(19)
(11)EP 2 969 580 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
29.07.2020 Bulletin 2020/31

(21)Application number: 13877604.2

(22)Date of filing:  11.10.2013
(51)International Patent Classification (IPC): 
B41M 5/333(2006.01)
B41M 5/327(2006.01)
(86)International application number:
PCT/US2013/064540
(87)International publication number:
WO 2014/143174 (18.09.2014 Gazette  2014/38)

(54)

THERMALLY-RESPONSIVE RECORD MATERIAL

WÄRMEEMPFINDLICHES AUFZEICHNUNGSMATERIAL

MATÉRIAU D'ENREGISTREMENT RÉAGISSANT À LA CHALEUR


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 14.03.2013 US 201313803824

(43)Date of publication of application:
20.01.2016 Bulletin 2016/03

(73)Proprietor: Appvion Operations, Inc.
Appleton WI 54912-0359 (US)

(72)Inventors:
  • CHAKAR, Fadi, Selim
    Appleton, WI 54915 (US)
  • FISHER, Mark, Robert
    Appleton, WI 54911 (US)

(74)Representative: Carpmaels & Ransford LLP 
One Southampton Row
London WC1B 5HA
London WC1B 5HA (GB)


(56)References cited: : 
EP-A1- 1 116 713
JP-A- H02 235 682
JP-A- H06 191 154
SU-A1- 455 182
US-A1- 2011 028 317
EP-A2- 0 421 278
JP-A- H05 193 261
JP-A- 2007 008 028
US-A- 5 066 634
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    FIELD OF THE INVENTION



    [0001] 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.

    DESCRIPTION OF THE RELATED ART



    [0002] Thermally-responsive record material systems are well known in the art and are described in many patents, for example. U.S. Patent Nos. 3,539,375 Baum; 3,674,535 Blose et al., 3,746,675 Blose et al., 4,151,748 Baum; 4,181,771 Hanson et al,; 4,246,318 Baum, and 4,470,057Glanz. 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.
    US 5 066 634 A discloses a heat-sensitive recording sheet comprising in a heat-sensitive color-developing layer both 4-hydroxy-4'-n-propoxydiphenylsulfone as an organic color-developing agent and a particular fluorane-leuco dye.
    EP 1 116 713 A1 discloses a urea-urethane compound; the disclosure relates also to a color-producing composition obtained by using the urea-urethane compound, and a recording material obtained by using the color-producing composition.
    SU 455 182 A1 discloses the production of temperature sensitive papers for determining the temperature in places where its measurement by means of devices is excluded.
    JP H06 191154 A discloses making whiteness and sensitivity to color development of a heat sensitive recording material favorable, by a method wherein a colorless heat sensitive color development layer containing donating, color-developing dye precursor, a developer and 3,3'-diaminodiphenyl sulfone is provided on a substrate. JP H02 235682 A discloses increasing the stable storage of a recorded image significantly without deterioration of the degree of whiteness or the fogging of a developed color by adding 4,4'-diaminodiphenyl sulfone to a recording layer.
    JP 2007 008028 A discloses providing a thermosensitive recording body, in which the change of a recording density due to the change of the humidity in recording environments is said to be little and, in addition, the recording sensitivity of which is said to be high.

    [0003] Thermally-responsive record materials have characteristic thermal response, desirably producing a colored image of sufficient intensity upon selective thermal exposure.

    [0004] 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.

    [0005] Thermally-responsive record materials are utilized in diverse application including for labeling, facsimile, point of sale printing, printing of tags and pressure sensitive labels.

    [0006] Kawakami, U.S. Patent 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. Patent 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.

    [0007] Shimura's isocyanate compounds are aromatic or heterocyclic isocyanate compounds such as also disclosed in Kabashima et al., U.S. Patent 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.

    [0008] 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 commonly employed.

    BRIEF DESCRIPTION OF THE DRAWINGS



    [0009] 

    Figure 1 depicts intensity of thermal record system with 4,4'-diaminodiphenyl sulfone in the absence and presence of an organic acid according to the invention.

    Figure 2 depicts the intensity of thermal record systems in the absence of an organic acid at vaiorus weight of coats.

    Figure 3 depicts the effects of filler on intensity on thermal record systems according to the invention.

    Figure 4 depicts various 4,4'-diaminodiphenyl sulfone and organic acid systems compared to systems without organic acid.


    DETAILED DESCRIPTION



    [0010] The invention is defined by the claims. 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 optimally, but preferably further comprising an organic acid which can be an aliphatic, cyclic or aromatic acid.

    [0011] 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.

    [0012] 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'.





    [0013] 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 aother 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 baed on weight of the heat sensitive coating..

    [0014] The organic acid is a compound selected from organic acids according to formula (1)

    wherein each R1 is independently selected from carboxy, hydrogen or a hydroxyl group, and wherein n is an integer from 1 to 2 or even from 1 to 4.
    R2 is selected from carboxy, alkoxy, alkenecarboxy, alkylcarboxy, alkanoate, and alkyl alkanoate.

    [0015] An exemplary list of organic acids according to formula 1 include:









    [0016] 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 I-enatiomers.







    [0017] 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.



    [0018] In a yet further embodiment, in the thermally-responsive record material described the fluoran is selected from the group consisting of:















    [0019] For convenience, the above dye precursors 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."

    [0020] In a yet further embodiment the thermal modifier compound is a saturated fatty acid amide or bisamide.

    [0021] In a yet further embodiment, in the thermally-responsive record material the thermal modifier compound is a fatty acid amide, and preferably the modifier compound is a fatty acid amide selected from

    or,

    wherein m is 1 to 23, n is 0 to 21.

    [0022] The fatty acid amides useful in the invention can include lauramide, myristamide, palmitamide, or stearamide.

    [0023] Preferably the amide alkyl length is anywhere from four to 24 carbons, or even from 4 to 18 carbons, or even from 8 to 22 carbons. Each respective alkyl length in the bisamide or diamide can be similar as in the monoamide in terms of carbon number. Optionally the amide is a bisamide of preferably of 8 to 48 carbons, or even from 4 to 24 carbons, or even from 8 to 36 carbons.

    [0024] The fatty acid bisamide can even include methylene bisamides such as methylene bis stearamide, or ethylene bisamides such as ethylene bis lauric acid amide, N,N-ethylene bis (stearamide), 1,2-bis (octanamido)ethane, 1,2-bis (hexanamido)ethane or N1N-ethylenebis (palmitamide).

    [0025] 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.

    [0026] 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.

    [0027] 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 fluroan coumponds. 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-methy1-7-3,5'6-tris(dimethylamino) spiro[9H-fluorene-9,1'(3'H)-isobenzofuran]-3'-one; 7-(1-ethyl-2-methyfindole-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-octy1-2-methylindole-3-yl)-7-(4-diethylamino-2-ethoxyphenyl)-5,7-dihy drofuro[3,4-b]pyridin-5-one; 3-diethylamino-7,8-benzofluoran; 3,3-bis(1-ethy1-2-methylindole-3-yl)phthalide; 3-diethylamino-7-anilinofluoran; 3-diethylamino-7-benzylaminofluoran; 3'-pheny1-7-dibenzylamino-2,2'-spirodi-[2H-1-benzopyran] and mixtures of any of the following.

    [0028] 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.

    [0029] 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.

    [0030] 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.

    [0031] 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.

    [0032] 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.

    [0033] 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.

    [0034] 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.

    [0035] 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.

    [0036] 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.

    [0037] 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.

    [0038] 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.

    [0039] 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.

    [0040] 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.

    [0041] 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.

    [0042] 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.

    [0043] 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 micrometres is achieved. The milling was accomplished in an attritor or other suitable milling device. The desired average particle size was less than 3 micrometres in each dispersion.

    [0044] 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.

