US3843384A - Heat-sensitive two color recording paper - Google Patents

Heat-sensitive two color recording paper Download PDF

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US3843384A
US3843384A US00261969A US26196972A US3843384A US 3843384 A US3843384 A US 3843384A US 00261969 A US00261969 A US 00261969A US 26196972 A US26196972 A US 26196972A US 3843384 A US3843384 A US 3843384A
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color
layer
heat
recording
forming
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K Adachi
T Takaoka
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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Priority claimed from JP46042341A external-priority patent/JPS5017865B1/ja
Priority claimed from JP46059395A external-priority patent/JPS5017866B2/ja
Priority claimed from JP46060752A external-priority patent/JPS5017867B2/ja
Priority claimed from JP46063815A external-priority patent/JPS5017868B2/ja
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/52—Compositions containing diazo compounds as photosensitive substances
    • 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
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/323—Organic colour formers, e.g. leuco dyes
    • 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
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds
    • B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
    • 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
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/423—Intermediate, backcoat, or covering layers characterised by non-macromolecular compounds, e.g. waxes
    • 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
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/165—Thermal imaging composition

Definitions

  • a heat-sensitive two color recording paper having first and second layers which individually develop different colors due to difference in quantity of heat applied to the paper surface, in which the color-developing component of the first layer is composed of (i) a triphenylmethane or fluoran type dye base having in the molecule a reactive color-developing component of the lactone or lactam type and (ii) a phenolic substance or an organic acid.
  • This recording paper contains polyether as a decolorizing agent for removing the color developed in the first layer, and the color of the first layer is removed at the time when the second layer develops a color, so that a clear two-colored record can be obtained.
  • This invention relates to heat-sensitive recording materials for use in information terminal machines such as, for example, facsimile, telegraphic machines, telewriters, electronic computers, various measuring machines and copying machines.
  • Recording materials which have heretofore been used in the above-mentioned machines are represented by conventional photographic materials, electrophotographic materials, electrostatic recording papers, electrolytic recording materials, diazo papers, etc. All these recording materials, however, require toners or developer and fixer at the image-forming step, so that the cleaning of recording machines and the supply of chemicals have been indispensable. Further, inks are used in the recording machines available at present, so that there have been such inconveniences from the standpoint of users that recording papers are stained with the inks, or solids formed due to vaporization of solvents used in the inks clog the inkdischarging holes of pens, with the result that figures to be recorded become thin or, in extreme cases, cannot be recorded. In order to overcome the above-mentioned drawbacks, many pressure-sensitive recording materials have come to be used. At present, however, the said recording materials are used as copying papers or teletyping papers in place of carbon papers, and thus are limited in uses.
  • thermofusible substance prepared by uniformly applying carbon or the like coloring pigment or dye powder onto a substrate, and coating on the resulting color layer a white and opaque thermofusible substance.
  • This sheet is of such a type that the thermofusible substance on the surface is scribed with a thermal pen to expose the lower color layer.
  • a recording material of this type has such drawbacks that wastes are formed and multi-color recording is impossible.
  • a recording material of such a type that a color is formed by the formation of a complex compound of an electron donor with an electron acceptor For example,
  • ferric s tearate and pyrogallol are independently dispersed in a binder, and the thus treated binder is softened by application of heat, whereby the two compounds react with each other to form a complex compound which forms a color.
  • the color developed in this case is dark brown.
  • the color developed in this case is cobalt blue. While this type suggests a promising way of heat-sensitive recording materials, there is a problem in how to obtain a record having 2 or more colors.
  • the heatsensitive material of the above-mentioned type (3) is a preferable material, since it gives a clear image by mere application of a thermal head.
  • high density informations have come to be required with the progress of society, and the demand for records having 2 or more colors is strong.
  • the present inventors made studies on the conventional heat-sensitive recording materials of this kind to find a heat-sensitive recording paper capable of forming clear two colors.
  • FIGS. 1 to 2 diagrammatically show the cross-sections of several recording papers of the present invention and FIGS. 4 and 5 show the cross-sections of recording papers for reference;
  • FIGS. 6 and 8 are individually a color development sensitivity curve showing the relation between temperature and reflective optical density;
  • FIG. 7 is a graph showing the relation between thermal head applying power and reflective optical density;
  • FIG. 9 is a graph showing the relation between width of line and reflective optical density.
  • the recording paper of the present invention is composed of a first heatsensitive recording material layer 1 which develops a color by the reaction of a triphenylmethane or fluoran type dye base (hereinafter referred to as color-forming dye) having in the molecule a reactive color-developing component of the lactone or lactam type with a phenolic substance or an organic acid (hereinafter referred to as color-forming agent); a second heat-sensitive recording material layer 2 which develops a color by the reaction of a diazo compound with an azo coupler; a layer 3 disposed between the said two layers 1 and 2 which contains a decolorizing agent for removing the color of the color-forming substance contained in the first layer 1; and a substrate 4.
  • a triphenylmethane or fluoran type dye hereinafter referred to as color-forming dye
  • color-forming agent a reactive color-developing component of the lactone or lactam type with a phenolic substance or an organic acid
  • FIG. 1 4 is a recording thermal head.
  • the color-forming dye 11 and the color-forming agent 12 have independently been dispersed as discontinuous particles into a film-forming binder 13, which is solid at normal temperature but is softened when heat is applied thereto. Accordingly, when the binder is heated by applying a certain quantity of heat to the surface of the recording material, the color-forming dye reacts with the color-forming agent to develop a color.
  • the diazo compound 21 and the azo coupler 22 have independently been dispersed as discontinuous particles into a film-forming binder 23, which is solid at normal temperature but is softened when heat is applied thereto. Accordingly, when the said binder is heated by applying a certain quantity of heat to the surface of the recording paper, the two compounds react with each other to develop a color different from the color of the first layer.
  • the recording materials constituting the above-mentioned first and second layers have individually been known as heat-sensitive recording materials of this kind.
