EP0123224A2 - Wärmeempfindliche Aufzeichnungsmaterialien - Google Patents

Wärmeempfindliche Aufzeichnungsmaterialien Download PDF

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Publication number
EP0123224A2
EP0123224A2 EP84104136A EP84104136A EP0123224A2 EP 0123224 A2 EP0123224 A2 EP 0123224A2 EP 84104136 A EP84104136 A EP 84104136A EP 84104136 A EP84104136 A EP 84104136A EP 0123224 A2 EP0123224 A2 EP 0123224A2
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EP
European Patent Office
Prior art keywords
microcapsules
heat sensitive
sensitive recording
recording material
present
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP84104136A
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English (en)
French (fr)
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EP0123224A3 (en
EP0123224B1 (de
Inventor
Toshimasa Usami
Toshiharu Tanaka
Fumiaki Shinozaki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP58065043A external-priority patent/JPS59190886A/ja
Priority claimed from JP58114752A external-priority patent/JPS606493A/ja
Priority claimed from JP58158469A external-priority patent/JPS6049991A/ja
Priority claimed from JP58169015A external-priority patent/JPS6061288A/ja
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0123224A2 publication Critical patent/EP0123224A2/de
Publication of EP0123224A3 publication Critical patent/EP0123224A3/en
Application granted granted Critical
Publication of EP0123224B1 publication Critical patent/EP0123224B1/de
Expired legal-status Critical Current

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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
    • 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
    • G03C1/002—Photosensitive materials containing microcapsules