    [0045] Color former and dye precursor are used interchangeable and as synonyms for purposes of the inventin. The abbreviations and dye precursor or color former numbers correspond to the following materials:
    Table 1
    DME dimethyldiphenoxyethane
    DPE 1,2-diphenoxyethane
    DMT dimethyl phthalate
       
    Dye, Formula # 
    Dye 1 3-diethylamino-6-methyl1-7-(2',4'dimethyl aniline) fluoran
    Dye 2 3-dibutylamino-6-methyl-7-anilino fluoran
    Dye 3 3-diethylamino-6-methyl-7-(3'-methylanilino) fluoran
    Dye 4 3-diethylamino-6-methyl-7-anilinofluoran
    Dye 5 3-(N-ethyl-N-p-tolylamino)-6-methyl-y-anilino fluoran
    Dye 6 3-pyrrolidino-6-methyl-7-anilino fluoran
    Dye 7 3-diethylamino-7-(dibenzylamino) fluoran
    Selvol 125, Sekisui Chemical Co., Ltd., Tokyo, Japan Polyvinyl alcohol

    CHROMOGENIC (DYE PRECURSOR) DISPERSIONS



    [0046] 
    DISPERSION A - CHROMOGENIC MATERIAL
    MaterialParts
    Chromogenic material 34.0
    Binder, 20% solution of Polyvinyl alcohol 27.0
    Dispersing and defoaming agents 4.0
    Water 35.0

    Dispersion A1 - Chromogenic material is Dye 1

    Dispersion A2 - Chromogenic material is Dye 2

    Dispersion A3 - Chromogenic material is Dye 3

    Dispersion A4 - Chromogenic material is Dye 4

    Dispersion A5 - Chromogenic material is Dye 5

    Dispersion A6 - Chromogenic material is Dye 6

    Dispersion A7 - Chromogenic material is Dye 7

    MaterialParts
    DISPERSION B - DEVELOPER MATERIAL 
    Acidic Material 39.0
    Binder, 20% solution of Polyvinyl alcohol 24.0
    Dispersing and defoaming agents 0.5
    Water 36.5

    Dispersion B1 - developer material is 4,4'-diaminodiphenyl sulfone

    Dispersion B2 - developer material is 3,3'-diaminodiphenyl sulfone


    DISPERSION C - MODIFIER MATERIAL



    [0047] 
    Modifier Material 25.0
    Binder, 20% solution of Polyvinylalcohol 20.0
    Dispersing and defoaming agents 1.0
    Water 54.0

    Dispersion C1 - modifier material is DPE

    Dispersion C2 - modifier material is DME

    Dispersion C3 - modifier material is DMT

    Dispersion C4 - modifier material is stearamide wax

    MaterialParts (by weight)
    Coating Formulation I. 
    Dispersion A (chromogen) 4.0
    Dispersion B (developer) 15.0
    Binder, 10% solution of polyvinyl alcohol 13.0
    Filler slurry, 30% in water 1.0
    Filler slurry, 21 % in water 24.0
    Additives (rheology modifier, lubricant, optical brightener) 2.0
    Water 41.0
    Coating Formulation II 
    Dispersion A (chromogen) 4.0
    Dispersion B (developer) 15.0
    Dispersion C (modifier) 3.0
    Binder, 10% solution of polyvinyl alcohol 13.0
    Filler slurry, 30% in water 1.0
    Filler slurry, 21% in water 24.0
    Additives (rheology modifier, lubricant, optical brightener) 2.0
    Water 38.0

    LIST OF EXAMPLES


    EXAMPLE 1



    [0048] Coating Formulation I using:

    Dispersion A1 (Dye 1)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)


    EXAMPLE 2



    [0049] Coating Formulation I using:

    Dispersion A1 (Dye 1)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)


    EXAMPLE 3



    [0050] Coating Formulation I using:

    Dispersion A2 (Dye 2)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)


    EXAMPLE 4



    [0051] Coating Formulation I using:

    Dispersion A2 (Dye 2)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)


    EXAMPLE 5



    [0052] Coating Formulation I using:

    Dispersion A3 (Dye 3)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)


    EXAMPLE 6



    [0053] Coating Formulation I using:

    Dispersion A3 (Dye 3)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)


    EXAMPLE 7



    [0054] Coating Formulation I using:

    Dispersion A4 (Dye 4)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)


    EXAMPLE 8



    [0055] Coating Formulation I using:

    Dispersion A4 (Dye 4)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)


    EXAMPLE 9



    [0056] Coating Formulation I using:

    Dispersion A5 (Dye 5)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)


    EXAMPLE 10



    [0057] Coating Formulation I using:

    Dispersion A5 (Dye 5)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)


    EXAMPLE 11



    [0058] Coating Formulation I using:

    Dispersion A6 (Dye 6)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)


    EXAMPLE 12



    [0059] Coating Formulation I using:

    Dispersion A6 (Dye 6)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)


    EXAMPLE 13



    [0060] Coating Formulation I using:

    Dispersion A7 (Dye 7)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)


    EXAMPLE 14.



    [0061] Coating Formulation I using:

    Dispersion A7 (Dye 7)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)


    EXAMPLE 15



    [0062] Coating Formulation II using:

    Dispersion A1 (Dye 1)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)

    Dispersion C1 (DPE)


    EXAMPLE 16



    [0063] Coating Formulation II using:

    Dispersion A1 (Dye 1)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)

    Dispersion C2 (DME)


    EXAMPLE 17



    [0064] Coating Formulation II using:

    Dispersion A1 (Dye 1)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)

    Dispersion C3 (DMT)


    EXAMPLE 18



    [0065] Coating Formulation II using:

    Dispersion A1 (Dye 1)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)

    Dispersion C4 (Stearamide wax)


    EXAMPLE 19



    [0066] Coating Formulation II using:

    Dispersion A1 (Dye 1)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)

    Dispersion C1 (DPE)


    EXAMPLE 20



    [0067] Coating Formulation II using:

    Dispersion A1 (Dye 1)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)

    Dispersion C2 (DME)


    EXAMPLE 21



    [0068] Coating Formulation II using:

    Dispersion A1 (Dye 1)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)

    Dispersion C3 (DMT)


    EXAMPLE 22



    [0069] Coating Formulation II using:

    Dispersion A1 (Dye 1)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)

    Dispersion C4 (stearamide wax)


    EXAMPLE 23



    [0070] Coating Formulation II using:

    Dispersion A2 (Dye 2)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)

    Dispersion C1 (DPE)


    EXAMPLE 24



    [0071] Coating Formulation II using:

    Dispersion A2 (Dye 2)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)

    Dispersion C2 (DME)


    EXAMPLE 25



    [0072] Coating Formulation II using:

    Dispersion A2 (Dye 2)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)

    Dispersion C3 (DMT)


    EXAMPLE 26



    [0073] Coating Formulation II using:

    Dispersion A2 (Dye 2)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)

    Dispersion C4 (stearamide wax)


    EXAMPLE 27



    [0074] Coating Formulation II using:

    Dispersion A2 (Dye 2)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)

    Dispersion C1 (DPE)


    EXAMPLE 28



    [0075] Coating Formulation II using:

    Dispersion A2 (Dye 2)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)

    Dispersion C2 (DME)


    EXAMPLE 29



    [0076] Coating Formulation II using:

    Dispersion A2 (Dye 2)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)

    Dispersion C3 (DMT)


    EXAMPLE 30



    [0077] Coating Formulation II using:

    Dispersion A2 (Dye 2)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)

    Dispersion C4 (stearamide wax)


    EXAMPLE 31



    [0078] Coating Formulation II using:

    Dispersion A3 (Dye 3)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)

    Dispersion C1 (DPE)


    EXAMPLE 32



    [0079] Coating Formulation II using:

    Dispersion A3 (Dye 3)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)

    Dispersion C2 (DME)


    EXAMPLE 33



    [0080] Coating Formulation II using:

    Dispersion A3 (Dye 3)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)

    Dispersion C3 (DMT)


    EXAMPLE 34



    [0081] Coating Formulation II using:

    Dispersion A3 (Dye 3)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)

    Dispersion C4 (stearamide wax)


    EXAMPLE 35



    [0082] Coating Formulation II using:

    Dispersion A3 (Dye 3)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)

    Dispersion C1 (DPE)


    EXAMPLE 36



    [0083] Coating Formulation II using:

    Dispersion A3 (Dye 3)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)

    Dispersion C2 (DME)


    EXAMPLE 37



    [0084] Coating Formulation II using:

    Dispersion A3 (Dye 3)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)

    Dispersion C3 (DMT)


    EXAMPLE 38



    [0085] Coating Formulation II using:

    Dispersion A3 (Dye 3)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)

    Dispersion C4 (stearamide wax)


    EXAMPLE 39



    [0086] Coating Formulation II using:

    Dispersion A4 (Dye 4)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)

    Dispersion C1 (DPE)


    EXAMPLE 40



    [0087] Coating Formulation II using:

    Dispersion A4 (Dye 4)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)

    Dispersion C2 (DME)


    EXAMPLE 41



    [0088] Coating Formulation II using:

    Dispersion A4 (Dye 4)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)

    Dispersion C3 (DMT)


    EXAMPLE 42



    [0089] Coating Formulation II using:

    Dispersion A4 (Dye 4)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)

    Dispersion C4 (stearamide wax)


    EXAMPLE 43



    [0090] Coating Formulation II using:

    Dispersion A4 (Dye 4)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)

    Dispersion C1 (DPE)


    EXAMPLE 44



    [0091] Coating Formulation II using:

    Dispersion A4 (Dye 4)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)

    Dispersion C2 (DME)


    EXAMPLE 45



    [0092] Coating Formulation II using:

    Dispersion A4 (Dye 4)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)

    Dispersion C3 (DMT)


    EXAMPLE 46



    [0093] Coating Formulation II using:

    Dispersion A4 (Dye 4)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)

    Dispersion C4 (stearamide wax)


    EXAMPLE 47



    [0094] Coating Formulation II using:

    Dispersion A5 (Dye 5)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)

