Thermally-reponsive record material

Abstract: Thermally-responsive record material comprises a substrate, a binder, a chromogenic material, an electron-accepting color developer which reacts with said chromogenic material to form a color, and a color-stabilizing resin. The color stabilizing resin comprises an addition product of a diolefinic alkylated or alkenylated cyclic hydrocarbon or an addition product of a phenol and a diolefinic alkylated or alkenylated cyclic hydrocarbon. The color-stabilizing resin, chromogenic material, and color developer together have a weight percent resin phenolic group (as defined) of about 5 or less. The heat-sensitive recording material has a fade index (as defined) greater than 45. The imaged record material resists fading when exposed to temperatures of 60°C for prolonged periods such as experienced in twenty-four hour oven tests.

Description: This invention relates to thermally-responsive record material, also termed heat-sensitive record material. Thermally-responsive or heat-sensitive record materials bear a thermally-sensitive color-forming composition typically comprising a basic chromogenic material and an electron-accepting acidic color developer material in substantially contiguous relationship, whereby the melting, softening or sublimation of either material produces a color, in other words a change-in-color reaction. Such 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; 3,674,535; 3,746,675; 4,151,748; 4,181,771; 4,246,318; and 4,470,057 to which reference can be made for additional information. In these systems, the basic chromogenic material and acidic color developer material are contained in a coating on a substrate which, when heated to a suitable temperature, melts, softens or sublimes to permit said materials to react, thereby producing a colored mark. The substrate is usually a sheet material. Thermally-responsive record materials have characteristic thermal responses, desirably producing a detectable image of certain intensity upon thermal exposure which can be in a selective pattern or manner. A drawback of thermally-responsive record materials limiting utilization in certain environments and applications has been the undesirable tendency of thermally-responsive record materials upon forming an image to not retain that image in its original integrity over time when the thermally-responsive record material is exposed to environments of high heat. As a result, a high degree of care and control in handling or storing imaged thermally-responsive record materials is required. This loss of image density or fade can be a serious problem whenever the integrity of records is diminished through improper record storage. To impart ability to a thermally-responsive record material to resist image fading in high heat environments would be an advance in the art and of commercial significance. It is an object of the present invention to provide a thermally-responsive record material having improved image retention and resistance to fade or erasure. The record material of the invention is remarkably resistant to fade or erasure from common external challenges particularly high heat such as in a 60°C oven over a 24-hour time period. JP-A-62282971 discloses a thermal recording sheet comprising a color forming layer consisting of a color forming compound, a color developing compound and a terpene polymer or a terpene/phenol copolymer. JP-A-62033678 and JP-A-59127794 each disclose a heat-sensitive recording material comprising a color former, a color developer and a binder which may be a terpene resin. JP-A-53017347 discloses a heat-sensitive recording paper comprising colour forming lactone compounds and color developing phenol compounds in a dispersion also containing a modified phenol resin. The modified phenol resin may be a phenol resin "denatured" by a terpene. According to the invention, there is provided thermally-responsive record material comprising a substrate bearing a thermally-sensitive color-forming