Definitions

  • This invention relates heat sensitive recording materials, and particularly to fixable diazo heat-sensitive recording materials. More particularly, the invention relates to heat sensitive recording materials which have excellent shelf life before heat recording, provide high coloring density as a result of heat recording, and can be fixed by light after heat recording.
  • a heat sensitive recording method has the advantages that (1) development is unnecessary, (2) when the support of the heat sensitive material is paper, the characteristics of the paper are similar to those of paper in general, (3) handling is easy, (4) a coloring density is high, (5) the recording device is simple and inexpensive, (6) noise is not generated on recording, etc., and hence the heat sensitive recording method is being widely used in facsimile and printer fields.
  • Heat sensitive recording materials for the recording method include predominantly a leuco coloring type heat sensitive recording material with excellent coloring density and coloring speed.
  • a leuco coloring type heat sensitive recording material has the disadvantages that the recording material is colored on handling, heating, or solvent treatment although after recording to stain the recorded image and also the recorded color images disappear due to the actior of plasticizers present in adhesive tape.
  • Japanese Patent Publication No. 14,531/1975 Japanese Patent Publication No. 14,531/1975
  • Japanese utility Model Publication (Unexamined) No. 125,354/1981 Japanese utility Model Publication (Unexamined) No. 125,354/1981
  • a method of using a heat sensitive recording material composed of a diazo compound, a coupling component, and an alkali generating agent or a coloring assistant and irradiating the recording material with light after heat recording to decompose the unreacted diazo compound, whereby further coloring of the recording material is stopped is known as a method of stopping coloring of unnecessary areas of a heat sensitive recording material after heat recording.
  • a waxy material or a hydrophobic polymer is dissolved in a solvent, a coloring component is dissolved or dispersed in the solution, and then the solvent is evaporated off to form microcapsules containing the coloring component.
  • the coloring component is incompletely encapsulated as the core material of the microcapsules and is uniformly mixed with the encapsulating material of the microcapsules.
  • pre- coupling gradually proceeds at the. interface of the walls of the microcapsules during storage of the recording material and hence the shelf life of the recording material is not satisfactory.
  • the walls of the microcapsules must be fused by heating for performing the coloring reaction, which results in a reduction in the heat coloring property. Furthermore, in the foregoing method, there is the difficult problem that after forming the microcapsules, the solvent used for dissolving the waxy material or the hydrophobic polymer must be removed and hence the foregoing method is still unsatisfactory in this point.
  • a first object of this invention is, therefore, to provide a heat sensitive recording material having excellent shelf life and high coloring speed and coloring density.
  • a second object of this invention is to provide a heat sensitive recording material capable of stopping the formation of coloring in unnecessary areas (hereinafter, referred to as "fixing") by photodecomposing unreacted diazo compound after heat recording.
  • a third object of this invention is to provide a heat sensitive recording material having excellent production aptitude.
  • a coloring activator a coloring assistant or activator
  • a heat sensitive recording material comprising a support having thereon a recording layer containing a diazo compound, a coupling component and a coloring activator, wherein at least one of the diazo compound,-the coupling component and the coloring activator is contained in microcapsules with the exclusion of the case that the three components are present in the same microcapsule, the wall of the microcapsules being formed around the core material by the polymerization of a reactant or reactants after dispersing the core material.
  • the wall of the microcapsules are composed of polyurethane, polyurea, polyamide or polyester.
  • the core materials are present in the microcapsules together with an organic solvent.
  • the core material is the diazo compound and the wall of said microcapsules is composed of a polymer formed around the core material by the reaction of a polyhydric isocyanate and a polyol.
  • the diazo compound is one represented by the general formula wherein Ar represents a substituted or unsubstituted aromatic moiety and X r represents an acid anion containing a perfluoroalkyl group or an acid anion containing a perfluoroalkenyl group.
  • microcapsules in this invention are not of the type that a coloring reaction occurs upon rupturing of microcapsules by heat or pressure to contact a reactive material present in the microcapsules as the core material and a reactive material present outside the microcapsules as used for conventional recording materials but of the type that the core material present in the microcapsules and a reactive material: present outside the microcapsules react through the walls of the microcapsules upon heating.
  • the wall of a microcapsule is formed by polymerization, the wall thus formed is not a completely impermeable film but is permeable to some extent.
  • the permeability of the wall of the microcapsule in the above-described conventional case results in a low molecular material gradually permeating therethrough over a long period of time.