    Dispersion C1 (DPE)


    EXAMPLE 48



    [0095] Coating Formulation II using:

    Dispersion A5 (Dye 5)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)

    Dispersion C2 (DME)


    EXAMPLE 49



    [0096] Coating Formulation II using:

    Dispersion A5 (Dye 5)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)

    Dispersion C3 (DMT)


    EXAMPLE 50



    [0097] Coating Formulation II using:

    Dispersion A5 (Dye 5)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)

    Dispersion C4 (stearamide wax)


    EXAMPLE 51



    [0098] Coating Formulation II using:

    Dispersion A5 (Dye 5)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)

    Dispersion C1 (DPE)


    EXAMPLE 52



    [0099] Coating Formulation II using:

    Dispersion A5 (Dye 5)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)

    Dispersion C2 (DME)


    EXAMPLE 53



    [0100] Coating Formulation II using:

    Dispersion A5 (Dye 5)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)

    Dispersion C3 (DMT)


    EXAMPLE 54



    [0101] Coating Formulation II using:

    Dispersion A5 (Dye 5)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)

    Dispersion C4 (stearamide wax)


    EXAMPLE 55



    [0102] Coating Formulation II using:

    Dispersion A6 (Dye 6)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)

    Dispersion C1 (DPE)


    EXAMPLE 56



    [0103] Coating Formulation II using:

    Dispersion A6 (Dye 6)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)

    Dispersion C2 (DME)


    EXAMPLE 57



    [0104] Coating Formulation II using:

    Dispersion A6 (Dye 6)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)

    Dispersion C3 (DMT)


    EXAMPLE 58



    [0105] Coating Formulation II using:

    Dispersion A6 (Dye 6)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)

    Dispersion C4 (stearamide wax)


    EXAMPLE 59



    [0106] Coating Formulation II using:

    Dispersion A6 (Dye 6)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)

    Dispersion C1 (DPE)


    EXAMPLE 60



    [0107] Coating Formulation II using:

    Dispersion A6 (Dye 6)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)

    Dispersion C2 (DME)


    EXAMPLE 61



    [0108] Coating Formulation II using:

    Dispersion A6 (Dye 6)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)

    Dispersion C3 (DMT)


    EXAMPLE 62



    [0109] Coating Formulation II using:

    Dispersion A6 (Dye 6)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)

    Dispersion C4 (stearamide wax)


    EXAMPLE 63



    [0110] Coating Formulation II using:

    Dispersion A7 (Dye 7)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)

    Dispersion C1 (DPE)


    EXAMPLE 64



    [0111] Coating Formulation II using:

    Dispersion A7 (Dye 7)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)

    Dispersion C2 (DME)


    EXAMPLE 65



    [0112] Coating Formulation II using:

    Dispersion A7 (Dye 7)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)

    Dispersion C3 (DMT)


    EXAMPLE 66



    [0113] Coating Formulation II using:

    Dispersion A7 (Dye 7)

    Dispersion B1 (4,4'-diaminodiphenyl sulfone)

    Dispersion C4 (stearamide wax)


    EXAMPLE 67



    [0114] Coating Formulation II using:

    Dispersion A7 (Dye 7)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)

    Dispersion C1 (DPE)


    EXAMPLE 68



    [0115] Coating Formulation II using:

    Dispersion A7 (Dye 7)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)

    Dispersion C2 (DME)


    EXAMPLE 69



    [0116] Coating Formulation II using:

    Dispersion A7 (Dye 7)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)

    Dispersion C3 (DMT)


    EXAMPLE 70



    [0117] Coating Formulation II using:

    Dispersion A7 (Dye 7)

    Dispersion B2 (3,3'-diaminodiphenyl sulfone)

    Dispersion C4 (stearamide wax)

    Table 2
    EXAMPLESTATUSEXAMPLESTATUS
    1 IMAGED (1.7; C) 36 IMAGED (0.1;F)
    2 IMAGED (0.2; F) 37 IMAGED (1.0; D)
    3 IMAGED (2.1; C) 38 IMAGED (1.8; C)
    4 IMAGED (1.7; C) 39 IMAGED (2.2; C)
    5 IMAGED (2.4; C) 40 IMAGED (2.1; C)
    6 IMAGED (1.0;D) 41 IMAGED (2.1; C)
    7 IMAGED (2.1; C) 42 PASS (2.5;B)
    8 - 43 IMAGED(1.7;C)
    9 PASS (2.5;B) 44 IMAGED (1.4;D)
    10 - 45 IMAGED (2.0; C)
    11 PASS (2.7;B) 46 IMAGED (2.2; C)
    12 - 47 PASS (2.6; B)
    13 IMAGED (0.0;F) 48 PASS (2.6;B)
    14 IMAGED (0.0;F) 49 PASS (2.6;B)
    15 IMAGED (1.7;C0 50 PASS (2.7;B)
    16 IMAGED (1.0;D) 51 IMAGED (1.7;C)
    17 IMAGED (1.6;C) 52 IMAGED (1.8;C)
    18 IMAGED(1.8;C) 53 IMAGED (1.8; C)
    19 IMAGED(0.0;F) 54 IMAGED (2.4; C)
    20 IMAGED (0.0;F) 55 PASS (2.5;B)
    21 IMAGED (0.0; F) 56 IMAGED (2.4;C)
    22 IMAGED (1.3; D) 57 PASS (2.5;B)
    23 PASS (2.5;B) 58 PASS(2.7;B)
    24 PASS (2.6; B) 59 IMAGED (2.3;C)
    25 PASS (2.5;B) 60 IMAGED (1.6;C)
    26 PASS (2.6;B) 61 IMAGED (2.0;C)
    27 IMAGED (1.5;C) 62 PASS (2.5;B)
    28 IMAGED (1.4; D) 63 IMAGED (0.0;F)
    29 IMAGED (1.7; C) 64 IMAGED (0.0; F)
    30 IMAGED (2.2; C) 65 IMAGED (1.6;C)
    31 IMAGED (2.1; C) 66 IMAGED (0.0;F)
    32 IMAGED (1.9;C) 67 IMAGED (0.0;F)
    33 IMAGED (1.7;C) 68 IMAGED (0.0;F)
    34 IMAGED (2.2; C) 69 IMAGED (0.0;F)
    35 IMAGED (0.5; D) 70 IMAGED (0.0;F)

    Tabulated Results of Examples 1-70


    Examples 1-70 were prepared at a weight of coat of 3.5#/3300ft^2' (1588g/307 sq. meters) (5.17g/sq. meter)



    [0118] Samples from the examples were imaged using an Atlantek 400 at a medium energy setting. Barcodes were scanned using a TRUCHECK verifier at 650nm wavelength. Barcode quality was assessed in accordance with ANSI's (American National Standards Institute) "Bar Code Print Quality Guideline", X3.182 published in 1990. The output of the ANSI method is a grade for any barcode on a scale of 0.0 to 4.0. It is also expressed as a letter grade A, B, C, D, and F based on measurements in each category. A grade of C or better generally scans with properly maintained scanners on a first pass.
    Table 3
    CONVERSION OF SYMBOL AVERAGE TO SYMBOL GRADE
    3.5<= A <=4.0
    2.5<= B <3.5
    1.5<= C <2.5
    0.5<= D <1.5
    F <0.5


    [0119] Often the marketplace will specify grade B or higher grade bar codes for labels and receipts to allow an extra margin of error to minimize misread barcodes.

    [0120] In the current invention, we rate a system as PASS if a barcode scans with an ANSI grade B or better. Systems rated "PASS" not only image but are also consistently scannable. We also rate a system as IMAGED if a barcode scans with an ANSI grade of C or lower but an image is visually perceivable.

    TEST METHOD



    [0121] A thermally imaged barcode was formed and scanned with a TRUECHECK VERIFIER at 650 nm.

    [0122] Scannability is defined in accordance with ANSI's "Bar Code Print Quality Guide," X3.182 published in 1990. In this invention we define a barcode as scannable if the overall ANSI grade is a B or better.

    [0123] In this test we define a barcode as fail if the overall ANSI grade is a C or lower. Although a barcode receiving a failing grade can still scan if rated C or better in well maintained equipment in the market place, systems rated as B are expected to perform adequately over a range of equipment.

    [0124] In this test, even if the bar code fails, the thermal image may still be legible to the human eye although susceptible to higher incidences of scanner misreads.

    [0125] Preferred modifiers include DMT, KS232, DPE, and stearamide wax with the wax most preferred.

