阅读说明：本技术 一种由低羟基纤维素酯制成的具有低双折射的人机界面显示器外壳 (Human-computer interface display shell with low birefringence and made of low-hydroxyl cellulose ester ) 是由 马库斯·大卫·谢尔比 劳拉·鲍尔·韦弗 托马斯·约瑟夫·佩科里尼 迈克尔·盖奇·阿姆斯特朗 于 2020-03-25 设计创作，主要内容包括：提供了一种用于人机界面(HMI)触摸面板显示器的光学透明保护外壳板,其中外壳板由包含纤维素酯的纤维素酯组合物形成,该纤维素酯具有低羟基含量以及2.85至3范围内的总取代度(DS)。(An optically transparent protective skin plate for a Human Machine Interface (HMI) touch panel display is provided, wherein the skin plate is formed from a cellulose ester composition comprising a cellulose ester having a low hydroxyl content and a total Degree of Substitution (DS) in the range of 2.85 to 3.)

1. A human-machine interface housing in the form of a sheet having a thickness of about 2mm to about 5mm comprising a cellulose ester composition comprising a cellulose ester having a low hydroxyl content and a total Degree of Substitution (DS) in the range of 2.85 to 3.

2. The human-machine interface housing of claim 1, wherein the cellulose ester has a DS in the range of 2.9 to 2.97.

3. The human-machine interface housing of claim 1 or 2, wherein the housing has a total optical delay range span of 160nm or less as measured by the difference between maximum and minimum delay values over a viewable area of an HMI faceplate.

4. The human-machine interface housing of claim 3, wherein the housing has a total optical delay range span of 100nm or less as measured by the difference between maximum and minimum delay values over a viewable area of an HMI faceplate.

5. The human-machine interface housing of any one of claims 1 to 4, further comprising one or more compensation film layers.

6. The human-machine interface housing of any one of claims 1 to 5 having a total optical retardation in the range:

(i) -from 100 to 100nm,

(ii)100 to 300nm, or

(iii) -100 to-300 nm.

7. The human-machine interface housing of claim 6, wherein the housing exhibits total optical retardation in the range of-80 nm to 80 nm.

8. The human-machine interface housing of claim 6, wherein the document exhibits a total optical retardation of 100nm to 260nm or-100 nm to-260 nm.

9. The human-machine interface housing of any one of claims 1 to 8, wherein the cellulose ester has a DSOH in the range of 0 to 0.15.

10. The human-machine interface housing of claim 9, wherein the cellulose ester has a DSOH in the range of 0.03 to 0.1.

11. The human-machine interface housing of any one of claims 1 to 10, wherein the cellulose ester composition further comprises up to 20 wt% of a plasticizer.

12. The human-machine interface housing of any one of claims 1 to 11, wherein the cellulose ester composition further comprises up to 20 wt% of a polymer miscible with the cellulose ester.

13. The human-machine interface housing of any one of claims 1 to 12, wherein the cellulose ester is selected from CAP, CAB, or a combination thereof.

14. The human-machine interface housing of any one of claims 1 to 13, wherein the cellulose ester is CAP.

15. The human-computer interface housing of any one of claims 1 to 14 wherein the housing further comprises a hard coating or an IML film.

16. The human-computer interface housing of claim 15, wherein the hard coating is selected from a silicone based hard coating, a (poly) siloxane based hard coating, a urethane based hard coating, or an acrylic based hard coating.

17. A method for manufacturing a human-machine interface housing according to any one of claims 1 to 16, comprising the steps of:

(a) providing a mold configured for injection molding, the mold comprising a gate at one end of the mold, the gate having an opening configured to introduce molten thermoplastic polymer into the mold and a mold width at the gate end of the mold of at least 150mm, wherein the gate opening has a width of at least 50% of the mold width; and

(b) injection molding the housing at a barrel temperature of at least the thermoplastic polymer Tg (° C) +60 ℃.

18. The method of claim 17, wherein the gate opening has a width that is at least 60% of the mold width.

19. The method of claim 17 or 18, wherein the barrel temperature is at least the thermoplastic polymer Tg (° c) +80 ℃.

20. The method of any one of claims 17-19, further comprising injection molding the housing at an injection speed of at least 5 cm/s.

Technical Field

The present invention relates generally to optically transparent panels, such as human interface touch displays; in particular, the present invention relates to certain plastic touch panel housings made from low hydroxyl cellulose esters.

Background

Human-machine interface (HMI) displays are becoming more common in automobiles because they provide passengers with more control over the interior through a single interface. For example, entertainment systems, air conditioning, lighting, etc. may be controlled by the single touch panel display through multiple selection options. HMI displays typically include some sort of optical module (e.g., a Liquid Crystal Display (LCD) panel, an Organic Light Emitting Diode (OLED), etc.) and a protective, optically transparent "touch panel" on a surface. Touch panels need to be both scratch resistant (allowing for frequent physical contact) and have very low optical birefringence to minimize optical shadowing.

Glass meets these criteria and is currently the material of choice, but is still considered to be inadequate because it adds additional weight and has poor impact resistance (which can lead to the risk of injury in a collision). Automobile manufacturers also desire greater design flexibility in automobile interiors, including larger and higher degree of curvature/definition HMI faceplates. This design is completely impractical for glass and therefore requires other options.

It has been desired to replace glass with plastic because it can be more easily molded into different shapes while still providing better impact strength. However, molded plastics tend to have residual orientation and stress that leads to optical birefringence in the panel. This birefringence in turn can lead to undesirable optical defects, most notably "shadowing". For example, shadows can occur whenever the driver looks at the HMI display wearing polarized sunglasses. The polarized lenses impart additional color and/or intensity gradations in the panel, making the panel look "mottled". The only way to eliminate this shadowing today is to use a very low birefringence material, such as glass, as the touch panel material.

It is also important to maintain low birefringence and optical clarity without sacrificing impact strength. Some polymers, such as acrylics, such as poly (methyl methacrylate) (PMMA), can be molded with sufficiently low birefringence, but these materials are inherently brittle and therefore unacceptable from a safety or reliability standpoint.

Disclosure of Invention

In one aspect, the present invention relates to an optically transparent protective housing or housing plate for a Human Machine Interface (HMI) touch panel display, wherein the housing plate is formed from a 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, where a DS of 0 indicates no ester pendant groups (i.e., pure cellulose) and a DS of 3 indicates a fully esterified cellulose ester. In embodiments, the DS is in the range of 2.9 to 2.97. It has been found that cellulose esters having the DS described herein can provide panels having substantially "zero birefringence" behavior. In embodiments, the acyl group may be selected from acetyl, propionyl, and butyryl, or a combination thereof. Cellulose esters substituted with these groups can maintain a high glass transition temperature. It is also contemplated that long chain acyl groups may be included, particularly at lower levels.

In an embodiment, the human-interface housing of the invention has a very low optical retardation, wherein all parts of the optical panel in the visible region have an in-plane optical retardation Re in the range of-100 nm to 100nm, and a thickness retardation Rth also in the range of-100 nm to 100 nm. Such a low retardation panel does not require any additional compensation film.

In another embodiment, all portions of the optical panel in the visible region have an in-plane optical retardation Re in the range of-80 nm to 80nm, and a thickness retardation Rth in the range of-100 nm to 100 nm.

In another embodiment, all portions of the optical panel in the visible region have an in-plane optical retardation, Re, in the range of-50 nm to 50nm, and a thickness retardation, Rth, in the range of-100 nm to 100 nm.

