Source: http://www.google.com/patents/US5939207?ie=ISO-8859-1&dq=5343970
Timestamp: 2014-10-22 07:10:00
Document Index: 642701832

Matched Legal Cases: ['art 1', 'art 2', 'art 1', 'art 2', 'art 1', 'art 1', 'art 2', 'art 1', 'art 2', 'in fine']

Patent US5939207 - Multilayer element with pigment layer on substrate - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsA thermal transfer ribbon having a pigmented layer with a unique combination of melt viscosity, hardness and mechanical properties and an ultra-thin release layer between the pigmented layer and a substrate is provided. The thermal transfer ribbon includes a release layer having a thickness of 0.1 to...http://www.google.com/patents/US5939207?utm_source=gb-gplus-sharePatent US5939207 - Multilayer element with pigment layer on substrateAdvanced Patent SearchPublication numberUS5939207 APublication typeGrantApplication numberUS 08/866,321Publication dateAug 17, 1999Filing dateMay 30, 1997Priority dateMay 30, 1997Fee statusLapsedPublication number08866321, 866321, US 5939207 A, US 5939207A, US-A-5939207, US5939207 A, US5939207AInventorsAlexander T. Fensore, Jeng-Li Liang, Thomas Rogers, Michael J. Wachowiak, Lan Jo YehOriginal AssigneeInternational Imaging Materials, Inc.Export CitationBiBTeX, EndNote, RefManPatent Citations (1), Referenced by (19), Classifications (22), Legal Events (4) External Links: USPTO, USPTO Assignment, EspacenetMultilayer element with pigment layer on substrateUS 5939207 AAbstract A thermal transfer ribbon having a pigmented layer with a unique combination of melt viscosity, hardness and mechanical properties and an ultra-thin release layer between the pigmented layer and a substrate is provided. The thermal transfer ribbon includes a release layer having a thickness of 0.1 to 1.0 micron provided on one side of the substrate, the release layer being composed of an ethylene vinylacetate copolymer, α-olefin maleic anhydride copolymer and wax. A pigmented layer is provided on the release layer and is composed of a low structure carbon black, a polystyrene resin and a polyacrylate resin. A heat-resistant backcoat is preferably provided on the back side of the substrate.
What is claimed is: 1. A thermal transfer ribbon comprising a support substrate, a release layer having a thickness of 0.1 to 1.0 micron provided on one side of the substrate and a pigmented layer provided on the release layer, wherein said release layer comprises an ethylene vinylacetate copolymer, an α-olefin maleic anhydride copolymer and wax and wherein the pigmented layer comprises a low structure carbon black, a polystyrene resin and a polyacrylate resin.
2. The thermal transfer ribbon of claim 1 wherein the amount of each of the ethylene vinylacetate copolymer and α-olefin maleic anhydride copolymer of the release layer is 5 to 15% by weight.
3. The thermal transfer ribbon of claim 2, wherein the amount of the ethylene vinylacetate copolymer is 11 to 13 percent by weight.
4. The thermal transfer ribbon of claim 3 wherein the amount of the α-olefin maleic anhydride copolymer is 10 to 13 percent by weight.
5. The thermal transfer ribbon of claim 2 wherein the ethylene vinylacetate copolymer contains between about 15 and 40 percent by weight of vinylacetate units.
6. The thermal transfer ribbon of claim 2 wherein the α-olefin of said α-olefin maleic anhydride copolymer has a chain length of C10 to C50.
7. The thermal transfer ribbon of claim 6 wherein the olefin:anhydride ratio of said α-olefin maleic anhydride copolymer is 1:1 to 1:4 in terms of weight.
8. The thermal transfer ribbon of claim 1 wherein the wax in said release layer is selected from the group consisting of microcrystalline wax, carnauba wax, petronaba wax, paraffin wax, candelilla wax and low molecular weight polyethylene.
9. The thermal transfer ribbon of claim 1 wherein the amount of wax in said release layer is 70 to 84 percent by weight.
10. The thermal transfer ribbon of claim 1 wherein the low structure carbon black of said pigmented layer has a dibutyl phthalate absorption value of 40 to 400 ml/100 g.