composition comprising a chromogen, an electron-accepting color developer which reacts with said chromogen to form a color, and a color stabilizing resin comprising a) an addition product of a phenol and a diolefinic alkylated or alkenylated cyclic hydrocarbon; or b) an addition product of phenol and α-pinene; the weight percent resin phenolic group, as defined herein, of the chromogen, developer, and stabilizing resin together being 5 or less. the thermally-responsive record material having a fade index, as defined herein, of at least 55.8 when placed in a 60°C oven for 24 hours. The thermally-responsive record material of the invention has the unexpected and remarkable properties of being capable of forming a high density image upon selective thermal contact and of retaining that image over time when handled or exposed to high heat such as in a 60°C oven for 24 hours. The remarkable ability of the composition of the heat-sensitive record material of the invention to impart fade and erasure resistance to thermally-responsive record materials is a significant advance in the art. The record materials of the invention were also found to resist fade from contact with other common external challenges such as oils, solvents, or plasticizers. However, these materials most consistently and unexpectedly stood out with reference to the herein-described high heat test. As stated above, the color-stabilizing resin is an addition product of a phenol and a diolefinic alkylated or alkenylated cyclic hydrocarbon, or an addition product of phenol and α-pinene. Preferred among the addition products of phenol and a diolefinic alkylated or alkenylated cyclic hydrocarbon are those in which the cyclic hydrocarbon is a terpene. Diolefinic terpenes include compounds such as limonene, α-terpinene, and the like. Methods of preparing terpene addition compounds or phenol terpene addition compounds are taught in U.S. Patent No. 2,811,564. The color-stabilizing resin by itself or in conjunction with other OH-bearing electron-donating chromogen materials or electron-accepting color developing materials has a weight percent phenolic group of 5 or less. The weight percent resin phenolic group of the stabilizing resin, chromogen, and developer are calculated by multiplying the weight percent phenolic group of the stabilizing resin by the weight of the stabilizing resin, then dividing by the sum of the weights of the chromogen, developer, and stabilizing resin, to yield a quotient, and multiplying the quotient by 100. The thermally-responsive record material of the invention has a fade index greater than 45 when placed in a 60°C oven for 24 hours. The method of calculation of the weight percent phenolic group and the fade index, and the reasoning underlying these methods, are as described in more detail later in this specification. Optionally, but preferably, a modifier (also known as a sensitizer) such as a 1,2-diphenoxyethane is included. Such material typically does not impart any image on its own and is not considered active in the formation of color but as a relatively low melting solid acts as a solvent to facilitate reaction between the mark-forming components. Other such modifiers are described in U.S. Patent No. 4,531,140. Other modifiers for example can include acetoacet-o-toluidine, phenyl-1-hydroxy-2-naphthoate, dibenzyloxalate, and parabenzylbiphenyl. The color-forming composition (or system) of the record material of this invention comprises chromogenic material in its substantially colorless state and acidic developer material. The color-forming system typically relies upon melting, softening, or subliming one or more of the components to achieve reactive, color-producing contact. 