In an embodiment, the outer shell plate can further comprise one or more compensation layers to provide an outer shell plate assembly, wherein the compensation layer(s) can provide the outer shell plate assembly with a total optical retardation that falls within an acceptable range for HMI shell applications. In an embodiment, the closure plate assembly exhibits a total optical retardation in a range selected from: (i) from-100 to 100nm, (ii) from 100 to 300nm, or (iii) from-100 to-300 nm; alternatively, the absolute value of the delay is 0 to 100 or 100 to 300. In other embodiments, the closure panel assembly exhibits a total optical retardation in a range selected from: (i) from-80 to 80nm, (ii) from 100 to 260nm, or (iii) from-100 to-260 nm; alternatively, the absolute value of the delay is 0 to 80 or 100 to 260. In another embodiment, the closure panel assembly exhibits a total optical retardation in a range selected from: (i) from-50 to 50nm, (ii) from 130 to 230nm, or (iii) from-130 to-230 nm; alternatively, the absolute value of the delay is 0 to 50 or 130 to 230. In an embodiment, the closure plate assembly exhibits an overall optical delay (as described above) over at least the visible portion of the HMI display.

Drawings

FIG. 1 is a typical cross-polarizer setup for measuring birefringence.

Fig. 2 is a close-up of the horizontal and vertical components of the waveform diagram delay and phase shift.

Fig. 3 depicts the effect of tilt angle on effective refractive index.

Fig. 4 depicts a schematic diagram of a typical LCD structure.

Fig. 5 is a schematic diagram of an LCD configuration assuming a polarized sunglasses is worn by an observer.

FIG. 6 is a schematic diagram of an LCD configuration assuming the addition of a compensation layer on the HMI touch screen.

FIG. 7 is a depiction of an injection mold containing a lap gate with an associated polymer flow front.

FIG. 8 is a depiction of an injection mold containing a fan gate with an associated polymer flow front.

Fig. 9 is a plot of Re and Rth values for molded plaques using Cellulose Acetate Propionate (CAP) of the present invention.

Detailed Description

Shadow is an optical defect that occurs when a passenger views the HMI display while wearing polarized sunglasses. It produces a brightness change from grey to white which has the effect that the display appears distorted and/or mottled. This distortion is caused by local variations in birefringence. Whereas birefringence refers to the difference in refractive index of a given transparent substrate in different directions, which is caused by stress and/or molecular orientation. This shading usually consists of a change in grey coloration, but when the optical birefringence is sufficiently large, it can even lead to a color shift in the display, starting with yellow and then orange, red, violet, up to the entire color spectrum. It is desirable that no color change occurs and the display maintains a uniform color, e.g. black or grey, but white is also acceptable.

The birefringence of a substrate is expressed as Δ, and is defined as the difference in refractive index n between any two mutually perpendicular directions. Typically, these directions will be related to, for example, the Machine Direction (MD), the Transverse Direction (TD), and the thickness direction (thick). If these directions are indicated by subscripts a, b, and c, three different values of birefringence can be calculated.

Δ_ab＝n_a-n_b

(1) Δ_bc＝n_b-n_c

Δ_ac＝n_a-n_c

Only two of the three are independent and the choice of which is best used depends on the application. Birefringence is a parameter that takes a vector by refractive index reflection. The refractive index, in turn, is an inverse measure of the speed of light in the medium, assuming that the light wave is polarized in that particular direction. Higher value of n means lower speed, so if n is_a＞n_bThis means that light waves polarized in the a direction will be more polarized than in the b directionPolarized light waves propagate more slowly. Thus, given a sufficient distance, the light wave along a will lag further behind b and become increasingly out of phase.

FIG. 1 shows the birefringence of a sample in a typical crossed polarizer configuration. The light source 1 provides random unpolarized light 2 to a first polarizer 10 having a polarization axis at +45 degrees from the vertical. The resulting polarized light 3 is then incident on a sample 20 of thickness L, the principal axes of which are aligned with the vertical and horizontal directions and each having a refractive index n_aAnd n_b。

For simplicity, the incident light wave 3 can be vectorially decomposed into electric field components along the vertical and horizontal axes and perpendicular to the propagation direction. Given the different refractive indices, each of these components will then propagate at a different velocity in the sample. Due to this difference in velocity, the emergent wavefronts 5 and 6 will be phase separated by a distance 8 (FIG. 2), which is denoted as the optical retardation. Retardation is expressed in nanometers, or as a fraction of the wavelength λ in the medium. For plastics, a white light source is assumed, with a wavelength of approximately 570 nm. Thus, a "quarter wave" retardation is a sample with a retardation of about 142nm (or one-fourth of 570 nm).

When the two components 5 and 6 reach the second polarizer 30, the waves are effectively recombined to produce an output wave 8 seen by an observer 90. If the delay is zero, the waves remain in phase and add back to their original amplitude and direction. Since the combined wave is now oriented at 90 degrees to the second polarizer, it will be completely blocked and there will be a black or zero state with no light transmission. This is the same black state that would be observed through two crossed polarizers in the absence of the sample.

Conversely, if the two components are out of phase, vector addition will result in a portion of the wave being aligned with the second polarizer, thereby causing it to be transmitted. This "light leakage" will vary with the level of retardation and will reach a maximum as the retardation increases and will eventually return to near zero at integer multiples of the wavelength of the hypothetical monochromatic light. If the delay is equal to λ, it is denoted as the first order extinction point. Likewise, additional extinction occurs at 2 λ, 3 λ, etc., denoted as second and third order extinction points, respectively.

For white or polychromatic light, each color corresponds to a different wavelength and, assuming constant retardation of the portion, each color will experience a different degree of extinction. For example, blue and violet are much shorter in wavelength than red, so as the retardation level increases they will experience more relative phase shift (e.g. if λ is 400nm, a 100nm retardation shift will be equivalent to a quarter-wave shift, but for a 600nm wavelength will only be a λ/6 shift). As the intensities of the various colors undergo different shifts, the color of the transmitted light also changes. At zero retardation, no light is transmitted and the color appears black. With increasing retardation, the color changes from black to dark gray and then to white at about 100 nm. White color is maintained between about 100nm and 300nm, and a shift towards yellow begins at 300 nm. From yellow to orange, then red and finally to violet at the first extinction point of 570 nm. Above 570nm, the color cycle is essentially repeated, although with some slightly different color shifts. However, in the case of HMI housing plates, retardation levels in excess of 570nm are unacceptably high from a shading perspective.

The retardation change from about-100 nm to +100nm typically appears black to gray with minimal shading. Also, retardation variation in the range of 100 to 300nm (or-100 to-300) provides a nearly uniform white appearance, and shows minimal shading. In an embodiment, both ranges are the delay targets of the present invention. In certain embodiments, the former range is a preferred target for the ultra-low retardation resins described herein. It should be noted that in any given range, lower delay variability across the entire tile is preferred, but this is believed to be the approximate maximum level of variability that can occur within this band while still maintaining reasonable optical uniformity.

The delay in any two directions (i, j) can be easily calculated from the thickness of the part L as follows:

(2) R_ij＝LΔ_ij

as with birefringence, there are multiple retardation values depending on the direction selected. For shading purposes, two values are of particular importance, denoted Re and Rth. They are defined as follows:

(3) Re＝R_MD-TD＝L(n_MD-n_TD)

(4)

this assumes that the a, b and c directions correspond to the MD, TD and thickness of the part, respectively. Re and Rth are important for shading for different reasons. Re represents the retardation and phase lag of a light wave propagating perpendicular to the surface, as shown in fig. 1. Note that Re is not bound by n_thickBecause the normal incident wave is polarized only in the plane direction (MD/TD).

However, for off-axis or oblique viewing, n must be taken into account_thickThus, Rth is required. This is illustrated in fig. 3, where light waves parallel to the page 65 are incident on the sample at an angle (the vector represents the direction and magnitude of the electric field component perpendicular to the direction of propagation). After refraction, the direction of this light component changes slightly to 66. The sample is assumed to have an anisotropic refractive index ellipsoid 60 in which the refractive index in the thickness direction 62 is smaller than the refractive index in the plane direction 61. This is typical of most films or molded parts having in-plane orientation.

