CA1121158A - Two color thermally sensitive record material system - Google Patents
Two color thermally sensitive record material systemInfo
- Publication number
- CA1121158A CA1121158A CA000317723A CA317723A CA1121158A CA 1121158 A CA1121158 A CA 1121158A CA 000317723 A CA000317723 A CA 000317723A CA 317723 A CA317723 A CA 317723A CA 1121158 A CA1121158 A CA 1121158A
- Authority
- CA
- Canada
- Prior art keywords
- color
- record
- record material
- thermally
- coreactant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/34—Multicolour thermography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/34—Multicolour thermography
- B41M5/345—Multicolour thermography by thermal transfer of dyes or pigments
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
- Color Printing (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
Docket No. 207?
Title of the Invention TWO COLOR THERMALLY SENSITIVE RECORD MATERIAL SYSTEM
Abstract of the Disclosure A thermally sensitive record medium is disclosed.
Data is generated on the record medium in response to an application of heat. The record medium is capable of generating data images in more than one color by exposing the medium to overlap or interference between two colors is avoided by utilizing at least one color-forming system which requires a thermal decomposition of one system component before it can be reacted to yield color.
The record material is made by coating individual layers, each containing a color-forming system or preferably by coating a single layer including all of the color-forming systems.
Title of the Invention TWO COLOR THERMALLY SENSITIVE RECORD MATERIAL SYSTEM
Abstract of the Disclosure A thermally sensitive record medium is disclosed.
Data is generated on the record medium in response to an application of heat. The record medium is capable of generating data images in more than one color by exposing the medium to overlap or interference between two colors is avoided by utilizing at least one color-forming system which requires a thermal decomposition of one system component before it can be reacted to yield color.
The record material is made by coating individual layers, each containing a color-forming system or preferably by coating a single layer including all of the color-forming systems.
Description
l~Z~ 8 Background of the Invention Field of the Invention - This invention relates to record media on which data are developed in response to an appLication of heat. It more particularly relates to such record media in the form of sheets coated by color-Eorming systems wherein a sheet includes more than one color-forming system. Specifically, it also pertains to such a coated sheet on which images can be generated in more than one color by subjecting areas of the sheet to different, particular, temperature levels to obtain different, particular, colors.
This invention particularly concerns a temper-ature sensitive record material of more than one color response wherein overlap and interference between the colors is minimized by utilizing, as at least one of the color-forming systems, a system which remains color-less until a decomposition temperature is reached for one of the components, only then enabling the component to take part in a coloration reaction. This invention, relating as it does to record sheets using such color-forming systems which are triggered by heat decomposi-tion, pertains to improved thermal record media having a relatively sharply-defined temperature above and below which images of distinctly difEerent color are generated.
This invention pertains to such record media including one or more coating layers of color-forming system materials.
Description of the Prior Art - United States Patent No. 3,293,055 issued December 20, 1966 on an application of the inventor herein, discloses a thermo-colorable record copy sheet wherein minute particles of the components of a color-forming system are dispersed into a polymeric binder and coated as a layer. The copy sheet is disclosed to yield a color when areas to be imaged are heated to a temperature suEficient to meLt one or both of the components. The only disclos-ed mechanism for color formation is fusion of the com-ponents. The disclosed record sheets gener~te a single color. The color-forming components are benzoindolino-spiropyran derivatives and metallic salts oE organic acids.
United States Patent No. 3,451,338 issued June 24, 1969 on an application of the inventor herein, discloses a temperature responsive and colorable record material which is similar to previously discussed 3,293,055. Again, color formation is accomplished by simple fusion. The disclosed sheets generate a single color. The color-forming components are benzoindolino-spiropyran derivatives and phenolic compounds.
Japanese Application No. Sho 47-86269, filed August 30, 1972, and disclosed April 24, 1974 as Japanese Disclosure No. Sho 49 43645 to Mitsubishi Paper Mills, Ltd., discloses a two-color thermal paper. The disclosed thermal paper includes both color-forming systems in a single coating layer. The chromogenic components are fluoran compounds and the coreactant component is a phenolic compound. For any given two-color system the phenolic coreactant and both of the fluorans are dispersed in the single coated layer and the developed color of any thermal image depends entirely on the melt-ing point of the fluoran compounds. The colors are each generated by a fluoran and the mechanism of color formation is always fusion of the component materials.
Any material impurities or mutual solution of the fluoran melts tend to cause an overlap in component melting;
points and an interference of the generation of one color with development of the other.
~Z11~3 Japanese Disclosure No. Sho 50-6349 disclosed January 23, 1975 as Application No. Sho 48-53703 filed May 16, 1973 in the name oE Mitsubishi Paper Mills, Ltd., also discloses a two-color thermal paper. This disclosure attempts to solve the problem of overlapping color formation in two-color record sheets by incorporat-ing a decolorizing material in the coating composition.
Two chromogenic materials, a phenolic coreactant and a decolorizing agent (such as a guanidine) are homo-geniously dispersed in a polymeric binder material,all in a single layer. As the sheet is heated, both chromogenic materials form color to yield the initial color image. When the temperature is increased still more, the decolorizing agent melts and decolors only one of the chromogenic materials. To the extent that the effects of the decolori~ing agent overlap or the decolorizing agent interferes with both of the chromo-genic materials, the difficulty of a broad temperature range requirement for adequate color differentiation persists.
Japanese Disclosure No. Sho 49-96738 disclosed September 12, 1974 as Application No. Sho 48-7003 filed January 17, 1973 in the name of Mitsubishi Paper Mills, Ltd., also discloses a two-color thermal paper. This thermal paper also includes a single layer embodiment.
The single layer includes an acid-reacting chromogen, a base-reacting chromogen, an acid coreactnat, and a base coreactant, all homogeneously dispersed in a poly-meric binder material. Color development depends upon fusion of at least the coreactant materials. The pairs of selected coreactants have different melting points.
The first to melt colors the appropriate chromogen and the second to melt neutralizes the first coreactant, ~ 5 ~
decolors the first chromogen, and colors the second chromogen. All components of the disclosed sheet are present in the sheet in a reactive condition. There is no preliminary reaction or decomposition required to prevent premature coloration.
Summary of the Invention In the field of thermal-responsive recording materials, there is considerable demand for an acceptable product which will yield more than one color of prlnted l~ data. Several products have been offered, but most suffer from a problem of developed color overlap within a relatively broad temperature range. When each oE
two colors are developed in broad and overlapping tem-perature ranges, the actual image color is only rela-tively gradually changed as the temperature is changed.
It is an object oE this invention to provide a thermal-responsive recording material having more than one color for data representation. It is further an object of this invention to provide such a recording material having several relatively narrow temperature ranges in which images develop in different colors.
It is a specific object of this invention to provide a two-color thermal record material having color-forming systems effective at different temperatures wherein color formation at the higher temperature first requires decomposition of a component to generate a color reactant.
It is also an object of this invention to provide such a thermal record material having only a single coating layer including more than one color-forming system. It is also an object of this invention to provide a thermal record material having more than one color-forming system, at least one of which includes a component requiring decomposition prior to color genera~
tion, and each oE which is incl~lded in a s~parate coating layer.
It is yet another object of this invention to provide a multi-color thermally responsive record material comprising a support sheet bearing a first thermally-sensitive color-Eorming composition comprising particles of a chromogenic material and a coreactant material in contiguous relationship whereby the melting or sublimation of either material produces a first change in color by reaction between the two, and a secon~
thermally-sensitive color-forming composition comprising particles of a thermally decomposable material and a coreactant material in contiguous relationship, whereby decomposition of the thermally decomposable materia]
forms a chromogenic material which produces a dif~erent change in color by reaction with the coreactant material, said decomposition occurring at a higher temperature than said melting or sublimations.
The record material of this invention provides additional color development within a relatively narrow temperature range. To give a specific example of such record material having two colors: (i) a low temperature color-forming system is provided which relies solely upon melting or sibliming (vaporizing of solid particles) one or more of the components to achieve reactive, color-producing, contact and (ii) a higher temperature color-forming system is provided which ultimately relies uponmelting or vaporizing one or more of the components but which first must generate one of the reactive com-ponents by decomposition of a material in the color-forr.ing system. The low and h gher temperature color-forming systems are coated onto a substrate which, when heated, yields an image in the configuration of the area heated and of a color corresponding to the tempera-ture reached. In heating the coated substrate, the color of the low tempe~ature color-forming system ~ .
6a develops at the color advent temperature for that system.