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 substrates or support members and are understood also to mean webs, ribbons, tapes, belts, films, labels, cards and the like. Sheets denote articles having two large surface dimensions and a comparatively 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 (regenerated cellulose) and synthetic polymeric sheets cast, extruded, or otherwise formed. The kind or type of substrate material is not critical. The components of the color-forming system are in a proximate relationship meaning, a substantially contiguous or near contiguous relationship, substantially homogeneously distributed throughout the coated layer material deposited on the substrate in one or more layers. In manufacturing the record material, a coating composition is prepared which generally includes a fine dispersion of the components of the color-forming system, binder material typically a polymeric material, surface active agents and other additives in an aqueous coating medium. The composition can additionally contain inert pigments, such as clay, talc, aluminum hydroxide, calcined kaolin clay and calcium carbonate; synthetic pigments, such as urea-formaldehyde resin pigments; natural waxes such as Carnauba wax; synthetic waxes; lubricants such as zinc stearate; wetting agents; defoamers, and antioxidants. The color-forming system components are substantially insoluble in the dispersion vehicle (preferably water) and are ground to an individual average particle size of between about 1 µm to about 10 µm, preferably less than 3 µm. A binder can be included. The binder can be a polymeric material and is substantially vehicle soluble although latexes are also eligible in some instances. Preferred water soluble binders include polyvinyl alcohol, hydroxy ethylcellulose, methylcellulose, methyl-hydroxypropylcellulose, starch, styrene maleic anhydride salts, modified starches, gelatin and the like. Eligible latex materials include polyacrylates, styrene-butadiene-rubber latexes, 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 3 to about 9 grams per square meter (gsm) and preferably about 5 to about 6 gsm. The practical amount of color-forming materials is controlled by economic considerations, functional parameters and desired handling characteristics of the coated sheets. Eligible chromogens, such as the phthalide, leucauramine and fluoran compounds, for use in the color-forming system are well known color-forming compounds. Examples of the compounds include Crystal Violet Lactone (3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalide, U.S. Patent No. Re. 23,024); phenyl-, indol-, pyrrol-, and carbazol-substituted phthalides (for example, in U.S. Patent Nos. 3,491,111; 3,491,112; 3,491,116; 3,509,174); nitro-, amino-, amido-, sulfonamido-, aminobenzylidene-, halo-, anilino-substituted fluorans (for example, in U.S. Patent Nos. 3,624,107; 3,627,787; 3,641,011; 3,642,828; 3,681,390); spirodipyrans (U.S. Patent No. 3,971,808); and pyridine and pyrazine compounds (for example, in U.S. Patent 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-fluoran (U.S. Patent No, 3,681,390); 2-anilino-3-methyl-6-dibutylamino-fluoran (U.S. Patent 4,510,513) also known as 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-methylindol-3-yl)-7-(4-diethyl-amino-2-ethoxyphenyl)-5,7-dihydrofuro[3,4-b]pyridin-5-one (U.S. Patent No. 4,246,318); 3-diethylamino-7-(2-chloroanilino)fluoran (U.S. Patent No. 3,920,510); 3-(N-methylcyclohexylamino)-6-methyl-7-anilinofluoran (U.S. Patent No. 3,959,571); 7-(1-octyl-2-methylindol-3-yl)-7-(4-diethyl-amino-2-ethoxyphenyl)-5,7-dihydrofuro[3,4-b]pyridin-5-one; 3-diethylamino-7,8-benzofluoran; 3,3-bis(1-ethyl-2-methylindol-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 above. Examples of eligible acidic or electron-accepting color-developer material include the compounds listed in U.S. Patent No. 3,539,375 as phenolic reactive material, particularly the monophenols and diphenols. Eligible acidic developer material also includes, without being considered as limiting, the following compounds which may be used individually or in mixtures: 4,4'-isopropylidine- diphenol (Bisphenol A); p-hydroxybenzaldehyde; p-hydroxybenzophenone; p-hydroxypropiophenone; 2,4-dihydroxybenzophenone; 