It is known that the refractive index varies between principal axes with an elliptical shape. For normal incidence, the polarization direction will correspond to the horizontal/planar refractive index 61. But as the angle increases, the effective index corresponds to the point on the ellipsoid where the polarization vectors intersect. The effective index approaches the thickness value 62 as the tilt angle increases. It should be noted that if the thickness and the in-plane refractive index are the same, as described below, then 60 will take the shape of a sphere rather than an ellipsoid, and thus the effective refractive index will not change with tilt angle. Ideally, we would like to have very small Rth and Re in the display housing to minimize any shading. It is also preferable that the value of Rth be equal to or close to Re so that no noticeable shading occurs when the viewing angle is changed.

It is important to note that shadowing and retardation occur only in the presence of an optical polarizer. In practice, shadowing occurs only when a retardation shift occurs between two polarizers (e.g., 10 and 30 in fig. 1). The effect of the polarizer pair is to first isolate a certain polarization direction, then allow the relative phase shift or retardation of the wave components, and then to recombine the polarization components vectorially so that constructive and destructive interference occurs. Without these polarizers, this interference does not occur. As such, unless the viewer wears polarized sunglasses, no shadows appear.

Although the display module itself has a pair of polarizers, the (HMI) touch panel is not between these polarizers and therefore no additional optical interference occurs. However, when wearing sunglasses, the situation changes because the touch panel is now located between the second polarizer of the LCD module and the polarized sunglasses. Sunglasses essentially incorporate a third polarizer, and hence a second polarizer pair, and all that is between these polarizers must now be taken into account when attempting to reduce shading. The following description of an example HMI faceplate is provided for further explanation.

Examples of LCD structures

A typical structure of an LCD-based HMI panel is shown in fig. 4. The only elements included are those optically relevant to the system, and other layers, such as those used for electrical switching and sensing, are not included in the figures. It should also be noted that there are many other design elements and structures that may be included in an LCD module (e.g., light diffusers, brightness enhancement films, color filters, etc.), but these are not critical to explaining optical shading or the present invention and are therefore not shown. It should be noted that these elements are typically present in the module in one of many possible forms, and that these variations may be included in embodiments of the invention.

The LCD module is very similar to the arrangement in fig. 1, except now the "sample" is replaced with a liquid crystal module 50. As previously described, first and second polarizer stacks 10, 30 and some sort of backlight 1 are present to provide illumination. The first polarizer has a polarization axis phi with respect to a reference perpendicular direction, and the second polarizer is typically rotated 90 degrees with respect to this direction. Typically, the angle φ is 45 degrees, but this is not required.

The polarizer typically also includes a protective or "compensation" film that sandwiches the active polarizing elements (13 and 33). They are denoted 11 and 12 for the first polarizer and 31 and 32 for the second polarizer. Layers 11 and 32 are typically made of solvent cast cellulose triacetate films or cycloolefins. Because they are "external" to the polarizer pair, they generally do not affect retardation, and thus their retardation is generally not critical. In contrast, layers 12 and 31 are between the polarizers, so their retardation affects the visual quality. For conventional LCD applications, these films are typically designed with specific specified Re and Rth in order to counteract any residual retardation in the liquid crystal module. By properly designing these compensation films, the viewing angle and contrast of the display are significantly increased.

The retardation effect discussed above with respect to fig. 1 is also applicable to liquid crystal displays, except that the liquid crystal module 50 is a material whose birefringence changes dynamically (as opposed to the static birefringence of the sample 20). There are different types of liquid crystal cells on the market, but regardless of the type, the liquid crystal molecules change direction and alignment in response to an applied voltage. By changing this arrangement and thus the birefringence, the brightness of light passing through can be modulated from dark to light using the principles previously described, thereby turning a given pixel on or off. By passing the light through a color filter, various colors can be obtained.

Upon exiting the second polarizer, the light will pass through the display housing 70. In most applications, such as a conventional LCD television, light will pass through the protective housing and reach the viewer. Since there is no other polarizer behind the housing, its retardation has no effect on the visual quality.

However, this situation can change if a 3 rd polarizer is introduced, for example, the viewer wears polarized sunglasses. This is indicated as 80 in fig. 5. These polarizers typically have vertically aligned polarization axes (0 degrees) because this may better reduce glare because most of the reflected light from the road and water surface is horizontally polarized. In this case, the layers 12, 31, 32, and 70 may all affect the retardation (except the liquid crystal module 50), and thus may affect the shading. Without sunglasses, only 12 and 31 have an effect on visual quality.

FIG. 6 illustrates another aspect of the present invention, including an additional optical compensation film, indicated at 71. As previously mentioned, films 12 and 31 are typically compensation films having the specified retardations Re and Rth and are designed to counteract some of the extraneous retardation from the liquid crystal module itself. By eliminating the unwanted delay in the module 50, panel manufacturers can significantly improve contrast and viewing angle performance.

In automobiles, these films (12 and 31) can also potentially affect shadows, so one option is to modify the retardation of these films even further to reduce the perception of shadows seen by passengers wearing polarized sunglasses. However, this option is not preferred because under normal conditions when sunglasses are not being worn, adjustment of the compensation films 12 and 31 can compromise visual performance. Instead, it may be preferable to add an additional compensation layer 71 to the touch panel itself, or to replace the location of or on top of layer 32. Films are easier to achieve a specified level of retardation than molded products, and this therefore provides an alternative way of increasing or decreasing the retardation as required. In embodiments, the film (shown on the touch surface) may also be applied to the surface as a protective layer having scratch resistance, hard coat, and the like. In an embodiment, such a film may also be applied to the underside of the panel (not shown), if desired. Application may be by direct adhesion, in-mold labeling/decoration, etc.

In embodiments, the HMI touch panel may be bonded to the liquid crystal display component/assembly with a Liquid Optically Clear Adhesive (LOCA) or Optically Clear Adhesive (OCA) film (or tape) (e.g., the touch panel may be bonded to a polarizer layer or a protective layer on a polarizer layer located between the liquid crystal module and the touch panel). Such adhesives may also be used to adhere a protective housing, such as a lens or hard coat, to a touch panel. In embodiments, the adhesive is cured with ultraviolet light (UV), heat, moisture, or a combination thereof, according to the manufacturer and specifications of the LOCA or OCA.

In embodiments, the LOCA or OCA may improve the optical performance of the display, for example by eliminating air gaps between the adhesive layers. In an embodiment, such optical coupling may improve contrast, and thus visibility, by reducing the amount of reflected light. Reflection from the touch panel screen or protective cover cap layer and the adhesive can reduce the visibility of the LCD. Reflection may be caused by an impedance mismatch between the air and the one or more layers. Reflection can make white brighter, but can dilute black and other colors, thereby reducing contrast. In certain embodiments, LOCA is selected to match the index of refraction of the HMI touch panel to minimize losses. In embodiments, the LCOA or OCA comprises acrylic-based and/or siloxane-based chemistry.

In an embodiment, the touch panel is molded with in-mold decoration (IMD) or in-mold label (IML) to provide indicia and/or passive tactile features. In embodiments, the IMD or IML is a thin film that transfers a decorated and/or UV-curable hardcoated surface to a plastic touch panel. The IML film has a coating against the mold. A molten thermoplastic (e.g., a cellulose ester thermoplastic) is injected such that it contacts the surface of the film facing the interior of the mold and has good adhesion to the thermoplastic. Once the molded part is released from the mold, the coating on the IML film will undergo a UV curing step that hardens the surface and can impart scratch and chemical resistance. Other functions that may be imparted to the outward facing surface (of the molded part) include anti-fingerprint (oleophobic properties), anti-glare, and/or anti-reflective properties. In an embodiment, the tag may be associated with a control function of the HMI unit. In embodiments, multicolor screen and offset printed graphics may be used to create the indicia or graphics. In certain embodiments, a second surface graphic is used in which the decoration is printed on the back side of a transparent backing film (e.g., a polycarbonate, acrylic, or cellulose film) and the plastic is contact-injected on the ink side of the film (e.g., during injection molding). This encapsulates the decoration between the film layer and the injected plastic so that the decoration does not wear out during use. In embodiments, a vision system may be used to ensure accurate label positioning and may verify label correctness. In embodiments, printing can be performed by any known method, such as digital printing (e.g., inkjet or xerography), spraying, transfer, flexographic printing, gravure printing, and the like.

