USRE32466E - Heat-sensitive color-forming recording material and process for preparation thereof - Google Patents
Heat-sensitive color-forming recording material and process for preparation thereof Download PDFInfo
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- USRE32466E USRE32466E US06/880,431 US88043186A USRE32466E US RE32466 E USRE32466 E US RE32466E US 88043186 A US88043186 A US 88043186A US RE32466 E USRE32466 E US RE32466E
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- color developer
- leuco
- leuco pigment
- pigment
- solid
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- 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
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/913—Material designed to be responsive to temperature, light, moisture
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
Definitions
- the present invention relates to a heat-sensitive color-forming recording material. More particularly, the present invention relates to a heat-sensitive recording material which is sensitized without substantial increase of the fog density.
- a leuco pigment and a color developer composed of an acidic substance has been widely used for recording of informations, for example, heat-sensitive recording, pressure-sensitive recording and electrostatic photographic recording.
- a recording element for heat-sensitive recording there has been used a recording material comprising a recording layer formed on a substrate, said recording layer being obtained by dispersing a leuco pigment which is colorless or has a light color in the normal state and a phenol which is solid at normal temperature but is heat-fusible, in a polymeric binder independently in separate phases.
- this heat-sensitive recording material color formation is effected when the leuco pigment and phenolic color developer are reacted with each other in the state activated by heat, especially in the fused state. Since fusion of the phenolic color developer or leuco pigment is not caused unless the temperature is considerably high, the heat sensitivity of the recording material is low and the density of a recorded image is generally low. Furthermore, since recording must be carried out at a high temperature, this recording material is disadvantageous in that a high temperature heat source is necessary. Moreover, the temperature of a transportation system in a heat-sensitive recording apparatus is elevated, and therefore, fogging is readily caused to occur.
- a heat-sensitive color-forming recording material which comprises a recording layer comprising a particulate phenolic color developer and a particulate leuco pigment, which are dispersed in a binder independently from each other, wherein the phenolic color developer and/or leuco pigment is present in the form of compatible solid particles with a substantially inactive organic solid medium having a melting or softening point lower than that of the phenolic color developer and/or leuco pigment and said organic solid medium is present in said compatible solid particles in an amount 2 to 250 times as large as the amount of the phenolic color developer and/or leuco pigment on the weight base.
- FIG. 1 is a graph showing the relation between the heating temperature and the reflection density in heat-sensitive recording materials according to the present invention.
- the phenolic color developer that is used in the present invention is solid at normal temperature and is heat-fusible and it is a prototropic phenol in the fuse state.
- the phenolic color developer there can be mentioned 4,4'-isopropylidene diphenol (bisphenol A), 4,4'-methylene-bis(phenol), 4,4'-isopropylidene-bis(2-chlorophenol), 4,4'-isopropylidene-bis(2,6-dichlorophenol), 4,4'-isopropylidene-bis(2-methylphenol), 4,4'-isopropylidene-bis(2-tert-butylphenol), 4,4'-sec-isobutylidene-bis(2-methylphenol), 4,4'-cyclohexylidene-diphenol, 2,2'-thiobis(4,6-dichlorophenol), p-tert-butylphenol, 3,4-dichlorodiphenol, o,o'-diphenol, 4-hydroxy
- leuco pigments customarily used for heat-sensitive recording materials of this type can be used in the present invention.
- triphenylmethane leuco pigments, fluoran type leuco pigments, spirooyran type leuco pigments, rhodamine lactam type pigments, auramine type leuco pigments and phenothiazine type leuco pigments may be used singly or in combination.
- Preferred examples are as follows.
- 3,3-Bis(p-dimethylaminophenyl)phthalide 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3,3-bis(p-dimethylaminophenyl)-6-diethylaminophthalide, 3,3-bis(p-dimethylaminophenyl)-6-diethylaminophthalide, 3,3-bis(p-dimethylaminophenyl)-6-methoxyphthalide, 4-hydroxy-4'-dimethyl-aminotriphenylmethane-lactone, and 4,4'-bishydroxy-3,3'-bis-diaminotriphenylmethane-lactone.
- 8'-Methoxybenzoindolinospiropyran 3-phenyl-8'-methoxybenzoindolinospiropyran, 6'-chloro-8'-methoxybenzoindolinospiropyran, 5,6'-dichloro-8'-methoxybenzoindolinospiropyran, 4,7,8'-trimethoxybenzoindolinospiropyran, benzo- ⁇ -naphthospiropyran, 3-methyl-di- ⁇ -naphthospiropyran and 1,3,3-trimethyl-6'-chloro-8'-methoxyindolinobenzospiropyran.
- the above-mentioned phenolic color developer and/or leuco pigment is combined with a specific organic solid medium which has a melting or softening point lower than that of the phenolic color developer and/or leuco pigment and is substantially inactive and compatible with the phenolic color developer and/or leuco pigments, especially water-insoluble one, and the phenolic color developer and/or leuco pigment is used in the form of compatible solid particles with said organic solid medium.
- the solid medium there are preferably used higher saturated fatty acids and their metal salts, amides, hydrazides, methylolated products and esters, though applicable solid media are not limited to these compounds.
- the higher saturated fatty acid there can be mentioned those having 6 to 30 carbon atoms, such as stearic acid, palmitic acid, myristic acid, lauric acid and behenic acid.
- the metal salt there can be mentioned zinc salts, calcium salts, magnesium salts, lead salts, cadmium salts, barium salts and aluminum salts.
- the amide there can be used not only monoamides of the above-mentioned fatty acids but also bis-amides such as ethylene-bis-stearylamide.
- hydrazide there can be used hydrazides of the above-mentioned fatty acids.
- methylolated product there can be used methylolated products of the above-mentioned fatty acid amides, such as stearylmethylolamide.
- ester there can be used triglyceride and glycol diesters of the above-mentioned fatty acids, such as beef tallow and hardened oil, sorbitan monoesters of the above-mentioned fatty acids, esters of the above-mentioned fatty acids with higher alcohols such as cetyl alcohol, and esters of the above-mentioned fatty acids with polyhydric alcohols such as ethylene glycol and propylene glycol.
- triglyceride and glycol diesters of the above-mentioned fatty acids such as beef tallow and hardened oil
- sorbitan monoesters of the above-mentioned fatty acids esters of the above-mentioned fatty acids with higher alcohols such as cetyl alcohol
- esters of the above-mentioned fatty acids with polyhydric alcohols such as ethylene glycol and propylene glycol.
- organic solid medium there can be mentioned higher alcohols having 16 to 30 carbon atoms, such as cetyl alcohol and stearyl alcohol, oxidized polyethylene waxes and alcohol- and acid-modified oxidized polyethylene waxes, microcrystalline wax, and natural waxes such as carnauba wax, candelilla wax and bees wax.
- higher alcohols having 16 to 30 carbon atoms such as cetyl alcohol and stearyl alcohol, oxidized polyethylene waxes and alcohol- and acid-modified oxidized polyethylene waxes, microcrystalline wax, and natural waxes such as carnauba wax, candelilla wax and bees wax.
- low-molecular-weight polymers of vinyl aromatic compounds such as styrene and vinyltoluene
- low-molecular-weight polymers of nitrogen-containing heterocyclic vinyl compounds such as 2-vinylpyridine.
- organic solid media that can be used in the present invention are not limited to those exemplified above.
- antioxidants, thermal stabilizers and ultraviolet ray absorbers may be used, so far as they are substantially inactive and compatible with the phenolic color developer or leuco pigments and have a melting point lower than that of the phenolic color developer or leuco pigment.
- solid medium of this type examples include sterically hindered phenols such as 2,6-di-tert-butyl-p-cresol, 2,2-methylene-bis(4-ethyl-6-tert-butylphenol), 2-hydroxy-4-methoxybenzophenone, phenyl salicylate, p-tertbutyl salicylate and 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and sulfur-containing organic compounds such as pentaerythritol tetrakis( ⁇ -laurylthiopropionate), zinc dibutyldithiocarbamate and 4,4'-dithiomorpholine.
- sterically hindered phenols such as 2,6-di-tert-butyl-p-cresol, 2,2-methylene-bis(4-ethyl-6-tert-butylphenol), 2-hydroxy-4-methoxybenzophenone, phenyl salicylate, p-tertbutyl sal
- High density polyethylene waxes and similar non-polar waxes becomes incompatible with the phenolic color developer or leuco pigment when their molecular weights are increased. Accordingly, use of these waxes are not preferred for attaining the objects of the present invention.
- a water-soluble solid medium such as an alkali metal salt of a higher fatty acid is not preferred because such solid medium is readily dissolved into water.
- an acidic solid medium such as a high fatty acid is not preferred as the solid medium for formation of compatible solid particles with the leuco pigment, because color formation takes place when such solid particles are prepared.
- a solid medium which is compatible with both the leuco pigment and the phenolic color developer such as a fatty acid amide, be used.
- the heat sensitivity is prominently improved over the sensitivity attained when the phenolic color developer or leuco pigment is singly incorporated into the binder in the form of particles.
- the above-mentioned solid medium should be used in an amount .[.2 to 250 times, especially 5 to 100 times,.]. .Iadd.of 0.2 to 250%, preferably 5 to 100% by weight, based on .Iaddend.the amount of the phenolic color developer and/or leuco pigment on the weight base.
