows the benefit (for the cellulosics tested) of having DS(tot) of about 2.85, or about 2.9, or higher.
In this example various CAPs were molded on a Toyo M90 injection molding machine. The plaque was nominally 10 cm×10 cm and was 2 mm thick. Screw speed was fixed at 50 RPM and cooling time in the mold varied from 18 to 30 seconds, being optimized for each sample (although it was later determined that mold cooling time had minimal effect on retardation). Injection pressure was nominally set at 1200 psi, with injection speed varied between a 0 and 100% speed setting on the machine. Typically faster rates gave the best optical performance.
CAP composition, properties, molding conditions, and retardation data is shown in Table 3. CE70 and 71 involved lower DS CAP and retardation values tended to be higher, regardless of how processing conditions were adjusted. The plaques look white and/or gray when viewed through crossed polarizers. Examples 72 through 74 were high DS CAP resins according to embodiments of the invention and retardation was reduced significantly. It was also determined that by profiling the injection pressure and reducing the pack and hold pressures relative to the injection pressure, the retardation in the gate region could be reduced to near zero (as in 73 and 74). Note that even though the retardation in the gate was near zero as measured with the polarimeter, there was still a violet hue to the material around the gate. As shown in a later example, this is due to dispersion of the retardation as a function of wavelength. It is believed that it is should be possible to eliminate this violet hue with further adjustments or it can be excluded from the viewing area of the display.
Example 75 had an intermediate DS and so its optical performance was borderline. Retardations shifted higher over most of the plaque and it was impossible to eliminate the retardation in the gate region.
In this example, a 2 mm thick HMI panel was molded on a 200 ton injection molding machine. The panel was 160 mm wide on the gated end and expanded to 200 mm on the far end. The length of the panel was 150 mm, with the part curving slightly to simulate a typical HMI touch cover. A fan gate was used that was roughly 65% of the width of the part. Mold temperature was set at 85° C. and barrel temperature was 215° C.
Screw speed was nominally 110 RPM with an injection rate of 7.5 cm/s for all of the runs which was near the max the molding machine would provide before flashing occurred. It was observed that lower birefringence was observed with faster injection rates, so a machine with higher clamp pressure should provide even better performance. Other variables had less of an effect on retardation.
Two CAP materials were molded, the first being identical to Ex 46 and having an FBV of 16. The second had a DS(Pr) of 2.04, a total DS of 2.94, and an FBV of 25. Both materials produced plaques that were near uniformly black when viewed through crossed polarizers. The only exception was a violet hue near the gate region. Both had retardations ranging from 0 nm to a maximum of about 35 nm when measured with the polarimeter and a white light source. There was no noticeable change in the plaque color when viewed from different angles.
The plaque for Ex. 100 was also measured using an ellipsometer and the data plotted in
Although not tabulated, when we measure values of Rth for other polymers like PC were measured, it was not uncommon to have very high values, often exceeding 1000 nm or more. It was discovered that it was very difficult to control Rth when the material had high SOC values and so producing a part with good viewing angle consistency can become very difficult.
To illustrate thermoforming as method for producing HMI panels, sheet was extruded from each of several resins and then thermoformed into a tray mold using a Hydratrim laboratory thermoformer. The sheet was nominally 0.6 mm thick and produced by extrusion on a 50 mm single screw extruder. The tray mold was for a dinner tray for frozen food items, and was 16 cm×12 cm, with a 4 cm depth of draw. Sheet was first preheated in an oven at 287° C. for 13 to 20 seconds, and then drawn into the mold with vacuum assist, before cooling. The mold was maintained at ambient conditions.
Comparative Example 200 used the same CAP as CE44 and had an FBV of 20. After forming, the bottom of the tray had variations of white and black color when viewed between crossed polarizers, with a range of retardation (Re) from about 0 to 125 nm.
Example 201 was produced using the same CAP resin as in Ex 47 that had an FBV of approximately 5. The retardation was consistently at or very near 0 nm across the bottom of the part and was uniformly black in appearance between crossed polarizers.
Example 202 was identical to 201 except it had 6% of Admex 770 polymeric plasticizer compounded in during formulation. It produced slightly more retardation than 201 with a maximum retardation of about 20 nm, but which was still almost solid black in appearance when viewed between crossed polarizers.
Example 203 was a cellulose tripropionate resin (CTP) similar to Ex 48 but also contained 15% of TEG-EH plasticizer. Parts formed had a range of retardation from about 0 to 40 nm. The part was fairly uniform black/gray with very little shadowing.
In this example two different CAP materials were molded into 10 cm×10 cm×2 mm thick plaques. CAP1 material was molded using a 1999 Toyo Si-110 injection molding machine with a GP Screw under the following conditions:
CAP 2 material was molded using a Toyo M90 injection molding machine under the following conditions:
The plaques were placed an ESPEC Model BTX-475 Environmental Chamber and exposed to conditions of 90° C. and 95% RH for 72 Hrs. The percent haze for each plaque before and after exposure were measured. The moisture absorption was also measured for each material. The CAP properties, as well as haze and moisture absorption data are listed in Table 4.
A review of Table 4 reveals that CAP material having the higher DS (or lower hydroxyl content), had less than 8% difference in moisture absorption, but significantly less haze (or haze increase) after exposure to the high temperature and humidity conditions.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2020/024561 | 3/25/2020 | WO | 00 |
| Number | Date | Country | |
|---|---|---|---|
| 62826068 | Mar 2019 | US |