1,1-bis(4-hydroxyphenyl)cyclohexane; salicyanilide; 4-hydroxy-2-methylacetophenone; 2-acetylbenzoic acid; m-hydroxyacetanilide; p-hydroxyacetanilide; 2,4-dihydroxyacetophenone; 4-hydroxy-4'-methylbenzophenone; 4,4'-dihydroxybenzophenone; bis(3-allyl-4-hydroxyphenyl) sulfone, 2,2-bis(4-hydroxy- phenyl)-4-methylpentane; benzyl-4-hydroxyphenyl ketone; 2,2-bis(4-hydroxyphenyl)-5-methylhexane; ethyl-4,4-bis(4-hydroxyphenyl)-pentanoate; isopropyl-4,4-bis(4-hydroxyphenyl)pentanoate; methyl-4,4-bis(4-hydroxyphenyl)pentanoate; allyl-4,4-bis(4-hydroxyphenyl)pentanoate; 3,3-bis(4-hydroxyphenyl)-pentane; 4,4-bis(4-hydroxyphenyl)-heptane; 2,2-bis(4-hydroxyphenyl)-1-phenylpropane; 2,2-bis(4-hydroxyphenyl)butane; 2,2'-methylene-bis(4-ethyl-6-tertiarybutylphenol); 4-hydroxycoumarin; 7-hydroxy-4-methylcoumarin; 2,2'-methylene-bis(4-octylphenol); 4,4'-sulfonyldiphenol; 4,4'-thiobis(6-tertiarybutyl-m-cresol); methyl-p-hydroxybenzoate; n-propyl-p-hydroxybenzoate; benzyl-p-hydroxybenzoate; 4-(4-(1-methylethoxy)phenyl) sulphonyl phenol. Preferred among these are the phenolic developer compounds. More preferred among the phenol compounds are 4,4'-isopropylindinediphenol, ethyl-4,4-bis(4-hydroxyphenyl)pentanoate, n-propyl-4,4-bis(4-hydroxyphenyl) pentanoate, isopropyl-4,4-bis(4-hydroxyphenyl)pentanoate, methyl-4,4-bis(4-hydroxyphenyl)pentanoate, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, p-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 1,1-bis(4-hydroxyphenyl)cyclohexane, and benzyl-p-hydroxybenzoate; 4-(4-(1-methylethoxy)phenyl)sulphonyl phenol and 4,4'-[1,3-phenylenebis(1-methylethylene]bisphenol. Acid compounds of other kind and types are eligible. Examples of such other compounds are phenolic novolak resins which are the product of reaction between, for example, formaldehyde and a phenol such as an alkylphenol, e.g., p-octylphenol, or other phenols such as p-phenylphenol, and the like; and acid mineral materials including colloidal silica, kaolin, bentonite, attapulgite, hallosyte, and the like. Some of the polymers and minerals do not melt but undergo color reaction on fusion of the chromogen. Of the foregoing particularly the phenol type of compounds are more preferable acidic developer materials. The following examples, some of which are controls or are comparative in nature, 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. Figure 1 is a graph of the dispersions of the weight percent resin phenolic group of the active components calculated as herein described and the fade index of the Examples. In all examples illustrating the present invention a dispersion of a particular system component was prepared by milling the component in an aqueous solution of the binder until a particle size of between about 1 µm and 10 µm was achieved. 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 and acidic material. The dispersions were mixed in the desired ratios and applied to a support with a wire wound rod and dried. Other non-active (as that term is understood in this application) materials such as modifiers, fillers, antioxidants, lubricants and waxes can be added if desired. The sheets may be calendered to improve smoothness. In the examples the thermal response of the sheets was checked by imaging with a Group III facsimile machine. The facsimile machine used included SHARP (trade mark) 220. The color produced was measured with a Macbeth (trade mark) RD514 densitometer, #106 filter. The dispersions were prepared in a quickie mill, attritor and small media mill. Nopco NDW is a trade mark for a sulfonated castor oil produced by Nopco Chemical Company. Surfynol 104 is a trade mark for a di-tertiary acetylene glycol surface active agent produced by Air Products and Chemicals, Inc. Zonarez is a trademark of Arizona Chemical Company. Zonarez 7125 is a polyterpene, more particularly an addition product of d-limonene. Piccofyn is a trademark of Hercules Inc. Piccofyn T-125 is an α-pinene and phenol addition product. Dispersion A-1 - Chromogenic Material is N-102 , 