As the temperature is increased further -- and this is most important to understanding of the present inven-tion -- no additional color is developed until the tem-perature is reached for decomposition oE that material in the high temperature color-Eorming system which must be decomposed to enter a color-forming reaction. When that decomposition temperature is reached, the second color is generated over the first color. As a rule, the first ~
~ 8 color has the appearance of a relatively pure hue such as red, blue~ green or the like and the second color has a more or less neutral hue resulting from combination of the hues Erom the Eirst and second color-forming systems. Generation of color in the higher temperature color-forming systems does not decolor or erase the first-developed color. The two colors are combined to provide the darkest images and the most effective use of color-forming materia]s.
The matter of the component decomposition is very important to this invention in permitting combin-ation of color-forming systems which develop individually at clearly-defined temperatures rather than together and gradually over a broad temperature range. Systems of the prior art which have relied on fusion (melting) or vaporization (incLuding sublimation of solid particles) of materials to generate colors generate a wide gradation of colors extending from the hue of the first, through all combinations of the first and the second, to the hue of the second. The melt formed by components of a first color-Eorming system tends to cause solution of components of a second color-forming system by lowering the component melting points. The sub-limation of one component of a first color-forming system causes particular problems when this component also reacts with a component of the second color-forming system. When, as in the present invention, a component decomposition is required before color reaction can occur, a melt or sublimation of one or more of the first system components has no effect.
The record material includes a substrate or support material which is generally in sheet form.
For purposes of describing this invention, sheets also mean webs, ribbons, tapes, belts, films, 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, trans~
parent or translucent and could, itself, be co]ored or not. The material can be Eibrous including, for example, paper and Eilamentous synthetic materials and it can be a Eilm including, for example, cellophane and synthetic polymeric sheets cast, extruded, or other-wise formed. The kernel of this invention resides in the combination of color-forming systems coating the sub-strate; and the kind or type of substrate material is not critical.
The components of the color-forming systems are in a conti~uous re]ationship, substantially homogene-ously ~istributed throughout the coated layer material deposited on the substrate. In manufacturing the record material, a coating composition is prepared which in-cludes a fine dispersion of the components of color-Eorming systems, polymeric binder material, and surface active, or other, additives in an aqueous coating medium.
The color-forming system components should be substan-tially water insoluble and ground to an individual average particle size of about 5 microns. The polymeric binder material should be substantially water soluble although latexes are also eligible in some instances.
Preferred water soluble binders include poly (vinyl alcohol), hydroxy ethylcellulose, methylcellulose, starch, modified starches, gelatin and the like. Eligible la~ex materials include polyacrylates, polyvinylacetates, polystyrene, and the like. The polymeric binder is used to protect the coated materials from brushing and handl-ing forces occasioned by storage and use of the thermal sheets. Binder should be present in an amount to afford ~ 5 ~
such protection and in an amount Less than will interfere with achieving reactive contact between color-Eorming reactive materials. An effective sheet is made with about ] to about 30 weight percent binder in the dried coating composition. The binder is preferably present as 5 to 30 weight percent of the dried coating.
Examples of eligible additives are surEace active agents such as defoamers including sodium lauryl sulfonate, octanol, acetylenic glycols, silicones, fatty acid esters, and the like. Also, if desired or required for a particular purpose, waxes, clays, fillers, color-ants, obscurants, and the like can be added to the coat-ing composition in amo~mts which do not adversely afEect the thermal response.
Coating weights are not of critical importance although, in sheets of more than a single layer, care must be exercised to utilize coating amounts sufficient to yield two distinctive colors and, at the same time, moderate to permit proper heat transfer from one layer to the next. As a general rule, the amounts of color-forming systems in the coating layers should be approxi-mately commensurate -- the weight of one not more than about ten times the weight of another, for example.
Coating weights for such layers can effectively be about 1.5 to about 8 and preferably about 3 to about 6 grams per square meter. As a practical matter, the lower limit for coating each layer is the amount required to provide the desired color response. As a general rule, material in layers beneath the surface làyer must be present in increased amounts so as to overcome masking effects of the layers above.
Sheets having only a single layer of thermally sensitive coating are preferred over sheets having ]o more than one layer. The coating weight for such sheets is not of critical importance so long as the proper amou~ts oE each color-orming system are present to yield adequate color development andcl color dlfferentia-tion at the marking temperature levels.
Benefits of the invention are realized to the extent that some of each of more than one eligible color-forming system is combined into a single coatlng layer. If each color is developed at its proper develop-ing temperature, and the materials are present in anamount adequate to discern the color, when developed, then the sheet demonstrates the invention. Generally, the coating weight oE all color-forming systems in a single coated layer will be greater than about 2 and not in excess of about 8 grams per square meter. The weight ratio of the materials of one color-forming system to another color-Eorming system is preferably between about 1 and about 10 for sheets having a single coated layer. In addition, the weight ratio of chromogenic material to coreactant for any given color-forming system is about 1 to about 12, preferably about 1 to about 6.
The practical minimum amount of color-forming materials is controlled by image darkness requirements and the practical maximum amount is controlled by economic considerations and desired handling characteris-tics of the coated sheets.
Sheets coated with a single layer exhibit advantages over other sheets by providing a sharper and more distinct thermal image in the generally thinner-coated materials. In a sheet of a single coated layer,both of the color-forming systems are in the top layer ~Z~L58 and all oE the components are intimately combined.
Moreover, sheets of a sin~le coated layer exhibit marked economic advantage over sheets requiring more than one layer, simply in decreased manuEacturing costs and de-creased materials costs. The single layer coated sheet of this invention exhibits more desirable handling characteristics than sheets requiring more than one coated layer.
Of the two types of color-forming systems, one relies on fusion (melting) or sublimation (vaporiza-tion of solid particles) of one or more components and the other relies on decomposition of one component prior to color reaction. The fusion or sublimation system generally utilizes acidic materials, such as phenolic compounds, and basic chromogenic materials which react with acidic materials. ~uch basic compounds include materials with a lactone ring, for example, phthalides or fluorans. Examples of eligible acid material include the compounds listed in United States Patent No.
3,451,338 as phenolic reactive materials, particularly the monophenols and diphenols. The list is exemplary only and not intended to be exhaustive -- 4-t-butyl phenol, 4-phenyl phenol, 4-hydroxydiphenyl oxide, -naphthol, -naphthol, methyl-4-hydroxybenzoate, 4-hydroxyacetophenone, 4-t-octylcatechol, 2,2'-dihydroxy-diphenyl, 2,2'-methylene bis (4-chlorophenol), 2,2'-methylene bis (4-methyl-6-t-butylphenol), 4,4'-isopro-pylidenediphenol, 4,4'-isopropylidene bis (2-chloro-phenol), 4,4'-isopropylidene bis 12,6-dibromophenol), 4,4'-isopropylidene bis (2,6-dichlorophenol), 4,4'-isopropylidene bis (2-methylphenol), 4,4'-isopropylidene bis (2,6-dimethylphenol), 4,4'-isopropylidene bis (2-t-butylphenol), 4,4'-sec.-~utylidene bis (2-methylphenol), 4,4'-cyclohexylidene phenol, 4,4'-cyclohexylidene bis (2-methylphenol), 2,2'-thio bis (4,6-dichlorophenol), 4,4'-thiodiphenol, and the like. Althou~h not preferred, other acid compounds o~ other kinds and types are 5~3 eligibl~. Examples of such other compounds are phenolic novolak resins which are the product of reaction between, Eor example, formalclehyde and a phenol such as an alkyl-phenol, e.g., p-octylphenol, or other phenols such as p-phenylphenol, and the like; and acid mineral materials including colloidal silica, kaolin, bentonite, attapul-gite, halloysite, and the like. Some of the polymers and minerals do not melt but undergo color reaction on fusion of the chromogen.
The eligible basic chromogenic compounds, such as the phthalide and fluoran compounds, Eor use in the fusion color-forming system are well known color-forming compounds. Examples of the compounds include Crystal Violet ~actone (3,3-bis(4-dimethylaminophenyl)-6-dimethylamino phthalide (U.S. Patent No. Re 23,024);
phenyl-, indol-, pyrol-, 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-, sulfon amido-, aminobenzylidene-, halo-, anilino-sub-stituted fluorans (for example, in U.S. Patent Nos.
3,624,107; 3,627,787; 3,641,011; 3,642,828; 3,681,390).
Other specifically eligible chromogens, not limiting the invention in any way, are: 6'-diethylamino-1', 2'-benzofluoran; 3,3-bis(l-ethyl-2-methyl-3-yl) phthalide;
6'-diethylamino-2r-anilinofluoran; 6'-diethylamino-2'-benzylaminofluoran; 6'-diethylamino-2'-butoxyfluoran;
and 6'-diethylamino-2'-bromo-3'-methylfluoran.