11. The thermal transfer ribbon of claim 10 wherein the oil absorption value is 40 to 50 ml/100 g.
12. The thermal transfer ribbon of claim 10 wherein the low structure carbon black has a particle size within the range of about 30 to 60 nm.
13. The thermal transfer ribbon of claim 10 wherein the amount of the low structure carbon black in said pigmented layer is between about 17 and 20 percent by weight.
14. The thermal transfer ribbon of claim 1 wherein the polystyrene resin of said pigmented layer has a Tg of from 40 to 110� C. and a MW of 1000 to 15000 g/mole.
15. The thermal transfer ribbon of claim 14 wherein said Tg is 40 to 70� C. and said MW is 1000 to 2000 g/mole.
16. The thermal transfer ribbon of claim 14 wherein the amount of polystyrene in said pigmented layer is in the range of about 23 to 28 percent.
17. The thermal transfer ribbon of claim 16 wherein said polystyrene resin is a copolymer of α-methylstyrene and either styrene or vinyltoluene.
18. The thermal transfer ribbon of claim 1 wherein the polyacrylate resin of said pigmented layer has a Tg within the range of 40 to 110� C. and an MW within the range of about 7000 to 300000 g/mole.
19. The thermal transfer ribbon of claim 18 wherein said Tg is 40 to 60� C. and said MW is 10000 to 50000 g/mole.
20. The thermal transfer ribbon of claim 18 wherein the amount of polyacrylate resin in said pigmented layer is within the range of from about 10 to 13 percent.
21. The thermal tranfer ribbon of claim 20 wherein said polyacrylate resin is a polymer of a methacrylate or a copolymer of a methacrylate with at least one of a methacrylic acid and an acrylamide.
22. The thermal transfer ribbon of claim 21 wherein said polyacrylate resin is a terpolymer of methylmethacrylate, methacrylic acid and N-butylmethacrylate having a range of methylmethacrylate in terms of mole percent of 30 to 80 percent.
23. The thermal transfer ribbon of claim 1 wherein a heat-resistant backcoat is provided on a side of the substrate opposite the side having the release layer and pigmented layer thereon.
24. The thermal transfer ribbon of claim 1 wherein said substrate is polyethylene terephthalate.
This invention relates to a thermal transfer ribbon for printing high density/high resolution bar codes for autoidentification.
Thermal transfer ribbons for printing black and colored images comprise a support substrate, ink-side coated layer(s) and a backcoat. Thermal transfer ribbons are used in tag and label applications to image various bar codes, human readable text and company logos. The printed tags and labels are usually comprised of low density/low resolution bar codes and images.
Recently, however, because of the availability of high resolution thermal print heads (200 to 400 dpi, i.e, heating elements per linear inch), end users of thermal transfer ribbons are now printing bar codes with an X dimension as small as 0.0025 inch. More complex logos are also being printed to take advantage of the availability of the higher resolution print heads.
An application where high density bar codes are being used is in the manufacturing of complex circuit boards. Common label sizes for circuit boards range from 5 mm to 15 mm in length. Despite the small size of such bar codes, they must be able to be identifiable.
Conventional thermal transfer ribbons do not image single isolated dots or fine line bar codes (lines with an X dimension of 1 dot) well. Conventional ribbons have heat-meltable ink layers composed primarily of wax or of both wax and resin. The wax-type thermal transfer ribbons can produce bar code images with sharp vertical lines, but the images have poor scratch resistance. The resin-type thermal transfer ribbons produce images with high scratch resistance, but poor fine line print quality.
In view of the foregoing, it is an object of the present invention to provide a thermal transfer ribbon that is capable of printing a highly scratch resistant, high density and high resolution bar code image.
SUMMARY OF THE INVENTION The above object and other objects are achieved according to the present invention by a thermal transfer ribbon having a pigmented layer with a unique combination of melt viscosity, hardness and mechanical properties and an ultra-thin release layer.
More particularly, the present invention is a thermal transfer ribbon comprising a support substrate; a release layer having a thickness of 0.1 to 1.0 micron provided on one side of the substrate and being composed of an ethylene vinylacetate copolymer, an α-olefin maleic anhydride copolymer and wax; a pigmented layer provided on the release layer and composed of a low structure carbon black, a polystyrene resin and a polyacrylate resin; and a heat-resistant backcoat provided on the other side of the substrate.