    [0126] Coat weight is 3.5#/ream.
    Table 4
     Dye 2Dye 6Dye 5Dye 4Dye 3Dye 1Dye 7
    44DDS 2.1 2.7 2.5 2.1 2.4 1.7 0.0
                   
    33DDS 1.7       1.0 0.2 0.0
                   
    44DDS/WAX 2.6 2.7 2.7 2.5 2.2 1.8 1.6
    33DDS/WAX 2.2 2.5 2.4 2.2 1.8 1.3 0.0
                   
    44DDS/DPE 2.5 2.5 2.6 2.2 2.1 1.7 0.0
    33DDS/DPE 1.5 2.3 1.7 1.7 0.5 0.0 0.0
                   
    44DDS/DME 2.6 2.4 1.8 2.1 1.9 1.0 0.0
    33DDS/DME 1.4 1.6 1.8 1.4 0.1 0.0 0.0
                   
    44DDS/DMT 2.5 2.5 2.5 2.1 1.7 1.6 0.0
    33DDS/DMT 1.7 2.0 1.8 2.0 1.0 0.0 0.0
    [MODIFIER]              

    CONVERSION OF SYMBOL AVERAGE TO SYMBOL GRADE



    [0127] 
    Table 5
    3.5<= A <=4.0
    2.5<= B <3.5
     
    1.5<= C <2.5
     
    0.5< D <1.5
    F <0.5


    [0128] Table 5 Groupings in Table 4 are shown by border (none, light, bold).
    WOC is weight of coat.
    #/ream is pounds per ream isbased on a 3300 sq. ft. ream. 1 Ib per 3300 sq. ft. - 0.45 kg/306.58 sq. meters.
    Odu is optical density unit.
    CHRMOGENIC DISPERSIONS
    DISPERSION AA - CHROMOGENIC MATERIAL - dye-1
    MaterialParts
    chromogenic material (dye 1) 34.0
    binder, 20% solution of polyvinyl alcohol 27.0
    dispersing and defoaming agents 4.0
    water 35.0
    DISPERSION BB - DEVELOPER MATERIAL 
    developer 39.0
    binder, 20% solution of polyvinyl alcohol 24.0
    dispersing and defoaming agents 0.5
    water 36.5
    Dispersion BB1 - 4,4'-diaminodipheryl sulfone  
    Dispersion BB2 - bisphenol S  
       
    DISPERSION CC - MODIFIER MATERIAL- stearamide wax 
    stearamide wax 25.0
    binder, 20% solution of polyvinyl alcohol 20.0
    dispersing and defoaming agents 1.0
    water 54.0
       
    DISPERSION DD - 
    organic acid 16.0
    binder, 20% solution of polyvinyl alcohol 15.0
    dispersing and defoaming agents 1.5
    water 67.5
       
    Dispersion DD1 - organic acid is coumaric acid  
    Dispersion DD2 - organic acid is salycilic acid  
    Dispersion DD3 - organic acid is 3-(4-hydroxyphenyl)propionic acid  
    Dispersion DD4 - organic acid is citric acid  
    Dispersion DD5 - organic acid is 3,4-dihydroxyphenyl acetic acid  
    Dispersion DD6 - organic acid is o-acetyl salicyclic acid  
       
    DISPERSION DDD. - 3-(2-hydroxyphenyl)propionic acid 
    3-(2-hydroxyphenyl)propionic acid 16.0
    dispersing and defoaming agents 1.5
    water 82.5
       
    SOLUTIONI - ascorbic acid 
    ascorbic acid 20
    water 80

    Filler Slurry - F



    [0129] 

    slurry F1:CaCO3 at 21% solids

    slurry F2: magnesium stearate at 21% solids

    slurry F3: magnesium hydroxide at 21% solids

    slurry F4: zinc stearate

    slurry F5: calcium stearate

    MaterialWeight (g)
      
    Coating Formulation I-I 
    Dispersion AA (chromogen-Dye 1) 7.4
    Dispersion BB (developer) 13.0
    Dispersion CC (modifier-stearamide wax) 1.9
    Dispersion DD (organic acid) 0.0
    Binder, 10% solution of polyvinyl alcohol 15.0
    amorphous silicon dioxide slurry, 30% in water 1.8
    slurry F 0.0
    additives (rheology modifier, lubricant, optical brightener) 4.0
    water 56.9
       
    Coating Formulation II-I 
    Dispersion AA (chromogen-Dye 1) 7.4
    Dispersion BB (developer) 13.0
    Dispersion CC (modifier-stearamide wax) 1.9
    Dispersion DD (organic acid) 13.0
    binder, 10% solution of polyvinyl alcohol 15.0
    amorphous silicon dioxide slurry, 30% solids 1.8
    slurry F 0.0
    additives (rheology modifier, lubricant, optical brightener) 4.0
    water 43.9
       
    Coating Formulation III 
       
    Dispersion AA (chromogen-Dye 1) 7.4
    Dispersion BB(developer) 13.0
    Dispersion CC (modifier-stearamide wax) 1.9
    Dispersion DD (organic acid) 0.0
    binder, 10% solution of polyvinyl alcohol 15.0
    amorphous silicon dioxide slurry, 30% solids 1.8
    slurry F 10.0
    additives (rheology modifier, lubricant, optical brightener) 4.0
    water 46.9
       
    Coating Formulation IV 
       
    Dispersion AA (chromogen-Dye 1) 7.4
    Dispersion BB (developer) 0.0
    Dispersion CC (modifier-stearamide wax) 1.9
    Dispersion DD (organic acid) 13.0
    binder, 10% solution of polyvinyl alcohol 15.0
    amorphous silicon dioxide slurry, 30% solids 1.8
    slurry F 10.0
    additives (rheology modifier, lubricant, optical brightener) 4.0
    water 46.9
    Coating Formulation V 
       
    Dispersion AA (chromogen-Dye 1) 7.4
    Dispersion BB (developer) 13.0
    Dispersion CC (modifier-stearamide wax) 1.9
    Dispersion DD (organic acid) 0.0
    binder, 10% solution of polyvinyl alcohol 15.0
    amorphous silicon dioxide slurry, 30% solids 1.8
    slurry F 10.0
    additives (rheology modifier, lubricant, optical brightener) 4.0
    water 46.9
       
    Coating Formulation VI 
       
    Dispersion AA (chromogen-Dye 1) 7.4
    Dispersion BB (developer) 13.0
    Dispersion CC (modifier-steramide wax) 1.9
    Dispersion DD (organic acid) 13.0
    binder, 10% solution of polyvinyl alcohol 15.0
    amorphous silicon dioxide slurry, 30% solids 1.8
    slurry F 10.0
    additives (rheology modifier, lubricant, optical brightener) 4.0
    water 33.9

    LIST OF EXAMPLES


    EXAMPLE 71.



    [0130] Coating Formulation I-I using:
    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    EXAMPLE 72.



    [0131] Coating Formulation II-I using:

    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    Dispersion DD3 (3-(4-hydroxyphenyl)propionic acid)


    EXAMPLE 73.



    [0132] Coating Formulation III using:

    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    F1 (CaCO3)


    EXAMPLE 74.



    [0133] Coating Formulation IV using:

    Dispersion DD3 (3-(4-hydroxyphenyl)propionic acid)

    slurry F1 (CaCO3)


    EXAMPLE 75.



    [0134] Coating Formulation V using:

    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    slurry F2 (magnesium stearate)


    EXAMPLE 76.



    [0135] Coating Formulation VI using:

    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    Dispersion DD3 (3-(4-hydroxyphenyl)propionic acid)

    slurry F1 (CaCO3)


    EXAMPLE 77.



    [0136] Coating Formulation VI using:

    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    Dispersion DD3 (3-(4-hydroxyphenyl)propionic acid)

    slurry F2 (magnesium stearate)


    EXAMPLE 78.



    [0137] Coating FormulationV I using:

    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    Dispersion DD3 (3-(4-hydroxyphenyl)propionic acid)

    slurry F3 (magnesium hydroxide)


    EXAMPLE 79.



    [0138] Coating Formulation VI using:

    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    Dispersion DD3 (3-(4-hydroxyphenyl)propionic acid)

    slurry F1 (calcium CaCO3)


    EXAMPLE 80.



    [0139] Coating Formulation VI using:

    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    Dispersion DD3 (3-(4-hydroxyphenyl)propionic acid)

    slurry F2 (magnesium stearate)


    EXAMPLE 81.



    [0140] Coating Formulation VI using:

    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    Dispersion DD3 (3-(4-hydroxyphenyl)propionic acid)

    slurry F3 (magnesium hydroxide)


    EXAMPLE 82.



    [0141] Coating Formulation VI using:

    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    Dispersion DD3 (3-(4-hydroxyphenyl)propionic acid)

    slurry F4 (zinc stearate)


    EXAMPLE 83.



    [0142] Coating Formulation VI using:

    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    Dispersion DD3 (3-(4-hydroxyphenyl)propionic acid)

    slurry F5 (calcium stearate)


    COMPARATIVE EXAMPLE 84.



