Patent Grant
8916496
This invention relates to a thermally-responsive record material. It more particularly relates to such record material of the type in the form of sheets coated with color-forming systems comprising chromogenic material (electron-donating dye precursors) and typically acidic color developer material. This invention particularly concerns a thermally-responsive record material capable of forming a substantially non-reversible image resistant to fade or erasure and useful for producing dark images or functional bar codes. The invention teaches an improved thermally-sensitive record material which when imaged exhibit useful image properties.
Thermally-responsive record material systems are well known in the art and are described in many patents, for example. U.S. Pat. No. 3,539,375 Baum; U.S. Pat. No. 3,674,535 Blose et al., U.S. Pat. No. 3,746,675 Blose et al., U.S. Pat. No. 4,151,748 Baum; U.S. Pat. No. 4,181,771 Hanson et al; U.S. Pat. No. 4,246,318 Baum, and U.S. Pat. No. 4,470,057 Glanz which are incorporated herein by reference. In these systems, basic colorless or lightly colored chromogenic material and acidic color developer material are contained in a coating on a substrate which, when heated to a suitable temperature, melts or softens to permit said materials to react, thereby producing a colored mark.
Thermally-responsive record materials have characteristic thermal response, desirably producing a colored image of sufficient intensity upon selective thermal exposure.
A need exists in the industry for thermally responsive record materials that are considered more environmentally friendly. A thermally-imaging formulation that can produce an image when heated to a suitable temperature and be more acceptable in the marketplace from environmental or safety considerations would be useful commercially.
Thermally-responsive record materials are utilized in diverse application including for labeling, facsimile, point of sale printing, printing of tags and pressure sensitive labels.
Kawakami, U.S. Pat. No. 5,464,804 teaches a thermal recording material wherein colorless dye is combined with an isocyanate and an amino compound. Similarly Shimura et al., U.S. Pat. No. 5,079,211 teaches forming a heat sensitive recording material by combining a fluoran compound with an aromatic isocyanate and an imino compound having at least one >C═NH which reacts with the isocyanate compound upon application of heat to form a color.
Shimura's isocyanate compounds are aromatic or heterocyclic isocyanate compounds such as also disclosed in Kabashima et al., U.S. Pat. No. 4,521,793. An aromatic isocyanate is reacted with an imino compound having at least one >C═NH group to effect color formation. In each case the isocyanate is reacted with the imino compound to form a complex that reacts with the dye.
The present invention is a departure from preceding art by foregoing the use of isocyanate materials. Isocyanates are disfavored in some environments and can even be hazardous. A thermally imaging system substantially-free of isocyanate would be commercially useful. Additionally the present invention advantageously provides an alternative to the typical phenolic developer common employed.
The invention teaches the use of a combination of non-phenolic developers for thermal sensitive recording materials. More specifically, this invention relates to using 4,4′-diaminodiphenyl sulfone and 3,3′-diaminodiphenyl sulfone and/or a mixture of both developers and a leuco dye and further comprising an organic acid which can be an aliphatic, cyclic or aromatic acid.
The present invention teaches that the intensity of leuco dye systems can be improved when reacted with 4,4′-diaminodiphenyl sulfone or 3,3′ diaminodiphenyl sulfone.
For ease of reference, 3,3′-diaminodiphenyl sulfone is sometimes referred to herein as Developer 3,3′. 4,4′-diaminodiphenyl sulfone is sometimes referred to as Developer 4,4′.
The invention describes a thermally-responsive record material substantially free of aromatic isocyanate. The record material comprises a support having provided thereon a heat-sensitive composition comprising a substantially colorless dye precursor comprising a leuco compound, a developer material and the organic acid. The developer material is selected from the group consisting of 4,4′-diaminodiphenyl sulfone and 3,3′-diaminodiphenyl sulfone, which upon being heated reacts with said dye precursor to develop color, and including a binder material. An optional modifier compound can also be employed. The optional modifier compound can be selected from the group consisting of a fatty acid amide such as stearamide wax, 1,2-diphenoxy ethane or dimethyl diphenoxy ethane, dimethyl phthalate. Optionally a filler such as calcium stearate, magnesium stearate, calcium carbonate, clays, kaolin and pigments can also be incorporated. Stearates such as magnesium stearate in one aspect are useful at up to 10% by weight, at from 10% to 15% by weight on in another aspect from 5% to 13% by weight, or from 5% even up to 13%, or even up to 20%, or even up to 30% by weight based on weight of the heat sensitive coating.