The thermal transfer ribbon of the present invention is capable of printing 3 to 10 mil vertical high resolution bar codes with an absence of line breakage and is capable of printing sharper 10 mil (1 mil=0.001 inches) horizontal bar codes. The printed images have excellent scratch durability.
BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a cross-section of a thermal transfer ribbon according to the present invention.
FIG. 2 shows a printed normal bar code with a finest line of 3.3 mil printed using a first prior art thermal transfer ribbon (prior art 1).
FIG. 3 shows a printed normal bar code with a finest line of 3.3 mil printed using a second prior art thermal transfer ribbon (prior art 2).
FIG. 4 shows a printed normal bar code with a finest line of 3.3 mil with a thermal transfer ribbon including only the top ink layer of the two-layered face coat of the present invention.
FIG. 5 shows a printed normal bar code with a finest line of 3.3 mil printed with a thermal transfer ribbon according to the present invention.
FIG. 6 shows a printed rotated bar code with 5.5 mil fine line printed using the first prior art thermal transfer ribbon (prior art 1).
FIG. 7 shows a printed rotated bar code with 5.5 mil fine line printed using the second prior art thermal transfer ribbon (prior art 2).
FIG. 8 shows a printed rotated bar code with 5.5 mil fine line printed with a thermal transfer ribbon including only the top ink layer of the two-layered face coat of the present invention.
FIG. 9 shows a printed rotated bar code with 5.5 mil fine line printed with a thermal transfer ribbon according to the present invention.
FIG. 10 shows a comparison of scratch resistance of bar codes printed using prior art thermal transfer ribbons (prior art 1 and 2) and using a thermal transfer ribbon according to the present invention.
DESCRIPTION OF PREFERRED EMBODIMENTS The thermal transfer ribbon of the present invention comprises a support substrate (hereinafter referred to simply as a "substrate"), a heat-resistant backcoat provided on one side, or surface, of the substrate and a face coating on the other side, or surface, of the substrate.
The substrate can be selected from a variety of materials provided that the materials are thermally and dimensionally stable. The substrate can be, for example, polyester film, polystyrene film, polysulfone film, polyvinyl alcohol film, polyimide film or other material known in the art for use as the support substrate of a thermal transfer sheet. The preferred substrate, from the standpoints of cost and heat resistance, is polyethylene terephthalate (PET). The thickness of the substrate can range from 2 to 30 μm. The preferred thickness when the substrate is PET is 3 to 7 μm. More preferably, the thickness is less than 6 μm.
The heat-resistant backcoat is provided on the side of the thermal transfer ribbon that contacts the print head during printing and provides good thermal and slip properties. During printing the heating elements of the print head provide pulses of heat of very short duration to cause transfer of the face coat to a receiver. The heating elements can reach temperatures as high as 350� C. The heat-resistant backcoat protects the substrate from these high temperatures and prevents melting or sticking of the substrate to the print head.
The backcoat contains a heat-resistant binder and one or more slip agents. The composition of the backcoat is not particularly limited as long as it provides sufficient heat resistance to protect the substrate and prevent sticking and provides good slip characteristics. A typical backcoat comprises the reaction product of a hydroxy group-containing silicone urethane polymer and an isocyanate crosslinking agent.
The backcoat has a thickness of about 0.1 to 0.5 μm and can be applied to the substrate by several methods. The materials can be melted and blended under heat and applied to the film in the melted state. Preferably, the materials are dissolved in an organic solvent or solvent mixture, applied to the substrate, and the solvent evaporated. In either case, the backcoat can be applied by any standard printing or coating technique. Examples of application methods include: direct and indirect gravure, gravure reverse coating, roll coating, and flow tube and Mayer rod coating.