The decomposition color-forming system is of two types - determined by the chromogenic or so-called color-forming material. One type of decomposing system ,~ ~
utilizes an organic substituted thioamide to generate hydrogen sulfide when heated to clecomposition tempera-ture. Examples o~ eligible thioamides, along with the temperature oE decomposition, are presented in the table, below.
Thioamide Decomposition Temp. (C) 1. thioazelamide 138-141
This invention particularly concerns a temper-ature sensitive record material of more than one color response wherein overlap and interference between the colors is minimized by utilizing, as at least one of the color-forming systems, a system which remains color-less until a decomposition temperature is reached for one of the components, only then enabling the component to take part in a coloration reaction. This invention, relating as it does to record sheets using such color-forming systems which are triggered by heat decomposi-tion, pertains to improved thermal record media having a relatively sharply-defined temperature above and below which images of distinctly difEerent color are generated.
This invention pertains to such record media including one or more coating layers of color-forming system materials.
Description of the Prior Art - United States Patent No. 3,293,055 issued December 20, 1966 on an application of the inventor herein, discloses a thermo-colorable record copy sheet wherein minute particles of the components of a color-forming system are dispersed into a polymeric binder and coated as a layer. The copy sheet is disclosed to yield a color when areas to be imaged are heated to a temperature suEficient to meLt one or both of the components. The only disclos-ed mechanism for color formation is fusion of the com-ponents. The disclosed record sheets gener~te a single color. The color-forming components are benzoindolino-spiropyran derivatives and metallic salts oE organic acids.
United States Patent No. 3,451,338 issued June 24, 1969 on an application of the inventor herein, discloses a temperature responsive and colorable record material which is similar to previously discussed 3,293,055. Again, color formation is accomplished by simple fusion. The disclosed sheets generate a single color. The color-forming components are benzoindolino-spiropyran derivatives and phenolic compounds.
Japanese Application No. Sho 47-86269, filed August 30, 1972, and disclosed April 24, 1974 as Japanese Disclosure No. Sho 49 43645 to Mitsubishi Paper Mills, Ltd., discloses a two-color thermal paper. The disclosed thermal paper includes both color-forming systems in a single coating layer. The chromogenic components are fluoran compounds and the coreactant component is a phenolic compound. For any given two-color system the phenolic coreactant and both of the fluorans are dispersed in the single coated layer and the developed color of any thermal image depends entirely on the melt-ing point of the fluoran compounds. The colors are each generated by a fluoran and the mechanism of color formation is always fusion of the component materials.
Any material impurities or mutual solution of the fluoran melts tend to cause an overlap in component melting;
points and an interference of the generation of one color with development of the other.
~Z11~3 Japanese Disclosure No. Sho 50-6349 disclosed January 23, 1975 as Application No. Sho 48-53703 filed May 16, 1973 in the name oE Mitsubishi Paper Mills, Ltd., also discloses a two-color thermal paper. This disclosure attempts to solve the problem of overlapping color formation in two-color record sheets by incorporat-ing a decolorizing material in the coating composition.
Two chromogenic materials, a phenolic coreactant and a decolorizing agent (such as a guanidine) are homo-geniously dispersed in a polymeric binder material,all in a single layer. As the sheet is heated, both chromogenic materials form color to yield the initial color image. When the temperature is increased still more, the decolorizing agent melts and decolors only one of the chromogenic materials. To the extent that the effects of the decolori~ing agent overlap or the decolorizing agent interferes with both of the chromo-genic materials, the difficulty of a broad temperature range requirement for adequate color differentiation persists.
Japanese Disclosure No. Sho 49-96738 disclosed September 12, 1974 as Application No. Sho 48-7003 filed January 17, 1973 in the name of Mitsubishi Paper Mills, Ltd., also discloses a two-color thermal paper. This thermal paper also includes a single layer embodiment.
The single layer includes an acid-reacting chromogen, a base-reacting chromogen, an acid coreactnat, and a base coreactant, all homogeneously dispersed in a poly-meric binder material. Color development depends upon fusion of at least the coreactant materials. The pairs of selected coreactants have different melting points.
The first to melt colors the appropriate chromogen and the second to melt neutralizes the first coreactant, ~ 5 ~
decolors the first chromogen, and colors the second chromogen. All components of the disclosed sheet are present in the sheet in a reactive condition. There is no preliminary reaction or decomposition required to prevent premature coloration.
Summary of the Invention In the field of thermal-responsive recording materials, there is considerable demand for an acceptable product which will yield more than one color of prlnted l~ data. Several products have been offered, but most suffer from a problem of developed color overlap within a relatively broad temperature range. When each oE
two colors are developed in broad and overlapping tem-perature ranges, the actual image color is only rela-tively gradually changed as the temperature is changed.
It is an object oE this invention to provide a thermal-responsive recording material having more than one color for data representation. It is further an object of this invention to provide such a recording material having several relatively narrow temperature ranges in which images develop in different colors.
It is a specific object of this invention to provide a two-color thermal record material having color-forming systems effective at different temperatures wherein color formation at the higher temperature first requires decomposition of a component to generate a color reactant.
It is also an object of this invention to provide such a thermal record material having only a single coating layer including more than one color-forming system. It is also an object of this invention to provide a thermal record material having more than one color-forming system, at least one of which includes a component requiring decomposition prior to color genera~
tion, and each oE which is incl~lded in a s~parate coating layer.
It is yet another object of this invention to provide a multi-color thermally responsive record material comprising a support sheet bearing a first thermally-sensitive color-Eorming composition comprising particles of a chromogenic material and a coreactant material in contiguous relationship whereby the melting or sublimation of either material produces a first change in color by reaction between the two, and a secon~
thermally-sensitive color-forming composition comprising particles of a thermally decomposable material and a coreactant material in contiguous relationship, whereby decomposition of the thermally decomposable materia]
forms a chromogenic material which produces a dif~erent change in color by reaction with the coreactant material, said decomposition occurring at a higher temperature than said melting or sublimations.
The record material of this invention provides additional color development within a relatively narrow temperature range. To give a specific example of such record material having two colors: (i) a low temperature color-forming system is provided which relies solely upon melting or sibliming (vaporizing of solid particles) one or more of the components to achieve reactive, color-producing, contact and (ii) a higher temperature color-forming system is provided which ultimately relies uponmelting or vaporizing one or more of the components but which first must generate one of the reactive com-ponents by decomposition of a material in the color-forr.ing system. The low and h gher temperature color-forming systems are coated onto a substrate which, when heated, yields an image in the configuration of the area heated and of a color corresponding to the tempera-ture reached. In heating the coated substrate, the color of the low tempe~ature color-forming system ~ .
6a develops at the color advent temperature for that system.
As the temperature is increased further -- and this is most important to understanding of the present inven-tion -- no additional color is developed until the tem-perature is reached for decomposition oE that material in the high temperature color-Eorming system which must be decomposed to enter a color-forming reaction. When that decomposition temperature is reached, the second color is generated over the first color. As a rule, the first ~
~ 8 color has the appearance of a relatively pure hue such as red, blue~ green or the like and the second color has a more or less neutral hue resulting from combination of the hues Erom the Eirst and second color-forming systems. Generation of color in the higher temperature color-forming systems does not decolor or erase the first-developed color. The two colors are combined to provide the darkest images and the most effective use of color-forming materia]s.
The matter of the component decomposition is very important to this invention in permitting combin-ation of color-forming systems which develop individually at clearly-defined temperatures rather than together and gradually over a broad temperature range. Systems of the prior art which have relied on fusion (melting) or vaporization (incLuding sublimation of solid particles) of materials to generate colors generate a wide gradation of colors extending from the hue of the first, through all combinations of the first and the second, to the hue of the second. The melt formed by components of a first color-Eorming system tends to cause solution of components of a second color-forming system by lowering the component melting points. The sub-limation of one component of a first color-forming system causes particular problems when this component also reacts with a component of the second color-forming system. When, as in the present invention, a component decomposition is required before color reaction can occur, a melt or sublimation of one or more of the first system components has no effect.
The record material includes a substrate or support material which is generally in sheet form.
For purposes of describing this invention, sheets also mean webs, ribbons, tapes, belts, films, 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, trans~
parent or translucent and could, itself, be co]ored or not. The material can be Eibrous including, for example, paper and Eilamentous synthetic materials and it can be a Eilm including, for example, cellophane and synthetic polymeric sheets cast, extruded, or other-wise formed. The kernel of this invention resides in the combination of color-forming systems coating the sub-strate; and the kind or type of substrate material is not critical.