The organic acid is a compound selected from organic acids according to formula (1)
An exemplary list of organic acids according to formula 1 include:
In a further aspect, the organic acid is an aliphatic or cylic organic acid. Exemplary aliphatic or cyclic organic acids include lactic acid and alkanedienoic acids such as 2,4-hexanedienoic acid or sorbic acid; alkanedioic acids such as butanedioic acid or succinic acid; hydroxyalkane tricarboxylic acids such as citric acid; dihydroxyfuran ones such as ascorbic acid, whether racemate, or d- or l- enantiomers.
The thermally imaging system of the invention yields a thermal image that can be read visually and/or can be decodable electronically such as in the form of a thermal barcode.
Electron-donating dye precursors are color formers generally known and commonly referred to as leuco dyes. For purpose of the invention, when referring to “colorless dye precursor” or “color former”, the terms are used interchangeably and are intended to encompass leuco dyes and chromogens include chormogenic compounds such as the pthhalide, leucoauramine and fluoroan compounds. These color formers are chromogenic materials or electron donating dye precursors and are well known colorless or slightly colored color-forming compounds for use in color-forming record systems. Examples of the compounds include Crystal Violet Lactone (3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalide), (U.S. Pat. No. RE 23,024); phenyl-, indolyl, pyrrolyl, and carbazolyl-substituted phthalides (for example, in U.S. Pat. Nos. 3,491,111; 3,491,112; 3,491,116; 3,509,174); nitro-, amino-, amido-, sulfonamido-, aminobenzylidene-, halo-, anilino-substituted fluorans (for example, the U.S. Pat. Nos. 3,624,107; 3,627,78; 3,641,011; 3,642,828; 3,681,390); spirodipyrans (U.S. Pat. No. 3,971,808); and pyridine and pyrazine compounds (for example, in U.S. Pat. Nos. 3,775,424 and 3,853,869). Other specifically eligible chromogenic compounds, not limiting the invention in any way, are: 3-diethylamino-6-methyl-7-anilino-flouran (U.S. Pat. No. 4,510,513); 3-dibutylamino-6-methyl-7-anilino-fluoran; 3-dibutylamino-7-(2-chloroanilino) fluoran; 3-(N-ethyl-N-tetrahydrofurfurylamino)-6-methyl-7-3,5′6-tris(dimethylamino) spiro[9H-fluorene-9,1′(3′H)-isobenzofuran]-3′-one; 7-(1-ethyl-2-methylindole-3-yl)-7-(4-diethylamino-2-ethoxyphenyl)-5,7-dihydrofuro[3,4-b]pyridin-5-one (U.S. Pat. No. 4,246,318); 3-diethylamino-7-(2-chloroanilino)fluoran (U.S. Pat. No. 3,920,510); 3-(N-methylcyclohexylamino)-6-methyl-7-anilinofluoran (U.S. Pat. No. 3,959,571); 7-(1-octyl-2-methylindole-3-yl)-7-(4-diethylamino-2-ethoxyphenyl)-5,7-dihydrofuro[3,4-b]pyridin-5-one; 3-diethylamino-7,8-benzofluoran; 3,3-bis(1-ethyl-2-methylindole-3-yl)phthalide; 3-diethylamino-7-anilinofluoran; 3-diethylamino-7-benzylaminofluoran; 3′-phenyl-7-dibenzylamino-2,2′-spirodi-[2H-1-benzopyran] and mixtures of any of the following.
In a further embodiment the invention comprises a thermally-responsive record material, wherein the substantially colorless dye precursor comprises a fluoran compound of the formula
wherein R1 is hydrogen or alkyl
wherein R2 is hydrogen or alkaryl;
wherein R3 is aryl when R2 is hydrogen, or alkaryl when R2 is alkaryl;
R4 and R5 are each independently selected from alkyl, aralkyl; or R4 and R5 form a four carbon ring pyrrolidine structure.
In a yet further embodiment, in the thermally-responsive record material described the fluoran is selected from the group consisting of:
For convenience, the above dye precursors (“color formers”) are referred to herein as the respective “dye,” by the structure number (e.g. “dye 1,” “dye 2,” “dye 3,” “dye 4,” “dye 5,” “dye 6,” and “dye 7.”
The record material according to the invention has a non-reversible image in that it is non-reversible under the action of heat. The coating of the record material of the invention is basically a dewatered solid at ambient temperature.