The face coat of the thermal transfer ribbon according to the present invention consists of two ink layers having optimal melt viscosities, hardness and mechanical properties. The two ink layers are an ultra-thin release layer that directly contacts the surface of the substrate opposite the surface having the backcoat and a top, pigmented layer. The components of the face coat are chosen so as to provide the following preferred ranges of melt viscosity (at 109� C.), elongation (at 32� C.) and break strength (at 32� C.) of said top, pigmented layer:
a) Melt Viscosity: Desired range=100 to 3000 cP More desired range=100 to 600 cP
b) Elongation: Desired range=100 to 400 μm More desired range=100 to 280 μm
c) Break Strength: Desired range=20 to 70 psi More desired range=40 to 70 psi
The release layer has a thickness of 0.1 to 1.0 μm and contains an ethylene vinylacetate (EVA) copolymer, an α-olefin maleic anhydride copolymer and wax.
The amount of each of the EVA copolymer and α-olefin maleic anhydride copolymer in the release layer is 5 to 15% by weight in terms of solids in the solid ink (release) layer. If the amount of each of these copolymers is less than about 5% by weight, the pigmented ink layer will not adhere well to the substrate and will flake. If the amount of each of these copolymers is greater than about 15%, the ink will not completely transfer to a receiver during printing. The preferred amount of the EVA copolymer in the release layer is 11 to 13% by weight. The preferred amount of the α-olefin maleic anhydride copolymer in the release layer is 10 to 13% by weight.
The EVA copolymer useful in the release layer contains between about 15 and 40% by weight and, preferably, 15 and 35% by weight of vinyl acetate units. A lower percentage of vinyl acetate in the copolymer will lower the melt viscosity of the release layer composition. Examples of EVA copolymers useful as a component of the release layer of the thermal transfer ribbon of the present invention and the properties of the copolymers that influence ink performance are listed in Table 1. Evaflex 577 is particularly preferred.
TABLE 1______________________________________Ethylene vinylacetate copolymer properties     %           Softening Point                            Melt IndexIngredient     Vinylacetate                 (� C.)                            (dg/minute)______________________________________Elvax 40W1     40          104         56Elvax 140W     33           74        400Elvax 150 33          110         43Elvax 205W     28           80        800Elvax 210W     28           82        400Elvax 220W     28           88        150Elvax 310 25           88        400Elvax 410 18           88        500Evaflex 5772     19          Melts at 72                            &gt;2000______________________________________ 1,2 Elvax and Evaflex are products of E. I. duPont de Nemours and Co., Inc.
The α-olefin of the α-olefin maleic anhydride copolymer useful as a component of the release layer has a chain length of C1 to C50 and, preferably, C20 to C50. The preferred olefin:anhydride ratio is 1:1 to 1:4 in terms of weight. Examples of suitable α-olefin maleic anhydride copolymers for use in the present invention and the properties of the copolymers that influence ink performance are listed in Table 2. Ceramer 67 is particularly preferred.
TABLE 2______________________________________&#945;-olefin maleic anhydride copolymer properties       Olefin Chain       Melting PointIngredient  Length      Mw                          (� C.)______________________________________Diacarna 30B1       C30 to C50                   ****    69Petrolite Q-00482       C14    9287   142Petrolite X-8034       C18 to C28                   5000    35Petrolite X-8039       C30    6909    65Petrolite X-8040       C24 to C28                   6588    73Petrolite X-8043       C8     3200   111Petrolite X-8044       C10    5000   108                          (softening point)Petrolite X-8047       C20    5000    46Petrolite X-8023       C20 to C30                   5000    35Ceramer 673       C50     721    97Ceramer 1608       .sub. C30+                   3096    77______________________________________ 1 Dicarna is a product of Mitsubishi Kasei 2 Petrolite and Ceramer are products of Petrolite Polymers Division
The wax provides appropriate release properties to the release layer. The wax should have a softening point of between about 70� and 120� C. Suitable waxes are believed to include microcrystalline wax, carnauba wax, Petronaba wax (synthetic carnauba wax), paraffin wax, candelilla wax, low molecular weight polyethylenes, Suncrowax HGLC (a synthetic wax), Kester #2 and Montan wax. Carnauba wax is preferred because it provides good line sharpness and durability. To impart optimal release properties to the release layer the amount of wax in the layer should be in the range of 70 and 84 solid % and, preferably, 75 and 80 solid %.
The thickness of release layer is between 0.1 and 1 μm. When the thickness of the release layer is greater than about 1.0 μm, the printed image has reduced durability. When the thickness is less than about 0.1 μm, ink transfer may be adversely affected. The release layer can be formed on the substrate by a conventional hot-melt or solvent coating method.