In embodiments, the thickness of a touch panel module constructed using IMD or IML is relatively thinner than a similar touch panel constructed using a printed layer bonded by LOCA or OCA. In embodiments, IMD technology may be used to provide hardcoat and/or ink transfer marks.

HMI display production

In one embodiment, the HMI touch panel is prepared by injection molding or Compression Injection Molding (CIM). Both techniques have been used to manufacture optical discs. A third option is to use thermoforming, in particular to make larger panels. Thermoforming requires extruding and forming a heated sheet into a mold. This has the advantage that larger size parts can be manufactured, but has the disadvantages of high scrap rates, possibly high stress levels, and difficulty in moulding lugs and attachment points.

One key aspect of any production technique is minimizing birefringence. There are two main types of birefringence, namely, orientation birefringence and "glassy" or stress-dependent birefringence. The former is caused by residual chain orientation left in the part after molding, while the latter is caused by thermal stresses formed during cooling of the part. For each production method, both parts will be changed independently.

Conventional polymers for automotive applications include Polycarbonate (PC) and PMMA. Among them, PC is inferior to PMMA in birefringence because a small change in residual stress (or residual orientation) causes a large change in birefringence. This sensitivity is usually quantified by the Stress Optical Coefficient (SOC), which is the birefringence change that occurs when the unit stress changes.

(5)Δ_ij＝SOC*(σ_i-σ_j)

Where σ i is the stress in the i direction. A given material has two SOC values, one for stresses above the glass transition temperature in the rubbery State (SOC)_R) And the other for the stress in the glassy State (SOC)_G). The former involves oriented birefringence, the latter is the more traditional stress-dependent birefringence. For PC, two SOC values are typicallyAre much higher than 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 significantly change SOC values, even to a point near zero. It has been found that this allows the birefringence to be adjusted more finely during moulding than polycarbonate or acrylic.

During injection molding, the mold geometry and gate effects are very important with respect to stress and birefringence. Fig. 7 shows a simple plaque mold 101 with an overlapping gate 102, and a flow front of polymer entering the mold 105. The polymer entering through the runner 100 has undergone orientation and alignment and continues as it enters the mold.

With such a small lap gate, a radially progressive flow similar to balloon expansion occurs. The polymer is stretched radially and circumferentially, which results in principal stresses σ r and σ in the radial and circumferential directions (108)_Θ. As shown in the above equation (5), birefringence increases with an increase in the relative stress difference, and the stress difference near the gate tends to be very high. Due to this radial stress mode, the orientation and birefringence curves will have similar radial geometry, which is used to magnify the shadow, since there will be more angular dependence. Thus, in embodiments, it is preferable to employ a wider fan or film gate that provides a more uniform flow front through the part. This is shown in fig. 8, where the flow from 106 is now more uniform and the molecular orientation is also more consistent throughout the entire section. This will reduce the angular dependence of the shadowing, as the stress difference 108 will be more consistent. In embodiments where the delay onset is very low, the angle dependence may not be a major factor and the choice of gate configuration is no longer critical.

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 articles, such as optical discs, this can reduce birefringence more than conventional injection molding alone.

Thermoforming is another alternative for producing display housings, which allows for larger panels than conventional injection molding. Thermoforming offers the additional advantage that multilayer structures can be easily produced. For example, the cellulose esters of the present invention can be coextruded between cap layers of PMMA to create a hardcoat surface. The three-layer sheet can then be thermoformed into the final part as long as the sheet and die temperatures are set to suit the materials involved.

Multilayer thermoforming offers the further advantage that the upper service temperature of the part can be adjusted by using layers with appropriate glass transition temperatures. Likewise, the cap layer can help act as a protective layer to prevent moisture from entering the sheet interior and to keep volatile compounds (e.g., plasticizers) inside the structure. This may allow the use of highly plasticized cellulose esters as the core layer, and harder cap layers (e.g., PMMA, PC) to seal the plasticizer and offset the lower Tg.

Any combination of layers is contemplated by the present invention, as it is critical that only the overall structure meet birefringence requirements, and that at least one layer contains the low hydroxyl cellulose esters of the present invention. Since the protective cap layer can be kept thin, even higher birefringence layers can be used, since the total retardation produced can be kept to a minimum.

In one embodiment, the component thickness of the HMI display ranges from about 1mm to about 10mm, or 1mm to 8mm, or 1mm to 5mm, or about 2mm to about 10mm, or 2mm to 8mm, or 2mm to 5mm, or greater than 2m to 5mm, or 2mm to 4mm, or from 2mm to 3 mm. Thickness has a significant effect on birefringence and retardation because, as previously mentioned, retardation is equal to birefringence multiplied by thickness. Thus, the thicker portion will have a higher delay, all things being equal. However, it has been found that thicker parts may have reduced filling pressure and therefore reduced levels of oriented birefringence. Therefore, even with higher thicknesses, the average birefringence across the entire part may be lower, and thus the overall retardation may sometimes be reduced. Thicker parts are preferred from the point of view of impact resistance and crashworthiness, but not too thick, as this adds additional weight. In an embodiment, the thickness is about 2 to 3 mm.

It has been found that higher polymer melt temperature molding can also help reduce birefringence by reducing viscosity, reducing overall stress and orientation formation. There is often a practical upper limit to molding of most materials before excessive degradation and/or flashing becomes a problem.

The mold temperature may also be increased to reduce stress, although this would result in longer cycle times (due to longer cooling cycles). The mold temperature has a particularly strong influence on the residual stress and the birefringence caused by the stress resulting from cooling. To help further reduce this, the part may also be annealed after molding at a temperature near the glass transition temperature Tg. This can minimize the stress component of birefringence, but generally does not affect oriented birefringence. Moreover, this is less desirable because it significantly increases cycle time and cost.

Other processing parameters, such as injection rate/pressure, can affect the formation of birefringence, and the fill rate can be plotted to optimize birefringence. It has been found that by operating at higher injection fill rates and/or mold fill pressures, particularly at the end of filling, birefringence can be reduced, particularly in the gate area. Likewise, the holding pressure should be kept high, but low enough to prevent flashing. If the filling rate is too low, the cooling effect during filling is considered too strong, which increases the orientation birefringence, since the material has to flow through the more viscous skin layers.

It was also observed that by plotting the pressure during filling, birefringence can be minimized, particularly in the gate region. It was found that a high initial fill rate and pack pressure, followed by a slight reduction in pack and hold pressures, reduced gate birefringence compared to a constant pressure profile.

Reducing the molecular weight of the polymer can reduce the viscosity and orientation that occurs during molding. However, lower molecular weights are generally a trade-off with toughness and impact strength.