The components of the color-forming systems are in a conti~uous re]ationship, substantially homogene-ously ~istributed throughout the coated layer material deposited on the substrate. In manufacturing the record material, a coating composition is prepared which in-cludes a fine dispersion of the components of color-Eorming systems, polymeric binder material, and surface active, or other, additives in an aqueous coating medium.
The color-forming system components should be substan-tially water insoluble and ground to an individual average particle size of about 5 microns. The polymeric binder material should be substantially water soluble although latexes are also eligible in some instances.
Preferred water soluble binders include poly (vinyl alcohol), hydroxy ethylcellulose, methylcellulose, starch, modified starches, gelatin and the like. Eligible la~ex materials include polyacrylates, polyvinylacetates, polystyrene, and the like. The polymeric binder is used to protect the coated materials from brushing and handl-ing forces occasioned by storage and use of the thermal sheets. Binder should be present in an amount to afford ~ 5 ~
such protection and in an amount Less than will interfere with achieving reactive contact between color-Eorming reactive materials. An effective sheet is made with about ] to about 30 weight percent binder in the dried coating composition. The binder is preferably present as 5 to 30 weight percent of the dried coating.
Examples of eligible additives are surEace active agents such as defoamers including sodium lauryl sulfonate, octanol, acetylenic glycols, silicones, fatty acid esters, and the like. Also, if desired or required for a particular purpose, waxes, clays, fillers, color-ants, obscurants, and the like can be added to the coat-ing composition in amo~mts which do not adversely afEect the thermal response.
Coating weights are not of critical importance although, in sheets of more than a single layer, care must be exercised to utilize coating amounts sufficient to yield two distinctive colors and, at the same time, moderate to permit proper heat transfer from one layer to the next. As a general rule, the amounts of color-forming systems in the coating layers should be approxi-mately commensurate -- the weight of one not more than about ten times the weight of another, for example.
Coating weights for such layers can effectively be about 1.5 to about 8 and preferably about 3 to about 6 grams per square meter. As a practical matter, the lower limit for coating each layer is the amount required to provide the desired color response. As a general rule, material in layers beneath the surface làyer must be present in increased amounts so as to overcome masking effects of the layers above.
Sheets having only a single layer of thermally sensitive coating are preferred over sheets having ]o more than one layer. The coating weight for such sheets is not of critical importance so long as the proper amou~ts oE each color-orming system are present to yield adequate color development andcl color dlfferentia-tion at the marking temperature levels.
Benefits of the invention are realized to the extent that some of each of more than one eligible color-forming system is combined into a single coatlng layer. If each color is developed at its proper develop-ing temperature, and the materials are present in anamount adequate to discern the color, when developed, then the sheet demonstrates the invention. Generally, the coating weight oE all color-forming systems in a single coated layer will be greater than about 2 and not in excess of about 8 grams per square meter. The weight ratio of the materials of one color-forming system to another color-Eorming system is preferably between about 1 and about 10 for sheets having a single coated layer. In addition, the weight ratio of chromogenic material to coreactant for any given color-forming system is about 1 to about 12, preferably about 1 to about 6.
The practical minimum amount of color-forming materials is controlled by image darkness requirements and the practical maximum amount is controlled by economic considerations and desired handling characteris-tics of the coated sheets.
Sheets coated with a single layer exhibit advantages over other sheets by providing a sharper and more distinct thermal image in the generally thinner-coated materials. In a sheet of a single coated layer,both of the color-forming systems are in the top layer ~Z~L58 and all oE the components are intimately combined.
Moreover, sheets of a sin~le coated layer exhibit marked economic advantage over sheets requiring more than one layer, simply in decreased manuEacturing costs and de-creased materials costs. The single layer coated sheet of this invention exhibits more desirable handling characteristics than sheets requiring more than one coated layer.
Of the two types of color-forming systems, one relies on fusion (melting) or sublimation (vaporiza-tion of solid particles) of one or more components and the other relies on decomposition of one component prior to color reaction. The fusion or sublimation system generally utilizes acidic materials, such as phenolic compounds, and basic chromogenic materials which react with acidic materials. ~uch basic compounds include materials with a lactone ring, for example, phthalides or fluorans. Examples of eligible acid material include the compounds listed in United States Patent No.
3,451,338 as phenolic reactive materials, particularly the monophenols and diphenols. The list is exemplary only and not intended to be exhaustive -- 4-t-butyl phenol, 4-phenyl phenol, 4-hydroxydiphenyl oxide, -naphthol, -naphthol, methyl-4-hydroxybenzoate, 4-hydroxyacetophenone, 4-t-octylcatechol, 2,2'-dihydroxy-diphenyl, 2,2'-methylene bis (4-chlorophenol), 2,2'-methylene bis (4-methyl-6-t-butylphenol), 4,4'-isopro-pylidenediphenol, 4,4'-isopropylidene bis (2-chloro-phenol), 4,4'-isopropylidene bis 12,6-dibromophenol), 4,4'-isopropylidene bis (2,6-dichlorophenol), 4,4'-isopropylidene bis (2-methylphenol), 4,4'-isopropylidene bis (2,6-dimethylphenol), 4,4'-isopropylidene bis (2-t-butylphenol), 4,4'-sec.-~utylidene bis (2-methylphenol), 4,4'-cyclohexylidene phenol, 4,4'-cyclohexylidene bis (2-methylphenol), 2,2'-thio bis (4,6-dichlorophenol), 4,4'-thiodiphenol, and the like. Althou~h not preferred, other acid compounds o~ other kinds and types are 5~3 eligibl~. Examples of such other compounds are phenolic novolak resins which are the product of reaction between, Eor example, formalclehyde and a phenol such as an alkyl-phenol, e.g., p-octylphenol, or other phenols such as p-phenylphenol, and the like; and acid mineral materials including colloidal silica, kaolin, bentonite, attapul-gite, halloysite, and the like. Some of the polymers and minerals do not melt but undergo color reaction on fusion of the chromogen.
The eligible basic chromogenic compounds, such as the phthalide and fluoran compounds, Eor use in the fusion color-forming system are well known color-forming compounds. Examples of the compounds include Crystal Violet ~actone (3,3-bis(4-dimethylaminophenyl)-6-dimethylamino phthalide (U.S. Patent No. Re 23,024);
phenyl-, indol-, pyrol-, 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-, sulfon amido-, aminobenzylidene-, halo-, anilino-sub-stituted fluorans (for example, in U.S. Patent Nos.
3,624,107; 3,627,787; 3,641,011; 3,642,828; 3,681,390).
Other specifically eligible chromogens, not limiting the invention in any way, are: 6'-diethylamino-1', 2'-benzofluoran; 3,3-bis(l-ethyl-2-methyl-3-yl) phthalide;
6'-diethylamino-2r-anilinofluoran; 6'-diethylamino-2'-benzylaminofluoran; 6'-diethylamino-2'-butoxyfluoran;
and 6'-diethylamino-2'-bromo-3'-methylfluoran.
The decomposition color-forming system is of two types - determined by the chromogenic or so-called color-forming material. One type of decomposing system ,~ ~
utilizes an organic substituted thioamide to generate hydrogen sulfide when heated to clecomposition tempera-ture. Examples o~ eligible thioamides, along with the temperature oE decomposition, are presented in the table, below.
Thioamide Decomposition Temp. (C) 1. thioazelamide 138-141
2. thioadipamide 187-lgO
3. diphenylthioacetamide 151-153
4. biphenylthioacetamide 170-174
5. p-chloro-phenylthloacetamide 126-129
6. benzoylthioacetamide 128-130
7. tetramethylenedithiopropionamide 119-121
8. phenoxythiopropionamide 91- 93 A general formula for eligible thioamides is given by R-CS-NH2 wherein R can be alkyl, aryl, aralkyl, alkyloxy, aryloxy, and the like.