  • the recording paper of the present invention is characterized in that a thermofusible polyether is used as the decolorizing agent for the color-developing substance of the first layer.
  • the quantity of heat (hereinafter referred to as heat A) necessary to develop the color of the first layer and the quantity of heat (hereinafter referred to as heat B) necessary to develop the color of the second layer are in such a relation as to satisfy the inequality A B.
  • the said decolorization agent is substantially solid at normal temperature, but is fused and fluidized when the heat B is applied to the paper surface. That is, when the quantity of heat applied to the paper surface in order to fiuidize the decoloring agent is deemed as heat C, the heats A, B and C are in such a relation as to satisfy the inequality A CB.
  • the quantities of heat applied to these layers 1, 2 and 3 are dependent on the temperature of the recording thermal head 5 to be contacted with the paper surface, the time of contact of the thermal head with the paper surface, and the thermal conductivity of the paper from the surface of each layer.
  • the quantity of heat applied to the first layer 1 is greater than the quantity of heat applied to the second layer 2, even though the temperature of the thermal head and the time of contact of thermal head with the paper surface are definite.
  • the temperature of the first layer is higher than that of the second layer. Accordingly, the color forming temperature of the second layer is not always required to be higher than that of the first layer. Generally, however, the color forming temperature of the second layer is made higher than that of the first layer.
  • the color formation mechanism of the first layer and the mechanism of removing the color formed in the first layer with the polyether in the inter layer are explained below.
  • a leuco dye base of the triphenylmethane type such as Crystal Violet Lactone forms a color by reaction with a phenolic substance such as phenol or cresol or with an inorganic or organic acid
  • a leuco dye base of the fluoran type also shows the same property as above. It is said that the mechanism of the above-mentioned reaction is such that the electron attractive acid attracts the electrons of amine of the dye base, whereby the dye base is ionized to form a color.
  • either one or both of the color-forming dye and color-forming agent may be dissolved in a thermoplastic substance such as polyvinyl alcohol or the like.
  • the color-forming dye forms a color due to such ionization as mentioned above, no color is formed in the presence of a polar solvent or the like substance which disturbs the ionization.
  • the fact that the color-forming dye brings about no color formation reaction in the presence of a polyether is utilized, so that in case the second layer is desired to be made visible, the color formed in the first layer is removed by the polyether to make the second layer clearly visible.
  • the recording paper of such a construction as shown in FIG. 1 can develop two brilliant colors by varying the quantity of heat applied.
  • the recording paper of the present invention is such that in forming the color of the second layer, the color formed in the first layer is removed by means of the polyether, as mentioned above, to obtain a color which has not been migrated with the color of the first layer. Accordingly, the color forming reaction of the second layer should not be affected by the polyether.
  • the combination of a diazo compound and an azo coupler is used as the color-forming component of the second layer.
  • the film-forming binder which separates the said two components from each other, is softened, with the result that the two components contact with each other and bring about a coupling reaction to form a color.
  • the second layer is different in color forming mechanism from the first layer which forms a color due to ionization of dye base, and the color forming reaction of the second layer is not affected at all by the polyether.
  • components which are not afiected by polyether and usable as color-forming components of the second layer there are combinations of electron acceptors and electron donors, in addition to the combination mentioned above.
  • the recording paper of the present invention may have such a construction as shown in FIG. 3. That is, the second layer 2 is a previously colored layer, and the inter layer 3 is composed of a thermoplastic polymer or wax 32, which itself can form a transparent thin layer, and a polyether 31 as the decolorizing agent.
  • the said polyether has been dispersed as particles into said polymer or wax so as to form a dispersed layer, and the thus formed inter layer 3 has been used to cover the colored layer, i.e. the second layer 2.
  • the inter layer 3 is fused by application of heat so that the color image formed in the first layer is decolored by the polyether and, at the same time, the second layer is made visible.
  • the color-forming component of the second layer 2 there may be used, like in the case of the first layer 1, a triphenylmethane or fluoran type dye base having in the molecule a reactive color-forming component of the lactone or lactam type. In this case, however, the color of the second layer is also removed by the polyether, so that the amount of the color-developing substance in the second layer should be made larger than that in the first layer.
  • the amount of the colordeveloping substance in the second layer is at least 5 parts by weight per part by weight of the color forming substance in the first layer.
  • the second layer can sufi'iciently develop a clear color even when the polyether is used in an amount sufficient to remove the color of the first layer.
  • FIG. 1 shows the case where the inter layer 3, which has been formed by dispersing particles of the polyether 31 in the thermoplastic binder 32 is disposed between the first and second layers. As shown in FIG. 2, however, it is also possible that the inter layer 3 is omitted, and. the. polyether 31 is dispersed in the second layer 2.
  • Colorforming dye Generally, a triphenylmethane type leuco dye base represented by the formula (I) shown below or a fluoran type dye base represented by the formula (II) shown below is used.
  • R Rx Z Ry wherein R R and R are individually a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group, a nitro group, an amino group, a dialkylamino group, a monoalkylamino group or an aryl group; and Z is an oxygen or sulfur atom necessary to form a heterocyclic group.
  • Binder When a dispersion formed by merely dispersing the aforesaid color-forming dye and color-forming agent in water or in a non-polar or slightly polar organic solvent is coated on a substrate, the resulting recording paper becomes high in fog or suffers from peeling and thus is low in practicality.
  • binder which can disperse and fix said color-forming dye and color-forming agent as discontinuous particles at normal temperature. Due to its inherent property, the binder is softened or melted when heat is applied thereto, whereby the formation of dye is promoted. Examples of such binder are as follows:
  • Natural rubber Synthetic rubbers Styrene-butadiene copolymers Chlorinated rubbers Polybutyl methacrylate These binders disperse and fix the aforesaid color-forming dyes and color-forming agents as discontinuous particles at temperatures below the heat recording temperature and, at the same time, play the role of adhering them to substrates. It is desirable to use a binder which is not easily discolored by heat.
  • additives In order to enhance the recording paper in whiteness and printability and to prevent the adhesion of thermal head, there may be used talc, titanium oxide, zinc oxide, calcium carbonate or the like. Further, in order to carry out the formation of dye at a sharp temperature, there may be used urea, thiourea, acetanilide, phthalic anhydride or the like thermofusible substance Alkyl resins which can melt the aforesaid color-forming dye and color-forming agent at the time of melting.
  • Decolorizing agent It is said that the formation mechanism of a color by use of the aforesaid color-forming agent and colorforming dye is such that an electron attractive acid attracts the electrons of amine of a dye base, thereby bringing about the ionization of the dye base. Accordingly, no color is developed in the presence of a polar solvent or the like substance which disturbs the ionization of dye base.
  • the present invention utilizes the fact that a substance, which has developed a color by use of the said color-forming dye and color-forming agent, is decolored in the presence of a polyether.
  • a polyether having such decolorizing efiect is represented by the general formula,
  • tM-Oix wherein x is an integer of 1 or more, and M is a methylene or polymethylene group or a derivative thereof.
  • Typical examples of such polyether are as follows:
  • R and R are individually a fatty acid chain
  • x and y are individually an integer of 1 or more.
  • Polyethylene glycol type nonionic surface active agents represented by the following general formulas:
  • decolorizing agents compounds having the skeleton in the molecules can be used as decolorizing agents in the present invention.
  • binders are solid at normal temperature. According to the capsulating technique at present, however, binders in the form of liquids may also be successfully used so far as the wall materials of capsules are suitably selected.
  • Second heat-sensitive recording material The first heat-sensitive recording material is decolorized with a decolorizer, but the second heat-sensitive recording material should not be decolorized with a decolorizer. It is therefore desirable that the second color-forming layer is composed of a substance which develops a color by application of heat larger in quantity than the heat required for decolorizing the first layer.
  • the above-mentioned substance are such combinations of electron acceptors and electron donors as mentioned below.
  • Electron acceptor Electron donor (1) Metal salts of long chain Phenols (e.g., ammonium salts of fatty acids (e.g., ferric tannic, gallic and salicylic stearate and ferric acids).
  • fatty acids e.g., ferric tannic, gallic and salicylic stearate and ferric acids.
  • Heavy metal salts of organic acids e.g., Ni, Co, Pb, Cu, Fe, Hg and Ag salts of acetic, stearic and palmitic acids.
  • Organic chelates e.g., thio- Sulfur compounds (e.g., sodium diphenyl carbazide and tetrathionate, sodium thiosuli'ate diphenyl carbazone). and thiourea).
  • Heavy metal salts of oxalic Sulfur compounds e.g., sodium acid (e.g., Ag, Pb, Hg tetrathionate, sodium thiosultate and Th salts). and thiourea).
  • Aliphatic ferric salts e.g., Aromatic polyhydroxy compounds ferric stearate
  • Aliphatic polyhydroxy compounds ferric stearate e.g., %4-dihydroxy tetraphenyl m ane
  • Cyclic organic reducing agents e.g., silver behenate and (e.g., protocatechuic acid and acidic silver phthalate). 2,3-dihydroxy-benzoic acid).
  • Alkaline earth metal salts e.g., aluminum salts
  • the second heat-sensitive recording material is composed mainly of at least one compound selected from diazo compounds and azo type diazo compounds, an azo coupler and a binder.
  • Diazo compounds and azo type diazo compounds It is desirable that these compounds are stable to light and is slightly colored or white or colorless.
  • binders examples include natural rubber, synthetic rubbers, chlorinated rubbers, alkyd resins, polystyrene, styrene-butadiene copolymers, polymethyl methacrylate, ethyl cellulose, nitrocellulose and polyvinyl carbazole.
  • Additives are used in order to prolong the second heat-sensitive recording material in life and to make brilliant the thermally formed colors.
  • a basic substance such as ammonium carbonate, ammonium salicylate, urea, thiourea or amine takes part in the thermal color-forming of the material
  • an organic acid such as palmitic acid, stearic acid, hydroquinone, resorcinol, salicylic acid, tartaric acid, citric acid or p-hydroxybenzoic acid, or a phenolic acid has etfect of enhancing the material in storage stability.
  • the recording paper of the present invention it is also possible to bring the recording paper of the present invention to such a construction that the second layer is composed of a colored layer and the inter layer, which covers the second layer, is composed of a lightscattering layer in which has been dispersed the aforesaid decolorizing agent in the form of particles, so that at the time of color formation, the inter layer is melted to remove the color developed in the first layer and, at the same time, to make the second layer visible.
  • the colored layer it is ideal to use a pigment or dye having a color which is complementary to the color to be developed in the first layer.
  • the binder used is a water-soluble polymer, not only the binder is easily applicable to the paper surface, but also the production cost of recording paper can advantageously be reduced.
  • pigment or dye to be used in the colored layer examples include carbon black (black), Benzidine Yellow (yellow), Chrome Vermilion (orange), Lake Red C (red), Toluidine Red (red), Phthalocyanine Blue (blue), Phthalocyanine green (green), Methyl Violet, Methylene Blue, Auramine O, Fuchsine NB, Congo Red and Acid Violet.
  • Evaluation method for investigating the effect of the present invention is as mentioned below.
  • a heat-sensitive recording sheet is colored for decolored by means of a metal stamp bed capable of being maintained at a definite temperature, and the colored or decolored image is represented by a reflective optical density (hereinafter referred to as R.O.D.), whereby a relative comparison can conveniently be made.
  • R.O.D. reflective optical density
  • the recording was effected by use of a column-shaped stainless steel-made stamp having an end diameter of mm. which had a heating portion in the interior, and a thermal head having silicon oxide film resistors as 10 heat-generating members, and the ROD. was measured by means of Automatic Equilibrium Densitometer NLM VI manufactured by Narumi Co. and Microdensitometer manufactured by Konishiroku Co.
  • the filter used was a gelatin filter produced by Kodak Co.
  • Referential Example 1 200 Parts by weight of an aqueous solution containing 10% by weight of a polyvinyl alcohol (PVA 205 produced by Kurare Co.) was mixed with 35 parts by weight of 3,3-bis(p-dimethylaminophenyl) G-dimethylaminophthalide as a color-forming dye, and the resulting mixture was pulverized in a ball mill for more than 1 hour to obtain a dispersion (hereinafter referred to as liquid A).
  • the color-forming dye had scarcely dissolved and had been dispersed in the form of fine particles of less than 5 microns.
  • aqueous solution containing 10% by Weight of polyvinyl alcohol was mixed with 35 parts by weight of bisphenol A as a color-forming agent, and the resulting mixture was pulverized in a ball mill for more than 1 hour to prepare a liquid B.
  • the color-forming agent had been dispersed in the form of fine particles of less than 5 microns.
  • the liquid A was mixed with 20 parts by weight of the liquid B by use of a homogenizing mixer.
  • the color-forming dye and the colorforming agent had individually been dispersed as fine particles and had individually been surrounded by the polyvinyl alcohol, so that it may be said that there was no direct contact between the two particles.
  • the thus obtained mixed liquid was coated by use of a wire bar on a white paper of 70 g./m. air-dried and then dried at a temperature of 40 to 45 C., on a photographic ferro plate to prepare a heat-sensitive one color recording paper. The amount of the coated mixture after drying was 5 g./m.
  • the thus prepared recording paper had such a construction as shown in FIG. 4.
  • the recording paper was colored by means of a stamp type color tester, whereby a clear blue image was obtained.
  • stamp temperatures are plotted on a horizontal axis and R.O.D. values on a vertical axis, there is obtained a curve corresponding to the H-D curve (characteristic curve) which is generally used in the photography.
  • the temperature giving an R.O.D. of fog (D +0.1 is referred to as color forming sensitivity and is represented by Ts
  • the said temperature Ts was C
  • the maximum density D max was 1.35
  • the ROD. of fog (D;) was 0.04 (refer to FIG. 6).
  • the recorded image thus obtained was sufficiently visible even when allowed to stand in a room for 6 months.
  • FIG. 5 A recording sheet of the construction as shown in FIG. 5:
  • liquids A and B as in Referential Example 1 were used.
  • a liquid C was prepared by dissolving 10 parts by weight of polyethylene glycol (#6,000, produced by Nippon Yushi Co.) in parts by weight of water.
  • the liquid C was coated by means of a wire bar on a white paper of 70 g./m. air-dried and then dried at a temperature of 40 to 45 C. by use of a photographic ferro plate to form a layer on the paper.
  • the same mixed liquid comprising the liquids A and B as in Referential Example 1 was coated by means of a wire bar on the abovementioned layer, air-dried and then dried at 40 to 45 C. by use of a photographic ferro plate to prepare a recording sheet.
  • the thus prepared recording sheet was recorded by means of a thermal recorder using a silicon oxide film resistor. The recording was effected at a pen speed of 300 mm./ sec. and the measurement of R.O.-D.
  • fluoran hydroxyethylene benzoate. sorbitan mono-oleate.
  • phenyl-5,7-dimethylbenzoic alcohol glycol fiuoran. acid. monostearate.
  • Liquids A and B corresponding to those in Referential Example 1 were prepared by use of the components shown below.
  • Liquid A Parts by weight 10% Binder solution 200 Color-forming dye 35 Liquid B:
  • Binder solution 200 Color-forming agent 35 These liquids were individually pulverized and dispersed by means of a ball mill for more than 1 hour, and
  • liquids C-1 and C2. were prepared by use of the components shown below.
  • the liquid C-2 was prepared by pulverizing in a ball mill for more than 1 hour a mixture comprising parts by weight of a polystyrene (Picolastic D 150, produced by 'Esso Standard Oil Co.), 70 parts by weight of a 1:1 mixed solution of toluene and benzene, and 20 parts by weight of a decolorizing agent.
  • the above-mentioned 3 kinds of liquids were individually coated on a coating paper of 70 g./m. and then dried to prepare a heatsensitive recording paper. Thereafter, the thus prepared recording paper was colored or decolored by use of a stamp type color-forming tester to measure such characteristics as mentioned in Referential Example 1.
  • a toluene-methanol mixed solution containing 20% by weight of polyvinyl butyral is equally divided into two to prepare liquids D and E.
  • the liquid D is mixed with 25 parts by weight of an electron donor
  • the liquid E is mixed with 25 parts by weight of an electron acceptor, and the resulting mixtures are individually pulverized by means of a ball mill for at least 2 hours.
  • the thus prepared electron donor dispersion and electron acceptor dispersion are mixed with each other in a weight ratio of 1:1.
  • liquids D and B were prepared by using ferric stearate as the electron acceptor and gallic acid as the electron donor.
  • the two liquids were mixed with each other in a ratio of 1:1, and the resulting mixture was coated on a paper and sufficiently dried to obtain a recording paper.
  • the thus obtained recording paper was colored by means of the stamp type color tester used in Referential Example 1, whereby a deep black color was obtained.
  • the color formation sensitive curve of the recording paper was as shown in FIG. 8.
  • Example 1 A second color layer-forming material containing cadminium stearate as an electron donor and diphenylcarbazone as an electron acceptor was coated on a high quality paper of microns in thickness, and then gradually dried at about 80 C. to form a second color layer on the paper. Thereafter, an inter layer-forming material containing polyethylene glycol was coated on the above-mentioned layer and then dried to form an inter layer. Subsequently, the mixed liquid prepared in Referential Example 1 was coated on the inter layer and then gradually dried to obtain a recording paper. The weights of the first color layer, the inter layer and the second color layer were 2 g./m. 0.2 g./m. and 5 g./m. respectively.
  • the thus obtained recording paper was recorded by means of a recorder using a thermal head, whereby the first layer formed a blue color when thermal head temperature was to C., and the second layer formed a red color when the thermal head temperature became more than 125 C. More particularly, the blue color was formed at 85 to 90 C. and completely disappeared at to C., and only the red color of the second layer 13 was formed at above 125 C. Subsequently, the two color recording paper was subjected to recording by means of a thermal printer using silicon oxide film resistors, whereby a blue color was formed at an imput energy of 7 mj./dot.
  • Example 10 Diphenylcarbazole as an electron acceptor, cadmium stearate as an electron donor and polypropylene glycol as a decolorizing agent were treated in the same manner as bl to Storage. in Example 9 to prepare a liquid. This liquid was coated Example 2 on the same paper as in Example 9 and then sufiiciently dried to form a layer on the paper.
  • a liquid A recordmg Paper was P' In same manner containing Leuco Crystal Violet as a color-forming dye as Example 3 except that 3dlmethylammo'sfl'dlmefh' and bisphenol A as a color-forming agent was coated on ylfluoran and blsphenol A were used as the colorfonmng the above-mentioned layer and then sufficiently dried to comlmnents of the first f Polypropylene glycol f obtain a recording paper.
  • the thus obtained recording used as dthe inter layer material, and ferric stearate, galhc paper was Subjected to recording by use of a 2 pen type acid an titanium oxide were used as the color-forming thermal recorder, which had been so designed that a components of the second layer.
  • ThlS recording paper was definite energy could always be applied to the paper by Subjected to recording by use of thermal head kept at 95 use of silicon oxide film resistors.
  • a brilliant 130 whereby a m red P was formed blue color was recorded on the first low energy side and a at i black color mlgrated wlth no red color brilliant red color was recorded on the high energy side.
  • fluoran 4-hydroxybenzoate. 8 do Polyethylene glycol mono- Cesium stearate 4-methoxy-l-hydroxy do Do.
  • diphen 7 Cxgstal violet lactone bisphenol Polyethylene glycol Silver hehenate procatechuic acid Blue Red. 8 (in Polypropylene glycol N-Dodecylthiourea guanidyl carbonate do Black.
  • Example 9 Liquid F: Parts by weight 200 Parts by weight of a 1:1 mixed liquid of the liquids 6 59 523; gig g' 3 D and E prepared in Referential Example 4 was mixed Llqllld G. with 50 parts by weight of a l1qu1d prepared by dispersing Diazo coupler 15 10 parts by weight of polyethylene glycol in 100 parts by 10% Binder Solution 100 weight of toluene, and the resulting mixed liquid was sufficiently stirred. This liquid was coated on a high quality Each of liquids F and G of the above compositions were paper of 80 microns in thickness in a proportion of 7 individually pulverized for more than 10 hours by means g./m. and then dried to form a layer on said paper.
  • a liquid was prepared in the same manner form dispersions.
  • the size of each dispersed particle after as in Referential Example 1 by use of 1,3,6-bis-fl-meththe pulverization was 0.1 to 5 microns.
  • Each 100 parts by oxyethoxyfluoran as a color-forming dye and bis-phenol Weight of the dispersions were mixed with each other by A as a color-forming agent.
  • This liquid was coated on the means of a homogenizing mixer. Subsequently, the mixed above-mentioned layer in a proportion of 2 g./m.
  • sufdispersion was coated on a paper, air-dried and then dried ficiently dried and then finished by use of a calender roll by use of a photographic ferro bed to prepare a recordto prepare a recording paper.
  • the amount of the dispersion coated was 3.5 paper was subjected to recording by use of a head made to 10 g./m.
  • the thus prepared recording paper was of silicon oxide film resistors arranged in one line in the tested by use of a stamp type color forming tester. The horizontal direction and 7 lines in the vertical direction. results obtained were as set forth in Table 3.
  • toluidide dlene copolymer. 11-3 4-eihloro-2,2-trichloromethy1 aniline 3-hydroxy-2-naphthanilide.. Polystyrene 127 0.85 0.08 Red.
  • Ts is a color forming sensitivity.
  • D- is a maximum density, and Df is a fog density.
  • Example 12 A recording sheet was prepared b use of the materials described in Example 11-1, and polyethylene glycol dispersed in a toluene solution of polystyrene was coated 1 6
  • Example 14 Recording sheets of the construction shown in FIG. 1: Using such components as in Table 4, heat-sensitive two color recording sheets were prepared in the same thereon in a proportion of 2 g./m. to form a layer 5 manner as in Example 12. The characteristics of the on the sheet. Subsequently, a color-forming component recording sheets were as set forth in Table 4.
  • glycol mopostearate 14-5 3-dlmethylarnino- 1-diazo-2-methylphenyl-5,7-dl- Polyproi-chloro- 90 130 125 0.65 0.75 0.13 Red Brownlsh methylfluoran. pylene benzene% purple. 14-5 p.Hydroxybenzo1c glycol. Zn 2- acld. 1,3,5-hydroxybenzene. Polyvinyl alcohoL. Ethyl cellulose.
  • the color of the first recording material was a brilliant bluish purple color (a cobalt color), and that of the second recording material was a reddish orange color.
  • Example 13 Recording sheet of the construction (FIG. 2) comprising a first recording material and a second recording material incorporated with a decolorizing agent:
  • Example 15 Parts by weight of polyethylene glycol was added to each of the liquids -F and G used in Example 11-1, and the resulting mixture was pulverized for more than 10 hours by means of a ball mill having an inner volume of 200 ml. The size of each dispersed particle was 0.1 to 5 microns.
  • each 50 parts by weight of the liquids F and G were quickly mixed with each other by means of a homogenizing mixer, and the resulting mixed liquid was coated on a paper of 70 g./m. airdried and then dried by use of a ferro bed to form a layer.
  • an equal amount of the first color-forming component of Example 12 was coated on said layer, and then air-dried to prepare a recording sheet.
  • the thus prepared recording sheet was investigated in characteristics by means of a stamp type color forming tester to obtain entirely the same results as in Example 12.
  • the emulsion was coated on a white paper of g./m. and then dried to form a layer on the paper.
  • the amount of the coated emulsion after drying was 7 g./m.
  • the thus coated paper was subjected to a calender roll to make the surface thereof sufliciently smooth, and then the liquid C-2 used in Referential Example 2 was coated on the paper surface and then dried to form a layer thereon.
  • the amount of the coated liquid after drying was 0.42 g./m.
  • an emulsion was prepared in the same manner as in Referential Example 1 by use of Crystal Violet Lactone as a color-forming dye and'bisphenol A as a color-forming agent. This emulsion was coated on the above-mentioned layer and then dried to obtain a recording paper. The amount of the coated emulsion after drying was 1 g./m.
  • the thus obtained recording paper was subjected to recording by use of a thermal recorder having silicon oxide films resisters as heat-generating members and under a speed condition of 200 m./sec., whereby a blue color could be recorded at 1.5 mi. and a red color at 2.5 mi.
  • the first and second colors were measured in reflective optical density by means of Konishiroku Microdensitometer using a filter. The results obtained were shown in Fig. 9, wherein the vertical axis shows the reflective optical density, and the horizontal axis shows the width of line.
  • Fig. 9-(A) is a graph showing the reflective optical densities of the first color formed at 1.5 mj., in which the solid line 1 represents the reflective optical densities of the first color when measured by use of a red filter (Ratten No. 25 produced by Kodak Co.), and the dotted line 2 represents those of a red color component detected in a more or less amount in the first color when measured by use of a blue filter (Ratten No. 55 produced by Kodak Co.).
  • the first color is a substantially complete blue color, though a more or less amount of red color was detected by the densitometer.
  • Fig. 9-(B) is a graph showing the reflective optical densities of the second color formed at 2.5 mj., in which the 18
  • the above-mentioned black coating layer was formed by coating on the paper a mixture of 100 parts by weight of an aqueous solution containing 4% by weight of polyvinyl alcohol and 10 parts by weight of carbon black.
  • the polyvinyl alcohol acted as a binder for the pigment solid line 3 represents the reflective optical densities of particles.
  • the thickness of the black coating layer was the second color when measured by use of the abovemade about 2 microns.
  • the dotted l ne 4 represents The above-mentioned opaque light-scattering particle those of a blue color component detected in a more or less layer of a fusible material was formed in such a manner amount in the second color when measured by use of the that 30 parts by weight of polyethylene glycol (average above-mentioned red filter.
  • the second color is molecular weight 7,000) and 100 parts by weight of a a s bs anti lly brllllflnt red color, though a more r 1 solution comprising acetone and toluene in a volume ratio amount of blue color was detected by the densitometer on f 1:1 were mixed i h 25 parts weight f a 1 wt both sides of the recorded Curve f t red 001011 percent solution of nitrocellulose in a 1:1 mixed solvent In the above manner, two blllllant could be of acetone and toluene, and the resulting mixture was recorded.
  • the thus recorded colors were sufficiently stable coated on the above-memioned black layer and then to Storagesufliciently dried with hot air at below 50 C.
  • the thicklfurther, th ah v recordmg pap r ness of the light-scattering particle layer was about 3 sub ected to recording by use of a head comprising s1l1con i Qxlde film reslstors of 7 dots and under a Speed eondl-
  • the black color of the aforesaid black layer had been tron of characters/sec, whereby a blue color could be protected substantially completely with the said lightrecorded at 6 1- and a brllllant red 00101 at 10 scattering particle layer, and hence was not visible.
  • Example 16 The thus obtained recording paper was subjected to recording at a speed of rum/sec. by means of the 011251 P p Were sueceeslvely coated 1n thls e 5 5 aforesaid recorder using silicon oxide film resistors, a Second color-formmg component eompl'lsmg whereby a black color could be recorded at an input engallic acid and Leuco Crystal Violet Lactone, 0.3 g./m.
  • the recording paper was tested in color forof a first eolor-developlng eomponent eompflsmg mation by use of the aforesaid stamp type color form- 9 'd1hydr0xybe11z0ate and P l f 30 ing tester, whereby a black color initiated to develop at quently, the coated paper was sufficlently dried to obtain and reached the maximum.
  • the opaque layer initiated to be made transrecol'dmg by e f the same recorder as Example parent at 75 C. and was completely made transparent at whereby tWQ bl'lnlant fed and blue Colors could be 90 C. to make the lower colored layer visible.
  • Example 17 In this corded as the first and Second colors, respectively 35 case, the fog density (density prior to recording) was Example 17 1
  • Example 19 Recording papers were prepared in the same manner as in Example 15, and then subjected to recording at a 5 Parts by weight of fuchsine was dissolved in speed of 60 mm./sec., using silicon oxide film resistors. 40 parts by weight of water. 10 Parts by weight of the re- The results obtained were as set forth in Table 5, in sulting solution was mixed with 30 parts by weight of a which the color formation temperatures are temperatures 4% aqueous polyvinyl alcohol solution, and the mixed of the heating portions of the silicon oxide film resistors.
  • polyrecording paper prepared by successively coating on a base paper in this order (i) a previously colored dye or pigment and a binder, (ii) polyether and polyethylene glycol derivatives dispersed as light-scattering particles into a thermoplastic polymer capable of forming by itself a transparent thin layer, and (iii) a color-forming substance comprising a leuco dye base of the triphenylmethane type, a dye of the fluoran type and a phenolic substance.
  • Example 18 Onto a continuous sheet-like paper of 75 microns in thickness were successively formed a black sub-coating layer and an opaque light-scattering particle layer (inter layer) of an inherently fusible material.
  • propylene glycol 10 parts by weight of nitrocellulose, 30 parts by weight of hydrogenated fatty oil wax and 10 parts by weight of talc were added to parts by weight of a mixed solution of acetone and toluene, and the resulting mixture was kneaded by means of a ball mill to form a dispersion. 10 Parts by weight of this dispersion was mixed with 10 parts by weight of a 1:1 mixed solution of acetone and toluene, and then coated on the surface of the aforesaid colored layer to form an opaque light-scattering layer. The thickness of the light-scattering layer after thorough drying was 4 microns.
  • a color-forming component comprising Leuco Crystal Violet Lactone as a color-forming dye and 2,2'-dihydroxydiphenyl as a color-forming agent was coated on the above-mentioned light-scattering layer.
  • the thus coated paper was dried to prepare a recording paper.
  • This recording paper was subjected to recording at a pen speed of 60 mm./sec. by use of a recorder having silicon oxide film resistors as heat-generating members.
  • the first color i.e. blue color, was formed at a thermal head temperature 6.
  • a heat-sensitive two color recording paper according to Claim 5 wherein the second layer is a previously of 120 C. and disappeared at 150 C., and, at the same colored layer, and the inter layer has been so constructed time, a red color initiated to be made visible and reached as to act as a protective layer for the second layer so that, the maXlmllm dens ty at 200 C.
  • the inter layer becomes substanbrilliant colors which had not been migrated with each i ll transparent to k h second 1 i ibl other; Of es colors, the fi color somewhat 8.
  • the recording papers were color'formmg subsiance of the first layer; measured in color formation temperatures and colors of 20 9.
  • the results obtained were as layers which individually develop difierent colors due to a set forth in Table 6.
  • bisphenol A cellulose. glycol genated fatty black.
  • bisphenol A polymer. alllrlylallyl blue. blue.
  • Rhodamine lactam 4- Nitro- Polyethylene -....do Carbon black”... 90 0., rcd 140 0., hydroxyacetophenone. cellulose. glycol. black.
  • a heat-sensitive two color recording paper which has a layer of a first heat-sensitive recording material prepared by dispersing, as discontinuous particles into a filmforming binder, a triphenylmethane or fluoran type noncolored dye base having in the molecule a reactive colordeveloping component of the lactone or lactam type, and a phenolic substance or an organic acid, said layer developing a color at the time of application of heat, by formation of a color-developing substance, and a layer of a second heat-sensitive recording material capable of developing at the time of application of heat a color different from the color of the aforesaid first layer, and which contains as a decolorizing agent for the color-developing substance contained in the first layer a thermofusible polyether which is substantially solid at normal temperature.
  • thermofusible polyether A heat-sensitive two color recording paper according to Claim 1, wherein the quantity of heat A necessary to develop the color of the first layer, the quantity of heat B necessary to form the color of the second layer, and the quantity of heat C necessary to fluidize the thermofusible polyether are in such a relation as to satisfy the inequality A CB.
  • a heat-sensitive two color recording paper according to Claim 1 wherein the second layer has such a construction that a diazo compound and an azo coupler have been used as color-forming components and have been dispersed as discontinuous particles into the film-forming binder.
  • V 5 A heat-sensitive two color recording paper according to Claim 1, wherein the polyether has been dispersed in the film-forming binder and disposed as an inter layer between the first layer and the second l yer.
  • a layer of a first heat-sensitive recording material prepared by dispersing, as discontinuous particles into a film-forming binder, a. triphenylmethane or fluoran-type non-colored dye base having in the molecule a reactive color-developing component of the lactone or lactam type, and a phenolic substance or an organic acid, said layer developing a color at the time of application of heat, and a layer of a second heat-sensitive recording material capable of developing at the time of application of heat a color diiferent from the color of the aforesaid first layer, the improvement which comprises employing in said recording paper a decolorizing agent for the color-developing substance formed in the first layer a thermofusible polyether which is substantially solid at normal temperature.
  • triphenylmethane or fluoran type non-colored dye base is selected from the group consisting of 3,3-bis(p-dimethylaminophenyl) -phthalide,
  • the heat-sensitive two color recording paper of claim 9 wherein said phenolic substance is selected from 22 tartaric acid, oxalic acid, maleic acid, citric acid, succinic acid, gallic acid, l-hydroxy-Z-naphthenic acid, and 2-hydroxy-p-toluyl acid.
  • said thermofusible polyether is selected claim 9 wherein said organic acid is selected from the from the group consisting of polyethylene glycol,
  • sorbitan monostearate polyoxyethylene sorbitan mono-oleate
  • polyethylene glycol monostearate polypropylene glycol
  • polyoxyethylene alkylamide polyoxyethylene alkylamine
  • polyoxyethylene alkylallyl ether polyoxymethylene

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JP46060752A JPS5017867B2 (enrdf_load_stackoverflow) 1971-08-10 1971-08-10
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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4025399A (en) * 1974-04-08 1977-05-24 Canon Kabushiki Kaisha Image recording member
US4030934A (en) * 1974-08-07 1977-06-21 Kawamura Seichu Kogyo Kabushiki Kaisha Coloring composition for line- or pattern- drawing elements
US4054684A (en) * 1974-12-03 1977-10-18 La Cellophane Composition for forming colored images, new recording material and process using same
EP0012587A1 (en) * 1978-12-14 1980-06-25 Ricoh Company, Ltd Thermo-sensitive multi-color recording material and process for preparation thereof
US4321092A (en) * 1973-07-27 1982-03-23 Kores Holding Zug Ag Pressure-sensitive duplicating material
US4332872A (en) * 1980-09-19 1982-06-01 Zingher Arthur R Optically annotatable recording film
US4348234A (en) * 1979-03-20 1982-09-07 Ciba-Geigy Corporation Coating compositions for the production of a recording material
US4525214A (en) * 1983-03-11 1985-06-25 The Mazer Corporation Crayon adapted for development of latent images
US4603202A (en) * 1983-10-14 1986-07-29 Basf Aktiengesellschaft Fluoran colorants for recording systems
US4958021A (en) * 1987-07-25 1990-09-18 Basf Aktiengesellschaft Benzopyran derivatives
US4965166A (en) * 1988-03-02 1990-10-23 Fuji Photo Film Co., Ltd. Multicolor recording material
US4985331A (en) * 1988-11-25 1991-01-15 Fuji Photo Film Co., Ltd. Multi-color recording materials
US5250493A (en) * 1990-11-22 1993-10-05 Ricoh Company, Ltd. Thermosensitive recording material
US5443908A (en) * 1990-09-17 1995-08-22 Mitsubishi Paper Mills Limited Heat sensitive recording composition and process for producing same
US5804528A (en) * 1995-11-20 1998-09-08 Oji Paper Co., Ltd. Thermosensitive recording material with a high fog resistance
US20030228439A1 (en) * 2002-05-30 2003-12-11 Fuji Photo Film Co., Ltd. Heat-sensitive recording material
WO2006114600A3 (en) * 2005-04-25 2007-05-10 Datalase Ltd Multi-colour printing
US20110065046A1 (en) * 2003-10-15 2011-03-17 Yukihiko Tanaka Photosensitive resin compositions and photosensitive dry films using the same
US9387714B2 (en) 2013-01-10 2016-07-12 Oji Holdings Corporation Multicolor thermal recording material, and method for color formation of said multicolor thermal recording material

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Publication number Priority date Publication date Assignee Title
CH578432A5 (enrdf_load_stackoverflow) * 1973-03-05 1976-08-13 Ciba Geigy Ag
JPS551919B2 (enrdf_load_stackoverflow) * 1973-08-08 1980-01-17
US4151748A (en) * 1977-12-15 1979-05-01 Ncr Corporation Two color thermally sensitive record material system
US4599630A (en) * 1983-11-15 1986-07-08 Ricoh Company, Ltd. Two-color thermosensitive recording material
JPH0755582B2 (ja) * 1984-07-27 1995-06-14 株式会社リコー 二色感熱記録型ラベル
JPH0710620B2 (ja) * 1985-03-28 1995-02-08 株式会社リコー ２色感熱記録型ラベル
JPS6242878A (ja) * 1985-08-10 1987-02-24 Ricoh Co Ltd 感熱記録材料
JP2626761B2 (ja) * 1987-05-29 1997-07-02 富士写真フイルム株式会社 カラー画像形成方法および記録材料
US5876898A (en) * 1995-07-18 1999-03-02 Mitsubishi Paper Mills Limited Heat sensitive recording material and recording method using the same

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4321092A (en) * 1973-07-27 1982-03-23 Kores Holding Zug Ag Pressure-sensitive duplicating material
US4025399A (en) * 1974-04-08 1977-05-24 Canon Kabushiki Kaisha Image recording member
US4030934A (en) * 1974-08-07 1977-06-21 Kawamura Seichu Kogyo Kabushiki Kaisha Coloring composition for line- or pattern- drawing elements
US4054684A (en) * 1974-12-03 1977-10-18 La Cellophane Composition for forming colored images, new recording material and process using same
EP0012587A1 (en) * 1978-12-14 1980-06-25 Ricoh Company, Ltd Thermo-sensitive multi-color recording material and process for preparation thereof
US4311750A (en) * 1978-12-14 1982-01-19 Ricoh Company Limited Thermo-sensitive multi-color recording material and process for preparation thereof
US4348234A (en) * 1979-03-20 1982-09-07 Ciba-Geigy Corporation Coating compositions for the production of a recording material
US4422671A (en) * 1979-03-20 1983-12-27 Ciba-Geigy Corporation Coating compositions for the production of a recording material
US4332872A (en) * 1980-09-19 1982-06-01 Zingher Arthur R Optically annotatable recording film
US4525214A (en) * 1983-03-11 1985-06-25 The Mazer Corporation Crayon adapted for development of latent images
US4603202A (en) * 1983-10-14 1986-07-29 Basf Aktiengesellschaft Fluoran colorants for recording systems
US4958021A (en) * 1987-07-25 1990-09-18 Basf Aktiengesellschaft Benzopyran derivatives
US4965166A (en) * 1988-03-02 1990-10-23 Fuji Photo Film Co., Ltd. Multicolor recording material
US4985331A (en) * 1988-11-25 1991-01-15 Fuji Photo Film Co., Ltd. Multi-color recording materials
US5443908A (en) * 1990-09-17 1995-08-22 Mitsubishi Paper Mills Limited Heat sensitive recording composition and process for producing same
US5250493A (en) * 1990-11-22 1993-10-05 Ricoh Company, Ltd. Thermosensitive recording material
US5804528A (en) * 1995-11-20 1998-09-08 Oji Paper Co., Ltd. Thermosensitive recording material with a high fog resistance
US20030228439A1 (en) * 2002-05-30 2003-12-11 Fuji Photo Film Co., Ltd. Heat-sensitive recording material
EP1367437A3 (en) * 2002-05-30 2004-06-30 Fuji Photo Film Co., Ltd. Heat-sensitive recording material
US20110065046A1 (en) * 2003-10-15 2011-03-17 Yukihiko Tanaka Photosensitive resin compositions and photosensitive dry films using the same
US8372577B2 (en) * 2003-10-15 2013-02-12 Tokyo Ohka Kogyo Co., Ltd. Photosensitive resin compositions and photosensitive dry films using the same
WO2006114600A3 (en) * 2005-04-25 2007-05-10 Datalase Ltd Multi-colour printing
US9387714B2 (en) 2013-01-10 2016-07-12 Oji Holdings Corporation Multicolor thermal recording material, and method for color formation of said multicolor thermal recording material

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DE2228581C3 (de) 1974-05-30
GB1400886A (en) 1975-07-16
CA959648A (en) 1974-12-24
DE2228581A1 (de) 1972-12-21
FR2142447A5 (enrdf_load_stackoverflow) 1973-01-26
DE2228581B2 (de) 1973-10-25
NL153130B (nl) 1977-05-16
NL7208043A (enrdf_load_stackoverflow) 1972-12-18

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