- the amount of the solid medium is too small and below the above range, the degree of reduction of the melting point is low and no prominent improvement of the heat sensitivity can be attained.
- the amount of the solid medium is too large and is beyond the above range, the entire concentration of the phenolic color developer or leuco pigment is reduced, and consequently, the image density is lowered.
- the above-mentioned compatible solid particles are prepared according to any of the following methods.
- a phenolic color developer or leuco pigment and a substantially inactive organic solid medium which has a melting or softening point lower than that of the phenolic color developer or leuco pigment and is compatible with the phenolic color developer or leuco pigments are dissolved in a solvent for them to form a mixed solution, and this solution is then mixed with a precipitating medium which is miscible with said solvent but is a non-solvent for the color developer or pigment and the solid medium to precipitate compatible solid particles of the phenolic color developer or leuco pigment and the organic solid medium.
- a water-miscible organic solvent is preferably used, and as the non-solvent, water is preferably used.
- water-miscible organic solvent there can be mentioned, for example, alcohols such as methanol, ethanol, propanol and diacetone alcohol, ketones such as acetone and methylethyl ketone, cyclic ethers such as dioxane and tetrahydrofuran, esters such as methyl cellosolve acetate, carbitol acetate and methylcarbitol acetate, sulfoxides such as dimethylsulfoxide, N,N-di-substituted amides such as dimethylformamide and dimethylacetamide, and lactones such as ⁇ -valerolactone.
- alcohols such as methanol, ethanol, propanol and diacetone alcohol
- ketones such as acetone and methylethyl ketone
- cyclic ethers such as dioxane
- the phenolic color developer or leuco pigment and the organic solid medium are dissolved in the organic solvent at the above-mentioned ratio so that the entire solid concentration is 10 to 50% by weight, especially 20 to 40% by weight.
- the resulting solution is mixed with water at a weight ratio of from 1/5 to 1/30, especially from 1/10 to 1/20, whereby compatible solid particles are precipitated, and these particles are then filtered, washed with water and dried according to need.
- a phenolic color developer or leuco pigment and a substantially inactive organic solid medium which has a melting or softening point lower than that of the phenolic color developer or leuco pigment and is compatible therewith are dissolved in a solvent for them at a high temperature and a high concentration to form a mixed solution, and the resulting solution is cooled to precipitate compatible solid particles of the phenolic color developer or leuco pigment and the organic solid medium.
- organic solvent there may be used not only the above-mentioned water-miscible organic solvents but also aromatic solvents such as benzene, toluene and xylene and halogenated hydrocarbon solvents such as chlorobenzene, and solvents having a high boiling point are especially preferred. It is preferred that the difference between the high temperature adopted for dissolution and the low temperature adopted for precipitation be at least 50° C., especially at least 70° C.
- a mixture of a phenolic color developer or leuco pigment and a substantially inactive organic solid medium which has a melting or softening point lower than that of the phenolic color developer or leuco pigment and is compatible therewith is molten, and the melt is granulated after cooling or under cooling to form compatible solid particles of the phenolic color developer or leuco pigment and the organic solid medium.
- a method in which a cooled melt is pulverized and is then sieved if necessary there may be adopted a method in which the melt is subjected to spray granulation.
- the number average particle size of the compatible solid particles be 0.1 to 3 microns, especially 0.2 to 2 microns.
- Water-soluble and water-dispersible binders customarily used for heat-sensitive recording materials of this type can be used as the binder in the present invention.
- the phenolic color developer and leuco pigment are dispersed in an aqueous medium containing the above-mentioned water-soluble or water-dispersible binder to form a coating liquid.
- the leuco pigment (A) and the phenolic color developer (B) be used at a weight ratio (A)/(B) of from 1/2.0 to 1/40, especially from 1/2.5 to 1/20. It also is preferred that the leuco pigment be made present in the recording layer in an amount of 2 to 30% by weight, especially 5 to 20% by weight, as dry solids based on the total composition. If the amount of the leuco pigment or phenolic color developer is too small and below the above range, the color density is reduced, and if the amount of the leuco pigment or phenolic color developer is increased beyond the above range, no particular improvement of the color density or other quality can be attained, but an economical disadvantage is brought about.
- the binder be used in an amount of 20 to 80% by weight, especially 25 to 60% by weight, based on the sum of the amounts of the leuco pigment and phenolic color developer, at least one of which is in the form of the above-mentioned compatible solid particles.
- this coating liquid For preparation of this coating liquid, there is preferably adopted a method in which one of the leuco pigment and phenolic color developer, at least one of which is in the form of the compatible solid particles, is added to a solution of the water-soluble or water-dispersible binder, the mixture is wet-pulverized to form a dispersion, and the other component is directly added to the dispersion or a dispersion of the other component is prepared in the same manner as described above and both the dispersions are mixed. From the viewpoint of the adaptability to the coating operation, it is preferred that the solid concentration of the coating liquid be 8 to 20% by weight.
- known additives may be added to the coating liquid according to known recipes.
- a white pigment such as titanium dioxide or a filler such as a clay or calcium carbonate may be added.
- an animal, vegetable or mineral wax such as paraffin wax or carnauba wax, stearic acid, an amide, soap or other derivative of a higher fatty acid or a synthetic waxy substance such as a polyethylene wax, a polypropylene wax or a polyethylene glycol.
- an alkanolamine such as triethanolamine or other organic base.
- a water resistance-imparting agent and a defoaming agent there may be added.
- the substrate on which the recording layer is to be formed there can optionally be used papers, non-woven fabrics, artificial papers, various films, metal foils and laminates thereof. It is preferred that the basis amount of the recording layer be 2 to 10 g/m 2 , especially 3 to 8 g/m 2 , in the dry state.
- the heat-sensitive recording element of the present invention can valuably be used as a recording element of a thermal head, a thermal pen, an infrared flash lamp or a laser device, which is used as the light source of a facsimile printer, a data communication device, a computer console unit, a measurement device, a passometer, a copying machine or the like.
- a mixture of 5 g of bisphenol A [2,2-bis(4'-hydroxyphenyl)propane] and 10, 25, 50, 100, 200, 300, 500, 1000, 2000, 3000 or 5000 mg of a fatty acid amide (a formaldehyde condensate of a mixture containing stearic acid amide and palmitic acid amide at a weight ratio of about 7/3) was dissolved in 10 to 15 g of diacetone alcohol under heating (120° C.), and the solution was gradually added to 300 ml of water and the mixture was stirred strongly. The formed white precipitate was washed with water, filtered and dried in an oven maintained at 60° C.
- the melting point of the so-prepared solid solution of bisphenol A and fatty acid amide was measured by a commercially available melting point measuring device (Micro Melting Point Apparatus Model No. 428 supplied by Shibayama Seisakusho). The obtained results are shown in Table 1.
- a liquid A' was prepared by using 100 parts of bisphenol A (comparative color former).
- the so formed liquid A or A' was mixed with the liquid B so that the weight ratio of the phenolic color developer to Crystal Violet Lactone was 5, and the resulting coating liquid was coated on a slick paper having a basis weight of 55 g/m 2 by a wire bar and dried at 60° C. to form a heat-sensitive recording paper having a coating amount of about 5 g/m 2 on the dry basis.
- the reflection density was measured by a commercially available densitometer (Macbeth RD-514) provided with a red filter. The obtained results are shown in Table 3.
- Example 3 a coating liquid was prepared by using the color developer (solid solution) of Example 2.
- the coating liquid was coated on a slick paper having a basis weight of 55 g/m 2 by a wire bar and dried at 60° C. to form a heat-sensitive recording paper having a coating amount of about 5 g/m 2 on the dry base.
- the heat-sensitive recording paper was passed at a speed of 4 cm/sec between heater rollers at various heating temperatures to effect color formation. The reflection density was measured. The obtained results are shown in FIG. 1.
- curve Blank shows the results obtained when bisphenol A alone was used
- curves A through J show the results obtained when the solid solutions (a) through (j) shown in Table 2 were used, respectively.
- the formed color had a higher density than that of the formed color in case of the curve Blank, if the comparison was made at the same heating temperature.
- Color developer described below were prepared by using the fatty acid amide used in Example 1 and bisphenol A, and they were subjected to the comparative test.
- a mixture of 100 parts of the fatty acid amide used in Example 1 and 50 parts of bisphenol A was heated and molten at 160° C. to dissolve them in each other sufficiently, and the melt was cooled and pulverized to form a solid solution which was used as the color developer.
- a coating liquid was prepared by mixing 5 parts of the liquid B with 25.3 parts of the dispersion A-(1) or 76 parts of the dispersion A-(2) and A-(3) so that the amount of bisphenol A of the color developer component was 5 times the amount of Crystal Violet Lactone.
- the coating liquid was coated on a slick paper and dried at 60° C. to form a heat-sensitive recording paper (having a coating amount of about 6 g/m 2 ).
- the heat-sensitive and pressure-sensitive color-forming characteristics of the recording paper were examined. The obtained results are shown in Table 4.