The second type of decomposing system utilizes a reaction-blocked benzoindolinospiropyran -- so-called "dicondensed" benzoindolinospiropyran compounds. These dicondensed compounds split into individual moieties at relatively low temperatures and one of the moieties is a chromogenic material. Examples of eligible diconden-sed spiropyran compounds, along with the temperature of decomposition, are presented in the table, below:
5 ~
].4 Spiropyran Decomposition remp~ (C) l. 4'-(l",3",3"-trimethylindolenyl) 205-207 -6'-chloro-8'-ethoxy-1,3,3 -trimethyl-benzoindo:lino-spiropyran 2. 4'-(1",3",3"-trimethylindolenyl) 204-206 -6'-chloro-8'-methoxy-1,3,3 -trimethyl benzoindolino-spiropyran 3. 4'-(1",3",3"-trimethylindolenyl) 208-210 -8'-methoxy-1,3,3,trimethyl-benzoindolino-spiropyran 4. 4'-(1",3",3"-trimethylindolenyl~ 200-202 -8'-ethoxy-1,2,2 trimethyl benzoindolino-spiropyran As a general rule, the blocking moiety is an indolenyl radical joined to the 4' position of a basic benzo-indolino-spiropyran molecule having the structure (with additional substitution in at least the 8' position):
1 ~ R2 CH
R2 !~
wherein Rl is a lower aLky'L or phenyl group. Most com-monly, Rl is methyl, R2 can be hydrogen, alkyl, alkoxy, halogen ancl the like. Specific examples oE the bloclced dicondensed benzoindolinospiropyrans represented by this formula have the Eollowing substituents (Rl is methyl and R2 is hydrogen unless some other group is indicated by position number):
8'-methoxy 3'-ethoxy l-phenyl-8'-methoxy 5-chloro-8'-methoxy 6'-chloro-8'-methoxy 5,6'-chloro-8'-methoxy 4,7,8'-trimethoxy Additional examples of eligible benzoindolino-spiropyran compounds which can be blocked at the 4' position by an indolenyl radical are found in previously-cited U.S. Patent Nos. 3,293,055 and 3,451,338.
The preparation of dicondensed benzo-indolinospiropyran chromogens is taught in Techniques of Chemistry, Vol. III "Photochromism" Chapter III pages 254-257, Wiley-Interscience 1971.
The dicondensed spiropyran compounds, once decomposed, are the same as the spiropyran compounds of U.S. Patent Nos. 3,293,055 (metallic salts) and 3,451,338 (phenolic compounds) and react with the core-actants described therein to yield color. Moreover, the hydrogen sulfide generated from decomposition of the thioamide compounds also reacts with several of the coreactants of U.S. Patent No. 3,293,055. For purposes of describing metallic coreactants eligible for use in this invention cations and anions will first be considered individually. Anions will first be considered individually. Anions are important only insofar as they provide a desired melting point or cation 5~
availability to the compound, as a whole. Generally eligible anions are resinate, naphthenate, stearate, oleate, acetylacetonate, acetate, undecylenate, ricino-late, and the like.
The eligible cations are generally at least divalent and are responsible Eor forming the color pro-duct of the decomposing color-forming system. Generally eligible cations are nickel, iron, lead, mercury, copper, cobalt, manganese, zinc, alumin-lm, magnesium, calcium, strontium, and the like. For use with t.he thioamides, the first six cations listed above can be used, forming a dark colored sulfide.
The temperatures at which the colors are gener-ated, in practice of this invention, are important only in that all of the color-forming temperatures must be within some reasonable range of intended operation and the individual color-Eorming temperatures for systems in a given thermal sheet must exhibit some reasonable separation. A reasonable range of intended operation is taken to be from about 60 to about 200 degrees centi-grade. A reasonable separation of color~forming temperatures is any separation greater than about 20 to about 30 centigrade degrees. Of course, even if the separation were less, the benefit of the present invention would be enjoyed to the extent that the fusion or sublimation coloration can be caused to occur before the coloration brought about by decomposition. The fusion or sublimation color-forming system is selected so as to produce color at a temperature lower than the temperature at which the decomposing color-forming systems react. More than one decomposing system can be used providing only that the individual systems do not interfere with each other or produce the same color.
Description oE _referred Embodiments In the following comparative example and the numbered examples illustrating the present invention all parts are parts by weight, all temperatures and degrees are centigrade, and all measurements are in the metric system, unless otherwise stated.
5E~
Comparative Example This example demonstrates overlap and inter-ference in the clevelopment of two color-forming systems when each system colors by means of fusion alone.
In this comparative example and in all follow-ing examples illustrating the present invention a disper-sion of a particular system component is prepared by milling the component in an aqueous solution of the binder until a predetermined particle size is achieved.
For convenience the binder material will always be poly (vinyl alcohol) of a film forming, water soluble, grade.
Use of poly (vinyl alcohol) in these examples must not be taken to mean that others of the disclosed binders are not eligible. The milling is accomplished in a ball mill or using an attritor and the desired partic]e size will be taken as about three microns unless other-wise specified. OE course, in the case of a liquid system component the milling is conducted in a high speed blender.
The proportions of the coating compositions are as follows:
~laterial }'a;rl_~
color system component 10-30 binder material 1- 5 surface active material 0- 0.1 water 65-89 In accordance with the description, individual coating composition dispersions are prepared with:
(1) 2'-methoxy-6'-diethylaminofluoran; (ii) 2'-anilino-6'-diethylaminofluoran; and (iii) 4,4'-isopropylidenedi-phenol.
Four parts of (iii) are mixed with one part of (i) and coated onto a paper sheet at a weight of about 5 grams per square meter (dry). This coating, when dried and heated to about 100 degrees yields a red color.
1~
Four parts of (iii) are mixed with one part of (ii) and coated onto a paper at about 5 grams per square meter (dry). This coating, when dried~ yieLds no color below about 110 degrees and turns green at about 120 degrees and above.
The two coating compositions made above are coated onto a single sheet in t~,~o layers. Additional samples are then combined and coated onto another sheet as a single layer. The two layer sheet turns blackish-red at about 100 degrees and the blackish-red color gradually clarkens to black as the temperature is raised to about 120 degrees. The single layer sheet turns black at about 100 degrees. In tl~e case of the singLe layer black development at low temperature, both chromo-genic materials colored together because the low tempera-ture melt oE one chromogenic material serves as a cosolvent for the other.
When the two coating compositions are coated onto a sheet as individual layers separated by a clear coating of insulating polymeric material, a red color develops at about 100 degrees and remains fairly pure in hue until the temperature is above about 110 degrees.
The combination of red and green produces a black color above about 120 degrees. The insulating third layer in such a coated sheet provides the desirable, sharp-color-charge character of the present invention but - requires a cumbersome and exp,ensive three layer construc-tion compared to the one or two layers herein.
The following Examples illustrate two-color thermally responsive record material systems of this invention:
Example I
Coating composition dispersions are prepared as follows:
A Crystal violet lactone 17 parts Binder 3 water 80 5 ~
B 4,4'-isopropylidenediphenol 22.5 parts binder ~.S
water 75 C thioadipamide ?2.5 parts binder .5 water 75 D nickel acetonylacetonate 22.5 parts binder ~,.5 water 75 E nickel naphthenate 27 parts binder 3 water 70 The dispersions are mixed as follows:
A 16 parts Il 2i5 } S i ~nd sheets are coated with the mi~ture at a weight of about 4.5 to 6.0 grams per square meter (dry) and dried.
It is recognized that the reactive components of A and B form one color and the components of D and ~ react with hydrogen sulfide from C to form another color.
The sheet, heated to about 120 degrees, exhibits a bright blue color. The bright blue remains pure to about 140 degrees and the color abruptly changes to black at about 149 degrees.
When the crystal violet lactone in A is replaced by 6'-diethylamino-1',2'-benzofluoran or 3,3-bis (1-ethyl-2-methyl-3-yl) phthalide (indolyl red), the color developed at 120 degrees is red.
When the crystal violet lactone in A is replaced by 6'-cliethylamino-2'-benzylamino Eluoran, the color developed at 120 degrees is green.
Sepflrate coatecl layers of A and B and of C, D and E also produce a thermal sheet having the desired color developing response.
Example_II
Coating composition dispersions are preparecl as follows:
A 2'-butoxy-6'-diethylamino fluoran17 parts binder 3 water 80 B 4'-l1",3",3"-trimethyl-indolenyl)-6'-chloro-8'-ethoxy-1,3,3-trimethyl benzoindolinospiropyran17 parts binder 3 water 80 C 4,4'-isopropylidene diphenol17 parts binder 3 water 80 The dispersions are mixed as follows:
A 10 parts and sheets are coated as in the previous example. Both the chromogenic material of A, and the spiropyran result-ing from decomposition of the component in B, react with the phenolic component of C. The sheet, heated to about 110 degrees, exhibits red color. The red remains fairly pure to about 140 degrees and turns brownish-black at about 150 degrees.
Example III
Coating composition dispe-rsions are prepared as ~oLlows:
A 4'-(1",3",3"-trimethyl-indolenyl)-6'-chloro-8'~methoxy-1,3,3,-trimethyl benzoindolinospiropyran 13 parts 2'-bromo-3'-methyl-6'-diethylamino-fl~loran 2 3,3-bis(l-ethyl-2-methyl-3-yl)phthalide 2 binder 3 water ~
B 4,4'-isopropylidene diphenol 9 parts ACRAWAX-C~ 8 binder 3 water ~0 ~Reaction product of hydrogenated caster oil and ethanolamine insoluble in boiling water, melting point of 140 to 143 degrees, flash point of .235 degrees (open cup), specific gravity of 0.97 at 25 degrees, available - as fine powder from Glycol Chemicals, Inc., N.Y., N.Y.