3-diethylamino-6-methyl-7-anilinofluoran. Parts N-102 94.95 PVA, Vinol 205, 20% in Water 81.00 Nopco NDW 0.23 Surfynol 104 1.13 Water 122.69 Dispersion A-2 - Chromogenic material is TECVIL , 3,3-bis(4-diethylaminophenyl)-6-dimethylaminophthalide. Dispersion prepared the same as A-1 but using TECVIL. Dispersion A-3 - Chromogenic material is PB63 , isomeric mixture of 7-(1-ethyl-2-methylindol-3-yl)-7-(4-diethylamine-2-ethoxyphenyl)-6,7-dihydrofuro[3,4-b]pyridin-5-one and 5-(1-ethyl-2-methylindol-3-yl)-5-(4-diethyiamine-2-ethoxyphenyl)-5,7-dihydrofuro[3,4-b]pyridin-7-one. Dispersion prepared the same as A-1 but using PB63. Dispersion B-1 - Acidic Material is AP-5 , 2,2-bis(4-hydroxyphenyl)-4-methyl pentane. Parts AP-5 102.00 PVA, Vinol 203, 28% in Water 62.14 Nopco NDW 0.12 Surfynol 104 0.48 Water 135.26 Dispersion B-2 - Acidic material is TGSA , Bis(3-alkyl-4-hydroxyphenyl)sulfone. Dispersion prepared the same as B-1 but using TGSA. Dispersion B-3 - Acidic material is Benzyl Paraben . Dispersion prepared the same as B-1 but using benzyl paraben, i.e. benzyl 4-hydroxybenzoate Dispersion B-4 - Acidic material is D8 , 4(4-(1-methylethoxy)phenyl)sulphonylphenol. Dispersion prepared the same as B-1 but using D8. Dispersion C-1 - Sensitizer is DPE , 1,2-diphenoxyethane. Parts DPE 102.00 PVA, Vinol 203, 28% in Water 62.14 Nopco NDW 0.12 Surfynol 104 0.48 Water 135.26 Dispersion C-2 - Sensitizer is DBO , dibenzyl oxalate. DBO 82.29 PVA, Vinol 203, 28% in Water 70.18 Nopco NDW 0.10 Surfynol 104 0.39 Water 123.64 Dispersion D-1 - Resin has 0% weight percent phenolic group of resin, Zonarez 7125 . . . Polyterpene Resin. 0% Hydroxyl Resin 17.00 PVA, Vinol 203, 28% in Water 10.36 Nopco NDW 0.02 Surfynol 104 0.08 Water 72.54 Dispersion D-2 - Resin melt has 3.2 weight percent phenolic group of resin, 88:12 . . . Zonarez 7125:Piccofyn T-125. Dispersion prepared the same as D-1 but using 3.2 weight percent phenolic group of resin resin. Dispersion D-3 - Resin melt has 6.75 weight percent phenolic group of resin, 75:25 . . . Zonarez 7125:Piccofyn T-125. Dispersion prepared the same as D-1 but using 6.75 weight percent phenolic group of resin resin. Dispersion D-4 - Resin melt has 8.1 weight percent phenolic group of resin, 70:30 . . . Zonarez 7125:Piccofyn T-125. Dispersion prepared the same as D-1 but using 8.1 weight percent phenolic group of resin resin. Dispersion D-5 - Resin melt has 9.2 weight percent phenolic group of resin, 66:34 . . . Zonarez 7125:Piccofyn T-125. Dispersion prepared the same as D-1 but using 9.2 weight percent phenolic group of resin resin. Dispersion D-6 - Resin melt has 10.8 weight percent phenolic group of resin, 60:40 . . . Zonarez 7125:Piccofyn T-125. Dispersion prepared the same as D-1 but using 10.8 weight percent phenolic group of resin. Dispersion D-7 - Resin melt has 13.5 weight percent phenolic group of resin, 50:50 . . . Zonarez 7125:Piccofyn T-125. Dispersion prepared the same as D-1 but using 13.5 weight percent phenolic group of resin. Dispersion D-8 - Resin melt has 20.2 weight percent phenolic group of resin, 25:75 . . . Zonarez 7125:Piccofyn T-125. Dispersion prepared the same as D-1 but using 20.2 weight percent phenolic group of resin. Dispersion D-9 - Resin melt has 27.0 weight percent phenolic group of resin, Piccofyn T-125 . . . Terpene-Phenol Addition Product. Dispersion prepared the same as D-1 but using 27 weight percent phenolic group of resin. The image fade and fade index after 24 hours in a 60°C oven are shown in Table 1. 60°C Oven Fade Test and The Calculation of Fade Index The 60°C oven fade test is a routine test used to simulate long term aging of a thermal print. In this test: 1. The sample may be imaged by a Dynamic tester, Fax machine (in this case a Sharp 220) or static tester. The sample must be imaged by sufficient energy to achieve an initial MacBeth reading of 1.1. 2. The image density is measured on a Macbeth densitometer and recorded. The unimaged sheet opacity (background) is measured by an opacimeter and recorded. 