    [0143] Coating Formulation VI using:

    Dispersion BB2 (Bisphenol S)

    Dispersion DD3 (3-(4-hydroxyphenyl)propionic acid)

    slurry F1 (CaCO3)


    COMPARATIVE EXAMPLE 85



    [0144] Coating Formulation VI using:

    Dispersion BB2 (Bisphenol S)

    Dispersion DD3 (3-(4-hydroxyphenyl)propionic acid)

    slurry F2 (magnesium stearate)


    EXAMPLE 86



    [0145] Coating Formulation VI using:

    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    Dispersion DD1 (coumaric acid)

    slurry F1 (CaCO3)


    EXAMPLE 87



    [0146] Coating Formulation VI using:

    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    Dispersion DD1 (coumaric acid)

    slurry F2 (magnesium stearate)


    EXAMPLE 88



    [0147] Coating Formulation VI using:

    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    Dispersion DD1 (coumaric acid)

    slurry F3 (magnesium hydroxide)


    EXAMPLE 89



    [0148] Coating Formulation VI using:

    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    slurry F4 (zinc stearate)


    EXAMPLE 90



    [0149] Coating Formulation VI using:

    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    Dispersion DD1 (coumaric acid)

    slurry F5 (calcium stearate)


    EXAMPLE 91



    [0150] Coating Formulation VI using:

    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    Dispersion DD3 (3-(4-hydroxyphenyl)propionic acid)

    slurry F1 (CaCO3)


    EXAMPLE 92



    [0151] Coating Formulation VI using:

    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    Dispersion DD3 (3-(4-hydroxyphenyl)propionic acid)

    slurry F2 (magnesium stearate)


    EXAMPLE 93



    [0152] Coating Formulation VI using:

    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    Solution I (ascorbic acid)

    slurry F1 (CaCO3)


    EXAMPLE 94



    [0153] Coating Formulation VI using:

    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    Solution I (ascorbic acid)

    slurry F2 (magnesium stearate)


    EXAMPLE 95



    [0154] Coating Formulation VI using:

    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    Dispersion DD1 (coumaric acid)

    slurry F1 (CaCO3)


    EXAMPLE 96



    [0155] Coating Formulation VI using:

    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    Dispersion DD1 (coumaric acid)

    slurry F2 (magnesium stearate)


    EXAMPLE 97



    [0156] Coating Formulation VI using:

    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    Dispersion DD5 (3,4-dihydroxyphenyl acetic acid)

    slurry F1 (CaCO3)


    EXAMPLE 98



    [0157] Coating Formulation VI using:

    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    Dispersion DD5 (3,4-dihydroxyphenyl acetic acid)

    slurry F2 (magnesium stearate)


    EXAMPLE 99



    [0158] Coating Formulation VI using:

    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    Dispersion DDD (3-(2-hydroxyphenyl)propionic acid)

    slurry F1 (CaCO3)


    EXAMPLE 100



    [0159] Coating Formulation VI using:

    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    Dispersion DDD (3-(2-hydroxyphenyl)propionic acid)

    slurry F2 (magnesium stearate)


    EXAMPLE 101



    [0160] Coating Formulation VI using:

    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    Dispersion DD2 (salicylic acid)

    slurry F1 (CaCO3)


    EXAMPLE 102



    [0161] Coating Formulation VI using:

    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    Dispersion DD2 (Ssalicylic acid)

    slurry F2 (magnesium stearate)


    EXAMPLE 103



    [0162] Coating Formulation VI using:

    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    Dispersion DD4 (citric acid)

    slurry F1 (CaCO3)


    EXAMPLE 104



    [0163] Coating Formulation VI using:

    Dispersion BB1 (4,4'-diaminodiphenyl sulfone)

    Dispersion DD4 (citric acid)

    slurry F2 (magnesium stearate)


    EXAMPLE 105



    [0164] Coating Formulation IV using:

    Dispersion DD6 (o-acetyl salicylic acid)

    slurry F2 (magnesium stearate)


    EXAMPLE 106



    [0165] Coating Formulation VI using:

    Dispersion BB1 (Developer 4,4')

    Dispersion DD6 (o-acetyl salicylic acid)

    slurry F2 (magnesium stearate)


    EXAMPLE 107



    [0166] Coating Formulation VI using:

    Dispersion BB1 (Developer 4,4')

    Dispersion DD6 (o-acetyl salicylic acid)

    slurry F2 (magnesium stearate)


    TABULATED RESULTS OF EXAMPLES 71-107



    [0167] Samples from the examples 70-107 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.

    [0168] 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.