The dispersions are mixed as follows:
A 45 parts B 102 parts and sheets are coated as in the previous examples.
Both the fluoran and the phthalide of dispersion A and the spiropyran resulting from the decomposition of the indolenyl-blocked spiropyran of dispersion A react with the diphenol of dispersion B. The sheet, heated to 110 degrees exhibits red color, remains fairly pure to about 140 degrees and turns black above about 150 degrees.
.~ , While particular embodiments of the present invention have been described, many other possible varia-tions and modif:ications within the spirit and scope of the invention are intended to be included within the scope of the appencled claims.
The second type of decomposing system utilizes a reaction-blocked benzoindolinospiropyran -- so-called "dicondensed" benzoindolinospiropyran compounds. These dicondensed compounds split into individual moieties at relatively low temperatures and one of the moieties is a chromogenic material. Examples of eligible diconden-sed spiropyran compounds, along with the temperature of decomposition, are presented in the table, below:
5 ~
].4 Spiropyran Decomposition remp~ (C) l. 4'-(l",3",3"-trimethylindolenyl) 205-207 -6'-chloro-8'-ethoxy-1,3,3 -trimethyl-benzoindo:lino-spiropyran 2. 4'-(1",3",3"-trimethylindolenyl) 204-206 -6'-chloro-8'-methoxy-1,3,3 -trimethyl benzoindolino-spiropyran 3. 4'-(1",3",3"-trimethylindolenyl) 208-210 -8'-methoxy-1,3,3,trimethyl-benzoindolino-spiropyran 4. 4'-(1",3",3"-trimethylindolenyl~ 200-202 -8'-ethoxy-1,2,2 trimethyl benzoindolino-spiropyran As a general rule, the blocking moiety is an indolenyl radical joined to the 4' position of a basic benzo-indolino-spiropyran molecule having the structure (with additional substitution in at least the 8' position):
1 ~ R2 CH
R2 !~
wherein Rl is a lower aLky'L or phenyl group. Most com-monly, Rl is methyl, R2 can be hydrogen, alkyl, alkoxy, halogen ancl the like. Specific examples oE the bloclced dicondensed benzoindolinospiropyrans represented by this formula have the Eollowing substituents (Rl is methyl and R2 is hydrogen unless some other group is indicated by position number):
8'-methoxy 3'-ethoxy l-phenyl-8'-methoxy 5-chloro-8'-methoxy 6'-chloro-8'-methoxy 5,6'-chloro-8'-methoxy 4,7,8'-trimethoxy Additional examples of eligible benzoindolino-spiropyran compounds which can be blocked at the 4' position by an indolenyl radical are found in previously-cited U.S. Patent Nos. 3,293,055 and 3,451,338.
The preparation of dicondensed benzo-indolinospiropyran chromogens is taught in Techniques of Chemistry, Vol. III "Photochromism" Chapter III pages 254-257, Wiley-Interscience 1971.
The dicondensed spiropyran compounds, once decomposed, are the same as the spiropyran compounds of U.S. Patent Nos. 3,293,055 (metallic salts) and 3,451,338 (phenolic compounds) and react with the core-actants described therein to yield color. Moreover, the hydrogen sulfide generated from decomposition of the thioamide compounds also reacts with several of the coreactants of U.S. Patent No. 3,293,055. For purposes of describing metallic coreactants eligible for use in this invention cations and anions will first be considered individually. Anions will first be considered individually. Anions are important only insofar as they provide a desired melting point or cation 5~
availability to the compound, as a whole. Generally eligible anions are resinate, naphthenate, stearate, oleate, acetylacetonate, acetate, undecylenate, ricino-late, and the like.
The eligible cations are generally at least divalent and are responsible Eor forming the color pro-duct of the decomposing color-forming system. Generally eligible cations are nickel, iron, lead, mercury, copper, cobalt, manganese, zinc, alumin-lm, magnesium, calcium, strontium, and the like. For use with t.he thioamides, the first six cations listed above can be used, forming a dark colored sulfide.
The temperatures at which the colors are gener-ated, in practice of this invention, are important only in that all of the color-forming temperatures must be within some reasonable range of intended operation and the individual color-Eorming temperatures for systems in a given thermal sheet must exhibit some reasonable separation. A reasonable range of intended operation is taken to be from about 60 to about 200 degrees centi-grade. A reasonable separation of color~forming temperatures is any separation greater than about 20 to about 30 centigrade degrees. Of course, even if the separation were less, the benefit of the present invention would be enjoyed to the extent that the fusion or sublimation coloration can be caused to occur before the coloration brought about by decomposition. The fusion or sublimation color-forming system is selected so as to produce color at a temperature lower than the temperature at which the decomposing color-forming systems react. More than one decomposing system can be used providing only that the individual systems do not interfere with each other or produce the same color.
Description oE _referred Embodiments In the following comparative example and the numbered examples illustrating the present invention all parts are parts by weight, all temperatures and degrees are centigrade, and all measurements are in the metric system, unless otherwise stated.
5E~
Comparative Example This example demonstrates overlap and inter-ference in the clevelopment of two color-forming systems when each system colors by means of fusion alone.
In this comparative example and in all follow-ing examples illustrating the present invention a disper-sion of a particular system component is prepared by milling the component in an aqueous solution of the binder until a predetermined particle size is achieved.
For convenience the binder material will always be poly (vinyl alcohol) of a film forming, water soluble, grade.
Use of poly (vinyl alcohol) in these examples must not be taken to mean that others of the disclosed binders are not eligible. The milling is accomplished in a ball mill or using an attritor and the desired partic]e size will be taken as about three microns unless other-wise specified. OE course, in the case of a liquid system component the milling is conducted in a high speed blender.
The proportions of the coating compositions are as follows:
~laterial }'a;rl_~
color system component 10-30 binder material 1- 5 surface active material 0- 0.1 water 65-89 In accordance with the description, individual coating composition dispersions are prepared with:
(1) 2'-methoxy-6'-diethylaminofluoran; (ii) 2'-anilino-6'-diethylaminofluoran; and (iii) 4,4'-isopropylidenedi-phenol.
Four parts of (iii) are mixed with one part of (i) and coated onto a paper sheet at a weight of about 5 grams per square meter (dry). This coating, when dried and heated to about 100 degrees yields a red color.
1~
Four parts of (iii) are mixed with one part of (ii) and coated onto a paper at about 5 grams per square meter (dry). This coating, when dried~ yieLds no color below about 110 degrees and turns green at about 120 degrees and above.
The two coating compositions made above are coated onto a single sheet in t~,~o layers. Additional samples are then combined and coated onto another sheet as a single layer. The two layer sheet turns blackish-red at about 100 degrees and the blackish-red color gradually clarkens to black as the temperature is raised to about 120 degrees. The single layer sheet turns black at about 100 degrees. In tl~e case of the singLe layer black development at low temperature, both chromo-genic materials colored together because the low tempera-ture melt oE one chromogenic material serves as a cosolvent for the other.
When the two coating compositions are coated onto a sheet as individual layers separated by a clear coating of insulating polymeric material, a red color develops at about 100 degrees and remains fairly pure in hue until the temperature is above about 110 degrees.
The combination of red and green produces a black color above about 120 degrees. The insulating third layer in such a coated sheet provides the desirable, sharp-color-charge character of the present invention but - requires a cumbersome and exp,ensive three layer construc-tion compared to the one or two layers herein.
The following Examples illustrate two-color thermally responsive record material systems of this invention:
Example I
Coating composition dispersions are prepared as follows:
A Crystal violet lactone 17 parts Binder 3 water 80 5 ~
B 4,4'-isopropylidenediphenol 22.5 parts binder ~.S
water 75 C thioadipamide ?2.5 parts binder .5 water 75 D nickel acetonylacetonate 22.5 parts binder ~,.5 water 75 E nickel naphthenate 27 parts binder 3 water 70 The dispersions are mixed as follows:
A 16 parts Il 2i5 } S i ~nd sheets are coated with the mi~ture at a weight of about 4.5 to 6.0 grams per square meter (dry) and dried.
It is recognized that the reactive components of A and B form one color and the components of D and ~ react with hydrogen sulfide from C to form another color.
The sheet, heated to about 120 degrees, exhibits a bright blue color. The bright blue remains pure to about 140 degrees and the color abruptly changes to black at about 149 degrees.