3. The imaged sample is then hung vertically in an oven at 60°C for 24 hrs. Multiple samples are hung so that free air flow between the samples is allowed. 4. At the end of the 24 hr. test period the sample is removed from the oven and the image density and background opacity are remeasured and recorded by the Macbeth densitometer and opacimeter, respectively. 5. Loss in image density (intensity) is calculated by subtracting the final image density from the initial density and dividing by initial density. This can be referred to as percent fade. 6. Any darkening of the background (unimaged area) can be determined from the difference in the final opacity from the initial opacity. Calculation of Fade Index The % fade as determined by step 5 above is a good indication of print stability as long as the background does not change. With thermal systems, exposure to low heat levels over long periods of time can gradually darken the background due to premature color formation. The question becomes one of determining what part of image stability is due to fade of the image versus premature background coloration. It is preferable to view the stability of a thermal image not in % fade but rather in % print remaining. The first portion of the fade index calculation does this conversion. M = % Image remaining = 100 - % Fade = 1- Macbeth Initial-Macbeth Final Macbeth initial x 100 or M = Macbeth final Macbeth initial x 100 The next step is to determine a factor to correct for background change after exposure. Background readings on the opacimeter are expressed as the actual opacimeter reading times 100 (ie. 0.845 x 100 = 84.5 reported). Additionally, the opacimeter scale is reversed. A value of 1 (100) represents the standard reference for a white surface. A 0 (zero) value is used as the standard reference for a black surface. The opacimeter measures the ability to hide the surface. Infinite thickness of the colored layer or image is assumed. Since our image color is black we can assume our scale goes from 1 to 0. In order to reverse the measured number, to get it on a "larger is better" or background whiteness remaining scale, the first step of this calculation is to subtract the actual opacimeter reading from one. W = 1 - I/I o where I/I o is the actual opacimeter reading A correction is done for the fact that we are not dealing with a surface of infinite thickness. The negative log of the opacimeter reading (in this case W) gives a good linear relationship between dye reacted and image intensity. B = -log W Now we can calculate a conversion factor. If B I represent the initial background and B F the final background, the increase in background or % of image stability due to background increase is: D = B I - B F B I We now know the % Image retained (M) and the image due to background increase (D). The question becomes, what part of the image stability is due to the fade of the image v. premature background coloration? We can calculate the image retention due to fade of the image v. premature background coloration as Fade Index = FI = M (1-D) Calculation of Weight Percent Resin Phenolic Group of Active Components The Weight % Resin Phenolic component of the active components (chromogen, developer and color stabilizing resin together) and thus contributed to by the addition product of a phenol and a diolefinic alkylated or alkenylated cyclic hydrocarbon, (conventionally referred to as polyterpene resin, polyterpene/terpene-phenol resin blend or terpene-phenol resin) is calculated as follows: Active components - chromogen (dye) - electron-accepting color developer (developer) - color stabilizing resin (resin) Wt % phenolic group of the resin is determined as follows: The procedures used to measure weight percent phenolic group are very similar to those used to measure hydroxyl unit; however, the data are treated somewhat differently. In this procedure, hydroxyl content is expressed as the weight of hypothetical phenolic group (-C 6 H 4 OH, molecular weight 