The color-forming system of the record material of this invention comprises the electron donating dye precursors, also known as chromogenic material, in its substantially colorless state together with an acidic developer material. The color-forming system relies upon melting, softening, or subliming one or more of the components to achieve reactive, color-producing contact with the chromogen. Substantially colorless for purposes of the invention is understood to mean colorless or lightly or faintly colored.
The record material includes a substrate or support material which is generally in sheet form. For purposes of this invention, sheets can be referred to as support members and are understood to also mean webs, ribbons, tapes, belts, films, cards and the like. Sheets denote articles having two large surface dimensions and a comparative small thickness dimension. The substrate or support material can be opaque, transparent or translucent and could, itself, be colored or not. The material can be fibrous including, for example, paper and filamentous synthetic materials. It can be a film including, for example, cellophane and synthetic polymeric sheets cast, extruded, or otherwise formed. The invention resides in the color-forming composition coated on the substrate. The kind or type of substrate material is not critical. In some embodiments neutral sized base paper is a preferred substrate.
The components of the heat sensitive coating are in substantially contiguous relationship, substantially homogeneously distributed throughout the coated layer or layers deposited on the substrate. For purposes of this invention the term substantially contiguous is understood to mean that the color-forming components are positioned in sufficient proximity such that upon melting, softening or subliming one or more of the components, a reactive color-forming contact between the components is achieved. As is readily apparent to the person of ordinary skill in this art, these reactive components accordingly can be in the same coated layer or layers, or individual components positioned in separate layers using multiple layers. In other words, one component can be positioned in the first layer, and developer or modifier or sensitizer components positioned in a subsequent layer or layers. All such arrangements are understood herein as being substantially contiguous.
The developer to dye precursor ratio by weight is maintained, at from 1:1 to about 4:1, or even from 0.1:1 to about 3:1, or even from 0.5:1 to about 2.5:1 or even from about 0.5:1 to about 5:1. Preferably the developer to dye precursor ratio is from about 1:1 to about 3:1. The modifier to dye precursor ratio by weight is preferably maintained at greater than 1:1, or even from 0.2:1 to about 2.5:1, or even from about 0.1:1 to about 3:1, or even from 0.1:1 to about 4:1.
In manufacturing the record material, a coating composition is prepared which includes a fine dispersion of the components of the color-forming system, and binder material, preferably polymeric binder such as polyvinyl alcohol. The composition of the invention can optionally include or be free of pigments including clays and fillers. Preferably, pigments, if included, are maintained at less than 13%, or even less than 20%, or even less than 30%, by weight of the heat sensitive coating composition of the invention.
The dispersion of the organic acids can be prepared by milling or milling in combination with the developer or in combination with the fillers or modifier prior to blending into a final coating. Optionally, the organic acid can be prepared as a solution instead of milling.
4,4′-diaminodiphenyl sulfone and 3,3′-diaminophenyl sulfone, respectively, in the presence of a color former (leuco dye) can yield an image readable to the human eye and a barcode that could be scanned. The system can be further optimally enhanced by selecting a modifier, such as a stearamide wax. The image intensity can be enhanced with the selection of leuco dyes, particularly of the fluoran class of color formers. A filler such as magnesium stearate can also be included.
In this invention, intensity is improved by introducing organic acids into the system. The organic acids, can be phenolic or non-phenolic in nature, cyclic or aliphatic, aromatic or, alkane type. Organic acids include ascorbic acid, citric acid, coumaric acid, salycilic acid, vanillic acid, cinnamic acid, o-acetyl salycilic acid, 3-(4-hydroxyphenyl)propionic acid, 3-(2-hyroxyphenyl propionic acid), 3,4-dihydroxyphenyl acetic acid. Other structures that could be used include vanillic acid, cinnamic acid, succinic acid, lactic acid and sorbic acid.
The heat-sensitive coating composition can additionally contain pigments, such as clay, talc, silicon dioxide, aluminum hydroxide, calcined kaolin clay and calcium carbonate, and urea-formaldehyde resin pigments at from 0 to 10% or even from 0 to 20% or even 0 to 30% by weight of the heat-sensitive coating. Other optional materials include natural waxes, Carnauba wax, synthetic waxes, lubricants such as zinc stearate; wetting agents; defoamers, modifiers and anti-oxidants. The modifier typically does not impart any image on its own but as a relatively low melt point solid, acts as a solvent to facilitate reaction between the mark-forming components of the color-forming system. Optionally the thermally-sensitive record material can be top coated with a polymeric material forming a top coating. Materials such as polyvinyl alcohol or any of various binder materials can also be used for this purpose.