- a mixture (100/2) of bisphenol A and a fatty acid amide (formaldehyde condensate of a mixture containing stearic acid amide and palmitic acid amide at a weight ratio of about 7/3)
- a mixture (100/2) of bisphenol A and a fatty acid amide (a mixture containing stearic acid amide and palmitic acid amide at a weight ratio of about 7/3)
- Coating liquids E-1 through E-9 were prepared by mixing 5 parts of the liquid D with 25 parts of the liquid C'-1 or 25.5 parts of the liquid C'-2, C'-3, C'-4, C'-5, C'-6, C'-7, C'-8 or C'-9 so that the amount of bisphenol A of the color developer component was 5 times the amount of Crystal Violet Lactone.
- the coating liquid was coated on a slick paper and dried to form a heat-sensitive recording paper having a coating amount of about 5 g/m 2 on the dry base.
- color formation was effected at various temperatures, and the reflection density was measured. The obtained results are shown in Table 5.
- Each solid solution was prepared by dissolving 10 parts by weight (all of "parts” given hereinafter are by weight) of Crystal Violet Lactone and a predetermined amount of the above-mentioned fatty acid amide in 35 to 60 parts of diacetone alcohol under heating at 120° C., mixing the solution with 500 parts of water and filtering, water-washing and drying (60° C.) the formed precipitate.
- the liquid A' was mixed with the liquid B so that the amount of the phenolic color developer was 5 times the amount of Crystal Violet Lactone on the weight base to form a coating liquid.
- the coating liquid was coated on a slick paper having a basis weight of 55 g/m 2 by a wire bar and dried at 60° C. to obtain a heat-sensitive recording paper having a coating amount of about 5 g/m 2 .
- the recording paper was passed at a speed of 4 cm/sec between rotary heater rollers (pressed under 1 Kg/cm) at a heating temperature (roller surface temperature) shown in Table 7 to effect coloration under heating.
- the reflection density of the formed color was measured by a commercially available densitometer (Macbeth RD-514 with a red filter). The obtained results are shown in Table 7.
- the obtained heat-sensitive recording papers were passed through heater rollers in the same manner as described in Example 8 and the reflection densities of the formed colors were measured. The obtained results are shown in Table 9.
- Rhodamine lactam type leuco pigment a spiropyran type leuco pigment, an Auramine type leuco pigment or a phenothiazine type leuco pigment was used instead of the above-mentioned leuco pigment.
- a solid solution was prepared from an organic solid medium shown in Table 10 and Crystal violet Lactone, and in the same manner as described in Example 8, a heat-sensitive recording paper was prepared by using the so prepared solid solution, 2,2-bis(4'-hydroxyphenyl)propane as a color developer and a 5% by weight aqueous solution of polyvinyl alcohol as a binder.
- the recording paper was passed through heater rollers to examine the color-forming property. The obtained results are shown in Table 10.
- the density of the formed color was higher than the density of the color formed when the leuco pigment was not formed into a solid solution.
- Example 8 The solid solutions described hereinbefore were prepared according to the method described in Example 8, that is, the first method described in the text of the instant specification.
- the second method When low density polyethylene or zinc stearate is used, the second method may be adopted, and when microcrystalline wax is used, the third method may be adopted.
- the so-formed solid solution was combined with the leuco pigment solid solution (3)-c of Example 9, and a heat-sensitive recording paper was prepared in the same manner as described in Example 8.
- the density of the formed color was 1.05.
- the density of the formed color was only 0.80.
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Abstract
Disclosed is a heat-sensitive color-forming recording material which comprises a recording layer comprising a particulate phenolic color developer and a particulate leuco pigment, which are dispersed in a binder independently from each other, wherein the phenolic color developer and/or leuco pigment is present in the form of compatible solid particles with a substantially inactive organic solid medium having a melting or softening point lower than that of the phenolic color developer and/or leuco pigment and said organic solid medium is present in said compatible solid particles in an amount .[.2 to 250 times as large as.]. .Iadd.of 0.2 to 250% by weight, based on .Iaddend.the amount of the phenolic color developer and/or leuco pigment on the weight base. This heat-sensitized color-forming recording material is highly sensitive without substantial increase of the fog density.
Description
This application is a division, of application Ser. No. 346,772, filed Feb. 8, 1982, now abandoned.
(1) Field of the Invention
The present invention relates to a heat-sensitive color-forming recording material. More particularly, the present invention relates to a heat-sensitive recording material which is sensitized without substantial increase of the fog density.
(2) Description of the Prior Art
The combination of a leuco pigment and a color developer composed of an acidic substance has been widely used for recording of informations, for example, heat-sensitive recording, pressure-sensitive recording and electrostatic photographic recording. For example, as a recording element for heat-sensitive recording, there has been used a recording material comprising a recording layer formed on a substrate, said recording layer being obtained by dispersing a leuco pigment which is colorless or has a light color in the normal state and a phenol which is solid at normal temperature but is heat-fusible, in a polymeric binder independently in separate phases.
In this heat-sensitive recording material, color formation is effected when the leuco pigment and phenolic color developer are reacted with each other in the state activated by heat, especially in the fused state. Since fusion of the phenolic color developer or leuco pigment is not caused unless the temperature is considerably high, the heat sensitivity of the recording material is low and the density of a recorded image is generally low. Furthermore, since recording must be carried out at a high temperature, this recording material is disadvantageous in that a high temperature heat source is necessary. Moreover, the temperature of a transportation system in a heat-sensitive recording apparatus is elevated, and therefore, fogging is readily caused to occur.
I found that when such phenolic color developer and/or leuco pigment is dispersed in a binder in the form of compatible solid particles with a substantially inactive organic solid medium which has a melting point or softening point lower than the melting point of the phenolic color developer and/or leuco pigment and also has a compatibility with the phenolic color developer and/or leuco pigment and a recording layer is formed from this dispersion, the heat sensitivity can be prominently improved without substantial increase of the fog density.
More specifically, in accordance with the present invention, there is provided a heat-sensitive color-forming recording material which comprises a recording layer comprising a particulate phenolic color developer and a particulate leuco pigment, which are dispersed in a binder independently from each other, wherein the phenolic color developer and/or leuco pigment is present in the form of compatible solid particles with a substantially inactive organic solid medium having a melting or softening point lower than that of the phenolic color developer and/or leuco pigment and said organic solid medium is present in said compatible solid particles in an amount 2 to 250 times as large as the amount of the phenolic color developer and/or leuco pigment on the weight base.
FIG. 1 is a graph showing the relation between the heating temperature and the reflection density in heat-sensitive recording materials according to the present invention.
The phenolic color developer that is used in the present invention is solid at normal temperature and is heat-fusible and it is a prototropic phenol in the fuse state. As preferred examples of the phenolic color developer, there can be mentioned 4,4'-isopropylidene diphenol (bisphenol A), 4,4'-methylene-bis(phenol), 4,4'-isopropylidene-bis(2-chlorophenol), 4,4'-isopropylidene-bis(2,6-dichlorophenol), 4,4'-isopropylidene-bis(2-methylphenol), 4,4'-isopropylidene-bis(2-tert-butylphenol), 4,4'-sec-isobutylidene-bis(2-methylphenol), 4,4'-cyclohexylidene-diphenol, 2,2'-thiobis(4,6-dichlorophenol), p-tert-butylphenol, 3,4-dichlorodiphenol, o,o'-diphenol, 4-hydroxydiphenoxide, 2,2'-dihydroxy-bisphenol, 2,2'-methylene-bis(4-chlorophenol), 2,6-dihydroxybenzoic acid and 1-hydroxy-2-napthoic acid.
All the leuco pigments customarily used for heat-sensitive recording materials of this type can be used in the present invention. For example, triphenylmethane leuco pigments, fluoran type leuco pigments, spirooyran type leuco pigments, rhodamine lactam type pigments, auramine type leuco pigments and phenothiazine type leuco pigments may be used singly or in combination. Preferred examples are as follows.
3,3-Bis(p-dimethylaminophenyl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3,3-bis(p-dimethylaminophenyl)-6-diethylaminophthalide, 3,3-bis(p-dimethylaminophenyl)-6-diethylaminophthalide, 3,3-bis(p-dimethylaminophenyl)-6-methoxyphthalide, 4-hydroxy-4'-dimethyl-aminotriphenylmethane-lactone, and 4,4'-bishydroxy-3,3'-bis-diaminotriphenylmethane-lactone.
3-Dimethylamino-5,7-dimethylfluoran, 3-diethylamino-5,7-dimethylfluoran, 3-diethylamino-6,7-dimethylfluoran, 3-cyclohexylamino-6-chlorofluoran, 3-dimethylamino-6-methoxyfluoran, 3,6-bis-β-methoxyethoxyfluoran, 3-diethylamino-7-dibenzylaminofluoran, 3-diethylamino-6-methyl-7-chlorofluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3,7-bisdiethylaminofluoran and 3-diethylamino-7-methoxyfluoran.
8'-Methoxybenzoindolinospiropyran, 3-phenyl-8'-methoxybenzoindolinospiropyran, 6'-chloro-8'-methoxybenzoindolinospiropyran, 5,6'-dichloro-8'-methoxybenzoindolinospiropyran, 4,7,8'-trimethoxybenzoindolinospiropyran, benzo-β-naphthospiropyran, 3-methyl-di-β-naphthospiropyran and 1,3,3-trimethyl-6'-chloro-8'-methoxyindolinobenzospiropyran.