93.11) which would possess the same number of phenolic hydroxyls as 1 gram of unknown sample, expressed as a percentage. Example--high purity phenolic material of definite chemical structure: 4-cumylphenol, molecular weight 212.3 Weight Percent Phenolic Group = (93.11/212.3) x 100 = 43.9% This method of defining hydroxyl content is slightly (about 1%) different than defining hydroxyl content as weight percent phenol. Phenol is, of course, a real material having a molecular weight of 94.1. Weight percent phenolic group is used in order to avoid possible misunderstanding that the phenol/terpene condensation products contain appreciable amounts of unbound phenol. In our procedure, solutions of high-purity paraalkylsubstituted phenols are prepared in tetrachloroethylene. The FTIR spectra are recorded and the integrated peak area (IPA) of the free phenolic hydroxyl absorption peak is recorded in absorbance units, which are proportional to concentration. A calibration plot is prepared by plotting IPA versus the product of weight percent phenolic group and solution concentration (in grams per milliliter). Solutions of unknown condensation products, having concentrations of about 1 to 10 milligrams per milliliter, are prepared in tetrachloroethylene. The IPA for these solutions is measured in the same way as for the standard solutions. Weight percent phenolic group is calculated by reading the result from the calibration curve and dividing by the solution concentration (g/ml). This method is based upon the two assumptions: 1) the only hydroxyls in the unknown condensation products are phenolic hydroxyls; 2) quantitation of phenolic compounds is accomplished by infrared spectroscopy. See Goddu, R.F., Analytical Chemistry , vol. 30, no. 12, December 1958, pp. 2009-2013. Table 1 is a test of the stability of image intensity in a test chamber at 60°C. The test chamber used was a constant temperature oven. As shown by Table 1, the record material according to the invention when imaged is considerably more resistant to fade or erasure as compared to record materials not having the combination of the invention. Table 2 lists the weight % resin phenolic group of active, meaning the % resin phenolic group of the active components calculated as described herein particularly under "Calculation of the Weight Percent Phenolic Group". The Fade Index is also calculated as herein described. In Tables 1 and 2, an asterisk indicates the presence of a Comparative Example not within the scope of the invention (the Control Examples are likewise not within the scope of the invention). Average Initial Image Intensity MacBeth Reading Average 24 Hr. 60°C Image Intensity MacBeth Reading Background Initial Background 24 Hr. 60°C Final Fade Index Control -1 1.19 0.47 83.5 80.2 35.9 Example-1* 1.15 0.82 85.0 83.0 67.1 Example-2 1.19 0.91 84.6 82.3 70.8 Example-3 1.22 0.97 83.9 80.9 72.1 Example-4 1.12 0.81 84.6 81.6 65.5 Example-5 1.20 0.97 83.9 79.6 70.4 Example-6 1.20 0.92 83.2 79.4 68.4 Example-7 1.17 0.93 81.5 76.9 68.6 Example-8 1.22 1.06 81.1 68.9 62.2 Example-9* 1.23 1.14 76.0 50.3 42.0 Control-2 1.23 0.39 86.1 79.7 25.6 Example-10* 1.32 0.65 86.5 73.8 32.9 Average Initial Image Intensity Average 24 Hr. 60°C Image Intensity Background Initial Background Final Fade Index Control 3 1.35 0.76 85.3 79.3 46.2 1.37 0.78 85.4 78.3 45.5 Example 19 1.32 0.88 85.6 82.3 57.8 1.41 0.94 85.9 81.7 60.4 Example 19a 1.33 0.92 85.4 81.7 61.8 Example 11 1.37 1.10 86.0 81.6 62.3 1.33 0.95 86.2 82.1 62 Example 19b 1.33 0.92 84.2 80.4 61.1 1.40 1.10 83.9 79.8 67.7 Example 11b 1.33 1.06 85.4 79.8 66.3 Example 19c 1.42 1.07 82.8 75.8 66.1 Example 11c 1.38 1.18 83.1 74.8 68.9 1.30 1.06 83.6 76.4 65.1 Example 11d 1.35 1.20 80.9 64.7 55.8 Example 11e* 1.35 1.31 82.8 37.3 25.8 Example 22* 1.36 1.32 82.3 27.2 17.9 Control 3 1.42 1.00 85.7 76.0 51.7 Example 20* 1.37 1.31 81.3 41.7 30.8 Example 21* 1.37 1.31 79.9 38.8 29.2 Example 11a* 1.37 1.19 86.8 82.7 75.3 Weight % Resin Phenolic Group of Active Fade Index