The second, i.e., top, layer of the face coat is a pigmented layer containing low structure carbon black, wax, a polystyrene resin and a polyacrylate resin. The top layer can range in thickness from about 1 to about 3 μm. A thickness greater than about 3 μm can cause flaking and reduced durability. The combination of polystyrene, polyacrylate resin and low structure carbon black can provide an ink with a low melt viscosity (e.g., 296 cP at 110� C. and a shear rate of 2155 sec-1), low tensile elongation and tensile strength (e.g., 276 μm and 63.5 psi, respectively, at 32� C. and a crosshead speed of 0.1 inch/minute) and high ink hardness (e.g., penetration=0.35% at 400� C.).
The carbon black of the top layer is a "low structure" carbon black having a dibutyl phthalate absorption value of 40 to 400 ml/100 g; preferably, 40 to 50 ml/100 g and, most preferably, 48 ml/100 g. A carbon black having a low oil absorption value reduces the melt viscosity of the ink. The particle size of the carbon black is preferably within the range of about 30 to 60 nm. This range of particle size provides a top layer having acceptable melt viscosity and darkness. The amount of pigment in the top ink layer should be between about 17 and 20% by weight. Carbon blacks that have been determined to produce good results in the thermal transfer ribbon of the present invention are listed in Table 3. All of the carbon blacks listed in Table 3 are the products of Degussa. Degussa Special Black 250 is preferred.
TABLE 3______________________________________Carbon black properties      Particle Size                DPB Oil AbsorptionCarbon Black      (nm)      (ml/100 g)     pH Value______________________________________Printex 140U      29        380            4Special Black 250      56        48             3Special Black 350      31        50             3Special Black 550      25        49             4Printex 25 56        46               9.5Printex 45 26        52             10Printex 55 25        48             10Printex 75 17        47               9.5Printex 85 16        48               9.5Printex 95 15        52               9.5______________________________________
The polystyrene resins that can be used as a component of the top ink layer are those having a Tg of from 40 to 110� C. and a MW of 1000 to 15000 g/mole. These ranges provide optimum melt viscosity and tensile properties of the ink layer. The preferred ranges of Tg and MW are 40 to 70� C. and 1000 to 2000 g/mole, respectively. The solid percentage of the polystyrene in the solid ink should be about 23 to 28%.
The polystyrene resins having the required Tg and MW are typically polystyrene copolymers and, more typically, copolymers of α-methylstyrene and either styrene or vinyl toluene. Polystyrene resins that have been determined to provide desired melt viscosity and tensile properties are listed in Table 4. Piccotex LC is preferred. All of the polystyrene resins listed in Table 4 are products of Hercules.
TABLE 4______________________________________Polystyrene propertiesPolystyrene           Tg       Softening PointResin     Composition (� C.)                         Mw                               (� C.)______________________________________Kristalex 31001     Styrene,     46     1600  100     &#945;-methyl styreneKristalex 3115     Styrene,     64     2500  115     &#945;-methyl styrenePiccotex 75     Vinyl toluene,                  29     1100   75     &#945;-methyl styrenePiccotex 100     Vinyl toluene                  42     2650   98     &#945;-methyl styrenePiccotex 120     Vinyl toluene,                  68     3800  118     &#945;-methyl styrenePiccotex LC     Vinyl toluene,                  43     1500   90     &#945;-methyl styreneEndex 155 Styrene,    100     8600  152     &#945;-methyl styreneEndex 160 Styrene,    105     11150 160     &#945;-methyl styrene______________________________________
The polyacrylate resin of the top, pigmented ink layer has a Tg within the range of 40 to 110� C. and a MW within the range of about 7000 to 30�104 g/mole. The preferred Tg and MW are 40 to 60� C. and 10000 to 50000 g/mole, respectively. These properties are chosen to provide optimum ink melt viscosity, tensile properties and hardness. The solid percentage of the polyacrylate resin in the ink should be about 10 to 13%.