    [0169] The data shown below depicts examples 71-107, 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.
    #/ream is pounds per ream based on a 3300 sq. ft. ream. 1lb per 3300 sq. ft. = 0.45 kg/306.58 sq. meters.
    Table 6
     THERMAL SYSTEMWOC1st bar Gretag IntensityBrightness UVEX
    ExampleDeveloperOrganic AcidModifierFillerLeuco Dye#/reamo.d. 
    71 Developer 4,4' - stearamide wax - Dye 1 3.0 0.83 89.0
    72 Developer 4,4' 3-(4-hydroxyphenyl)propionic acid stearamide wax - Dye 1 3.0 1.53 89.0
    73 Developer 4,4' - stearamide wax CaCO3 Dye 1 4.6 0.90 89.0
    74 - 3-(4-hydroxyphenyl)propionic acid stearamide wax CaCO3 Dye 1 4.9 0.63 87.3
    75 Developer 4,4' - stearamide wax magnesium stearate Dye 1 5.6 0.70 89.0
    76 Developer 4,4' 3-(4-hydroxyphenyl)propionic acid stearamide wax CaCO3 Dye 1 4.8 1.34 88.4
    77 Developer 4,4' 3.(4-hydroxyphenyl)propionic acid stearamide wax magnesium stearate Dye 1 5.0 2.05 84.0
    78 Developer 4,4' 3-(4-hydroxyphenyl)propionic acid stearamide wax magnesium hydroxide Dye 1 5.4 1.50 88.0
    79 Developer 4,4' 3-(4-hydroxyphenyl)propionic acid stearamide wax CaCO3 Dye 1 3.1 1.00 89.0
    80 Developer 4,4' 3-(4-hydroxyphenyl)propionic acid stearamide wax magnesium stearate Dye 1 3.2 1.60 85.7
    81 Developer 4,4' 3-(4-hydroxyphenyl)propionic acid stearamide wax magnesium hydroxide Dye 1 2.8 1.20 88.7
    82 Developer 4,4' 3-(4-hydroxyphenyl)propionic acid stearamide wax zinc stearate Dye 1 2.6 1.50 89.6
    83 Developer 4,4' 3-(4-hydroxyphenyl)propionic acid stearamide wax calcium stearate Dye 1 2.8 1.40 84.1
    84 Bis S 3-(4-hydroxyphenyl)propionic acid stearamide wax CaCO3 Dye 1 3.7 2.49 78.0
    85 Bis S 3-(4-hydroxyphenyl)propionic acid stearamide wax magnesium stearate Dye 1 3.6 2.48 69.6
    86 Developer 4,4' coumaric acid stearamide wax CaCO3 Dye 1 2.7 1.23 89.1
    87 Developer 4,4' coumaric acid stearamide wax magnesium stearate Dye 1 2.6 1.43 89.1
    88 Developer 4,4' coumaric acid stearamide wax magnesium hydroxide Dye 1 2.6 1.19 88.7
    89 Developer 4,4' coumaric acid stearamide wax zinc stearate Dye 1 2.6 1.65 89.1
    90 Developer 4,4' coumaric acid stearamide wax calcium stearate Dye 1 2.6 1.41 89.3
    91 Developer 4,4' 3-(4-hydroxyphenyl)propionic acid stearamide wax CaCO3 Dye 1 2.4 1.01 88.9
    92 Developer 4,4' 3-(4-hydroxyphenyl)propionic acid stearamide wax magnesium stearate Dye 1 2.2 1.38 86.4
    93 Developer 4,4' ascorbic acid stearamide wax CaCO3 Dye 1 2.5 0.90 82.4
    94 Developer 4,4' ascorbic acid stearamide wax magnesium stearate Dye 1 2.1 1.08 84.9
    95 Developer 4,4' coumaric acid stearamide wax CaCO3 Dye 1 2.6 1.34 88.8
    96 Developer 4,4' coumaric acid stearamide wax magnesium stearate Dye 1 2.4 1.43 88.9
    97 Developer 4,4' 3,4-dihydroxyphenyl acetic acid stearamide wax CaCO3 Dye 1 2.3 0.93 80.9
    98 Developer 4,4' 3,4-dihydroxyphenyl acetic acid stearamide wax magnesium stearate Dye 1 2.4 1.37 79.5
    99 Developer 4,4' 3-(2-hydroxyphenyl)propionic acid stearamide wax CaCO3 Dye 1 2.4 1.00 89.0
    100 Developer 4,4' 3-(2-hydroxyphenyl)propionic acid stearamide wax magnesium stearate Dye 1 2.2 1.38 84.8
    101 Developer 4,4' salicylic acid stearamide wax CaCO3 Dye 1 2.4 1.07 84.8
    102 Developer 4,4' salicylic acid stearamide wax magnesium stearate Dye 1 2.5 1.29 83.6
    103 Developer 4,4' citric acid stearamide wax CaCO3 Dye 1 2.3 0.70 89.1
    104 Developer 4,4' citric acid stearamide wax magnesium stearate Dye 1 2.1 1.30 85.0
    105 - o-acetyl salicylic acid stearamide wax magnesium stearate Dye 1 2.5 0.40 88.6
    106 Developer 4,4' o-acetyl salicylic acid stearamide wax magnesium stearate Dye 1 1.7 1.00 86.5
    107 Developer 4,4' o-acetyl salicylic acid stearamide wax magnesium stearate Dye 1 2.7 1.37 85.9
    Table 7. General overview of the examples and data.
     THERMAL SYSTEMWOC1st bar Gretag IntensityBrightness UVEX
    ExampleDeveloperOrganic AcidFillerLeuco Dye#/reamo.d. 
    71 Developer 4,4' - - Dye 1 3.0 0.83 89.0
    72 Developer 4,4' 3-(4-hydroxyphenyl)propionic acid - Dye 1 3.0 1.53 89.0
    73 Developer 4,4' - CaCO3 Dye 1 4.6 0.90 89.0
    74 - 3-(4-hydroxyphenyl)propionic acid CaCO3 Dye 1 4.9 0.63 87.3
    75 Developer 4,4' - magnesium stearate Dye 1 5.6 0.70 89.0
    76 Developer 4,4' 3-(4-hydroxyphenyl)propionic acid CaCO3 Dye 1 4.8 1.34 88.4
    77 Developer 4,4' 3-(4-hydroxyphenyl)propionic acid magnesium stearate Dye 1 5.0 2.05 84.0
    78 Developer 4,4' 3-(4-hydroxyphenyl)propionic acid magnesium hydroxide Dye 1 5.4 1.50 88.0
    79 Developer 4,4' 3-(4-hydroxyphenyl)propionic acid CaCO3 Dye 1 3.1 1.00 89.0
    80 Developer 4,4' 3-(4-hydroxyphenyl)propionic acid magnesium stearate Dye 1 3.2 1.60 85.7
    81 Developer 4,4' 3-(4-hydroxyphenyl)propionic acid magnesium hydroxide Dye 1 2.8 1.20 88.7
    82 Developer 4,4' 3-(4-hydroxyphenyl)propionic acid zinc stearate Dye 1 2.6 1.50 89.6
    83 Developer 4,4' 3-(4-hydroxyphenyl)propionic acid calcium stearate Dye 1 2.8 1.40 84.1
    84 Bis S 3-(4-hydroxyphenyl)propionic acid CaCO3 Dye 1 3.7 2.49 78.0
    85 Bis S 3-(4-hydroxyphenyl)propionic acid magnesium stearate Dye 1 3.6 2.48 69.6
    86 Developer 4,4' coumaric acid CaCO3 Dye 1 2.7 1.23 89.1
    87 Developer 4,4' coumaric acid magnesium stearate Dye 1 2,6 1.43 89.1
    88 Developer 4,4' coumaric acid magnesium hydroxide Dye 1 2.6 1.19 88.7
    89 Developer 4,4' coumaric acid zinc stearate Dye 1 2,6 1.65 89.1
    90 Developer 4,4' coumaric acid calcium stearate Dye 1 2.6 1.41 89.3
    91 Developer 4,4' 3-(4-hydroxyphenyl)propionic acid CaCO3 Dye 1 2.4 10.01 88.9
    92 Developer 4,4' 3-(4-hydroxyphenyl)propionic acid magnesium stearate Dye 1 2.2 1.38 86.4
    93 Developer 4,4' ascorbic acid CaCO3 Dye 1 2.5 0.90 82.4
    94 Developer 4,4' ascorbic acid magnesium stearate Dye 1 2.1 1.08 84.9
    95 Developer 4,4' coumaric acid CaC03 Dye 1 2.6 1.34 88.8
    96 Developer 4,4' coumaric acid magnesium stearate Dye 1 2.4 1.43 88.9
    97 Developer 4,4' 3,4-dihydroxyphenyl acetic acid CaCO3 Dye 1 2.3 0.93 80.9
    98 Developer 4,4' 3,4-dihydroxyphenyl acetic acid magnesium stearate Dye 1 2.4 1.37 79.5
    99 Developer 4,4' 3-(2-hydroxyphenyl)propionic acid CaCO3 Dye 1 2.4 1.00 89.0
    100 Developer 4,4' 3-(2-hydroxyphenyl)propionic acid magnesium stearate Dye 1 2.2 1.38 84.8
    101 Developer 4,4' salicylic acid CaCO3 Dye 1 2.4 1.07 84.8
    102 Developer 4,4' salicylic acid magnesium stearate Dye 1 2.5 1.29 83.6
    103 Developer 4,4' citric acid CaCO3 Dye 1 2.3 0.70 89.1
    104 Developer 4,4' citric acid magnesium stearate Dye 1 2.1 1.30 85.0
    105 - o-acetyl salicylic acid magnesium stearate Dye 1 2.5 0.40 88.6
    106 Developer 4,4' o-acetyl salicylic acid magnesium stearate Dye 1 1.7 1.00 86.5
    107 Developer 4,4' o-acetyl salicylic acid magnesium stearate Dye 1 2.7 1.37 85.9


    [0170] 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 Figure 1). This held true even at weight of coats as high as 5.6#/ream (for Example 4). Diamino diphenyl sulfone and organic acid used in combination surprisingly achieve an intensity boost (see example 2 and Figure 1). When used in combination, high image intensities and at much reduced weight of coats are achieved. Diaminodiphenyl sulfone system in the absence of the acid gets saturated in terms of image intensity. This is reflected by the fact that the intensity does not increase as the coat weight increases (see examples 1,3, and 5, and Figure 2). Example 5 uses a different filler. Examples 2 and 10 show the effect on intesntiy in the presence and absence of magnesium stearate.

    [0171] 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 ued 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.

    [0172] Comparing examples, 2,9, and 10, these examplesdemonstrate that CaCO3 can mask the image but that magnesium stearate improves the imaget. Ideally, the use of no filler is preferred (Example 2). Magnesium stearate can be optionally added, does not display masking and enhance intensity.

    [0173] 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.

    [0174] 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 modifers as in the diaminodiphenyl sulfone/organic acid systems.

    [0175] 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 Figure 4). Other leuco dyes would also be functional in a diaminodiphenyl sulfone/organic acid/magnesium stearate record material coating.

    [0176] 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.

    [0177] 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.

    [0178] 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. 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 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.


    Claims

    1. Use of 4,4'-diaminodiphenylsulfone and 3,3'-diaminodiphenylsulfone and/or a mixture of both as a developer material in a thermally-responsive record material, wherein the record material is substantially free of aromatic isocyanate, the record material comprising a support having provided thereon a heat-sensitive composition comprising:

    a substantially colorless leuco dye color former comprising a fluoran;

    the developer material, which upon being heated reacts with said color former to develop color;

    and a binder material.


     
    2. The use according to claim 1

    (a) wherein the heat-sensitive composition comprises in addition a modifier compound; or

    (b) wherein the heat-sensitive composition comprises in addition a modifier compound selected from the group consisting of fatty acid amide, 1,2-diphenoxy ethane, dimethyl diphenoxy ethane, and dimethyl phthalate.


     
    3. The use according to claim 1,

    (a) wherein the substantially colorless color former 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; or

    (b) wherein the heat-sensitive composition comprises in addition a modifier compound selected from the group consisting of fatty acid amide, 1,2-diphenoxy ethane, dimethyl diphenoxy ethane, and dimethyl phthalate, and wherein the substantially colorless color former comprises a fluoran compound selected from the group consisting of:











    and,


     
    4. The use according to claim 1 wherein the heat sensitive composition includes in addition a modifier compound which is a fatty acid amide.
     
    5. The use according to claim 4

    (a) wherein the fatty acid amide is selected from an alkyl amide, a bis methylene alkyl-amide, and a bis ethylene alkyl amide; or

    (b) wherein the modifier compound is a fatty acid amide selected from

    or,

    wherein m is an integer from 1 to 23, n is an integer 0 to 21; or

    (c) wherein the fatty acid amide is selected from the group consisting of stearamide, methylene bis stearamide, lauramide, myristamide, palmitoleamide, oleamide, and linoleamide; or

    (d) wherein the modifier compound is stearamide wax.


     
    6. The use according to claim 1 wherein the heat sensitive composition comprises in addition an organic acid.
     
    7. The use according to claim 6 wherein the organic acid is a compound according to the formula

    wherein each R1 is independently selected from carboxy, hydrogen or hydroxyl, wherein n is an integer from 1 to 4;

    wherein R2 is selected from carboxy, alkenecarboxy, alkcarboxy, alkanoate, and alkyl alkanoate.


