THERMALLY RESPONSIVE RECORD MATERIAL

Abstract: Thermally responsive record material uses a 2,2-bis(3'-alkyl-4'hydroxyphenyl)-4-methylbutane as co-reactant. The hydroxyphenyl groups may carry a 5'-alkyl group. Such record material has improved thermal response and is particularly suitable for use in facsimile equipment.

Description: This invention relates to thermally responsive record material and particularly to such record material in the form of sheets coated with colour forming systems comprising chromogenic material and acidic colour developer material. This invention particularly concerns thermally responsive record material with improved colour forming efficiency and/or image density. Thermally responsive record material systems are well known in the art and are described in many patents, for example US Patents Nos. 3539375, 3674535, 3746675, 4151748, 4181771, and 4246318. In such systems, basic chromogenic material and acidic colour developer material are contained in a coating on a substrate which, when heated to a suitable temperature, melts or softens to permit the said materials to react, thereby producing a coloured mark. In this art and as used herein, by the term 'thermal response' is meant the temperature at which a thermally responsive record material produces a coloured image of sufficient intensity (density). The desired temperature of imaging varies with the type of application of the thermally responsive product and the equipment in which the imaging is to be performed. The ability to modify the temperature at which a satisfactorily intense thermal image is produced for any given combination of chromogenic material and developer material is a much sought after and very valuable feature. It is also desirable to increase the efficiency of thermal image formation. This is advantageous as, for example, it is possible to obtain the same image intensity with a lower amount of reactants, or to obtain a more intense image with the same amount of reactants, or a combination of these. One of the use for thermally responsive record material which is enjoying increasing importance is facsimile reproduction. Alternative terms for facsimile are telecopying and remote copying. In the facsimile system, images transmitted electronically are reproduced as hard copy. The trend in facsimile equipment is towards shorter transmission times and higher resolution of the facsimile produced image. This trend required thermally responsive record material with increased sensitivity. Increases in the sensitivity of thermally responsive record material have been achieved through the incorporation of a phenyl hydroxynaphthoate compound or a hydroxyanilide compound in the colour forming composition along with the chromogenic material and developer material as disclosed in co-pending European Patent Applications Nos. 83304172.6 (Publication No. 0100196) and 85303166.4 (Publication No. ). Another means of achieving increased sensitivity is presented in US Patent No. 4436783 which discloses thermosensitive recording material containing as the colour developer a fused mixture comprising a bisphenol compound and another phenolic compound, wherein the fused mixture has a melting point lower than that of the bisphenol compound. US Patent No. 3539375 discloses, as developer material in a thermally responsive reord sheet, 4,4'- iso propylidene-bis(2-tertiarybutylphenol) and 4,4'- sec butylidene-bis(2-methylphenol). The applicants have discovered that a thermally responsive record material employing a colour forming composition comprising chromogenic material and, as a colour developer, certain substituted bisphenol compounds produces enhanced thermal sensitivity and/or enhanced image density and/or improved background coloration characteristics. The present invention, accordingly, provides thermally responsive record material comprising a support member bearing a coating of a thermally sensitive colour forming composition comprising chromogenic material, as a co-reactant for the colour forming composition, at least one bisphenol compound having the formula (I): wherein each R₁ is a C₁ to C₄ alkyl or C₁ or C₂ alkoxy group; and each R₂ is a hydrogen atom or a C₁ to C₄ alkyl group, and a binder therefor. In particular the invention includes thermally responsive record material as described above wherein the co-reactant is at least one, but preferably only one, bisphenol compound of the formula (II): where R is a C₁ to C₄ alkyl group. The record material includes a substrate or support material which is generally in sheet form. As used herein the term 'sheet' or 'sheets' mean(s) article(s) having two relatively large surface dimensions and a relatively small third (thickness) dimension and includes webs, ribbons, tapes, belts, films and cards. The substrate or support material can be opaque, transparent or translucent and can, itself, be coloured or uncoloured. 