9-(p-Nitroanilino)3,6-bis(diethylamino)-9-xanthyl-o-benzoic acid lactam and
2-[3,6-bis(diethylamino)-9-(o-chloroanilino)xanthyl]-benzoic acid lactam.
2,5-Dichloro-N-phenyl-leucoauramine, 4,4'-bisdimethylamino-3,4-chlorophenyl-leucoauramine and 4,4'-bis-dimethylaminopiperazine hydrol.
Benzoyl leuco methylene blue, p-chlorobenzoyl leuco methylene blue, 3,4-dichlorobenzoyl leuco methylene blue and p-methoxybenzoyl leuco methylene blue.
According to the present invention, the above-mentioned phenolic color developer and/or leuco pigment is combined with a specific organic solid medium which has a melting or softening point lower than that of the phenolic color developer and/or leuco pigment and is substantially inactive and compatible with the phenolic color developer and/or leuco pigments, especially water-insoluble one, and the phenolic color developer and/or leuco pigment is used in the form of compatible solid particles with said organic solid medium.
As the solid medium, there are preferably used higher saturated fatty acids and their metal salts, amides, hydrazides, methylolated products and esters, though applicable solid media are not limited to these compounds. As preferred examples of the higher saturated fatty acid, there can be mentioned those having 6 to 30 carbon atoms, such as stearic acid, palmitic acid, myristic acid, lauric acid and behenic acid. As the metal salt, there can be mentioned zinc salts, calcium salts, magnesium salts, lead salts, cadmium salts, barium salts and aluminum salts. As the amide, there can be used not only monoamides of the above-mentioned fatty acids but also bis-amides such as ethylene-bis-stearylamide. As the hydrazide, there can be used hydrazides of the above-mentioned fatty acids. As the methylolated product, there can be used methylolated products of the above-mentioned fatty acid amides, such as stearylmethylolamide. As the ester, there can be used triglyceride and glycol diesters of the above-mentioned fatty acids, such as beef tallow and hardened oil, sorbitan monoesters of the above-mentioned fatty acids, esters of the above-mentioned fatty acids with higher alcohols such as cetyl alcohol, and esters of the above-mentioned fatty acids with polyhydric alcohols such as ethylene glycol and propylene glycol.
As other preferred examples of organic solid medium, there can be mentioned higher alcohols having 16 to 30 carbon atoms, such as cetyl alcohol and stearyl alcohol, oxidized polyethylene waxes and alcohol- and acid-modified oxidized polyethylene waxes, microcrystalline wax, and natural waxes such as carnauba wax, candelilla wax and bees wax.
Furthermore, there may be used low-molecular-weight polymers of vinyl aromatic compounds such as styrene and vinyltoluene and low-molecular-weight polymers of nitrogen-containing heterocyclic vinyl compounds such as 2-vinylpyridine.
The kinds of organic solid media that can be used in the present invention are not limited to those exemplified above. For example, antioxidants, thermal stabilizers and ultraviolet ray absorbers may be used, so far as they are substantially inactive and compatible with the phenolic color developer or leuco pigments and have a melting point lower than that of the phenolic color developer or leuco pigment. Examples of the solid medium of this type include sterically hindered phenols such as 2,6-di-tert-butyl-p-cresol, 2,2-methylene-bis(4-ethyl-6-tert-butylphenol), 2-hydroxy-4-methoxybenzophenone, phenyl salicylate, p-tertbutyl salicylate and 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and sulfur-containing organic compounds such as pentaerythritol tetrakis(β-laurylthiopropionate), zinc dibutyldithiocarbamate and 4,4'-dithiomorpholine.
High density polyethylene waxes and similar non-polar waxes becomes incompatible with the phenolic color developer or leuco pigment when their molecular weights are increased. Accordingly, use of these waxes are not preferred for attaining the objects of the present invention. When the recording layer is formed by using an aqueous coating composition, use of a water-soluble solid medium such as an alkali metal salt of a higher fatty acid is not preferred because such solid medium is readily dissolved into water.
Moreover, an acidic solid medium such as a high fatty acid is not preferred as the solid medium for formation of compatible solid particles with the leuco pigment, because color formation takes place when such solid particles are prepared.
When both the leuco pigment and the phenolic color developer are used simultaneously for formation of compatible solid particles, it is preferred that a solid medium which is compatible with both the leuco pigment and the phenolic color developer, such as a fatty acid amide, be used.
In the present invention, when the phenolic color developer and/or leuco pigment is dispersed and made present in the binder of the recording layer in the form of compatible solid particles with the above-mentioned solid medium, the heat sensitivity is prominently improved over the sensitivity attained when the phenolic color developer or leuco pigment is singly incorporated into the binder in the form of particles. For example, when a color former composed of bisphenol A is employed and particles of this color developer are dispersed in a binder, there is obtained only an image having a reflection density of 0.35 at 120° C., whereas when bisphenol A is used in the form of compatible solid particles with ethylene-bis-stearylamide, the reflection image density is increased to 1.05, that is, a level 3 times as high as the above reflection density, under the same recording conditions. It is believed that the reason is that the melting point of the phenolic color developer is reduced in the form of the above-mentioned compatible solid particles, the prototropy becomes possible at a lower temperature. Furthermore, for example, when a leuco pigment composed of Crystal Violet Lactone is used, if recording is carried out at 110° C., an image having a reflection density of only 0.40 is obtained. On the other hand, when Crystal Violet Lacton is used in the form of compatible solid particles with 10% by weight of an oxidized polyethylene wax, an image having a reflection density of 0.76 can be obtained and the reflection density is increased to a level about 2 times as high as the above reflection density. It is believed that the reason is that the melting point of the leuco pigment is reduced in the form of the above-mentioned compatible solid particles and activation of the leuco pigment becomes possible at a lower temperature.
In the present invention, it is important that the above-mentioned solid medium should be used in an amount .[.2 to 250 times, especially 5 to 100 times,.]. .Iadd.of 0.2 to 250%, preferably 5 to 100% by weight, based on .Iaddend.the amount of the phenolic color developer and/or leuco pigment on the weight base. When the amount of the solid medium is too small and below the above range, the degree of reduction of the melting point is low and no prominent improvement of the heat sensitivity can be attained. On the other hand, if the amount of the solid medium is too large and is beyond the above range, the entire concentration of the phenolic color developer or leuco pigment is reduced, and consequently, the image density is lowered.
In the present invention, the above-mentioned compatible solid particles are prepared according to any of the following methods.
According to the first method of the present invention, a phenolic color developer or leuco pigment and a substantially inactive organic solid medium which has a melting or softening point lower than that of the phenolic color developer or leuco pigment and is compatible with the phenolic color developer or leuco pigments are dissolved in a solvent for them to form a mixed solution, and this solution is then mixed with a precipitating medium which is miscible with said solvent but is a non-solvent for the color developer or pigment and the solid medium to precipitate compatible solid particles of the phenolic color developer or leuco pigment and the organic solid medium.
As the solvent, a water-miscible organic solvent is preferably used, and as the non-solvent, water is preferably used. As the water-miscible organic solvent, there can be mentioned, for example, alcohols such as methanol, ethanol, propanol and diacetone alcohol, ketones such as acetone and methylethyl ketone, cyclic ethers such as dioxane and tetrahydrofuran, esters such as methyl cellosolve acetate, carbitol acetate and methylcarbitol acetate, sulfoxides such as dimethylsulfoxide, N,N-di-substituted amides such as dimethylformamide and dimethylacetamide, and lactones such as γ-valerolactone. The phenolic color developer or leuco pigment and the organic solid medium are dissolved in the organic solvent at the above-mentioned ratio so that the entire solid concentration is 10 to 50% by weight, especially 20 to 40% by weight. The resulting solution is mixed with water at a weight ratio of from 1/5 to 1/30, especially from 1/10 to 1/20, whereby compatible solid particles are precipitated, and these particles are then filtered, washed with water and dried according to need.
According to the second method of the present invention, a phenolic color developer or leuco pigment and a substantially inactive organic solid medium which has a melting or softening point lower than that of the phenolic color developer or leuco pigment and is compatible therewith are dissolved in a solvent for them at a high temperature and a high concentration to form a mixed solution, and the resulting solution is cooled to precipitate compatible solid particles of the phenolic color developer or leuco pigment and the organic solid medium.
As the organic solvent, there may be used not only the above-mentioned water-miscible organic solvents but also aromatic solvents such as benzene, toluene and xylene and halogenated hydrocarbon solvents such as chlorobenzene, and solvents having a high boiling point are especially preferred. It is preferred that the difference between the high temperature adopted for dissolution and the low temperature adopted for precipitation be at least 50° C., especially at least 70° C.
According to the third method, a mixture of a phenolic color developer or leuco pigment and a substantially inactive organic solid medium which has a melting or softening point lower than that of the phenolic color developer or leuco pigment and is compatible therewith is molten, and the melt is granulated after cooling or under cooling to form compatible solid particles of the phenolic color developer or leuco pigment and the organic solid medium. For granulation of the melt, there may be adopted a method in which a cooled melt is pulverized and is then sieved if necessary, and a method in which the melt is subjected to spray granulation.
From the viewpoints of the resolving power and the heat sensitivity, it is preferred that the number average particle size of the compatible solid particles be 0.1 to 3 microns, especially 0.2 to 2 microns.