     
    8. The use according to claim 7

    (a) wherein the organic acid is o-acetyl salicyclic acid, coumaric acid, salicylic acid, vanillic acid, cinnamic acid, 3-(4-hydroxyphenyl)propionic acid, 2-(2-hydroxyphenyl)propionic acid, or 3,4-dihydroxyphenyl acetic acid; or

    (b) wherein the organic acid is selected from the group consisting of alkanedienoic acid, alkanedioic acid, hydroxyalkanetricarboxylic acid, and dihydroxyfuranone; or

    (c) wherein the organic acid is citric acid, ascorbic acid, sorbic acid or succinic acid.


     
    9. The use according to claim 6 wherein the heat-sensitive composition includes in addition a modifier compound selected from stearamide, methylene bis stearamide, lauramide, myristamide, palmitoleamide, oleamide and linoleamide.
     
    10. The use according to claim 1

    (a) wherein the heat sensitive composition includes in addition a metal stearate; or

    (b) wherein the heat sensitive composition includes in addition magnesium stearate.


     
    11. The use according to claim 6,

    (a) wherein the substantially colorless color former 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; or

    (b) wherein the substantially colorless color former comprises a fluoran compound selected from the group consisting of:











    and,


     
    12. The use according to claim 1 wherein the heat sensitive composition is applied onto the support at from 2 to 8 gsm.
     
    13. The use according to claim 1, wherein the thermally-responsive record material has an ANSI grade of B or better.
     
    14. The use according to claim 1 wherein the record material includes in addition a polymeric top coat.
     
    15. The use according to claim 1 wherein the heat-sensitive composition comprises in addition a modifier compound, wherein the ratio by weight of developer to color former is from 0.5:1 to 5:1, and wherein the modifier to color former ratio by weight is from 0.1:1 to 4:1.
     
    16. The use according to claim 1, wherein the use is in an improved bar code

    (a) comprising a thermally responsive record material as defined in claim 1; or

    (b) comprising a thermally responsive record material as defined in claim 1, having an ANSI grading of C or better; or

    (c) comprising a thermally responsive record material as defined in claim 1, wherein the flouran dye is selected from group consisting of:

    3-diethylamino-6-methyl1-7-(2',4'dimethyl aniline) fluoran,

    3-dibutylamino-6-methyl-7-anilino fluoran,

    3-diethylamino-6-methyl-7-(3'-methylanilino) fluoran,

    3-diethylamino-6-methyl-7-anilinofluoran,

    3-pyrrolidino-6-methyl-7-anilino fluoran, and

    3-diethylamino-7-(dibenzylamino) fluoran, and, including in addition magnesium stearate.


     


    Ansprüche

    1. Verwendung von 4,4'-Diaminodiphenylsulfon und 3,3'-Diaminodiphenylsulfon und/oder einer Mischung davon als Entwicklermaterial in einem wärmeempfindlichen Aufzeichnungsmaterial, wobei das Aufzeichnungsmaterial weitgehend frei von aromatischem Isocyanat ist, wobei das Aufzeichnungsmaterial einen Träger umfasst, auf dem eine wärmeempfindliche Zusammensetzung angeordnet ist, die Folgendes umfasst:

    einen weitgehend farblosen Leuko-Farbstoff-Farbbildner, der ein Fluoran umfasst;

    das Entwicklermaterial, das beim Erhitzen mit dem Farbbildner unter Entwicklung von Farbe reagiert;

    und ein Bindermaterial.


     
    2. Verwendung nach Anspruch 1,

    (a) wobei die wärmeempfindliche Zusammensetzung zusätzlich eine Modifikatorverbindung umfasst oder

    (b) wobei die wärmeempfindliche Zusammensetzung zusätzlich eine Modifikatorverbindung aus der Gruppe bestehend aus Fettsäureamid, 1,2-Diphenoxyethan, Dimethyldiphenoxyethan und Dimethylphthalat umfasst.


     
    3. Verwendung nach Anspruch 1,

    (a) wobei der weitgehend farblose Farbbildner eine Fluoranverbindung der Formel

    umfasst,

    wobei R1 für Wasserstoff oder Alkyl steht;

    wobei R2 für Wasserstoff oder Alkaryl steht;

    wobei R3 für Aryl steht, wenn R2 für Wasserstoff steht, oder für Aralkyl steht, wenn R2 für Aralkyl steht;

    R4 und R5 jeweils unabhängig aus Alkyl und Aralkyl ausgewählt sind oder R4 und R5 eine Pyrrolidin-Ringstruktur mit vier Kohlenstoffatomen bilden; oder

    (b) wobei die wärmeempfindliche Zusammensetzung zusätzlich eine Modifikatorverbindung aus der Gruppe bestehend aus Fettsäureamid, 1,2-Diphenoxyethan, Dimethyldiphenoxyethan und Dimethylphthalat umfasst und wobei der weitgehend farblose Farbbildner eine Fluoranverbindung aus der Gruppe bestehend aus











    und

    umfasst.


     
    4. Verwendung nach Anspruch 1, wobei die wärmeempfindliche Zusammensetzung zusätzlich eine Modifikatorverbindung enthält, bei der es sich um ein Fettsäureamid handelt.
     
    5. Verwendung nach Anspruch 4,

    (a) wobei das Fettsäureamid aus einem Alkylamid, einem Bismethylenalkylamid und einem Bisethylenalkylamid ausgewählt ist; oder

    (b) wobei es sich bei der Modifikatorverbindung um ein Fettsäureamid handelt, das aus

    oder

    ausgewählt ist, wobei m für eine ganze Zahl von 1 bis 23 steht und n für eine ganze Zahl von 0 bis 21 steht; oder

    (c) wobei das Fettsäureamid aus der Gruppe bestehend aus Stearamid, Methylenbisstearamid, Lauramid, Myristamid, Palmitoleamid, Oleamid und Linoleamid ausgewählt ist; oder

    (d) wobei es sich bei der Modifikatorverbindung um Stearamidwachs handelt.


     
    6. Verwendung nach Anspruch 1, wobei die wärmeempfindliche Zusammensetzung zusätzlich eine organische Säure enthält.
     
    7. Verwendung nach Anspruch 6, wobei es sich bei der organischen Säure um eine Verbindung gemäß der Formel

    handelt,

    wobei R1 jeweils unabhängig aus Carboxy, Wasserstoff oder Hydroxyl ausgewählt ist, wobei n für eine ganze Zahl von 1 bis 4 steht;

    wobei R2 aus Carboxy, Alkencarboxy, Alkcarboxy, Alkanoat und Alkylalkanoat ausgewählt ist.


     
    8. Verwendung nach Anspruch 7,

    (a) wobei es sich bei der organischen Säure um o-Acetylsalicylsäure, Cumarinsäure, Salicylsäure, Vanillinsäure, Zimtsäure, 3-(4-Hydroxyphenyl)-propionsäure, 2-(2-Hydroxyphenyl)propionsäure oder 3,4-Dihydroxyphenylessigsäure handelt; oder

    (b) wobei die organische Säure aus der Gruppe bestehend aus Alkandiensäure, Alkandisäure, Hydroxyalkantricarbonsäure und Dihydroxyfuranon ausgewählt ist; oder

    (c) wobei es sich bei der organischen Säure um Citronensäure, Ascorbinsäure, Sorbinsäure oder Bernsteinsäure handelt.


     
    9. Verwendung nach Anspruch 6, wobei die wärmeempfindliche Zusammensetzung außerdem eine Modifikatorverbindung enthält, die aus Stearamid, Methylenbisstearamid, Lauramid, Myristamid, Palmitoleamid, Oleamid und Linoleamid ausgewählt ist.
     
    10. Verwendung nach Anspruch 1,

    (a) wobei die wärmeempfindliche Zusammensetzung außerdem ein Metallstearat enthält; oder

    (b) wobei die wärmeempfindliche Zusammensetzung außerdem Magnesiumstearat enthält.


     
    11. Verwendung nach Anspruch 6,

    (a) wobei der weitgehend farblose Farbbildner eine Fluoranverbindung der Formel

    umfasst,

    wobei R1 für Wasserstoff oder Alkyl steht;

    wobei R2 für Wasserstoff oder Alkaryl steht;

    wobei R3 für Aryl steht, wenn R2 für Wasserstoff steht, oder für Aralkyl steht, wenn R2 für Aralkyl steht;

    R4 und R5 jeweils unabhängig aus Alkyl und Aralkyl ausgewählt sind oder R4 und R5 eine Pyrrolidin-Ringstruktur mit vier Kohlenstoffatomen bilden; oder

    (b) wobei der weitgehend farblose Farbbildner eine Fluoranverbindung aus der Gruppe bestehend aus











    und

    umfasst.


     
    12. Verwendung nach Anspruch 1, wobei die wärmeempfindliche Zusammensetzung in einer Menge von 2 bis 8 gsm auf dem Träger aufgebracht ist.
     