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 particular nature of the substrate material is not critical. Although they are not required to carry out this invention, the inclusion of certain sensitizing materials in the colour forming systems provides a further improvement in properties, especially background stability. Materials such as phenyl 1-hydroxy- 2-napthoate, stearamide and p-hydroxyoctadecananilide are useful as such sensitizing materials. The inclusion of such a sensitizing material or materials forms a specific although subsidiary feature of this invention. The components of the colour forming system are in a contiquous relationship in the coating on the substrate and are usually finely divided solid particles substantially homogeneously distributed throughout the coating. The record material can be manufactured, using a coating composition which includes a fine dispersion of the chromogenic material, the colour developer, the polymeric binder material, surface active agents and other additives in a vehicle which is usually water. The composition may also contain chemically 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 Carnuba wax; synthetic waxes such as amide waxes especially stearamide waxes; lubricants such as zinc stearate; wetting agents and defoamers. The components of the colour forming system will usually be substantially insoluble in the dispersion vehicle, which is preferably water, and are typically ground to an individual average particle size of between about 1 and about 10 and preferably about 3 my m (microns). The polymeric binder material is usually substantially vehicle soluble although latexes are also suitable in some instances. Suitable water soluble binders include polyvinyl alcohol, hydroxy ethylcellulose, methylcellulose, hydroxypropylmethylcellulose, starch, modified starches, gelatin and mixtures thereof, especially polyvinyl alcohol, methylcellulose, starch and mixtures thereof. A particularly suitable binder is a mixture of polyvinyl alcohol, methylcellulose and starch. Suitable latex materials include polyacrylates, polyvinylacetates and polystyrene latexes. The polymeric binder is used to bind the other components of the coating composition (apart from the vehicle) to the substrate and to protect the coated materials from brushing and handling forces occasioned by storage and use of the sheets of record material. The binder should be present in an amount to afford such protection and in an amount less than will interfere with achieving reactive contact between colour forming reactive materials. The (dry) weight of the coating will typically be in the range 3 to 9 grams per square metre (gsm) and preferably about 5 to about 6 gsm. The specific amount of colour forming materials in any particular case will be determined by economic considerations, functional parameters and desired handling characteristics of the coated sheets. Suitable chromogenic compounds, include the well known colour forming compounds, such as phthalides, leucauramines, fluorans, spirodipyrans and pyridine and pyrazine chromogenic materials. Suitable phthalides include Crystal Violet Lactone which is 3,3-bis(4'-di-methylaminophenyl)-6-dimethylaminophthalide, as described in US Reissue Patent No. 23024, phenyl-, indol-, pyrrol-, and carbazol-substituted phthalides as described in US Patent Nos. 3491111, 3491112, 3491116 and 3509174; suitable fluorans include nitro-, amino-, amido-, sulfonamido-, aminobenzylidene-, halo- and anilino- substituted fluorans as described in US Patent Nos. 3624107, 3627787, 3641011, 3462828 and 3681390; suitable spirodipyrans include those described in US Patent No. 3971808; and suitable pyridine and pyrazine chromogenic compounds include those described in US Patent Nos. 3775424 and 3853869. Specifically suitable chromogenic compounds include: 3-diethylamino-6-methyl-7-anilinofluoran, described in US Patent No. 3681390 and also known as N-102, 7-(1-ethyl-2-methylindol-3-yl)-7-(4-diethylamino- 2-ethoxyphenyl)-5,7-dihydrofuro[3,4-b]pyridin-5-one, described in US Patent No. 4246318, 3-diethylamino- 7-(2-chloroanilino)fluoran, described in US Patent No. 3920510, 3-(N-methylcyclohexyamino)-6-methyl- 7-anilinofluoran, described in US Patent No. 3959571, 7-(1-octyl-2-methylindol-3-yl)-7-(4-diethylamino- 2-ethoxyphenyl)-5,7-dihydrofuro[3,4-b]pyridin-5-one, 3-diethylamino-7,8 benzofluoran, 3,3-bis(1-ethyl-2- methylindol-3-yl)phthalide, 3,3-bis(1-octyl- 2-methylindol-3-yl)phthalide, 3-diethylamino-7-anlilino- fluoran, 3-diethylamino-7-benzylaminofluoran, 3-pyrrolidino-7-dibenzylaminofluoran, 3'-phenyl-7-dibenzyl- amino-2,2'-spiro-di[2H-1-benzopyran], 3-bis(4'-dimethylaminophenyl)-6-dimethylaminophthalide and mixtures thereof. 3-diethylamino-6-methyl-7-anilinofluoran is especially preferred as a chromogenic material. The following Examples illustrate the invention. In these Examples all parts are by weight, all solutions are in water and all measurements are in SI units unless otherwise stated. The co-reactant materials used in the present invention can be made by procedures described, for example, in US Patent Nos. 2775620 and 2917550. 