Water-soluble and water-dispersible binders customarily used for heat-sensitive recording materials of this type can be used as the binder in the present invention. As preferred examples, there can be mentioned polyvinyl alcohol, starch, carboxymethylated starch, hydroxyethylated starch, carboxymethyl cellulose, ethyl cellulose, gum arabic, gelatin, casein, polyvinyl pyrrolidone, polyacrylamide, styrene-maleic acid salt copolymers, vinyl ether-maleic acid salt copolymers and styrenebutadiene copolymer latices.
The phenolic color developer and leuco pigment, at least one of which is in the form of the above-mentioned compatible solid particles, are dispersed in an aqueous medium containing the above-mentioned water-soluble or water-dispersible binder to form a coating liquid.
In the present invention, it is preferred that the leuco pigment (A) and the phenolic color developer (B) be used at a weight ratio (A)/(B) of from 1/2.0 to 1/40, especially from 1/2.5 to 1/20. It also is preferred that the leuco pigment be made present in the recording layer in an amount of 2 to 30% by weight, especially 5 to 20% by weight, as dry solids based on the total composition. If the amount of the leuco pigment or phenolic color developer is too small and below the above range, the color density is reduced, and if the amount of the leuco pigment or phenolic color developer is increased beyond the above range, no particular improvement of the color density or other quality can be attained, but an economical disadvantage is brought about.
It is preferred that the binder be used in an amount of 20 to 80% by weight, especially 25 to 60% by weight, based on the sum of the amounts of the leuco pigment and phenolic color developer, at least one of which is in the form of the above-mentioned compatible solid particles.
For preparation of this coating liquid, there is preferably adopted a method in which one of the leuco pigment and phenolic color developer, at least one of which is in the form of the compatible solid particles, is added to a solution of the water-soluble or water-dispersible binder, the mixture is wet-pulverized to form a dispersion, and the other component is directly added to the dispersion or a dispersion of the other component is prepared in the same manner as described above and both the dispersions are mixed. From the viewpoint of the adaptability to the coating operation, it is preferred that the solid concentration of the coating liquid be 8 to 20% by weight.
In order to improve various characteristics of the heat-sensitive recording layer, known additives may be added to the coating liquid according to known recipes. For instance, in order to improve the whiteness of the recording layer or attain a bulking effect, a white pigment such as titanium dioxide or a filler such as a clay or calcium carbonate may be added. Furthermore, in order to adjust the recording sensitivity, there may be added an animal, vegetable or mineral wax such as paraffin wax or carnauba wax, stearic acid, an amide, soap or other derivative of a higher fatty acid or a synthetic waxy substance such as a polyethylene wax, a polypropylene wax or a polyethylene glycol. Moreover, in order to prevent coloration of the background, there may be added an alkanolamine such as triethanolamine or other organic base. Still further, there may be added a water resistance-imparting agent and a defoaming agent.
As the substrate on which the recording layer is to be formed, there can optionally be used papers, non-woven fabrics, artificial papers, various films, metal foils and laminates thereof. It is preferred that the basis amount of the recording layer be 2 to 10 g/m2, especially 3 to 8 g/m2, in the dry state.
The heat-sensitive recording element of the present invention can valuably be used as a recording element of a thermal head, a thermal pen, an infrared flash lamp or a laser device, which is used as the light source of a facsimile printer, a data communication device, a computer console unit, a measurement device, a passometer, a copying machine or the like.
The present invention will now be described in detail with reference to the following Examples that by no means limit the scope of the invention.
A mixture of 5 g of bisphenol A [2,2-bis(4'-hydroxyphenyl)propane] and 10, 25, 50, 100, 200, 300, 500, 1000, 2000, 3000 or 5000 mg of a fatty acid amide (a formaldehyde condensate of a mixture containing stearic acid amide and palmitic acid amide at a weight ratio of about 7/3) was dissolved in 10 to 15 g of diacetone alcohol under heating (120° C.), and the solution was gradually added to 300 ml of water and the mixture was stirred strongly. The formed white precipitate was washed with water, filtered and dried in an oven maintained at 60° C.
The melting point of the so-prepared solid solution of bisphenol A and fatty acid amide was measured by a commercially available melting point measuring device (Micro Melting Point Apparatus Model No. 428 supplied by Shibayama Seisakusho). The obtained results are shown in Table 1.
From the results shown in Table 1, it will readily be understood that the melting-initiating temperature of bisphenol A is lowered if it is formed into a solid solution with the fatty acid amide.
TABLE 1
______________________________________
Melting Temperature
Range (°C.) (melting-
Content* initiating temperature
(% by weight) to melting-completing
Compound of Fatty Acid Amide
temperature)
______________________________________
bisphenol A
-- 156 (single substance)
fatty acid amide
-- 143 (single substance)
solid solution (1)
0.2 132-156
solid solution (2)
0.5 120-154
solid solution (3)
1.0 115-154
solid solution (4)
2.0 105-156
solid solution (5)
4.0 94-156
solid solution (6)
6.0 105-152
solid solution (7)
10 95-155
solid solution (8)
20 81-151
solid solution (9)
40 78-140
solid solution (10)
60 68-116
solid solution (11)
100 78-112
______________________________________
Note:
*the amount (% by weight based on bisphenol A) of the fatty acid amide
solid disolved in bisphenol A
In the same manner as described in Example 1, 5 g of bisphenol A and 0.2 g (2% by weight) of a compound shown in Table 2 were commonly dissolved and precipitated to form solid solutions. The melting temperature ranges of the solid solutions were measured to obtain the results shown in Table 2.
TABLE 2
______________________________________
Melting Tempera-
Compound Composition ture Range (°C.)
______________________________________
Compound of Example 1
solid solu-.sup.1*
106-154
tion(a)
Compound of Example 1
solid solu-*.sup.2
111-156
tion(b)
Compound of Example 1
solid solu-*.sup.3
105-156
tion(c)
ethylene-bis stearic
single 141-145
acid amide substance
ethylene-bis stearic
solid solu- 112-156
acid amide tion(d)
7/3 mixture of stearic acid
single sub- 98-101
amide and palmitic acid amide
stance
7/3 mixture of stearic acid
solid solu- 95-151
amide and palmitic acid amide
tion(e)
zinc stearate single 122
substance
zinc stearate solid solu- 121-154
tion(f)
mixture of stearic acid amide
single 104
and vehenic acid amide
substance
mixture of stearic acid amide
solid solu- 112-161
and vehenic acid amide
tion(g)
4,4'-dithiodimorpholine
single 122
substance
4,1'-dithiodimorpholine
solid solu- 81-156
tion(h)
zinc dibutyldithiocarbamate
single 104
substance
zinc dibutyldithiocarbamate
solid solu- 102-151
tion(i)
oxidized low density
single 110
polyethylene wax
substance
oxidized low density
solid solu- 103-156
polyethylene wax
ion(j)
______________________________________
Note:
*.sup.1 solid solution(4) of Example 1 having an amide content of 2%
*.sup.2 tetrahydrofuran was used instead of diacetone alcohol, dissolutio
was effected at room temperature and precipitation was then conducted
*.sup.3 after heating dissolution, water was poured into the solution to
effect precipitation
From the results shown in Table 2, it will readily be understood that the melting-initiating temperature is lowered by formation of the solid solution.
In a ball mill, 100 parts by weight (all "parts" given hereinafter are by weight) of the solid solution obtained in Example 1, 670 parts of an aqueous solution containing 5% by weight of polyvinyl alcohol and 100 parts of water were mixed and pulverized for 5 hours to form a liquid A (A-1 through A-11).
In a ball mill, 50 parts of Crystal Violet Lactone, 330 parts of an aqueous solution containing 5% by weight of polyvinyl alcohol and 50 parts of water were mixed and pulverized for 5 hours to form a liquid B.
For comparison, in the same manner as described above with respect to the liquid A, a liquid A' was prepared by using 100 parts of bisphenol A (comparative color former).
The so formed liquid A or A' was mixed with the liquid B so that the weight ratio of the phenolic color developer to Crystal Violet Lactone was 5, and the resulting coating liquid was coated on a slick paper having a basis weight of 55 g/m2 by a wire bar and dried at 60° C. to form a heat-sensitive recording paper having a coating amount of about 5 g/m2 on the dry basis. The heat-sensitive recording paper was passed at a speed of 4 cm/sec between rotary heater rollers (pressed under 1 Kg/cm; surface temperature=130° C.) to effect coloration under heating. The reflection density was measured by a commercially available densitometer (Macbeth RD-514) provided with a red filter. The obtained results are shown in Table 3.
TABLE 3
______________________________________
Color Former Reflection Density
______________________________________
comparative color developer
0.80
(bisphenol A)
color developer of present
invention
solid solution (1)
1.05
solid solution (2)
1.12
solid solution (3)
1.13
solid solution (4)
1.15
solid solution (5)
1.18
solid solution (6)
1.20
solid solution (7)
1.23
solid solution (8)
1.25
solid solution (9)
1.23
solid solution (10
1.18
solid solution (11)
0.98
______________________________________
From the results shown in Table 3, it will readily be understood that a highest sensitizing effect is obtained in the solid solutions (7) and (8), namely when the amount of the acid amide to be solid-dissolved is 10 to 40%, while the sensitizing effect is reduced if the amount of the acid amide solid-dissolved is increased beyond this level. It was confirmed that if the amount of the acid amide solid-dissolved is 30% or larger, there is not a pressure-sensitive color-forming characteristic. That is, no color was formed even if the recording layer was scratched by a wire, a spike or a nail.
In the same manner as described in Example 3, a coating liquid was prepared by using the color developer (solid solution) of Example 2. The coating liquid was coated on a slick paper having a basis weight of 55 g/m2 by a wire bar and dried at 60° C. to form a heat-sensitive recording paper having a coating amount of about 5 g/m2 on the dry base. The heat-sensitive recording paper was passed at a speed of 4 cm/sec between heater rollers at various heating temperatures to effect color formation. The reflection density was measured. The obtained results are shown in FIG. 1.
In FIG. 1, curve Blank shows the results obtained when bisphenol A alone was used, and curves A through J show the results obtained when the solid solutions (a) through (j) shown in Table 2 were used, respectively. In case of each of the curves A through J, the formed color had a higher density than that of the formed color in case of the curve Blank, if the comparison was made at the same heating temperature.
When a fluoran type leuco pigment, a spiropyran type leuco pigment, a Rhodamine type leuco pigment, an Auramine type leuco pigment or a phenothiadine type leuco pigment was used instead of the triphenylmethane type leuco pigment such as Crystal Violet Lactone, similar results were obtained.
Color developer described below were prepared by using the fatty acid amide used in Example 1 and bisphenol A, and they were subjected to the comparative test.
Bisphenol A alone was used as the color developer.
A mere mixture of 100 parts of the fatty acid amide used in Example 1 and 50 parts of bisphenol A was used as the color developer.
A mixture of 100 parts of the fatty acid amide used in Example 1 and 50 parts of bisphenol A was heated and molten at 160° C. to dissolve them in each other sufficiently, and the melt was cooled and pulverized to form a solid solution which was used as the color developer.
In the same manner as described in Example 3, 100 parts of the color developer, 670 parts of an aqueous solution containing 5% by weight of polyvinyl alcohol and 100 parts of water were mixed and pulverized to form a color developer dispersion A-(1), A(2) and A-(3).
In the same manner as described above, a dispersion containing 50 parts of Crystal Violet Lactone (liquid B) was prepared.
A coating liquid was prepared by mixing 5 parts of the liquid B with 25.3 parts of the dispersion A-(1) or 76 parts of the dispersion A-(2) and A-(3) so that the amount of bisphenol A of the color developer component was 5 times the amount of Crystal Violet Lactone. The coating liquid was coated on a slick paper and dried at 60° C. to form a heat-sensitive recording paper (having a coating amount of about 6 g/m2). The heat-sensitive and pressure-sensitive color-forming characteristics of the recording paper were examined. The obtained results are shown in Table 4.
TABLE 4
______________________________________
Heat-Sensitive Color
Formation (reflection
Pressure-Sensitive
density Color Formation
Color Developer
120° C.
130° C.
140° C.
(scratched by nail)
______________________________________
1 (compar- 0.35 0.83 1.05 blue color formation
ison
2 (compar- 0.20 0.31 0.67 no color formation
sion
3 (presemt 0.42 0.92 1.10 no color formation
invention
______________________________________
From the results shown in Table 4, it is seen that when the fatty acid amide is merely mixed with bisphenol A, the susceptibility to coloration under pressure is effectively reduced but the heat sensitivity is rather degraded. It also is seen that in the heat-sensitive recording paper prepared according to the present invention, the heat sensitivity is excellent and the effect of preventing color formation under pressure is very good.
In order to examine the effects attained by using the color developer in the form of a solid solution, the following comparative experiment was carried out.
C-1:
Bisphenol A alone
C-2:
A mixture (100/2) of bisphenol A and a fatty acid amide (formaldehyde condensate of a mixture containing stearic acid amide and palmitic acid amide at a weight ratio of about 7/3)
C-3:
A solid solution of C-2 (prepared in the same manner as described in Example 1)
C-4:
A mixture (100/2) of bisphenol A and ethylene-bis-stearic acid amide
C-5:
A solid solution of C-4 (prepared in the same manner as described in Example 1)
C-6:
A mixture (100/2) of bisphenol A and a fatty acid amide (a mixture containing stearic acid amide and palmitic acid amide at a weight ratio of about 7/3)
C-7:
A solid solution of C-6 (prepared in the same manner as described in Example 1)
C-8:
A mixture (100/2) of bisphenol A and zinc stearate
C-9:
A solid solution of C-8 (prepared in the same manner as described in Example 1)
In a ball mill, 100 parts of the color developer C, 170 parts of an aqueous solution containing 20% by weight of etherified starch and 340 parts of water were mixed and pulverized for 5 hours to form a liquid C' (C'-1 through C'-9).
In a ball mill, 50 parts of Crystal Violet Lactone, 85 parts of an aqueous solution containing 20% by weight of etherified starch and 170 parts of water were mixed and pulverized for 5 hours to obtain a liquid D.
Coating liquids E-1 through E-9 were prepared by mixing 5 parts of the liquid D with 25 parts of the liquid C'-1 or 25.5 parts of the liquid C'-2, C'-3, C'-4, C'-5, C'-6, C'-7, C'-8 or C'-9 so that the amount of bisphenol A of the color developer component was 5 times the amount of Crystal Violet Lactone.
The coating liquid was coated on a slick paper and dried to form a heat-sensitive recording paper having a coating amount of about 5 g/m2 on the dry base. In the same manner as described in Example 4, color formation was effected at various temperatures, and the reflection density was measured. The obtained results are shown in Table 5.
TABLE 5
______________________________________
Reflection Density
Heating Temperature (°C.)
Color Developer
100 110 120 130 140
______________________________________
C-1 (blank) 0.25 0.32 10.48 0.80 1.17
C-2 (comparison)
0.25 0.34 0.55 0.84 1.06
C-3 (present inven-
0.30 0.64 1.10 1.34 1.42
tion)
C-4 (comparison)
0.24 0.32 0.51 0.94 1.21
C-5 (present inven-
0.28 0.57 0.92 129 1.39
tion)
C-6 (comparison)
0.44 0.58 0.76 1.01 1.09
C-7 (present inven-
0.67 1.01 1.11 1.26 1.30
tion)
C-8 (comparison)
0.25 0.32 0.46 0.88 1.05
C-9 (present inven-
0.25 0.32 0.55 0.92 1.15
tion)
______________________________________
From the results shown in Table 5, it will readily be understood that when a phenolic color developer is made present in the form of a solid solution with an organic solid medium having a compatibility with the phenolic color developer, the density of the formed color is increased over the density obtained when the phenolic color developer is made present in the form of a mere mixture with the organic solid medium (both the components are independently dispersed).
As another method for formation of the solid solution, there could be adopted a method in which bisphenol A and the organic solid medium compatible therewith were dissolved in hot chlorobenzene (120° C.) at a high concentration (for example, 150%), the solution was cooled to 5° C. and filtered, and the collected precipitate was dried at 60° C. to form a solid solution. From the results of the experiment conducted separately, it was confirmed that a color developer having a high sensitivity could be similarly obtained according to this method.
In the same manner as described in Example 3, a solid solution was prepared except that bisphenol S [bis(4'-hydroxyphenyl)sulfone, melting point=246.0° to 248° C.] was used instead of bisphenol A and a mixture containing stearic acid amide and palmitic acid amide at a ratio of 7/3 was used as the fatty acid amide, and the color formation test was carried out in the same manner as described in Example 3. The obtained results are shown in Table 6.
TABLE 6
______________________________________
Reflection Density
Composition (bisphenol S/fatty acid
Heating Temp-
amide) of Solid Solution
erature (°C.)
100/0 100/10 100/20 100/40
100/60
______________________________________
140 0.25 0.65 1.02 0.79 0.75
150 0.26 0.96 1.08 1.10 1.08
160 0.27 1.02 1.13 1.26 1.11
______________________________________
From the results shown in Table 6, it will readily be understood that when the phenolic color developer is used in the form of a solid solution with a compatible organic solid medium, the heat sensitivity can be increased and a highest effect can be obtained when the content of the organic solid medium in the solid solution is about 40% based on the phenolic color developer.
In order to examine the effects attained by using a leuco pigment in the form of a solid solution, the following comparative experiment was carried out.
A-1:
Crystal Violet Lactone alone
The following mixtures (comparisons) of Crystal Violet Lactone (A-1) and a fatty acid amide (a mixture containing stearic acid amide and palmitic acid amide at a ratio of about 7/3) differing in the weight ratio [(A-1)/fatty acid amide weight ratio] were used (both the components were present in the form of independent particles).
A-2:
(A-1)/fatty acid amide ratio=10/1
A-3:
(A-1)/fatty acid amide ratio=10/2.5
A-4:
(A-1)/fatty acid amide ratio=10/5
A-5:
(A-1)/fatty acid amide ratio=10/10
A-6:
(A-1)/fatty acid amide ratio=10/25
The following solid solutions of Crystal Violet Lactone (A-1) and the fatty acid amide according to the present invention (present in the form of compatible solid particles of both the components) were used.
Each solid solution was prepared by dissolving 10 parts by weight (all of "parts" given hereinafter are by weight) of Crystal Violet Lactone and a predetermined amount of the above-mentioned fatty acid amide in 35 to 60 parts of diacetone alcohol under heating at 120° C., mixing the solution with 500 parts of water and filtering, water-washing and drying (60° C.) the formed precipitate.
A-7:
Solid solution of A-2
A-8
Solid solution of A-3
A-9:
Solid solution of A-4
A-10:
Solid solution of A-5
A-11:
Solid solution of A-6
In a ball mill, 10 parts of the leuco pigment A-1, the mixture A-2, A-3, A-4, A-5 or A-6 or the solid solution A-7, A-8, A-9, A-10 or A-11, 67 parts of an aqueous solution containing 5% by weight of polyvinyl alcohol and 10 parts of water were mixed and pulverized for 5 hours to obtain a liquid A' (A'-1 through A'-11).
In a ball mill, 100 parts of 2,4-dihydroxybenzophenone, 670 parts of an aqueous solution containing 5% by weight of polyvinyl alcohol and 100 parts of water were mixed and pulverized for 5 hours to form a liquid B.
The liquid A' was mixed with the liquid B so that the amount of the phenolic color developer was 5 times the amount of Crystal Violet Lactone on the weight base to form a coating liquid. The coating liquid was coated on a slick paper having a basis weight of 55 g/m2 by a wire bar and dried at 60° C. to obtain a heat-sensitive recording paper having a coating amount of about 5 g/m2. The recording paper was passed at a speed of 4 cm/sec between rotary heater rollers (pressed under 1 Kg/cm) at a heating temperature (roller surface temperature) shown in Table 7 to effect coloration under heating. The reflection density of the formed color was measured by a commercially available densitometer (Macbeth RD-514 with a red filter). The obtained results are shown in Table 7.
From the results shown in Table 7, it will readily be understood that in case of a mixed dispersion of the leuco pigment and the fatty acid amide, the density of the formed color is lower than the density of the color formed in case of the leuco pigment alone, whereas in case of a solid solution dispersion of the leuco pigment and the fatty acid amide, the density of the formed color is much higher than the density of the color formed when the leuco pigment alone is used. It will also be seen that when the amount of the fatty acid amide exceeds 100% by weight based on the leuco pigment in the solid solution, the density of the formed color is reduced at a higher temperature and that it is preferred that the amount of the fatty acid amide be 5 to 100% by weight based on the leuco pigment.
TABLE 7
______________________________________
Reflection Density
Form of Leuco
Heating Temperature (°C.)
Pigment 90 100 110 120 130 140
______________________________________
A-1 alone 0.07 0.20 0.38 0.70 0.82 1.10
dispersed mixture
particles
A-2 0.07 0.13 0.22 0.48 0.68 0.96
A-3 0.09 0.15 0.27 0.58 0.86 1.00
A-4 0.08 0.14 0.26 0.45 0.62 0.76
A-5 0.07 0.13 0.22 0.42 0.60 0.77
A-6 0.07 0.11 0.18 0.38 0.56 0.73
compatible solid
particles (solid
solution)
A-7 0.30 0.54 0.78 0.89 1.05 1.10
A-8 0.36 0.68 0.90 0.99 1.07 1.13
A-9 0.28 0.46 0.66 0.88 0.94 1.00
A-10 0.22 0.56 0.77 0.87 0.93 0.90
A-11 0.22 0.56 0.81 0.84 0.80 0.76
______________________________________
In the same manner as described in Example 8, heat-sensitive recording papers were prepared from combinations shown in Table 8.
The obtained heat-sensitive recording papers were passed through heater rollers in the same manner as described in Example 8 and the reflection densities of the formed colors were measured. The obtained results are shown in Table 9.
TABLE 8
__________________________________________________________________________
Combina- Compatible Organic Phenolic Color
tion Leuco Pigment
Solid Medium
Form and Weight Ratio of Particles
Developer
Binder
__________________________________________________________________________
(1)-a
fluoran type leuco
-- dispersed single substance
p-vinylphenol
polyvinyl
pigment(green) particles polymer alcohol
color forming, (m.p. = 190° C.)
m.p. = 163°)
(1)-b
fluoran type leuco
fatty acid amide*.sup.1
dispersed mixture particles
p-vinylphenol
polyvinyl
pigment (green
(m.p. = 108°C.)
(10/2.5) polymer alcohol
color forming, (m.p. = 190° C.)
m.p. = 163°)
(1)-c
fluoran type leuco
fatty acid amide*.sup.1
dispersed solid solution particles
p-vinylphenol
polyvinyl
pigment (green
(m.p. = 108° C.)
(10/2.5) polymer alcohol
color forming, (m.p. = 190° C.)
mp. = 163°)
(2)-a
fluoran type leuco
-- dispersed single substance
4,4'-thio-bis
etherified
pigment (green particles (6-tert-butyl
starch*.sup.2
color forming, 3-methylphenol)
m.p. = 163°) (m.p. = 160° C.)
(2)-b
fluoran type leuco
fatty acid amide*.sup.1
dispersed mixture particles
4,4'-thio-bis
etherfied
pigment (green
(m.p. = 108° C.)
(10/2.5) (6-tert-butyl-
starch*.sup.2
color forming, 3-methylphenol
m.p. = 163°) (m.p. = 160° C.)
(2)-c
fluoran type leuco
fatty acid amide*.sup.1
dispersed solid solution
4,4'-thio-bis
etherified
pigment (green
(m.p. = 108° C.)
particles (10/2.5)
(6-tert-butyl-
starch*.sup.2
color forming, 3-methylphenol)
m.p. = 163°) (m.p. = 160° C.)
(3)-a
Crystal Violet
-- dispersed single substance
2,2-bis(4'-
etherified
Lactone (m.p. = particles hydroxyphenyl)
starch*.sup.2
180° C.) propane
(m.p. = 156° C.)
(3)-b
Crystal Violet
oxidized polyethy-
dispersed mixture particles
2,2-bis(4'-
etherified
Lactone (m.p. =
lene (m.p. = 98° C.)
(10/1) hydroxyphenyl)
starch*.sup.2
180° C.) propane
(m.p. = 156° C.)
(3)-c
Crystal Violet
oxidized polyethy-
dispersed solid solution particles
2,2-bis(4'-
etherified
Lactone (m.p. =
lene (m.p. = 98° C.)
(10/1) hydroxyphenyl)
starch*.sup.2
180° C.) propane
(m.p. = 156° C.)
(4)-a
Crystal Violet
-- dispersed single substance particles
2,2-bis(4'-
etherified
Lactone (m.p. = hydroxyphenyl)
starch*.sup.2
180° C.) propane
(m.p. = 156° C.)
(4)-b
Crystal Violet
4-vinylpyridine
dispersed moisture particles
2,2-bis(4'-
etherfied
Lactone (m.p. =
polymer (s.p =
(10/2.5 ) hydroxphenyl)
starch*.sup.2
180° C.)
110° C.) propane
(m.p. = 156° C.)
(4)-c
Crystal Violet
4-vinylpyridine
dispersed solid solution particles
2,2-bis(4'-
etherfied
Lactone (m.p. =
polymer (s.p =
(10/2.5) hydroxphenyl)
starch*.sup.2
180° C.)
110° C.) propane
(m.p. = 156° C.)
__________________________________________________________________________
Note:
*.sup.1 formaldehyde condensate of a mixture containing stearic acid amid
and palmitic acid amide at a ratio of about 7/3
*.sup.2 used in the form as aqueous solution having a concentration of 20
by weight
TABLE 9
______________________________________
Combination
Heating Temperature (°C.)
Reflection Density*
______________________________________
(1)-a 160 0.32
(1)-b 160 0.73
(1)-c 160 1.19
(2)-a 150 0.70
(2)-b 150 1.00
(2)-c 150 1.28
(3)-a 110 0.40
(3)-b 110 0.39
(3)-c 110 0.76
(3)-a 130 0.85
(3)-b 130 1.00
(3)-c 130 1.31
(4)-a 130 0.85
(4)-b 130 0.88
(4)-c 130 1.23
______________________________________
Note:
*neutral filter was used for the measurement of the green color
From the results shown in Table 9, it will readily be understood that in each combination, a color having a higher density is obtained in a recording paper prepared by using the leuco pigment and organic solid medium in the form of compatible solid particles.
A similar tendency was observed when a Rhodamine lactam type leuco pigment, a spiropyran type leuco pigment, an Auramine type leuco pigment or a phenothiazine type leuco pigment was used instead of the above-mentioned leuco pigment.
A solid solution was prepared from an organic solid medium shown in Table 10 and Crystal violet Lactone, and in the same manner as described in Example 8, a heat-sensitive recording paper was prepared by using the so prepared solid solution, 2,2-bis(4'-hydroxyphenyl)propane as a color developer and a 5% by weight aqueous solution of polyvinyl alcohol as a binder. The recording paper was passed through heater rollers to examine the color-forming property. The obtained results are shown in Table 10.
TABLE 10
______________________________________
Pigment/ Heating Tem-
Reflec-
Medium perature tion
Organic Solid Medium
Weight Ratio
(°C.)