Polyacrylate resins having the Tg and MW required to obtain optimum ink properties are typically polymers and copolymers of methacrylates, methacrylic acids and acrylamides. The preferred polyacrylate resin is a terpolymer of methylmethacrylate, methacrylic acid and n-butyl methacrylate having a range of MMA in terms of mole percent of 30 to 80%. Polyacrylate resins that have been determined to be particularly useful in the present invention and their properties are listed in Table 5. Dianal MB-2543 is a preferred polyacrylate resin.
TABLE 5______________________________________Polyacrylate resins and their propertiesPolyacrylate              TgResin      Composition    (� C.)                            Mw______________________________________BR-71      MMA             55    60000BR-80      MMA            105    95000BR-85      MMA            105    280000BR-106     MMA/nBMA/MAA    50    60000BR-107     MMA/nBMA/MAA    50    60000MB-2543    MMA/nBMA/MAA    50    35000MB-2594    MA/IBMA/        80     7000      BMA/AAMB-2595    MA/IBMA/        80     7000      BMA/AAMB2616     MMA/nBMA/MAA    50    20000QR-13811      MMA/BMA        105    100000______________________________________ MMA = Methylmethacrylate, nBMA = nButylmethacrylate, MAA = Methacrylic acid, IBMA = Isobutylmethacrylate, BMA = Isobornylmethacrylate, AA = Acrylamide, MA = Methylacrylate 1 QR1381 is a product of Rohm and Haas. All others are products of Dianal America.
In preparing the face coat of the thermal transfer ribbon of the present invention, the release layer is first applied to the base ribbon typically as a solution by conventional methods and apparatus well known to those of ordinary skill in the art. The solvent is then removed, typically by evaporation.
The top, pigmented layer is then typically applied to the release layer as a solution also by conventional methods and apparatus well known to those of ordinary skill in the art. The solvent is then removed, typically by evaporation.
FIG. 1 illustrates the construction of the thermal transfer ribbon according to the present invention. Layer 2 is the top ink layer described above and which contains low structure carbon black and polystyrene and polyacrylate resins having the ranges of Tg and MW required to provide optimum ink melt viscosity, tensile properties and hardness.
Layer 1 is the release layer described above and which is composed of the specified ethylene vinylacetate copolymer, α-olefin maleic anhydride copolymer and wax in the specified amounts.
Tables 6 and 7 show preferred formulations for layer 2 and layer 1. These formulations were determined using a systematic design approach and method as described below.
TABLE 6______________________________________Ink formula for layer 2Material    Chemical Names    % in Dry Ink______________________________________Carnauba Wax IP       Carnauba Wax      34-42PEG 400 Monostearate       Polyethylene Glycol compound                         0.72-0.88Piccotex LC Polystyrene Resin 23-28Dianal 2543 Polyacrylate Resin                         10-13Special Black 250       Carbon Black      17-20Dioctyl Phthalate       Dioctyl Phthalate 3-4Homogenol L-18       Polycarboxylic Acid                         4-5______________________________________
TABLE 7______________________________________Ink formula for layer 1Material Name        Chemical Name   % in Dry Ink______________________________________Carnauba Wax IP        Carnauba Wax    75-84Ceramer 67   &#945;-Olefin Maleic Anhydride                        10-13        CopolymerEvaflex 577  Ethylene Vinyl Acetate                        11-13        Copolymer______________________________________
A. Vertical Bar Codes
FIGS. 2 through 5 illustrate a comparison of the vertical fine line print quality of print samples generated using the ribbon construction described in this invention with print samples generated using prior art. FIGS. 2 and 3 show print samples generated using prior art 1 and prior art 2. Prior art 1 is a wax/resin ribbon which has a high scratch resistance, but prints vertical bar codes with poor line integrity. Prior art 2 is an all wax ribbon which prints vertical bar codes with high line integrity, but has very low durability. FIG. 4 is a print sample generated using a PET film coated only with layer 2 described in Table 6. FIG. 5 is a print sample generated using a PET film coated with layers 1 and 2 described in Table 6. The ribbon configuration of each of FIGS. 4 and 5 can produce high resolution 3 to 10 mil vertical bar codes without any line breakage. These ribbon configurations also have high scratch resistance.
The line sharpness and the number of breaks in the fine lines were improved by reducing the melt viscosity of layer 2 compared to the melt viscosity used in the prior art. Reducing the melt viscosity of the ink increases its fluidity and permits more ink to penetrate into the pores of the receiver during the printing process. This improves the adhesion of the ink to the receiver and reduces the number of line breaks caused by ink not completely transferring to the receiver.
Table 8 shows the effect of the polystyrene, polyacrylate resin, and carbon black on the melt viscosity of the ink described in this invention relative to the prior art. The dibutyl phthalate (DBP) absorption values listed in Table 8 reflect the structure of the carbon black.
As shown in Table 8, the ink Prior Art A has a melt viscosity of 2700 cP and a correspondingly poor fine line print quality. Ink A represents an ink that used the same pigment that was used in the Prior Art, but Ink A used a different vehicle system containing a polystyrene resin and a methylmethacrylate resin. This change resulted in a melt viscosity of 585 cP. Ink A showed reduced line breakage and improved image sharpness compared to the prior art when used to print high resolution bar codes. A lower structure carbon black was used in Ink B-S in conjunction with the same vehicle system that was used in ink A. The lower structure carbon black reduced the melt viscosity to a value of 296 cP, and excellent high resolution bar code print quality was observed.
TABLE 8______________________________________Fine line printing improvement due to low melt viscosity.Fine line quality was graded on a visual scale from 1 to 5.5 = excellent and 1 = poor   Carbon Black              Contains   DBP        Polystyrene                        Melt    Fine Line   absorption and       Viscosity                                QualityInk     (ml/100 g) Methacrylate                        (cP)    (3.3 mil line)______________________________________Prior Art A   115        no        2700    2A       115        yes        585    3B-S      48        yes        296    5______________________________________
B. Horizontal (Rotated) Bar Codes
Excess ink transfer (trailing edge) in rotated bar codes can cause scanning failure from a verifier. Due to low tensile elongation and cohesive strength, brittle inks produce sharper rotated bar codes. The sharp rotated bar code is a result of a clean ink cleavage that occurs when the ribbon strips away from the receiver. In contrast, a ductile ink tends to have a higher tensile elongation and is tougher to break. Ink filamentation also occurs when a ductile ink cleaves at the ribbon stripping point.
Two approaches were used to eliminate trailing edge in rotated bar codes. The first method is to make the ink more brittle and lower its tensile strength and elongation. Table 9 shows that the incorporation of high Tg Piccotex (α-methyl polystyrene/vinyl toluene) tackifier lowers the ink's tensile strength and elongation. In addition to the substitution of high Tg Piccotex, a high Tg polyacrylate can reduce the tensile strength and elongation even further. FIGS. 6 through 8 show that the trailing edge of print samples generated using only layer 2 listed in Table 6 is improved in comparison to that of prior art. Prior art gives either a broad line or does not transfer the ink completely.
A second approach is to incorporate an undercoat (release layer) with the formulation listed in Table 7. This undercoat not only improves scratch durability, but also improves trailing edge. FIG. 9 shows that the line sharpness of the rotated bar code is improved and better than the prior art.
TABLE 9__________________________________________________________________________Mechanical properties of top coat inks                              Trailing Edge       Polyacrylate                 Break strength                              6 ips,Polystyrene        solid                 at 32� C.                        Elongation                              9.9 milFormulation Mw    Tg Mw           Tg %  psi    micrometer                              energy + 10__________________________________________________________________________INK C 1100    29 35000            50              11.2                 41.6   308.1 2INK B-S 1500    43 35000            50              11.2                 63.51  276   3INK D 3800    68 35000            50              11.2                 46.3   109.5 3INK E 1500    43 15000           100              6  32     101.1 3__________________________________________________________________________
High ink hardness provides excellent scratch durability. Table 10 shows that ink will have a scratch resistance of 5 (the best) if the ink penetration is less than 0.35%. High Tg polystyrene resins such as the ones used in inks B and D have better scratch durability due to low ink penetration. In contrast, Ink C utilizes a polystyrene resin with a Tg of 29� C. and has a scratch resistance of only 3. The molecular weight and chemistry of the polyacrylate resin will also affect the ink penetration and scratch resistance. High molecular weight polyacrylate used in ink F produces better scratch resistance than the polyacrylate used in ink E. Ink B-S uses a methacrylate terpolymer that is more sterically hindered due to the methyl group on the backbone. Ink F uses a methacrylate/acrylate terpolymer in which the acrylate portion does not have a methyl group on the side chain which reduces the steric hindrance in this terpolymer. The added steric hindrance in the methacrylate terpolymer used in ink B-S makes the methacrylate more rigid and this will make the ink harder increasing scratch resistance. This is why ink B-S gives excellent durability even though the MW of the methacrylate terpolymer in ink B-S is lower than the acrylate containing terpolymer used in ink F. Overall ink B not only retains a level of 5 in scratch durability, it also gives a level of 5 in fine line printing. FIG. 10 shows this formulation has a scratch resistance equal to that of prior art.
TABLE 10__________________________________________________________________________Ink hardness                      Ink                      penetration                            ScratchPiccotex    Acrylate       40C,  DurabilityFormulation Mw    Tg Mw            Tg  Solid %                      50 mins                            250 cycles__________________________________________________________________________INK C 1100    29 35000            50  11.2  1.20% 3INK B-S 1500    43 35000            50  11.2  0.35% 5INK D 3800    68 35000            50  11.2  0.01% 5INK E 1500    43 70K/25K            35,105                12%,50/50                      0.74% 4INK F 1500    43 70K/40K            35,105                12%,50/50                      0.32% 5INK G 1500    43 70K/15K            35,105                12%,50/50                      0.22% 5__________________________________________________________________________
D. Measurement of ink properties
The melt viscosities in Table 8 were measured using a HAAKE VT 500 viscometer operated at a shear rate of 2155 sec-1 and a temperature of 109� C.
2. Ink hardness/penetration
A disc-shape sample (10 mm diameter and 2 mm thickness) is formed by solidifying the ink from a heated aluminum mold. This sample is then placed into a test chamber of Perkin-Elmer TMA7. Isothermal penetration tests are performed at 40� C. and under a load of 100 miliNewton. The degree of penetration reflects ink hardness.
A rectangular specimen (10 mm width�50 mm length�1 mm thickness) is formed by solidifying the ink from a heated aluminum mold. The tensile strength and elongation at break are measured using a SinTech tensile tester. The sample is tested at 32� C. and with a cross head speed of 0.1 in/min.
E. Thermal Transfer Print Quality Testing
A thermal transfer label printer with a printhead resolution of 300 dpi was used to produce print samples on various receivers. Testing includes fine line (1 X dimension bars) printability, normal bar codes, rotated bar code quality (trailing edge defect), voiding, and image durability.
1. Fine Line Print Testing
Fine line printing, also known as line integrity, is the ability of a printing system to image lines at X dimensions of 1 dot. For our testing a Code 39, 3.3 mil bar code printed in the normal orientation was used. Burn energies on the printer were adjusted until bar breakage in the 3.3 mil bars were minimized. This was done by using a 10X loupe and paying close attention, so that the bars were not beginning to bloom, thus masking the evaluation. Two consecutive labels were imaged with the first label being discarded to avoid any printer startup defects. When the burn energy was optimized each sample was graded using the 10X loupe on a scale of 0-5, with 0 being the worst.
2. Print Quality of Normal Bar Codes
Grading of the normal oriented bar codes was performed at the same burn energies as for fine line. Again a 10X loupe was used to analyze the bars for voiding, blooming, and ticking. Scoring was based on a range 0-5, with 0 being the worst.
3. Print Quality of Rotated Bar Codes
A 10 mil Code 39 bar code was utilized to analyze the amount of trailing edge defect for each printing system. Burn energies were adjusted until an average bar growth of +/-0.03 was achieved. Average bar growth as measured with a verifier with a 6 mil aperture, a visible red light at 660 nanometers, and with a scanning accuracy of ten cycles. Trailing edge was then graded on a scale of 0-5, with 0 being the worst. Again a 10X loupe was used for the grading.
Also the rotated bars were evaluated for voiding. The same grading system was used based on the severity of the voiding. Voiding could be either fibers from the receiver showing through or from incomplete ink transfer.
4. Image Durability
Ink durability testing was performed using a A.A.T.C.C. Crockmeter at 250 cycles. A tip from a light wand verifier was the device used in the scratching of the printed image.
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