When the crystal violet lactone in A is replaced by 6'-diethylamino-1',2'-benzofluoran or 3,3-bis (1-ethyl-2-methyl-3-yl) phthalide (indolyl red), the color developed at 120 degrees is red.
When the crystal violet lactone in A is replaced by 6'-cliethylamino-2'-benzylamino Eluoran, the color developed at 120 degrees is green.
Sepflrate coatecl layers of A and B and of C, D and E also produce a thermal sheet having the desired color developing response.
Example_II
Coating composition dispersions are preparecl as follows:
A 2'-butoxy-6'-diethylamino fluoran17 parts binder 3 water 80 B 4'-l1",3",3"-trimethyl-indolenyl)-6'-chloro-8'-ethoxy-1,3,3-trimethyl benzoindolinospiropyran17 parts binder 3 water 80 C 4,4'-isopropylidene diphenol17 parts binder 3 water 80 The dispersions are mixed as follows:
A 10 parts and sheets are coated as in the previous example. Both the chromogenic material of A, and the spiropyran result-ing from decomposition of the component in B, react with the phenolic component of C. The sheet, heated to about 110 degrees, exhibits red color. The red remains fairly pure to about 140 degrees and turns brownish-black at about 150 degrees.
Example III
Coating composition dispe-rsions are prepared as ~oLlows:
A 4'-(1",3",3"-trimethyl-indolenyl)-6'-chloro-8'~methoxy-1,3,3,-trimethyl benzoindolinospiropyran 13 parts 2'-bromo-3'-methyl-6'-diethylamino-fl~loran 2 3,3-bis(l-ethyl-2-methyl-3-yl)phthalide 2 binder 3 water ~
B 4,4'-isopropylidene diphenol 9 parts ACRAWAX-C~ 8 binder 3 water ~0 ~Reaction product of hydrogenated caster oil and ethanolamine insoluble in boiling water, melting point of 140 to 143 degrees, flash point of .235 degrees (open cup), specific gravity of 0.97 at 25 degrees, available - as fine powder from Glycol Chemicals, Inc., N.Y., N.Y.
The dispersions are mixed as follows:
A 45 parts B 102 parts and sheets are coated as in the previous examples.
Both the fluoran and the phthalide of dispersion A and the spiropyran resulting from the decomposition of the indolenyl-blocked spiropyran of dispersion A react with the diphenol of dispersion B. The sheet, heated to 110 degrees exhibits red color, remains fairly pure to about 140 degrees and turns black above about 150 degrees.
.~ , While particular embodiments of the present invention have been described, many other possible varia-tions and modif:ications within the spirit and scope of the invention are intended to be included within the scope of the appencled claims.
Claims (15)
1. A multi-color thermally responsive record material com-prising A support sheet bearing a first thermally-sensitive color-forming composition comprising particles of a chromogenic material and a coreact-tant material in contiguous relationship whereby the melting or sublima-tion of either material produces a first change in color by reaction be-tween the two, and a second thermally-sensitive color-forming composition comprising particles of a thermally de-composable material and a coreact-tant material in contiguous relationship, whereby decomposition of the thermally decomposable material forms a chromogenic material which pro-duces a different change in color by reaction with the coreactant mate-rial, said decomposition occurring at a higher temperature than said melt-ing or sublimations.
2. The record material of claim 1 in which the first and second compositions are in separate contiguous superposed layers on the support sheet.
3. The record material of claim 1 in which a binder and the first and second compositions form a single layer on the support sheet.
4. The record material of claim 3 in which the chromogenic material of the first composition is selected from a lactone and a flou-ran and the coreactant of the first composition is a phenolic compound.
5. The record material of claim 4 in which the thermally de-composable material is selected from the group consisting of organic sub-stituted thioamides and dicondensed benzoindolinospiropyrans.
6. The record material of claim 5 in which the thermally de-composable material is a thioamide of the general formula in which R is selected from alkyl, aryl, aralkyl alkyloxy and aryloxy and the coreactant is a divalent metal compound in which the metal is selected from nickel, iron, lead mercury, copper and cobalt.
7. The record materlal of claim 5 in which the thermally de-composable material is a reaction-blocked benzoindolinospiropyran and the coreactant is selected from phenolic compounds and divalent metal compounds.
8. The record material of claim 7 in which the benzoindolino-spiropyran is substituted in the 4'position with an indolenyl radical and in the 8' position with an alkoxy radical.
9. The record material of claim 8 in which the coreactant is a phenollc compound.
10. The record material of claim 9 in which the phenolic com-pound is selected from monophenols and diphenols.
11. The record material of claim 1 in which the first composi-tion comprises 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 2'-bromo-3'-methyl-6'-diethylaminofluoran and 4,4'-isopropyl-indenediphenol; and the second composition comprises 4'-(1",3",3"-trimethyl-indoLenyl)-6'-chloro-8'-alkoxy-1,3,3-trimethyl benzoindolinospiropyran in which the alkoxy is selected from methoxy and ethoxy, and 4,4'-isopropylindenediphenol.
12. The record material o claim 11 in which the alkoxy is ethoxy.
13. The record material of claim 1 in which the first composi-tion comprises 2'-butoxy-6'-diethylaminofluoran and 4,4'-isopropylidenedi-phenol; and the second composition comprises 4'-(1",3",3"-trimethyl-indo-lenyl)-6'-chloro-8'-ethoxy-1,3,3-trirnethyl benzoindolinospiropyran and 4,4'-isopropylidenediphenol.
14. The record material of claim 1 in which the first composi-tion comprises 3,3-bis(l-ethyl-2-methylindol-3-yl)phthalide and 4,4'-thio-diphenol; and the second composition comprises 4'-(1",3",3"-trirnethyl-indolenyl)-6'-chloro-8'-methoxy-1,3,3-trimethyl benzoindolinospiropyran and 4,4'-thiodiphenol.
15. The record material of claim 1 in which the first compo-sition comprises 3,3-bis(4-dimethylaminophenyl)-6-dimethylamino phthalide and 4,4'-isopropylindenediphenol and the second composition comprises thioadipamide and nickel acetonylacetonate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/861,046 US4151748A (en) | 1977-12-15 | 1977-12-15 | Two color thermally sensitive record material system |
| US861,046 | 1977-12-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1121158A true CA1121158A (en) | 1982-04-06 |
Family
ID=25334724
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000317723A Expired CA1121158A (en) | 1977-12-15 | 1978-12-11 | Two color thermally sensitive record material system |
Country Status (20)
| Country | Link |
|---|---|
| US (1) | US4151748A (en) |
| JP (1) | JPS5822357B2 (en) |
| AT (1) | AT373827B (en) |
| AU (1) | AU512720B2 (en) |
| BE (1) | BE872635A (en) |
| BR (1) | BR7808195A (en) |
| CA (1) | CA1121158A (en) |
| CH (1) | CH628574A5 (en) |
| DE (1) | DE2853120C2 (en) |
| DK (1) | DK561678A (en) |
| ES (1) | ES476050A1 (en) |
| FI (1) | FI65190C (en) |
| FR (1) | FR2415009B1 (en) |
| GB (2) | GB2011105B (en) |
| HK (2) | HK74484A (en) |
| IE (1) | IE47515B1 (en) |
| LU (1) | LU80650A1 (en) |
| NL (1) | NL170827C (en) |
| SE (1) | SE443535B (en) |
| ZA (1) | ZA786661B (en) |
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| US4339207A (en) * | 1978-09-28 | 1982-07-13 | Akzona Incorporated | Temperature indicating compositions of matter |