In embodiments, the cellulose esters useful in the present invention may be of sufficient content of C₃-C₁₀Any cellulose ester of a salt or ester moiety of an acid, preferably a propionate and/or butyrate moiety. Cellulose esters useful in the present invention generally comprise recurring units of the structure:

wherein R is¹、R²And R³Independently selected from the group consisting of hydrogen or straight alkanoyl groups having 2-10 carbon atoms. For cellulose esters, the substitution level is typically expressed in terms of Degree of Substitution (DS), which is the average number of non-OH substituents per anhydroglucose unit (AGU). Typically, conventional cellulose contains three hydroxyl groups in each AGU unit that may be substituted; thus, DS may have a value between 0 and 3. However, low molecular weight cellulose mixed esters may have an overall degree of substitution slightly above 3 due to the contribution of the end groups. Natural cellulose is a large polysaccharide with a degree of polymerization of 250-. However, as the degree of polymerization decreases, as in low molecular weight cellulose mixed esters, the end groups of the polysaccharide backbone become relatively more important, resulting in a DS that can exceed 3.0. Since DS is a statistical average, a value of 1 does not guarantee that each AGU has a single substituent. In some cases, there may be unsubstituted anhydroglucose units, some with two substituents and some with three substituents, and typically this value is a non-integer. The total DS is defined as the average of all substituents per anhydroglucose unit. The degree of substitution per AGU may also refer to a specific substituent, such as hydroxy, acetyl, butyryl or propionyl. In embodiments, the degree of polymerization of the cellulose ester is lower than the degree of polymerization of the native cellulose. In embodiments, n is an integer ranging 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) housing in the form of a sheet having a thickness of about 2mm to about 5mm comprising a melt processable cellulose ester having a total Degree of Substitution (DS) of 2.85 to 3 is provided. In an embodiment, the DS is in the range of 2.9 to 2.97 and more closely represents "zero birefringence" behavior. Alternatively, DS may be expressed in terms of the number of hydroxyl groups DSOH. In embodiments, the cellulose ester has a DSOH in the range of 0 to 0.15, or 0.03 to 0.1. In embodiments, the acyl group preferably consists of acetyl, propionyl, and butyryl.

By having the overall DS within the ranges discussed herein, it has been found that the refractive index perpendicular to the backbone is approximately equal to the refractive index parallel to the backbone. Thus, the birefringence of the monomer is close to zero, SOC_RThe value is also very close to zero. Thus, any orientation that occurs during the molding/shaping process has a negligible effect on birefringence and/or retardation. Conversely, when the total DS is below about 2.85, it has been found that sufficient hydroxyl groups are present such that the refractive index along the chain axis relative to the perpendicular is significantly higher, the SOC_RNo longer negligible.

In the examples, the cellulose ester composition may also contain up to 20 wt% plasticizer, although automotive restrictions on Volatile Organic Compounds (VOCs) indicate that ideally the plasticizer level should be zero, or very close to zero, unless the cellulose ester is sealed with a varnish or paint. Alternatively, if a multi-layer thermoforming process is used, the cellulose ester may be sandwiched between layers, which helps prevent plasticizer migration. In an embodiment, a relatively low volatility high molecular weight plasticizer may be used.

Also, in embodiments, up to about 20 wt% of the miscible polymer may be blended with the cellulose ester. Examples include certain ethylene vinyl acetate (EVAc) copolymers, certain aliphatic polyesters such as poly (butylene succinate) and/or poly (ethylene succinate), polyvinylidene fluoride (PVDF), epoxy resins, polyvinylpyrrolidone, and the like.

In embodiments, the cellulose ester composition may also contain typical additives including impact modifiers, processing aids, stabilizers, UV protectors, colorants, and the like.

Due to applicability and processability requirements, in the examples, the Tg of the cellulose ester plus any plasticizer/modifier is in the range of 105 ℃ to 160 ℃, 105 ℃ to 150 ℃, 110 ℃ to 160 ℃, or 120 ℃ to 150 ℃. In an embodiment, the lower Tg limit may be determined by requirements related to high temperatures that may occur in the interior of the automobile, particularly in hotter climates. In such embodiments, the display housing must not warp, creep, or otherwise deform under these conditions. In the examples, the higher Tg temperature requirement can be determined by requirements related to melt processability limitations. As Tg increases, the processing temperature required to fully melt and plasticize the resin also increases, and higher melting temperatures can lead to increased yellowing and degradation. It should be noted that in the case of a multilayer thermoformed HMI shell, the Tg limitation is not so limited as long as the additional layers provide the necessary high temperature stiffness to support the faceplate.

As mentioned previously, molecular weight is also important because it affects strength and birefringence. In the examples, the number average molecular weight (polystyrene equivalent) should ideally be between about 40000 g/mole and 80000 g/mole to maintain adequate toughness. High molecular weight materials have better toughness, but flow orientation and birefringence tend to increase. Fortunately, using low hydroxyl resins according to the examples herein, it has been found that the material is relatively insensitive to flow orientation and therefore higher molecular weights can be used. The only limitation is processability, since very high molecular weights are more viscous and therefore more difficult to inject into complex molds.

Alternatively, the molecular weight may be defined indirectly in terms of Falling Ball Viscosity (FBV), as described in the American Society for Testing and Materials (ASTM) D817 and D1343. In embodiments, the cellulose articles of the present disclosure may have an FBV in the range of 5 to 30 seconds. Below this range the material tends to be too brittle, whereas above this range the viscosity is too high.

In embodiments, preferred cellulose esters for use in the present invention include cellulose acetate propionate, cellulose propionate (or cellulose tripropionate, CTP), and cellulose acetate butyrate. In the examples, the degree of substitution of acetyl ds (ac) should be less than about 2.1, more preferably less than about 1.7, due to Tg limitations. It has been found that high acetyl levels tend to result in too high a Tg, limiting processability. In contrast, materials such as Cellulose Triacetate (CTA) and Cellulose Acetate (CA) are not preferred because they are difficult to melt process, for example, in the absence of large amounts of plasticizer (although they may be used as a protective or compensation layer).

In certain embodiments, the human-interface housing of the present invention has a very low optical retardation, wherein all portions of the optical panel in the visible region have an in-plane optical retardation, Re, in the range of-100 nm to 100nm, and a thickness retardation, Rth, also in the range of-100 nm to 100 nm. Such a low retardation panel does not require any additional compensation film.

In another embodiment, all portions of the optical panel in the visible region have an in-plane optical retardation Re in the range of-80 nm to 80nm, and a thickness retardation Rth in the range of-100 nm to 100 nm.

In another embodiment, all portions of the optical panel in the visible region have an in-plane optical retardation, Re, in the range of-50 nm to 50nm, and a thickness retardation, Rth, in the range of-100 nm to 100 nm.

In certain embodiments, the human-machine interface housing of the present invention further comprises one or more compensation layers and has a total optical retardation in the range

(i) -from 100 to 100nm,

(ii)100 to 300nm, or

(iii) -100 to-300 nm.

In other embodiments, the human-machine interface housing of the present invention further comprises one or more compensation layers having a total optical retardation in the range of-80 to 80nm, 100nm to 260nm, or-100 nm to-260 nm.

In another embodiment, the human interface housing of the invention further comprises one or more compensation layers having a total optical retardation in the range of (i) -50 to 50nm or (ii)150 to 250nm or (iii) -250 to-150 nm.

As described herein, conventional stabilizers, catalysts, impact modifiers, flame retardants, reinforcing agents, and the like, as are well known in the plastics art, may be used, provided the type and/or amount of such additives does not result in an outer shell having unacceptable optical or strength properties. Examples of additives contemplated for use include those available from BASFAndantioxidants, and obtainable from basfAndlight stabilizers.

As described herein, the use of plasticizers is also an option, although the parts generally must meet certain limitations associated with volatile organic compounds, and thus the plasticized cellulose esters are preferably sealed by the use of capping layers (e.g., multilayer coextrusion and thermoforming), by coinjection, or by the use of a varnish or sealant layer.

In embodiments, in addition to having a Tg (as described herein), the display panel must also meet certain impact requirements. In an embodiment, a skin plate made from a cellulose ester composition having a thickness of 1mm to 10mm, or 1mm to 8mm, or 1mm to 5mm, or 2mm to 10mm, or 2mm to 8mm, or 2mm to 5mm is capable of withstanding impact from a height of 20 inches (50.8cm) with a 1.05kg steel ball at both room temperature and-30 ℃ without breaking. The height represents an impact energy of 5.2 joules. Due to the variety of available panel geometries, the panel was supported by a 4 inch (10.2cm) diameter tube, receiving an impact at the center of the panel or tile.

In order for the HMI display panel to be shadow-free, it is important that the total retardation of all "optically active layers" fall within one of two ranges:

the first is from-100 nm to 100nm, or-80 nm to 80nm, since this constitutes the "grey" area on the Michel-Levy diagram for light transmission through crossed polarizers using a uniform white light source. The display within this delay range will always be black or grey, so the shading is minimal.

The second is 100nm to 300nm or-100 nm to-300 nm, or 100nm to 260nm or-100 nm to-260 nm, since this constitutes the "white" part of the light transmission. Although the panel will appear uniformly white rather than gray, the shading here will also be minimal.

The reason for targeting one of these two regions is that the color change is very small for a given change in retardation. In contrast, for retardations in the range of greater than 260nm or greater than 300nm (or less than-260 nm or less than-300 nm), the effective color changes rapidly through non-gray values (initially yellow) as the retardation increases. Therefore, even a slight change in retardation will produce a noticeable color shift. It should also be noted that if one portion of the panel is in a gray area and another portion is in a "white" area, then an unacceptably noticeable shadow will appear. The entire viewing area (or in one embodiment, the entire panel) should be in one or the other area, but not both. Again, these ranges listed are considered acceptable minima, but even lower variation ranges around 0nm or about 180nm (or-180 nm) are preferred.

With the above acceptable range, generally spanning 200nm or 160nm of delay, it is desirable that the difference between the maximum and minimum delay of the component (at least over the viewable area of the HMI housing) be less than or equal to about 200nm or 160 nm. In an embodiment, the maximum variation in retardation that a component can have across the entire viewable area and still be acceptable is 160 nm. However, if the average retardation of the component is not within the target range, it can be offset by adding an optically active compensation layer to the housing plate.

For example, a component with an average retardation of 100nm (150 nm maximum and 50nm minimum) would have unacceptable shading if used alone, since part of the retardation is in the gray area and part is in the white area. However, since the retardation range (max-min) is only 100nm, the average value can be shifted down using a-100 nm optically active compensation layer. This shifts the average to 0nm, the minimum to-50 nm, and the maximum to 50 nm. All spots are now within the-80 to +80nm grey region, so shading is minimized. Alternatively, the average value may be moved upward so that the entire range falls within the white area.

It should be noted that the 200nm range is essentially the minimum required to remain within the gray or white band. In embodiments, the difference in the maximum and minimum retardations Re of the cellulose ester component in the viewable area will be less than or equal to about 160nm, or preferably less than or equal to 100 nm. The narrower the range of delay values encountered across the component, the lower the shading.

To minimize distortion when viewed at off-angles, it is important that both the in-plane Re and the thickness retardation Rth remain low. Ideally, if both Re and Rth remain close to zero, the display will show the same from all viewing angles. As Re increases, there is more optical distortion, and this will depend on how the in-plane refractive index of the film changes relative to the refractive index in the thickness direction. Also, for higher values of Re, it is more difficult to define an accurate Rth target that will completely eliminate off-axis distortion.

The "optically active layer" constitutes all layers between the second polarizer of the display 33 and the polarizing sunglasses 80. Thus, the outer protective layer 32 of the second polarizer, the HMI display 70, and any protective/compensation layers applied to the display 71 (or alternatively applied between 32 and 70) may be considered optically active layers. The sum of the in-plane retardance should be substantially within one of the two ranges. It is acceptable that if areas around or on the edges of the gate are hidden (e.g., outside the viewable area of the HMI housing) and/or removed as part of the installation, these areas may be outside of an acceptable range.

In an embodiment, the display panel has a thickness of 2 to 5mm, or 2 to 4mm, or 2 to 3mm, and will withstand an impact of dropping from a height of 20 inches (50.8cm) at room temperature and-30 ℃ using a 1.05kg steel ball without cracking. In an embodiment, the HMI display housing is larger than a typical molded optical disk and is asymmetric in geometry, both of which make it more difficult to meet low birefringence requirements (as described herein).

In embodiments, the HMI enclosure panel is produced by injection molding, compression injection molding, or thermoforming, and may optionally be annealed to further reduce birefringence. In an embodiment, the housing is injection molded and the gate is at least 50% or more, or at least 60%, or at least 70%, or at least 80% of the width of the housing at the inlet side of the mold, in order to reduce the angular dependence of the retardation.

In one aspect, a method for fabricating a human interface housing is provided, comprising the steps of:

(a) providing a mold configured for injection molding, the mold comprising a gate at one end of the mold, the gate having an opening configured to introduce molten thermoplastic polymer into the mold, and a mold width at the gate end of the mold of at least 150mm, wherein the gate opening has a width of at least 50% of the mold width; and

(b) the housing is injection molded at a barrel temperature of at least the thermoplastic polymer Tg (° C) +60 ℃.

In an embodiment, the gate opening has a width of at least 60% of the mold width. In embodiments, the barrel temperature is at least the thermoplastic polymer Tg (. degree. C.) +80 ℃.

The optically active layer can be prepared by a variety of methods including solvent casting, extrusion, stretching, and the like. In embodiments, the compensation layer may be made of one or more cellulose esters. In another embodiment, the compensation layer may be made of oriented polycarbonate, for example in the case of a normal quarter-wave plate film. Additional layers may also be added to improve scratch resistance, glare, etc. For example, these "hard coat" layers may be applied to the compensation film and then adhered to the display panel using in-mold labeling techniques, direct adhesion, coating, or other methods known in the art. In an embodiment, the hard coating is selected from a silicone based hard coating, a (poly) siloxane based hard coating, a urethane based hard coating, or an acrylic based hard coating.

It has also been found that molded articles made from cellulose esters having a low hydroxyl content or higher DS (total), as described herein, retain optical clarity (i.e., have less haze increase) when exposed to heat and humidity than cellulose esters having a higher hydroxyl content or lower DS. Thus, in another aspect, a molded article having improved resistance to moisture induced haze is provided. In embodiments, such molded articles are made from cellulose esters having a total Degree of Substitution (DS) in the range of 2.85 to 3. In embodiments, the DS is in the range of 2.9 to 2.97. In embodiments, high heat and/or humidity exposure refers to the higher temperature and humidity environmental conditions experienced by typical consumer products (e.g., products that may be placed in a dishwasher or resident in an automobile interior). In embodiments, the temperature range may be 27 ℃ to 100 ℃, or 38 ℃ to 95 ℃, or 38 ℃ to 78 ℃, and in embodiments, the humidity may be in the Relative Humidity (RH) range of 80% to 100%, or 90% to 100%.

Cellulose ester compositions having low hydroxyl content (as described herein) can be used to provide molded articles having high optical clarity requirements and which will be exposed to high heat and/or humidity when the article is used. For example, articles placed into a dishwasher, or otherwise subjected to heat and humidity (e.g., certain vehicle components), may benefit from the use of cellulose ester compositions having low hydroxyl content (as described herein). Thus, in one aspect, the present invention is directed to the use of cellulose esters having low hydroxyl content (as described herein) for molded articles requiring high optical quality, which may be exposed to high heat and/or humidity during use. In one aspect, the present invention is directed to the use of a cellulose ester having a low hydroxyl content (as described herein) for molded articles having a reduced increase in haze when exposed to high heat and/or humidity during use as compared to similar articles prepared from cellulose esters having higher hydroxyl contents.

The invention may be further illustrated by the following examples of specific 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.

Experimental part

The following experimental methods were used to characterize the molded articles of the present invention.

Melt flow rate or Melt Flow Index (MFI) was measured at 300 ℃ under a load of 1.2kg according to ASTM D-1238.

Optical birefringence in the plane (Re) is characterized by one of two methods. The first is by using Streinoptics^TMPS-100SF polarimeter. Testing in "plane polarization" mode, using the rotation analyser method or by Strainoptics^TMThe LWC-100 wedge compensator is optimized quantitatively. Measurements are taken at multiple points throughout the part and the maximum and minimum points are also recorded.

When Re and Rth values are desired, Woolam is used^TMThe ellipsometer performs the test. The ellipsometer makes a series of measurements at different tilt angles and then extrapolates the retardation results to a full 90 degree tilt to determine Rth.

The impact strength was measured at room temperature and-30 ℃. The impact was performed by dropping 1.05kg of steel balls from a height of 4 inches (10cm) and 20 inches (50.8 cm). The panels were supported by 4 inch (10.2cm) diameter tubes. This height represents a maximum impact energy of 5.2 joules, and the sample must withstand the impact without cracking or breaking to pass the test.

The degree of substitution of the cellulose esters reported in the following examples was determined by nuclear magnetic resonance hydrogen spectroscopy using a JEOL type 600 Nuclear Magnetic Resonance (NMR) spectrometer operating at 600 MHz. The sample tube size was 5mm, the sample temperature was 80 ℃, and dimethylsulfoxide-d 6 and a few drops of deuterated trifluoroacetic acid were used as solvents. The pulse delay was 5 seconds and 64 scans were obtained for each experiment.

Unless otherwise indicated, the glass transition temperature Tg was determined on non-plasticized samples using a TA DSC 2920 instrument from a Thermal analyzer (Thermal analysis Instruments) using a Differential Scanning Calorimeter (DSC) at a temperature ramp rate of 20 ℃/minute according to ASTM D3418. The Tg values were taken from the second heating cycle measurement to ensure a clear indication of the transition and removal of any residual water. Melting points were also measured using DSC according to ASTM D3418. Falling ball viscosity is measured in an ASTM A solvent using ASTM method D1343-91.

Percent haze and light transmittance were measured on 102mm x 2mm injection molded plaques using a Hunterlab Ultrascan VIS dual beam spectrophotometer according to ASTM D1003, section 8, procedure B.

The moisture content of the plaques was measured by the thermogravimetric analyzer (TGA) method as follows: about 2mg of sample was cut from the edge of a 2mm thick injection molded plaque and loaded into a TA Instruments Q5000SA vapor sorption analyzer. The sample was dried at 60 ℃ and 0% relative humidity for 240 minutes (4 hours). The drying step is finishedAfter this time, the sample was equilibrated at 30 ℃ and 90% relative humidity for 300 minutes (5 hours). The percent weight gain (of water) was measured over this time frame and at the end of 300 minutes. The final weight gain percentage is the reported moisture absorption value.Comparative examples 1-30 shadow of plaque Molding and processing conditions Sound box

Rectangular plaques were injection molded on a Toyo Plastar TM-200G2 molding machine having a 50mm screw and an injection capacity of 397 cc. Design experiments were performed using various processing conditions and resins. Rectangular plaques of dimensions 10.2cm by 15.2cm and a thickness of 2.5mm were prepared. The mold was filled with film gates along the entire 10.2cm short side of the plaque.

Three polycarbonate resins were molded, including Makrolon^TM2458(19MVR or 20MFR), Makrolon^TM2207(35MVR or 38MFR) and Tarflon^TMLC1500(65MVR or 70 MFR). Makrolon resin is supplied by Bayer (Bayer) (Covestro), and Tarlon resin is supplied by Idemitsu Kosan. In addition to the polycarbonate samples, the PMMA polymer Acrylite was tested^TMH12 (winning Industries) as a control, and a commercial Cellulose Acetate Propionate (CAP) Eastman Treva GC6021 (Eastman chemical company) with a total DS of 2.68.

The mold temperature for the PMMA and CAP samples was fixed at 82 ℃ and the mold temperature for the polycarbonate samples was fixed at 88 ℃. Both barrel temperature and injection speed were varied to determine optimal conditions. The retardation value (Re) was then measured at 1cm from the gate, at the center of the plaque and 1cm from the non-gate end of the plaque. Maxima and minima were also recorded throughout the part, but excluding the 2cm region near the gate. It is known that the level of retardation near the gate area will be higher, but given that such high retardation can be incorporated into a larger gate area that will be removed and/or hidden upon final assembly of the panel. The molding conditions and test results are listed in table 1.

A review of Table 1 shows that for the polycarbonate samples, only sample CE18 falls within the desired target retardation range (-100 to 100nm) and/or the retardation change is less than the more preferred 100nm range. This was generated using a 65MVR sample run at a hotter barrel temperature and a fast injection rate. As previously mentioned, the gating area must be excluded from the viewing area of the panel in order for this portion to be acceptable, but it can potentially be used without an additional compensation layer.

Sample CE14 was in a wider range of 200nm, but for HMI applications the average value needed to be shifted by the compensation film. The performance will not be as good as CE18, but still acceptable for some applications. Sample CE17 had a mid-range performance with a retardation range falling within the mid-range of 160 nm. If the gate area is excluded from the visible area, this portion is acceptable without the compensation layer and will fall between the shadowing performance of CE14 and CE 18.

For other PC samples, the processing conditions did not produce sufficiently low delay variation and unacceptable shadowing occurred. Also, the samples with lower MVR were not even close to the desired retardation target.

The acrylic samples (CE19 to CE24) had low retardation profiles, but were not usable due to their low impact strength (impact data not shown). If impact strength is acceptable, these can be used without a compensation layer, although CE19 and CE21 require that the gate area be excluded from the viewable area.

The CAP samples (CE25 to CE30) had higher retardation than the cellulose of the present invention. As described herein, these CAP samples have a lower DS than cellulose according to the invention. Only CE26 and CE30 have acceptably low delay variation. CE26 may be used for "white" areas without compensators if a small portion of the gate area is excluded from the visible area. CE30 would need to compensate for the film to move the average retardation down to the gray areas or up to the white areas. The gate area of CE30 also needs to be excluded from the visible area.

Comparative examples 40-48 SOC data

The glass state SOC values (SOCg) and the rubber state SOC values (SOCr) were measured for a range of materials. The SOCg was estimated by loading the stretch rod on an Instron tensile test stand and gradually stressing the part while measuring the change in delay. The stress remains linear below the yield point. The retardation values are then converted to birefringence through the thickness of the part and the birefringence is plotted against stress. The slope of the graph is the SOCg value.

SOCr values were determined by stretching film samples at different draw ratios using a Brueckner laboratory film stretcher. The initial film sample is 100mm x 100mm and is typically 200 to 250 μm thick. The samples were nominally stretched to different stretch ratios at temperatures about 10 ℃ above Tg. After stretching, the retardation value is measured and compared with the stress in the film at the end of stretching (measured by a load cell built into the film stretcher). SOCr can then be estimated from a plot of birefringence at different stretch ratios versus stress difference in the film at each given stretch ratio.

The actual SOC values are listed in Table 2. It should be noted that the PC and PMMA values were obtained from the literature (Winberger-Friedl, R (1991) by optical techniques for determining Orientation, stress and density distribution in injection-molded amorphous polymers, (origin, stress and density distributions in injection-molded amorphous polymers defined by optical techniques), Angstrom temperature: Angstrom university of Physician technology, DOI: 10.6100/IR 364279). The CTA values were determined from Cellulose (Cellulose) (2015) 22: 3003 and 3012.

The values of SOCg were all comparable except for PMMA which was slightly negative and the PC value was much higher. On the other hand, the range of variation of the SOCr values is much larger. For example, PMMA is known to vary significantly with orientation temperature and is therefore within the listed range. For cellulose esters, it can be observed that the SOCr value is a strong function of the total DS. As DS approaches 3, the SOCr value decreases and actually crosses zero and becomes negative as in the case of cellulose triacetate. Therefore, for low birefringence molding, a composition with a SOCr close to zero is desired. This indicates a benefit (for the cellulose tested) of a ds (tot) of about 2.85 or about 2.9 or higher.

Examples 70 to 75-plaques molded by CAP

In this example, various CAPs were molded on a Toyo M90 injection molding machine. The plaque was nominally 10cm by 10cm and had a thickness of 2 mm. The screw speed was fixed at 50RPM and the cooling time in the mold was varied from 18 to 30 seconds, with optimization for each sample (although it was later determined that the effect of mold cooling time on delay was minimal). The injection pressure was nominally set at 1200psi and the injection speed varied between 0% and 100% speeds set on the machine. Generally, faster rates give the best optical performance.

The composition, properties, molding conditions, and delay data of CAP are shown in Table 3. CE70 and 71 relate to a lower DS CAP, and the delay values tend to be higher regardless of the process conditions. The plaque appeared white and/or gray when viewed through crossed polarizers. Examples 72-74 are high DS CAP resins according to embodiments of the invention with significantly reduced delays. It was also determined that by plotting the injection pressure and reducing the pack and hold pressures relative to the injection pressure, the delay in the gate area could be reduced to near zero (as in 73 and 74). It should be noted that even if the retardation in the gate measured with a polarimeter is close to zero, the material around the gate still presents a purple hue. As shown in the examples that follow, this is because the dispersion of the delay is a function of wavelength. It is believed that this purple hue should be eliminated by further adjustment or may be excluded from the viewing area of the display.

Example 75 has a moderate DS and therefore its optical performance is marginal. The delay is shifted higher over most of the plaque and it is not possible to eliminate the delay in the gate area.

Examples 100 to 101 HMI faceplates made from CAP

In this example, a 2mm thick HMI faceplate was molded on a 200 ton injection molding machine. The panel was 160mm wide at the gate end and expanded to 200mm at the distal end. The length of the faceplate is 150mm with the components slightly bent to simulate a typical HMI touch housing. A fan gate of approximately 65% of the part width was used. The die temperature was set at 85 ℃ and the barrel temperature at 215 ℃.

For all runs, the screw speed was nominally 110RPM, and the injection rate was 7.5cm/s, approaching the maximum speed that the molding machine would provide before flash occurred. It was observed that the faster the injection rate, the lower the birefringence was observed, and therefore a machine with higher clamping pressure should provide even better performance. The other variables have less effect on the delay.

Two CAP materials were molded, the first being the same as example 46, with an FBV of 16. The second DS (Pr) was 2.04, the total DS was 2.94, and the FBV was 25, both materials produced nearly uniformly black plaques when viewed through crossed polarizers. The only exception is the purple hue near the gate area. Both have a retardation range of 0nm to a maximum of about 35nm when measured with a polarimeter and a white light source. The color of the plaque did not change significantly when viewed from different angles.

Plaques of example 100 were also measured using an ellipsometer and the data are plotted in fig. 9, with Re and Rth both as a function of wavelength. It should be noted that the Re value is uniformly low except at the gate and at very short wavelengths (i.e., blue/violet region). This dispersing effect seems to be the cause of the purple color. All Rth values are low and below 100nm (or above-100 nm) except for extremely long wavelengths (almost infrared region), which is why there is no significant change in color when the viewing angle is changed.

Although not tabulated, it is not uncommon to have very high values (typically over 1000nm or higher) when we measure Rth values for other polymers such as PC. It has been found that when the material has a high SOC value, it is difficult to control Rth, and thus it may become very difficult to produce parts with good viewing angle uniformity.

Examples 200 to 203 thermoformed parts

To illustrate thermoforming as a method of producing HMI faceplates, a sheet was extruded from each of several resins and then thermoformed to a pallet mold using a hydradtim lab thermoformer. The sheets were nominally 0.6mm thick and were produced by extrusion on a 50mm single screw extruder. The tray mold is a dish for frozen food, measuring 16cm by 12cm, with a drawing depth of 4 cm. The sheet was first preheated in an oven at 287 ℃ for 13 to 20 seconds and then drawn into the mold with vacuum assistance before cooling. The mold was kept at ambient conditions.

Comparative example 200 used the same CAP as CE44 and an FBV of 20. After shaping, the tray bottom had a variation of white and black, with a retardation (Re) ranging from about 0 to 125nm, when viewed between crossed polarizers.

Example 201 was prepared using the same CAP resin as example 47 with an FBV of about 5. The retardation was always 0nm or very close to 0nm at the bottom of the cell, and the appearance between crossed polarizers was uniformly black.

Example 202 was the same as 201 except that 6% Admex 770 polymeric plasticizer was added during the formulation. It produced slightly more retardation than 201, with a maximum retardation of about 20nm, but still had an almost pure black appearance when viewed between crossed polarizers.

Example 203 is a cellulose tripropionate resin (CTP) similar to example 48, but also containing 15% TEG-EH plasticizer. The resulting features have a retardation range of about 0 to 40 nm. The part is fairly uniform black/grey with little shading.

Example 300 haze due to humidity

In this example, two different CAP materials were molded into plaques of 10cm by 2mm thickness. The CAP1 material was molded using a 1999Toyo Si-110 injection molding machine and GP screws under the following conditions:

barrel temperature: 485 degree F

Temperature of the die: 185 degree F

Injection/packing/holding pressure: 800/700/500psi

Injection/encapsulation/retention time: 10/4/8 seconds

Screw position: 2 inch

Screw speed: 150rpm

Cooling time: 8 seconds

Back pressure: 100psi

CAP 2 material was molded using a Toyo M90 injection molding machine under the following conditions:

barrel temperature: 485 degree F

Temperature of the die: 220 degree F

Injection pressure: 1500psi

Cooling time: 18 seconds

Plaques were placed in an environmental chamber of the type ESPECBTX-475 and exposed to 90 ℃ and 95% RH for 72 hours. The percent haze of each plaque before and after exposure was measured. The moisture absorption rate of each material was also measured. CAP performance and haze and moisture absorption data are listed in table 4.

Review of table 4 shows that CAP materials with higher DS (or lower hydroxyl content) have less than 8% difference in moisture pick-up after exposure to high temperature and high humidity conditions, but have significantly less haze (or increased haze).

TABLE 1 plaque injection Molding data

TABLE 2 SOC data

Numbering	Description of the invention	DS(tot)	DS(Ac)	DS(Pr)	SOCg	SOCr
							CE40	PMMA				-4.4	-20 to +70
CE41	PC				89	345
							CE42	CA	2.44	2.44	0	12
CE43	CTA	2.97	2.97	0	16	-40
							CE44	CAP	2.7	0.07	2.63	18.3	870
CE45	CAP	2.81	0.83	1.98		105
							46	CAP	2.93	1.06	1.87	11	38
47	CAP	2.95	1.52	1.43	11.6	100
							48	CTP	2.93	0	2.93	17.6

TABLE 3 CAP plaque data

Sample (I)	DS(Pr)	DS(tot)	FBV	T charging barrel	T-shaped die	% velocity	Re gate	Center of Re	Re edge
										CE70	2.63	2.7	20	252	252	100	-114	211	68
CE71	2.63	2.7	20	252	252	50	-57	257	57
										72	1.87	2.93	16	252	252	60	-684	11	6
73	2.04	2.96	12	227	243	75	0	23	23
										74	1.95	2.93	14	227	243	75	0	17	17
75	2	2.84	7	252	257	50	-530	63	23

TABLE 4 CAP haze test data

Sample (I)	DS (Total)	DS(Ac)	DS(Pr)	Haze 0Hr	Haze 72Hr	Rate of moisture absorption
							CAP1	2.66	0.02	2.64	1.5	93.0	3.47％
CAP2	2.88	1.02	1.86	3.8	12.0	3.22％