The color-forming system components are substantially insoluble in the dispersion vehicle (preferably water) and are ground to an individual average particle size of less than 10 microns, preferably less than 3 microns. The polymeric binder material is substantially vehicle soluble although latexes are also eligible in some instances. Preferred water soluble binders, which can also be used as topcoats, include polyvinyl alcohol, hydroxy ethylcellulose, methylcellulose, methyl-hydroxypropylcellulose, starch, modified starches, gelatin and the like. Eligible latex materials for the binder and/or topcoat include polyacrylates, styrene-butadiene-rubber latexes, styrene acrylics, polyvinylacetates, polystyrene, and the like. The polymeric binder is used to protect the coated materials from brushing and handling forces occasioned by storage and use of thermal sheets. Binder should be present in an amount to afford such protection and in an amount less than will interfere with achieving reactive contact between color-forming reactive materials.
Coating weights can effectively be about 1 to about 9 grams per square meter (gsm) or even from 0.5 to about 10 gsm and preferably about 3 to about 6 gsm and more preferably from 3 to 5 gsm. The practical amount of color-forming materials is controlled by economic considerations, functional parameters and desired handling characteristics of the coated sheets.
The thermally response record material of the invention is particularly advantageous for bar codes. Bar codes provide a convenient means for computerized inventory or goods handling and tracking. To function properly, it is necessary that the bar code have high print contrast signal, and that the thermally-responsive material on which the bar code is imaged resist unwanted bar width growth after imaging. The characters or bars must not only be intensely imaged, but must be sharp, and unbroken or free of pin holes. It is also necessary that when read by a scanner that a high percentage of scans result in successful decoding of the information in the bar code. The percentage of successful decodes of the bar code information must be maintained at a high value for the thermally-responsive record material to gain wide commercial acceptance for use in bar coding applications.
To form a bar code, the heat sensitive layer on the support is imaged by selective application of heat in the pattern of a bar code. The thermally responsive record material composition described herein enables imaging on the record material of an improved bar code of any type, including one and two dimension pattern bar codes. Bar codes are well known and typically comprise a plurality of uniformly spaced apart parallel vertical lines, often of differing thicknesses forming a row extending from a common horizontal axis. The horizontal axis is generally not shown but is a convenient reference point for descriptive purposes. The spaced apart parallel neutral lines are arranged in a row. Bar codes are a machine readable representation of data and can be one dimension or two dimension patterns, graphics, or other imaged patterns relying on interpretive software to decode the bar code when scanned.
The following examples are given to illustrate some of the features of the present invention and should not be considered as limiting. In these examples all parts or proportions are by weight and all measurements are in the metric system, unless otherwise stated.
In all examples illustrating the present invention a dispersion of a particular system component can be prepared by milling the component in an aqueous solution of the binder until a particle size of less than 10 microns is achieved. The milling was accomplished in an attritor or other suitable milling device. The desired average particle size was less than 3 microns in each dispersion.
The thermally-responsive sheets were made by making separate dispersions of chromogenic material, modifier material, and developer material. The dispersions are mixed in the desired ratios and applied to a support with a wire wound rod and dried. Other materials such as fillers, antioxidants, lubricants and waxes can be added if desired. The sheets may be calendered to improve smoothness.
The abbreviations and dye precursor numbers correspond to the following materials:
Coating Formulation I Using:
Coating Formulation II Using:
Coating Formulation III Using:
Coating Formulation IV Using:
Coating Formulation V Using:
Coating Formulation VI Using:
Coating Formulation VI Using:
Coating Formulation VI Using:
Coating Formulation VI Using:
Coating Formulation VI Using:
Coating Formulation VI Using:
Coating Formulation VI Using:
Coating Formulation VI Using:
Coating Formulation VI Using:
Coating Formulation VI Using:
Coating Formulation VI Using:
Coating Formulation VI Using:
Coating Formulation VI Using:
Coating Formulation VI Using:
Coating Formulation VI Using:
Coating Formulation VI Using:
Coating Formulation VI Using:
Coating Formulation VI Using:
Coating Formulation VI Using:
Coating Formulation VI Using:
Coating Formulation VI Using:
Coating Formulation VI Using:
Coating Formulation VI Using:
Coating Formulation VI Using:
Coating Formulation VI Using:
Coating Formulation VI Using:
Coating Formulation VI Using:
Coating Formulation VI Using:
Coating Formulation VI Using:
Coating Formulation IV Using:
Coating Formulation VI Using:
Coating Formulation VI Using:
Samples from the examples 1-37 described above were imaged using an Atlantek 400 at a medium energy setting. The thermal Image intensity was recorded using a Gretag densitometer. The units of image density are referred to as optical density units, also known as o.d.u. The higher the o.d.u, the more intense or blacker the image is. The brightness readings of the samples were also measured and recorded.