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 micron and 10 my m was achieved. The milling was accomplished in an attritor, small media mill, or other suitable dispersing device. The desired average particle size was about 1-3 my m in each dispersion. In these examples separate dispersions comprising the chromogenic compound (Component A), the acidic developer material (Component B), and the sensitizer materials (Components C, D and E) were prepared. *Equal parts of the defoamer Nopko NDW (sulfonated caster oil produced by Nopko Chemical Company) and the dispersing agent Surfynol 104 (a di-tertiary acetylene glycol surface active agent produced by Air Products and Chemicals Inc.) were employed. The chromogenic compounds employed in the examples are listed in Table 1. Table 1 The acidic developer materials employed in the examples are listed in Table 2. Table 2 Mixtures of dispersion A and B, mixtures of dispersions A, B and C, mixtures of dispersions A, B and D and mixtures of dispersions A, B and E were made. In all cases the following materials were added to the resulting mixtures: 1. A 68% kaolin clay slurry in water (designated hereinbelow as "clay"); 2. A 10% solution of polyvinyl alcohol in water (designated hereinbelow as "PVA"); 3. Water. In some cases one or more of the following materials was added to the resulting mixture: 1. Zinc stearate, 21% dispersion; 2. Urea-formaldehyde resin pigment; 3. Micronized silica, i.e. finely divided silica produced in a "Micronizer" mill. In Table 3 are listed each of these mixtures, including the components added and the parts by weight of each. Each mixture of Table 3 was applied to paper and dried, yielding a dry coat weight of about 5.2 to about 5.9 gsm. TABLE 3 Thermally sensitive record material sheets coated with one of the mixtures of Table 3 were imaged by contacting the coated sheet with a metallic imaging block at the indicated temperature for 5 seconds. The intensity of each image was measured by means of a reflectance reading using a Macbeth reflectance densitometer. A reading of 0 indicates no discernable image. The intensity of each image is a factor, among other things, of the nature and type of chromogenic compound employed. A value of about 0.9 or greater usually indicates good image development. The intensities of the images are set out in Table 4 below. The background colouration in some of the thermally sensitive record material sheets was determined before calendering, after calendering and after aging the calendered sheets for three days. The intensity of the background coloration was measured by means of a reflectance reading using a Bausch & Lomb Opacimeter. A reading of 92 indicates no discernable colour and the higher the value the less background coloration. The background data are entered in Table 5. TABLE 5 From the data of Tables 4 and 5 it is readily apparent that thermally responsive materials comprising the developer materials of the present invention produce substantially enhaned image intensities and/or enhanced thermal sensitivity and/or improved background coloration compared to corresponding thermally responsive recording material comprising previously known co-reactant material. TABLE 4

Claims: 1. Thermally responsive record material comprising a support member bearing a coating of a thermally sensitive colour forming composition comprising chromogenic material, as a co-reactant for the colour forming composition, at least one bisphenol compound having the formula (I): wherein each R₁ is a C₁ to C₄ alkyl or C₁ or C₂ alkoxy group; and each R₂ is a hydrogen atom or a C₁ to C₄ alkyl group, and a binder therefor. 2. Record material as claimed in claim 1 wherein the co-reactant is at least one, but preferably only one, bisphenol compounds of the formula (II): where R is a C₁ to C₄ alkyl group. 3. Record material as claimed in claim 2 wherein the co-reactant is a single compound of the formula (II). 4. Record material as claimed in any one of claims 1 to 3 wherein the co-reactant is or includes 2,2-bis(4-hydroxy- 3-methylphenyl)-4-methylpentane, 2,2-bis(4-hydroxy-­ 3-isopropylphenyl)-4-methylpentane or 2,2-bis(hydroxy-­ 3-tert.butylphenyl)-4-methylpentane. 5. Record material as claimed in any one of claims 1 to 4 wherein the chromogenic material is 3-diethylamino- 6-methyl-7-anilino-fluoran; 7-(1-ethyl-2-methylindol- 3-yl)-7-(4-diethylamino-2-ethoxyphenyl)-5,7- dihydrofuro- [3,4-b]pyridin-5-one; 3-diethylamino-7-(2-chloroanilino)- fluoran; 3-(N-methylcyclohexylamino)-6-methyl-7-anilino- fluoran; 7-(1-octyl-2-methylindol-3-yl)-7-(4-diethylamino­ -2- ethoxyphenyl)-5,7-dihydrofuro[3,4-b]pyridin-5-one; 3'-phenyl-7-dibenzylamino-2,2'-spiro-di[2H-1- benzopyran]; 3,3-bis(4-dimethylaminophenyl)-6- dimethylamino-phthalide; 3-(2-hydroxy-4- diethylaminophenyl)-3-(2,4-dimethoxy -5- anilinophenyl)phthalide; 3-(2-hydroxy-4- diethylamino­ phenyl)-3-(2,4-dimethoxy-5- (4-chloroanilino)phenyl)- phthalide; or a mixture thereof. 6. Record material as claimed in any one of claims 1 to 5 wherein the binder is polyvinyl alcohol, methylcellulose, hydroxypropylmethylcellulose, starch, hydroxyethyl­ cellulose, styrene-butadiene latex or a mixture thereof. 7. Record material as claimed in claim 6 wherein the binder is a mixture of polyvinyl alcohol, methylcellulose and styrene-butadiene latex.

Inventors: GLANZ, KENNETH D.
Applicants: APPLETON PAPERS INC.
Application year: 1985
Main classification: B41M5
IPC codes: B41M5