| US4362645A (en) * | 1978-09-28 | 1982-12-07 | Akzona, Inc. | Temperature indicating compositions of matter |
| JPS5581194A (en) * | 1978-12-14 | 1980-06-18 | Ricoh Co Ltd | Polychromic heat sensitive recording material |
| US4363664A (en) * | 1980-01-25 | 1982-12-14 | Sterling Drug Inc. | Novel compositions and processes |
| US4424990A (en) | 1980-01-30 | 1984-01-10 | Raychem Corporation | Thermochromic compositions |
| JPS5736694A (en) * | 1980-08-15 | 1982-02-27 | Mitsui Toatsu Chem Inc | Heat-sensitive recording material |
| JPS5738187A (en) * | 1980-08-19 | 1982-03-02 | Mitsui Toatsu Chem Inc | Heat-sensitive recording material |
| JPS5739987A (en) * | 1980-08-25 | 1982-03-05 | Mitsui Toatsu Chem Inc | Heat-sensitive recording material |
| JPS5741996A (en) * | 1980-08-27 | 1982-03-09 | Mitsui Toatsu Chem Inc | Heat-sensitive recording medium |
| US4450023A (en) * | 1981-06-12 | 1984-05-22 | N.V. Raychem S.A. | Thermochromic composition |
| GB2116735B (en) * | 1982-02-27 | 1986-11-26 | Arthur R Zingher | Optically annotatable recording film |
| US4533640A (en) * | 1984-02-21 | 1985-08-06 | Shafer Jules A | Accumulated thermal exposure responder and method of use |
| US4711815A (en) * | 1985-03-07 | 1987-12-08 | Matsushita Electric Industrial Co., Ltd. | Recording medium |
| JP2566628B2 (en) * | 1988-08-24 | 1996-12-25 | 保土谷化学工業株式会社 | Fluorane compound and recording material |
| JPH0647464B2 (en) * | 1990-03-20 | 1994-06-22 | 工業技術院長 | Temperature indicating material and manufacturing method thereof |
| GB9116626D0 (en) * | 1991-08-01 | 1991-09-18 | Univ Strathclyde | Improvements in and relating to ropes |
| US5290704A (en) * | 1993-03-19 | 1994-03-01 | Valence Technology, Inc. | Method of detecting organic solvent vapors |
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| BR112020019124A2 (en) | 2018-03-23 | 2021-01-12 | Appvion Operations, Inc. | DIRECT THERMAL RECORDING MEDIA BASED ON SELECTIVE STATE CHANGE |
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| EP4021734A1 (en) | 2019-09-25 | 2022-07-06 | Appvion, LLC | Direct thermal recording media with perforated particles |
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| US1924793A (en) * | 1927-06-30 | 1933-08-29 | Laske Frans | Paint for indicating heat |
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| US3121650A (en) * | 1960-07-28 | 1964-02-18 | Minnesota Mining & Mfg | Right-reading reproduction of printed originals |
| US3471422A (en) * | 1961-05-22 | 1969-10-07 | Tempil Corp | Time-temperature responsive color changing typographic printing ink composition |
| FR1373659A (en) * | 1961-10-05 | 1964-10-02 | Ncr Co | Thermally colored reproduction sheet |
| BE623057A (en) * | 1961-10-05 | |||
| GB1051616A (en) * | 1962-11-19 | |||
| DE1251348B (en) * | 1964-05-11 | |||
| FR1440892A (en) * | 1964-05-11 | 1966-06-03 | Ncr Co | Recording material |
| JPS4833206B1 (en) * | 1970-04-28 | 1973-10-12 | ||
| GB1337757A (en) * | 1970-10-19 | 1973-11-21 | Columbia Ribbon Carbon Mfg | Thermographic copy sheets |
| JPS507216Y2 (en) * | 1971-03-18 | 1975-03-03 | ||
| DE2228581C3 (en) * | 1971-06-14 | 1974-05-30 | Matsushita Electric Industrial Co. Ltd., Kadoma, Osaka (Japan) | Two-color heat-sensitive recording material |
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| CA987103A (en) * | 1972-02-17 | 1976-04-13 | Kinichi Adachi | Dichromatic thermo-sensitive paper |
| JPS4969A (en) * | 1972-04-13 | 1974-01-05 | ||
| GB1432771A (en) * | 1972-06-26 | 1976-04-22 | Agfa Gevaert | Recording method |
| JPS4946659B2 (en) * | 1972-07-10 | 1974-12-11 | ||
| JPS4937917A (en) * | 1972-08-10 | 1974-04-09 | ||
| FR2211673B1 (en) * | 1972-12-22 | 1976-04-23 | Robillard Jean | |
| CH578432A5 (en) * | 1973-03-05 | 1976-08-13 | Ciba Geigy Ag | |
| JPS49122345A (en) * | 1973-03-23 | 1974-11-22 | ||
| US4010033A (en) * | 1973-08-03 | 1977-03-01 | Agence Nationale De Valorisation De La Recherche (Anvar) | Photosensitive layer and method of forming a photographic image therefrom |
| US4020232A (en) * | 1974-05-17 | 1977-04-26 | Mitsubishi Paper Mills, Ltd. | Heat-sensitive recording sheets |
| FR2271938A1 (en) * | 1974-05-24 | 1975-12-19 | Issec | Thermochromic compsns. for thermographic recording - giving variety of colours with phenolic cpds. and chelating cpds. |
| JPS5223806B2 (en) * | 1974-05-30 | 1977-06-27 | ||
| JPS515792A (en) * | 1974-07-05 | 1976-01-17 | Mitsubishi Heavy Ind Ltd | MEKANIKARUDORAIBUSHIKI HANSOSOCHI |
| JPS5211231A (en) * | 1975-07-16 | 1977-01-28 | Matsushita Electric Ind Co Ltd | Thermoplastic resin composition |
| GB1563175A (en) * | 1977-03-04 | 1980-03-19 | Lawton W | Heat-sensitive recording composition with mixed colour precursors |
-
1977
- 1977-12-15 US US05/861,046 patent/US4151748A/en not_active Expired - Lifetime
-
1978
- 1978-11-23 IE IE2316/78A patent/IE47515B1/en unknown
- 1978-11-27 ZA ZA00786661A patent/ZA786661B/en unknown
- 1978-12-01 GB GB7846938A patent/GB2011105B/en not_active Expired
- 1978-12-01 GB GB8041273A patent/GB2064153B/en not_active Expired
- 1978-12-05 FI FI783739A patent/FI65190C/en not_active IP Right Cessation
- 1978-12-06 SE SE7812551A patent/SE443535B/en unknown
- 1978-12-07 AU AU42280/78A patent/AU512720B2/en not_active Expired
- 1978-12-08 BE BE192221A patent/BE872635A/en not_active IP Right Cessation
- 1978-12-08 DE DE2853120A patent/DE2853120C2/en not_active Expired
- 1978-12-11 JP JP53152133A patent/JPS5822357B2/en not_active Expired
- 1978-12-11 CA CA000317723A patent/CA1121158A/en not_active Expired
- 1978-12-12 AT AT0884278A patent/AT373827B/en not_active IP Right Cessation
- 1978-12-13 CH CH1267678A patent/CH628574A5/en not_active IP Right Cessation
- 1978-12-13 LU LU80650A patent/LU80650A1/en unknown
- 1978-12-14 FR FR7835233A patent/FR2415009B1/en not_active Expired
- 1978-12-14 NL NLAANVRAGE7812167,A patent/NL170827C/en not_active IP Right Cessation
- 1978-12-14 DK DK561678A patent/DK561678A/en not_active Application Discontinuation
- 1978-12-14 BR BR7808195A patent/BR7808195A/en unknown
- 1978-12-15 ES ES476050A patent/ES476050A1/en not_active Expired
-
1984
- 1984-09-27 HK HK744/84A patent/HK74484A/en unknown
- 1984-09-27 HK HK736/84A patent/HK73684A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| IE782316L (en) | 1979-06-15 |
| BE872635A (en) | 1979-03-30 |
| AT373827B (en) | 1984-02-27 |
| GB2064153B (en) | 1983-01-12 |
| NL7812167A (en) | 1979-06-19 |
| SE7812551L (en) | 1979-06-16 |
| FI65190C (en) | 1984-04-10 |
| GB2064153A (en) | 1981-06-10 |
| FI65190B (en) | 1983-12-30 |
| LU80650A1 (en) | 1979-04-13 |
| FI783739A (en) | 1979-06-16 |
| JPS5822357B2 (en) | 1983-05-09 |
| DE2853120A1 (en) | 1979-06-21 |
| ATA884278A (en) | 1983-07-15 |
| SE443535B (en) | 1986-03-03 |
| FR2415009A1 (en) | 1979-08-17 |
| NL170827C (en) | 1983-01-03 |
| HK73684A (en) | 1984-10-05 |
| NL170827B (en) | 1982-08-02 |
| GB2011105B (en) | 1982-05-26 |
| AU512720B2 (en) | 1980-10-23 |
| JPS5492264A (en) | 1979-07-21 |
| ES476050A1 (en) | 1979-06-16 |
| FR2415009B1 (en) | 1985-11-22 |
| DK561678A (en) | 1979-06-16 |
| DE2853120C2 (en) | 1983-06-09 |
| ZA786661B (en) | 1979-10-31 |
| GB2011105A (en) | 1979-07-04 |
| AU4228078A (en) | 1979-06-21 |
| US4151748A (en) | 1979-05-01 |
| HK74484A (en) | 1984-10-05 |
| BR7808195A (en) | 1979-07-31 |
| IE47515B1 (en) | 1984-04-04 |
| CH628574A5 (en) | 1982-03-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |