White plastic sheet with low metamerism

Abstract

A metamerism-resistant printable plastic sheet, especially white sheet, in which the desired shade of white can be easily specified or adjusted. This is achieved by separately controlling the opacity and the brightness. The opacity is controlled by the concentration of white pigment in a plastic base layer and the brightness is controlled by the concentration of an optical brightener in a plastic print layer bonded to, and preferably coextruded with, the base layer. Such a sheet can be bonded to one or both sides of a rigid core to create a graphics board, or used as a stand-alone flexible print sheet. Preferably, the plastic print layer comprises a polymer resin that is inherently resistant to a yellowing reaction from exposure to UV light.

Claims

1. A rigid display board comprising a flat, rigid cellular foam core and a printable sheet bonded to the cellular foam core, wherein the printable sheet comprises: a base layer containing pigment and an unpigmented plastic print layer containing an optical brightener in this order on the cellular foam core, and wherein the print layer is bonded to the base layer.

2. The rigid display board of claim 1, wherein the base layer is opaque white plastic and the print layer is unpigmented plastic with dispersed optical brightener.

3. The rigid display board of claim 1, wherein the base layer is a polystyrene containing TiO.sub.2 pigment and the print layer is clear-to-translucent polystyrene containing a fluorescent optical brightener.

4. The rigid display board of claim 1, wherein the sheet has a thickness in the range of about 10-80 mils; the base layer is an opaque plastic containing TiO.sub.2 pigment; the print layer is a clear-to-translucent plastic with homogenously dispersed optical brightener that absorbs UV light in the invisible range of 300-400 nm and fluoresces in the visible range.

5. The rigid display board of claim 4, wherein the print layer has a thickness in the range of 2%-50% of the thickness of the sheet.

6. The rigid display board of claim 5, wherein the print layer is a clear-to-translucent resin with a fluorescent optical brightener constituting 0.01 wt. % to 0.10 wt. % of the print layer; the base layer is pigmented with TiO.sub.2 in the range of about 1 wt. % to 30 wt. % of the base layer.

7. The rigid display board of claim 1, wherein the foam core has opposite flat sides and one of said printable sheets is bonded to each side of the core.

8. The rigid display board of claim 1, wherein the sheet consists essentially of a base layer that is non-white opaque plastic and a print layer that is plastic with dispersed optical brightener.

9. The rigid display board of claim 1, wherein the base layer is a polystyrene containing non-white pigment and the print layer is clear-to-translucent polystyrene containing a fluorescent optical brightener.

10. The rigid display board of claim 1, wherein the sheet has a thickness in the range of about 10-80 mils; the base layer is non-white pigmented plastic; the print layer is a clear-to-translucent plastic with homogenously dispersed optical brightener that absorbs UV light in the invisible range of 300-400 nm and fluoresces in the visible range.

11. The rigid display board of claim 1, wherein the print layer has a thickness in the range of 2%-50% of the thickness of the sheet.

12. The rigid display board of claim 1, wherein the print layer is tinted.

13. The rigid display board of claim 1, wherein the print layer is translucent.

14. The rigid display board of claim 1, wherein the base layer consists essentially of a pigmented plastic without optical brightener and the print layer consists essentially of clear plastic with optical brightener.

15. The rigid display board of claim 1, wherein the print layer has a yellowing index of less than 5.

16. The rigid display board of claim 15, wherein the print layer consists essentially of a polymer resin which has an inherent yellowing index of less than 5.

17. The rigid display board of claim 16, wherein the print layer consists essentially of a polymer resin which has an inherent yellowing index of less than 3.

18. The printable sheet of claim 15, wherein the printable sheet has a thickness in the range of about 10-80 mils.

19. A rigid display board comprising: a flat, rigid cellular foam core and a printable sheet bonded to the cellular foam core, wherein the printable sheet comprises a base layer containing pigment and an unpigmented plastic print layer containing an optical brightener in this order on the cellular foam core, and wherein the print layer comprises an acrylic resin and is bonded to the base layer.

20. A rigid display board comprising a flat, rigid cellular foam core and a printable sheet bonded to the cellular foam core, wherein the printable sheet consists of a base layer containing TiO2 pigment without optical brightener, and an unpigmented plastic print layer containing an optical brightener at a concentration of 0.01 wt. % to 0.10 wt. % of the print layer in this order on the cellular foam core, and wherein the print layer is bonded to the base layer.

21. The rigid display board of claim 20, wherein the print layer comprises an acrylic resin.

22. The rigid display board of claim 20, wherein the print layer is white, constituted from a cream-hazed ASA resin impregnated with TiO2 pigment, and a blue dye.

Description

BRIEF DESCRIPTION OF THE DRAWING

(1) FIG. 1 schematically shows equipment for coextruding an unpigmented thermoplastic resin print layer with dispersed optical brightener onto a pigmented base layer and the resulting printable sheet; and

(2) FIG. 2 shows the printable sheet bonded to a mounting substrate such a foam board.

DETAILED DESCRIPTION

(3) The preferred embodiment, for producing a white sheet, will be described in detail but it should be appreciated that the key feature of separating opacity from brightness can be implemented in a non-white context.

(4) FIG. 1 shows an extrusion system 10 including a coextrusion die block 12 supplied by a source 14 of clear (unpigmented) thermoplastic polystyrene resin with dispersed optical brightener and another source 16 of white pigmented thermoplastic polystyrene resin, at a temperature in the rage of about 180-210 deg. C. The hot coextruded laminate 18 is chilled between rollers 20 to produce the printable sheet 22 consisting essentially of a clear resin print layer 24 with dispersed optical brightener bonded to a white pigmented base layer 26.

(5) FIG. 2 shows the printable or printed white sheet 22 in an end use context, bonded to a relatively rigid foam board 28 or the like.

(6) The discovery at the core of the present invention was arrived at after extensive trials and re-trials that eventually deviated from conventional thinking in the graphics industry. Initial trials were conducted to determine whether white color matching and low metamerism could be achieved with no optical brightener in a white single layer extruded polystyrene sheet. Color was matched against the target Tango paper color under a D50 proofing light source, but when the light source and color temperature changed the color comparison based on a visual perception was no longer a match. Further trials were based on compounding an optical brightener at various loading levels into the pigmented polystyrene white resin to achieve these two objectives. Both anatase and rutile types of TiO.sub.2, were tested to determine if any one was a better candidate for success. It became clear that these objectives could not be achieved with the simple standard solution of a direct addition of OB into a white extruded resin. The test samples were either too bright or white when viewed under lighting conditions with high UV irradiance (i.e., daylight) or too yellow when viewed under lower color temperature light sources.

(7) The solution was achieved by bonding, e.g., coextruding, a white pigmented plastic base layer with a top print layer of clear (translucent) resin containing homogeneously dispersed OB. The OB can be in the range of about at 0.01 wt. %-0.10 wt. % of the print layer and the base layer can contain about 1-30 wt. % white pigment, e.g., TiO.sub.2. The thickness of the print layer can be in the range of about 2%-50% of the total thickness of the composite plastic sheet.

(8) This approach allows one to make the base layer in the co-extrusion as opaque as needed using any amount of the brightest (rutile) version of TiO.sub.2, without the yellowing of a high loading of OB. With the cost of OB source material much greater than the cost of plastic sheet resin, there is also a significant cost advantage achieved by the need for only a low concentration of OB. This separation of brightness control from opacity control provides the ability to cost-effectively manufacture the kind of opaque plastic sheet demanded by the graphics printing industry.

(9) The optical brightener is a yellow crystalline substance and as a consequence imposes a limit on how much can be added into a resin before an undesirable yellow tint is perceived. By adding the OB into a clear co-extruded layer with no TiO.sub.2 masking, effective loading levels relative to a mono-sheet are much reduced with no increase in yellow color from the OB. The print layer with OB will appear as a clear translucent film before it is bonded to the base layer.

(10) Another advantageous aspect of separating brightness control from opacity control is the ability to make a very bright white sheet by the independent adjustment of either one or both of the color of the base white sheet or the addition of a greater amount of OB into the top viewing layer. This level of whiteness and brightness under different lightening conditions is not possible by merely adding OB into single layer of white-pigmented resin.

(11) It should be appreciated that a thin opaque plastic sheet is not amenable to brightening by incorporating an OB due to the high loading of TiO.sub.2 required to achieve minimum opacity. This is not a problem for brightening thick pigmented sheets such as used for the inside panels of appliances such as refrigerator, where the sheet might be ten times thicker than facing for graphics mounting boards. With a thick sheet, the TiO.sub.2 loading can be very low to achieve the same apparent opacity, so the low surface concentration of TiO.sub.2 does not significantly mask the effectiveness of the OB.

(12) So-called delta-E and b* Value calculations are well known in the graphics industry for characterizing color. The accompanying TABLE A clearly show that Sample #3 (New co-extruded plastic sheet according to the present invention) is far superior in matching the color of the Tango white paper and with far less metamerism under the various light sources used for the measurements.

(13) CIE LAB calculations reported in TABLE B clearly show that Sample #4 (New co-extruded plastic sheet according to the present invention) is far superior in matching the b* value (an indicator of an OB effect) of the Tango control paper.

(14) The tendency of a white colored object to change color in different lighting environments is significant. This metameric shift in white will have a tendency to display toward yellow. This is shown in TABLE A by the range of values for each different white sample under four different light sources. The average range of all the Samples except #3 is 0.9 to 1.2. This is an indication of significant color shift (metamerism). Sample #3 is the invention and shows a much lower value of 0.4 (lower metamerism). Such low metamerism can be achieved for white color targets at least within the white color range of most commercial foam board.

(15) In order to look at a specific color shift, TABLE B shows the b* value in the CIE LAB color space where negative b* is blue and positive b* is yellow. Note the Tango white paper value of 4.35 and the inventive Sample #4 value at 4.13 are similar and show much more in the blue spectrum than all the other samples. These two samples contain an optical brightener and the OB is what is responsible for the shift into the blue range. This fluorescence of the OB is the mechanism that masks the yellowness of the white TiO.sub.2 pigmented layer and since the small concentration of OB (0.05 wt. %) added to the top clear layer in adds no color to the white pigment it is an indirect, invisible way to tint or color the white base layer. In a traditional white color of a single layer product one would add a tinting blue/purple dye or pigment into the white resin prior to extrusion to mask the yellowness. This method will lower the brightness of the white color and has a tendency to add other undesirable qualities as muddiness to the color.

(16) The apparent brightness of the white color that contains an OB may change based on the amount of UV emitted by the light source. However, the white color will not take on the degree of yellowness seen with a non-OB enhanced white sample. There is some degree of UV light in most of the common lighting environments to which these products are exposed and enough to activate the OB and counter the tendency to take on a color shift. The new novel way (co-extrusion of a clear translucent OB print layer on a white pigmented base layer), is a cost-effective solution to achieve low metameric shift in the color of a white plastic film sheet.

(17) The tests as reported in TABLES A and B were performed under the following conditions:

(18) Foam board: polystyrene foam core with paper or plastic facers.

(19) Facers: 10-15 mils attached to the foam core by extruded adhesives (1 mil of adhesive).

(20) Foam core: core-density 2-10 lb./ft3; thickness 0.060-2.0 inches.

(21) Paper facers: Mead Westvaco 10-15 mil Tango Advantage white clay coated paper containing OB on test side.

(22) Plastic facers: High Impact Polystyrene (HIP).

(23) Duraplast: Plastics foam board (Gilman Bros.) with 12 mil HIPS polystyrene sheet with no OB.

(24) New: Inventive foam board (Gilman Bros.) with 12 polystyrene sheet with 0.05% wt. OB Navapal (Sunbelt Corp.) powder in the 3.0 mil top layer only (2,5-Thiophenediylbis(5-tert-butyl-1,3-benzoxazole).

(25) TABLE-US-00001 TABLE A Delta-E Calculations on X-Rite Unfiltered spectrophotometer Control Specimen 10 PT. Tango Advantage White Paper by MeadWestvaco. Incan- Day- D-50 descent light Florescent Average Range 1. Duraplast 3.8 3.1 4.0 3.4 3.6 0.9 No OB 2. Duraplast 3.9 3.0 4.1 3.8 3.7 1.1 color match No OB 3. New 1.0 0.7 1.1 0.7 0.9 0.4 Top side measurement 0.05 wt. % OB in top layer 4. New 5.1 4.5 5.4 5.3 5.1 0.9 Bottom side measurement No OB 5. United Ultra 5.0 4.2 5.2 4.8 4.8 1.0 No OB 6. United DP 4.0 2.8 3.6 3.9 3.6 1.2 No OB 7. 3A Smart-X 6.2 5.4 6.6 6.3 6.1 1.2

(26) Smart-X is a trademark of 3M Composites and Ultra and Ultra DP are trademarks of United Industries. This study compares the measured difference in color from a control white paper (Tango used by Gilman as Insite foamboard facers) to various polystyrene faced foam board products in the market under various lighting conditions. Industry standards for a color match vary however Pantonecolor systems recommends <2-3 delta-E points. For colors as Grey and White lower delta-E values would be recommended as one can see differences as little as 0.5 under certain conditions. It should be noted Item #3 New has the lowest delta-E by far of all tested products.

(27) TABLE-US-00002 TABLE B CIE LAB Color Measurements on an X-Rite Spectrophotometer D-50 Proofing Illuminant 1. Tango Advantage White Paper 4.35 Yes OB 2. Duraplast 2.91 No OB 3. Duraplast 1.46 color match No OB 4. New 4.13 Top side measurement 0.05 wt. % OB in top layer 5. New 0.31 Bottom side measurement No OB 6. United Ultra No OB 2.30 7. United DP No OB 1.56 8. 3A Smart-X 0.53 9. Sample 1213 2.41 one layer film sample 0.022% OB dispersed in the entire sample 10. Sample 1214 1.67 One layer 0.011% OB Dispersed in entire sample

(28) Sample #4 New comes very close to matching Tango white paper sample. The backside of New Sample #5 with no OB is very yellow. When the clear layer is co-extruded note the improvement in Sample #4. Sample #9 with OB in a single layer film is not as blue as Sample #1 or #4.

(29) It should be appreciated that the base layer provides the opacity, determined by the pigment loading, but this does not preclude the presence of other material. The plastic print layer provides the brightening effect to the underlying opacity of the base layer, without interfering significantly with the underlying pigmentation. The print layer can thus include low levels of dye or pigment, for tinting (shading), so long as the print layer remains transparent or translucent. Thus, the print layer can be considered as clear-to-translucent. In most contexts, however, the base layer would not contain an optical brightener and the print layer would be clear, i.e., without any tinting agent.

(30) It should be further appreciated that although the print layer of the sheet will normally have an exposed, printable surface, the base layer could be sandwiched between the print layer and another plastic layer. Also, the sheets could be bonded other than by coextrusion, including coating or laminating.

(31) The delta E values in Table A indicate differences among different kinds of printable sheets under different light conditions. Delta E can also indicate the extent of color change of a given print sheet over time. Delta E for a given sheet can be especially large as a result of print layer exposure to sunlight, and even long term exposure to many kinds of artificial light. To overcome this tendency according to an embodiment of the present invention, the material used to extrude the print layer can be selected from resins in which the polymers inherently do not exhibit a significant discoloration reaction with UV light. Acrylics are one such class of resins, in which the polymers are relatively immune to a yellowing reaction from exposure to UV light. Acrylics are generally more expensive that styrene, but some have similar extrusion processing characteristics.

(32) Although it is known to add a so called UVA package to resins for the purpose of minimizing discoloration due to UV exposure, these additives absorb UV light and convert it to heat. If used with OB impregnated resins for a clear or tinted print layer according to the present invention, the additive would absorb UV while the OB relies on UV for the desired florescence. If the OB is more heavily loaded to overcome the counter effects of the UVA package, the powdered OB material itself begins to act like a yellow pigment, thereby discoloring the print layer.

(33) As noted previously, two advantages of the present invention are that by separating the optically brightened print layer from the pigmented base layer, a bright white print sheet can be obtained with a relatively low OB loading and whiteness can be matched against other plastic or paper printable sheets. A further advantage of low OB loading in an inherently UV resistant print layer is resistance to yellow fading due to either or both of UV absorption and OB overload.

(34) Therefore, in the preferred embodiment the resin of the print layer is inherently relatively insensitive to discoloration from UV exposure. Acrylic resins or resins containing acrylic compounds such as ASA (acrylonitrile styrene acrylate), would be effective in this regard as well as exhibiting compatibility with coextrusion of a pigmented polystyrene base layer and unpigmented, OB impregnated print layer. Examples include Solarkote H310M Acrylic from Altuglas International, Arkema Group, Bristol PA and GELOY ASA XTWE270M from Sabic Corporation, Houston, Tex.

(35) Further guidance can be obtained from The Effects of UV Light and Weather on Plastics and Elastomers, by Laurence W. McKeen, (William Andrew, Inc. 2nd Edition, Copyright 2007). Data presented therein compares, inter alia, the delta E experienced by white ASA and white HIPS (high impact styrene), in Florida sun for a period of 12 months. The delta E for the HIPS was approximately 15, whereas the delta E for the ASA was approximately 2. Similarly, a comparison made according to the ASTM D1925 standard, shows that after two years of equivalent weathering, a simple polycarbonate exhibited a yellowness index of 10, a polycarbonate with UVA package exhibited an index of over 3, whereas the index for an untreated acrylic was less than one. Yellowness index is a type of laboratory measurement (the b value) where the higher the number the more yellow the color. ASTM D1925 was withdrawn in 1995, but the experimental results are still valid for present purposes. For the preferred embodiment, the print layer should comprise a resin that has an inherent yellowness index lower than 5, especially lower than 2.

(36) As another example of a suitable print layer, some natural ASA resin is not transparent and has a cream haze. It can still be used for the print layer if a light impregnation of TiO2 pigment is used (2-15 wt. %) with a blue dye to make the resin white before impregnation with OB. If the print layer is made white translucent with a low degree of opacity then the OB would work without being countered with a higher loading of TiO2. No UVA would be needed. This should have a good non-yellowing light exposure rating, similar to an acrylic.

(37) It should be appreciated that the basic concept of separating the opacity from the brightness in a respective two plastic layers can be implemented in a preferred embodiment, where no brightener is in the opaque layer and no pigment is in the brightened layer. However, slight variations where brightener and pigment are in the same layer, which nevertheless achieve equivalent functionality and provide similar advantages not available in the prior art, are encompassed within the broad scope of the present invention.