Density
______________________________________
-- 10/0 140 1.05
low density polyethy-
10/2 140 1.28
lene(m.p. = 110° C.)
zinc dibutyldithiocar-
10/1 140 1.22
bamate(m.p. = 103° C.)
styrene homopolymer
10/2 140 1.27
(s.p = 125° C.)
microcrystalline wax
10/1 140 1.29
(m.p. = 110° C.)
zinc stearate (m.p. =
10/1 140 1.28
122° C.)
______________________________________
In each case, the density of the formed color was higher than the density of the color formed when the leuco pigment was not formed into a solid solution.
The solid solutions described hereinbefore were prepared according to the method described in Example 8, that is, the first method described in the text of the instant specification. When low density polyethylene or zinc stearate is used, the second method may be adopted, and when microcrystalline wax is used, the third method may be adopted.
In 250 parts of diacetone alcohol were dissolved 100 parts of 2,2'-bis(4'-hydroxyphenyl)propane and 10 parts of erucic acid amide (having a melting point of 79° C.) under heating, and the formed solution was poured into 3600 parts of water to precipitate a solid solution of the color developer. The precipitate was recovered by filtration, washed with water and dried at 60° C. For comparison, a color developer composed of a mixture containing 2,2'-bis(4'-hydroxyphenyl)propane and erucic acid amide at a weight ratio of 10/1 was separately prepared. The so-formed solid solution was combined with the leuco pigment solid solution (3)-c of Example 9, and a heat-sensitive recording paper was prepared in the same manner as described in Example 8. The recording paper was passed through heater rollers (surface temperature=100° C.). The density of the formed color was 1.05. When the comparative color developer was used, the density of the formed color was only 0.80.
Claims (6)
1. A heat-sensitive color-forming recording material which comprises a recording layer comprising a particulate phenolic color developer and a particulate leuco pigment, which are dispersed in a binder independently from each other, wherein the phenolic color developer and/or leuco pigment is present in the form of compatible solid particles with a substantially inactive organic solid medium selected from the group consisting of sterically hindered phenol compounds, said organic solid medium having a melting or softening point lower than that of the phenolic color developer and/or leuco pigment and said organic solid medium is present in said compatible solid particles in an amount .[.2 to 250 times as large as.]. .Iadd.of 0.2 to 250% by weight, based on .Iaddend.the amount of the phenolic color developer and/or leuco pigment on the weight base.
2. A recording material as set forth in claim 1, wherein the organic solid medium is present in an amount of 5 to 100% by weight based on the phenolic color former and/or leuco pigment.
3. A recording material as set forth in claim 1, wherein the number average particle size of the compatible solid particles is 0.1 to 3 microns.
4. A recording material as set forth in claim 1, wherein the binder is a water-soluble or water-dispersible binder.
5. A recording material as set forth in claim 1, wherein the recording layer contains the leuco pigment and the phenolic color former at a weight ratio of from 1/2 to 1/40 and the amount of the leuco pigment is 2 to 30% by weight based on the total recording layer.
6. A recording material as set forth in claim 1 wherein the organic solid medium is a sterically hindered phenol selected from the group consisting of 2,6-di-tert-butyl-p-cresol, 2,2-methylene-bis(4-ethyl-6-tertbutylphenol), 2-hydroxy-4-methoxybenzophenone, phenyl salicylate, p-tert-butyl salicylate and 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56-16821 | 1981-02-09 | ||
| JP56016820A JPS57131594A (en) | 1981-02-09 | 1981-02-09 | Heat-sensitive recording body and manufacture thereof |
| JP56016821A JPS57131595A (en) | 1981-02-09 | 1981-02-09 | Heat-sensitive color developing recording body and manufacture thereof |
| JP56-16820 | 1981-02-09 |
Related Parent Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06346772 Division | 1982-02-08 | ||
| US06/506,227 Reissue US4459336A (en) | 1981-02-09 | 1983-06-23 | Heat-sensitive color-forming recording material and process for preparation thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USRE32466E true USRE32466E (en) | 1987-07-28 |
Family
ID=26353235
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/506,227 Ceased US4459336A (en) | 1981-02-09 | 1983-06-23 | Heat-sensitive color-forming recording material and process for preparation thereof |
| US06/880,431 Expired - Lifetime USRE32466E (en) | 1981-02-09 | 1986-06-30 | Heat-sensitive color-forming recording material and process for preparation thereof |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/506,227 Ceased US4459336A (en) | 1981-02-09 | 1983-06-23 | Heat-sensitive color-forming recording material and process for preparation thereof |
Country Status (3)
| Country | Link |
|---|---|
| US (2) | US4459336A (en) |
| EP (2) | EP0058083B1 (en) |
| DE (1) | DE3276629D1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59120492A (en) * | 1982-12-27 | 1984-07-12 | Pilot Ink Co Ltd | Reversible heat-sensitive recording material |
| JPS60264285A (en) * | 1984-06-13 | 1985-12-27 | Pilot Ink Co Ltd | Reversible thermal recording composition |
| US5309561A (en) * | 1990-09-28 | 1994-05-03 | Tandem Computers Incorporated | Synchronous processor unit with interconnected, separately clocked processor sections which are automatically synchronized for data transfer operations |
| JP3539532B2 (en) * | 1995-07-04 | 2004-07-07 | 株式会社リコー | Thermal recording material |
| US6300277B1 (en) * | 1998-07-09 | 2001-10-09 | Ricoh Company Ltd. | Thermosensitive recording material |
| DE19857717B4 (en) * | 1998-12-15 | 2012-08-02 | Air Liquide Deutschland Gmbh | Device for receiving electronic data carriers for compressed gas cylinders and corresponding compressed gas cylinder |
| JP2000318324A (en) | 1999-03-05 | 2000-11-21 | Nippon Paper Industries Co Ltd | Heat-sensitive recording body |
| JP2002086915A (en) * | 2000-09-11 | 2002-03-26 | Fuji Photo Film Co Ltd | Thermal recording material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4032690A (en) * | 1975-01-24 | 1977-06-28 | Mitsubishi Paper Mills, Ltd. | Thermosensitive recording material |
| US4236732A (en) * | 1976-10-16 | 1980-12-02 | Kanzaki Paper Manufacturing Co., Ltd. | Heat-sensitive record material |
| US4287264A (en) * | 1980-03-07 | 1981-09-01 | Labelon Corporation | Heat sensitive coating |
| US4295888A (en) * | 1976-01-19 | 1981-10-20 | Imperial Chemical Industries Limited | Solvent compositions |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1360581A (en) * | 1971-03-30 | 1974-07-17 | Fuji Photo Film Co Ltd | Thermosensitive recording material |
| IT991891B (en) * | 1973-07-27 | 1975-08-30 | Olivetti & Co Spa | IMPROVEMENTS IN A THERMO-SENSITIVE ELEMENT AND ITS CONDITIONS OF USE IN REPRODUCTION AND THERMO-GRAPHIC RECORDING SYSTEMS |
| JPS5323205A (en) * | 1976-08-16 | 1978-03-03 | Nakayo Telecommunications | Low current telephone control system |
| US4180405A (en) * | 1977-02-25 | 1979-12-25 | Graphic Controls Corporation | Heat-sensitive recording composition with mixed color precursors |
| SE445627B (en) * | 1978-08-01 | 1986-07-07 | Ricoh Kk | TERRIBLE REGISTRATION SHEET CONSISTING OF BEARER AND TERRIBLE LAYER |
| JPS5521274A (en) * | 1978-08-03 | 1980-02-15 | Ricoh Co Ltd | Heat responsive recording material |
| JPS5926477B2 (en) * | 1978-10-19 | 1984-06-27 | 保土谷化学工業株式会社 | thermal recording paper |
| JPS5734995A (en) * | 1980-08-12 | 1982-02-25 | Fuji Photo Film Co Ltd | Heat sensitive recording material |
-
1982
- 1982-02-09 DE DE8282300629T patent/DE3276629D1/en not_active Expired
- 1982-02-09 EP EP82300629A patent/EP0058083B1/en not_active Expired
- 1982-02-09 EP EP84114994A patent/EP0151733B1/en not_active Expired
-
1983
- 1983-06-23 US US06/506,227 patent/US4459336A/en not_active Ceased
-
1986
- 1986-06-30 US US06/880,431 patent/USRE32466E/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4032690A (en) * | 1975-01-24 | 1977-06-28 | Mitsubishi Paper Mills, Ltd. | Thermosensitive recording material |
| US4295888A (en) * | 1976-01-19 | 1981-10-20 | Imperial Chemical Industries Limited | Solvent compositions |
| US4236732A (en) * | 1976-10-16 | 1980-12-02 | Kanzaki Paper Manufacturing Co., Ltd. | Heat-sensitive record material |
| US4287264A (en) * | 1980-03-07 | 1981-09-01 | Labelon Corporation | Heat sensitive coating |
Also Published As
| Publication number | Publication date |
|---|---|
| US4459336A (en) | 1984-07-10 |
| EP0151733B1 (en) | 1988-06-08 |
| EP0058083A3 (en) | 1982-12-29 |
| EP0058083A2 (en) | 1982-08-18 |
| EP0058083B1 (en) | 1987-06-24 |
| EP0151733A1 (en) | 1985-08-21 |
| DE3276629D1 (en) | 1987-07-30 |
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