Control 1 No resin 35.9 Example 1* 0 67.1 Example 2 0.56 70.8 Example 3 1.22 72.1 Example 4 1.42 65.5 Example 5 1.61 70.4 Example 6 1.89 68.4 Example 7 2.36 68.6 Example 8 3.54 62.2 Example 9* 4.78 42 Control 3 No resin 46.2 Control 3 No resin 45.5 Example 19 0.97 57.8 Example 19 0.97 60.4 Example 19a 1.28 61.8 Example 11 1.71 62.3 Example 11 1.71 62 Example 19b 1.88 61.1 Example 19b 1.88 67.7 Example 11b 2.24 66.3 Example 19c 2.78 66.1 Example 11c 3.3 68.9 Example 11c 3.3 65.1 Example 11d 4.88 55.8 Example 11e* 6.59 25.8 Example 22* 7.98 17.9 Control 3 No resin 51.7 Example 20* 5.76 30.8 Example 21* 6.13 29.2 Example 11a* 0 75.3 The principles, preferred embodiments, and modes of operation of the present invention have been described in the foregoing specification. The invention which is intended to be protected herein, however, is not to be construed as limited to the particular forms disclosed, since these are to be regarded as illustrative rather than restrictive. Variations and changes can be made by those skilled in the art without departing from the spirit and scope of the invention. Obvious and included variations would clearly include for example, rather than applying the components of the color forming system in one coating, multiple layers of the individual components can be applied. For example, a layer with modifier and developer and resin can be top coated with a layer containing chromogen and modifier. Another workable variation, equally within the scope of the invention would be to apply to a substrate a coating of developer, resin, and modifier over which is top coated a dispersion of chromogen, resin, developer and modifier. Other such structural variations would be clearly evident to the skilled worker in the art all without departing from the scope of the claims.

Claims: Thermally-responsive record material comprising a substrate bearing a thermally-sensitive color-forming composition comprising a chromogen, an electron-accepting color developer which reacts with said chromogen to form a color, and a color stabilizing resin comprising a) an addition product of a phenol and a diolefinic alkylated or alkenylated cyclic hydrocarbon; or b) an addition product of phenol and α-pinene; the weight percent resin phenolic group, as defined herein, of the chromogen, developer, and stabilizing resin together being 5 or less, the thermally-responsive record material having a fade index, as defined herein, of at least 55.8 when placed in a 60°C oven for 24 hours. Thermally-responsive record material according to Claim 1 wherein the cyclic hydrocarbon of the addition product is a terpene. Thermally-responsive record material according to Claim 2 wherein the color stabilizing resin is a polyterpene resin. Thermally-responsive record material according to Claim 2 or Claim 3 wherein the color stabilizing resin is an addition product of limonene, preferably d-limonene. Thermally-responsive record material according to Claim 1 wherein the color stabilizing resin is a combination of a polyterpene resin and an addition product of phenol and α-pinene. Thermally-responsive record material according to Claim 5 wherein the polyterpene resin is derived from limonene, preferably d-limonene. Thermally-responsive record material according to any preceding claim wherein the chromogen is a 3-dialkylamino-6-methyl-7-anilinofluoran, and the electron -accepting color developer is 2,2-bis(4-hydroxyphenyl)-4-methylpentane. Thermally-responsive record material according to any preceding claim including in addition a sensitizer comprising 1,2-diphenoxyethane. Thermally-responsive record material according to any preceding claim comprising polyvinylalcohol or hydroxypropyl methylcellulose as a binder.

Inventors: BARTMAN GERALD CHARLES, SANDS PEGGY DOROTHY, VERVACKE STEVEN LAWRENCE, BARTMAN, GERALD CHARLES, SANDS, PEGGY DOROTHY, VERVACKE, STEVEN LAWRENCE
Applicants: APPLETON PAPER INC, APPLETON PAPERS INC.
Application year: 1992
Main classification: B41M5
IPC codes: B41M5