    13. Verwendung nach Anspruch 1, wobei das wärmeempfindliche Aufzeichnungsmaterial eine ANSI-Einstufung von B oder besser aufweist.
     
    14. Verwendung nach Anspruch 1, wobei das Aufzeichnungsmaterial außerdem eine polymere Deckschicht umfasst.
     
    15. Verwendung nach Anspruch 1, wobei die wärmeempfindliche Zusammensetzung außerdem eine Modifikatorverbindung umfasst, wobei das Gewichtsverhältnis von Entwickler zu Farbbildner 0,5:1 bis 5:1 beträgt und wobei das Gewichtsverhältnis von Modifikator zu Farbbildner 0,1:1 bis 4:1 beträgt.
     
    16. Verwendung nach Anspruch 1, wobei die Verwendung in einem verbesserten Strichcode erfolgt,

    (a) der ein wärmeempfindliches Aufzeichnungsmaterial gemäß Anspruch 1 umfasst; oder

    (b) der ein wärmeempfindliches Aufzeichnungsmaterial gemäß Anspruch 1 umfasst und eine ANSI-Einstufung von C oder besser aufweist; oder

    (c) der ein wärmeempfindliches Aufzeichnungsmaterial gemäß Anspruch 1 umfasst, wobei der Fluoran-Farbstoff aus der Gruppe bestehend aus

    3-Diethylamino-6-methyll-7-(2',4'-dimethylanilin)fluoran,

    3-Dibutylamino-6-methyl-7-anilinofluoran,

    3-Diethylamino-6-methyl-7-(3'-methylanilino)-fluoran,

    3-Diethylamino-6-methyl-7-anilinofluoran,

    3-Pyrrolidino-6-methyl-7-anilinofluoran und

    3-Diethylamino-7-(dibenzylamino)fluoran

    ausgewählt ist, und außerdem Magnesiumstearat enthält.


     


    Revendications

    1. Utilisation de 4,4'-diaminodiphénylsulfone et de 3,3'-diaminodiphénylsulfone et/ou d'un mélange des deux en tant que matériau de développement dans un matériau d'enregistrement sensible à la chaleur, le matériau d'enregistrement étant sensiblement exempt d'isocyanate aromatique, le matériau d'enregistrement comprenant un support possédant, disposée sur celui-ci, une composition sensible à la chaleur comprenant :

    un agent chromogène de leuco-colorant sensiblement incolore comprenant un fluorane ;

    le matériau de développement, qui réagit par chauffage avec ledit agent chromogène pour développer une couleur ;

    et un matériau liant.


     
    2. Utilisation selon la revendication 1

    (a) la composition sensible à la chaleur comprenant de plus un composé modificateur ; ou

    (b) la composition sensible à la chaleur comprenant de plus un composé modificateur choisi dans le groupe constitué par un amide d'acide gras, le 1,2-diphénoxyéthane, le diméthyldiphénoxyéthane, et le phtalate de diméthyle.


     
    3. Utilisation selon la revendication 1,

    (a) l'agent chromogène sensiblement incolore comprenant un composé de type fluorane de formule

    R1 étant hydrogène ou alkyle

    R2 étant hydrogène ou alkaryle ;

    R3 étant aryle lorsque R2 est hydrogène, ou alkaryle lorsque R2 est alkaryle ;

    R4 et R5 étant chacun indépendamment choisis parmi alkyle, alkaryle ; ou R4 et R5 formant une structure de type pyrrolidine à cycle à quatre carbones ; ou

    (b) la composition sensible à la chaleur comprenant de plus un composé modificateur choisi dans le groupe constitué par un amide d'acide gras, le 1,2-diphénoxyéthane, le diméthyldiphénoxyéthane, et le phtalate de diméthyle, et l'agent chromogène sensiblement incolore comprenant un composé de type fluorane choisi dans le groupe constitué par :











    et,


     
    4. Utilisation selon la revendication 1, la composition sensible à la chaleur comprenant de plus un composé modificateur qui est un amide d'acide gras.
     
    5. Utilisation selon la revendication 4

    (a) l'amide d'acide gras étant choisi parmi un alkylamide, un bis-méthylène-alkylamide, et un bis-éthylène-alkylamide ; ou

    (b) le composé modificateur étant un amide d'acide gras choisi parmi

    et,

    m étant un entier de 1 à 23, n étant un entier de 0 à 21 ; ou

    (c) l'amide d'acide gras étant choisi dans le groupe constitué par le stéaramide, le méthylène-bis-stéaramide, le lauramide, le myristamide, le palmitoléamide, l'oléamide, et le linoléamide ; ou

    (d) le composé modificateur étant une cire de stéaramide.


     
    6. Utilisation selon la revendication 1, la composition sensible à la chaleur comprenant de plus un acide organique.
     
    7. Utilisation selon la revendication 6, l'acide organique étant un composé selon la formule

    chaque R1 étant indépendamment choisi parmi carboxy, hydrogène et hydroxyle, n étant un entier de 1 à 4 ;

    R2 étant choisi parmi carboxy, alcènecarboxy, alkcarboxy, alcanoate et alcanoate d'alkyle.


     
    8. Utilisation selon la revendication 7

    (a) l'acide organique étant l'acide o-acétylsalicylique, l'acide coumarique, l'acide salicylique, l'acide vanillique, l'acide cinnamique, l'acide 3-(4-hydroxyphényl)propionique, l'acide 2-(2-hydroxyphényl)propionique, ou l'acide 3,4-dihydroxyphénylacétique ; ou

    (b) l'acide organique étant choisi dans le groupe constitué par un acide alcanediénoïque, un acide alcanedioïque, un acide hydroxyalcanetricarboxylique, et une dihydroxyfurannone ; ou

    (c) l'acide organique étant l'acide citrique, l'acide ascorbique, l'acide sorbique ou l'acide succinique.


     
    9. Utilisation selon la revendication 6, la composition sensible à la chaleur comprenant de plus un composé modificateur choisi parmi le stéaramide, le méthylène-bis-stéaramide, le lauramide, le myristamide, le palmitoléamide, l'oléamide et le linoléamide.
     
    10. Utilisation selon la revendication 1

    (a) la composition sensible à la chaleur comprenant de plus un stéarate métallique ; ou

    (b) la composition sensible à la chaleur comprenant de plus du stéarate de magnésium.


     
    11. Utilisation selon la revendication 6,

    (a) l'agent chromogène sensiblement incolore comprenant un composé de type fluorane de formule

    R1 étant hydrogène ou alkyle

    R2 étant hydrogène ou alkaryle ;

    R3 étant aryle lorsque R2 est hydrogène, ou alkaryle lorsque R2 est alkaryle ;

    R4 et R5 étant chacun indépendamment choisis parmi alkyle, alkaryle ; ou R4 et R5 formant une structure de type pyrrolidine à cycle à quatre carbones ; ou

    (b) l'agent chromogène sensiblement incolore comprenant un composé de type fluorane choisi dans le groupe constitué par :











    et,


     
    12. Utilisation selon la revendication 1, la composition sensible à la chaleur étant appliquée sur le support à raison de 2 à 8 g/m2.
     
    13. Utilisation selon la revendication 1, le matériau d'enregistrement sensible à la chaleur possédant une qualité ANSI de B ou mieux.
     
    14. Utilisation selon la revendication 1, le matériau d'enregistrement comprenant de plus un revêtement de finition polymérique.
     
    15. Utilisation selon la revendication 1, la composition sensible à la chaleur comprenant de plus un composé modificateur, le rapport en poids d'agent développeur à agent chromogène étant de 0,5:1 à 5:1, et le rapport en poids d'agent modificateur à agent chromogène étant de 0,1:1 à 4:1.
     
    16. Utilisation selon la revendication 1, l'utilisation étant destinée à un code-barre amélioré

    (a) comprenant un matériau d'enregistrement sensible à la chaleur tel que défini selon la revendication 1 ; ou

    (b) comprenant un matériau d'enregistrement sensible à chaleur tel que défini selon la revendication 1, possédant une qualité ANSI de C ou mieux ;ou

    (c) comprenant un matériau d'enregistrement sensible à la chaleur tel que défini selon la revendication 1, le colorant de type fluorane étant choisi dans un groupe constitué par :

    3-diéthylamino-6-méthyll-7-(2',4'-diméthylaniline)fluorane,

    3-dibutylamino-6-méthyl-7-anilino-fluorane,

    3-diéthylamino-6-méthyl-7-(3'-méthylanilino)fluorane,

    3-diéthylamino-6-méthyl-7-anilinofluorane,

    3-pyrrolidino-6-méthyl-7-anilino-fluorane, et

    3-diéthylamino-7-(dibenzylamino)fluorane, et,

    comprenant de plus du stéarate de magnésium.


     




    Drawing

















    Cited references

    REFERENCES CITED IN THE DESCRIPTION



    This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

    Patent documents cited in the description




    Non-patent literature cited in the description