In the Brightness UVEX readings, the UV component of the brightness was filtered out so as not to introduce any bias from the fluorescent or optical brighteners that is added into a coating formulation.
The data shown below depicts examples 1-37, describing, weight of coat (“WOC”), intensity, and brightness. Weight of coats were determined analytically, whereby the amount of dye was extracted and quantified using a spectrophotometer.
In this invention, a significant and considerable increase in image intensity is obtained when an organic acid is used in combination with 4,4′-diaminodiphenyl sulfone and/or 3,3′-diaminodiphenyl sulfone with a color former. An organic acid alone, i.e. with no diaminodiphenyl sulfone, in the presence of a color former yields a thermal image lacking strong intensity (see Example 4 and 35, and
The filler further enhances the image intensity of the 4,4′-diaminodiphenyl sulfone. For example, the substitution of calcium carbonate, a typical filler used in direct thermal coatings, with magnesium stearate, yields an improved intensity when used with an organic acid. Optionally, and optimally the product is topcoated. In non-topcoated products, calcium carbonate can be added to the thermal coating in part to address printhead residue. In topcoated products, fillers, such as calcium carbonate or kaolin clays are added, usually at lower concentrations.
Comparing examples, 2,9, and 10, these examples demonstrate that CaCO3 can mask the image but that magnesium stearate improves the image. Ideally, the use of no filler is preferred (Example 2). Magnesium stearate can be optionally added, does not display masking and enhance intensity.
When other fillers were evaluated including magnesium hydroxide, calcium stearate, and zinc stearate, at a given coat weight, magnesium stearate˜zinc stearate>calcium stearate>magnesium hydroxide>calcium carbonate.
Surprisingly, the benefits seen with magnesium stearate appear to be unique to the two diaminodiphenyl sulfones This is based on the examples, 14 and 15 using Bisphenol S as the developer. For example 14, samples were prepared using CaCO3, whereas samples from example 15 were generated using magnesium stearate. The results showed that at equal weight of coats, the intensity of both systems were equivalent, suggesting that the Bis S/organic acid system is not as sensitive to the presence of fillers or modifiers as in the diaminodiphenyl sulfone/organic acid systems.
The examples demonstrate the benefits on image intensity by incorporating organic acids into 4,4′ diaminodiphenyl sulfone systems utilizing a series of various fillers and the color former dye 2 (see
All percentages and ratios are calculated by weight unless otherwise indicated. All percentages and ratios are calculated based on the total composition unless otherwise indicated.
It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.
Uses of singular terms such as “a,” “an,” are intended to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms “comprising,” “having,” “including,” and “containing” are to be construed as open-ended terms. All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference. Any description of certain embodiments as “preferred” embodiments, and other recitation of embodiments, features, or ranges as being preferred, or suggestion that such are preferred, is not deemed to be limiting. The invention is deemed to encompass embodiments that are presently deemed to be less preferred and that may be described herein as such. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended to illuminate the invention and does not pose a limitation on the scope of the invention. Any statement herein as to the nature or benefits of the invention or of the preferred embodiments is not intended to be limiting. This invention includes all modifications and equivalents of the subject matter recited herein as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context. The description herein of any reference or patent, even if identified as “prior,” is not intended to constitute a concession that such reference or patent is available as prior art against the present invention. No unclaimed language should be deemed to limit the invention in scope. Any statements or suggestions herein that certain features constitute a component of the claimed invention are not intended to be limiting unless reflected in the appended claims.
This application under 35 USC §111(a) is a continuation-in-part and claims benefits per 35 USC §120 to U.S. application Ser. No. 13/803,824 filed Mar. 14, 2013, now pending, and incorporated herein by reference.
| Number | Date | Country |
|---|---|---|
| 06-191154 | Jul 1994 | JP |
| Number | Date | Country | |
|---|---|---|---|
| 20140263673 A1 | Sep 2014 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 13803824 | Mar 2013 | US |
| Child | 14051906 | US |