  • the phenomenon that a reactive material permeates instantly through the wall of the microcapsule on heating as in the present invention is not yet known. Accordingly, in the case of the microcapsules in this invention it is unnecessary to fuse the wall of the microcapsules by heating and the wall may be formed using a polymer having a high melting point, which provides the heat sensitive recording material with excellent shelf life.
  • the heat sensitive recording material contains (a) a diazo compound, (b) a coupling component and (c) a coloring activator in the recording layer in a form that one or two of these three components are present in microcapsules (when two components are encapsulated, the components may be present in the same microcapsules or in differentmicrocapsules) , the wall of the microcapsules being composed of a high molecular weight compound formed around the core material by polymerization after emulsifying the core material in a reactant for the high molecular material.
  • the diazo compound used in this invention is a diazonium salt represented by general formula (I) or unsubstituted wherein Ar represents a substituted/aromatic moiety; N 2 + represents a diazonium group and X represents an acid anion, preferably an acid anion containing a perfluoroalkyl group or an acid anion containing perfluoroalkenyl group, which can be colored by undergoing a coupling reaction with the coupling component and.can be decomposed by light.
  • Ar represents a substituted/aromatic moiety
  • N 2 + represents a diazonium group
  • X represents an acid anion, preferably an acid anion containing a perfluoroalkyl group or an acid anion containing perfluoroalkenyl group, which can be colored by undergoing a coupling reaction with the coupling component and.can be decomposed by light.
  • the substituted aromatic moiety represented by Ar are, preferably, represented by general formula wherein Y represents a substituted amino group, an alkoxy group having 1 to 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, an arylamino group having 6 to 18 carbon atoms, or an acylamino group having 1 to 18 carbon atoms; said substituted amino group preferably including a dialkylamino group having 1 to 36 carbon atoms, an arylamino group having 6 to 18 carbon atoms, a morpholino group, a hydrogen piperidino group, a pyrrolidino group, etc., and R represents/ an alkyl group having 1 to 5 carbon atoms, a halogen atom (e.g., I, Br, Cl, F), an alkoxy group having 1 to 18 carbon atoms, or an arylamino group having 1 to 18 carbon atoms.
  • Y represents a substituted amino group, an alkoxy group having 1 to
  • diazonium compounds forming salts are 4-diazo-l-dimethylaminobenzene, 4-diazo-l-diethyl- aminobenzene, 4-diazo-l-dipropylaminobenzene, 4-diazo-l-dibenzylaminobenzene, 4-diazo-l-dibenzylaminobenzene, 4-diazo-1-ethylhydroxyethylaminobenzene, 4-diazo-l-diethylamino-3-methoxybenzene, 4-diazo-l-dimethylamino-2-methylbenzene, 4-diazo-l-benzylamino-2,5-diethoxybenzene, 4-diazo-l-morpholino- benzene, 4-diazo-l-morpholino-2,5-diethoxybenzene, 4-diazo-1-morpholino-2,5-dibutoxybenzene, 4-diazo-l-anil
  • Suitable acid anions are C n F 2n+l COO- (wherein n is 3 to 9), C m F 2m+1 SO 3 - (wherein m is 2 to 8), (ClF 2l+1 SO 2 ) 2 CH - (wherein l is 1 to 18), BF 4 - PF 6 - , etc.
  • acid anions having a perfluoroalkyl group or a perfluoroalkenyl group each having less than 20 carbon atoms are preferred since the increase of fog at shelf life of the heat sensitive recording material is less.
  • diazo compounds diazonium salts which can be used in this invention are as follows:
  • the coupling component used in this invention is a compound which forms a dye upon coupling with the diazo compound (diazonium salt) under basic conditions.
  • suitable coupling components are resorcin, fluoroglucin, sodium 2,3-dihydroxynaphthalene-6-sulfonate, 1-hydroxy-2-naphthoic acid morpholinopropylamide, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,3-dihydroxy-6-sulfanilnaphthalene, 2-hydroxy-3-naphthoic acid morpholinopropylamide, 2-hydroxy-3-naphthoic acid anilide, 2-hydroxy-3-naphthoic acid-2'-methylanilide, 2-hydroxy-3-naphthoic acid ethanolamide, 2-hydroxy-3-naphthoic acid octylamide, 2-hydroxy-3-naphthoic acid-N-dodecyl-
  • a sparingly water-soluble or water insoluble basic material or a material generating an alkali upon heating is used as the coloring activator.
  • coloring activators which can be used in this invention include nitrogen-containing compounds such as inorganic and organic ammonium salts, organic amines, amides, urea and derivatives thereof, thiourea and derivatives thereof, thiazoles, pyrroles, pyrimidines, piprazines, guanidines, indoles, imidazoles, imidazolines, triazoles, morpholines, piperidines, amidines, formazines, pyridines, etc.
  • nitrogen-containing compounds such as inorganic and organic ammonium salts, organic amines, amides, urea and derivatives thereof, thiourea and derivatives thereof, thiazoles, pyrroles, pyrimidines, piprazines, guanidines, indoles, imidazoles, imidazolines, triazoles, morpholines, piperidines, amidines, formazines, pyridines, etc.
  • coloring activators are ammonium acetate, tricyclohexylamine, tribenzylamine, octadecyl- benzylamine, stearylamine, allylurea, thiourea, methylthiourea, allylthiourea, ethylenethiourea, 2-benzylimidazole, 4-phenyl- imidazole, 2-phenyl-4-methylimidazole, 2-undecyl-imidazoline, 2,4,5-trifuryl-2-imidazoline, 1,2-diphenyl-4,4-dimethyl-2-imidazoline, 2-phenyl-2-imidazoline, 1,2,3,-triphenylguanidine, 1,2-ditolylguanidine, 1,2-dichlorohexylguanidine, 1,2,3-tri- cyclohexylguanidine, guanidine trichloroacetate, N,N'- dibenzylpiperazine, 4,4''-
  • the core material in the microcapsules may be a solution, a semi-solid, or a solid but a solution is preferred since in this case, the core material immediately permeates or reacts to form color at heat recording. Accordingly, it is preferred to use a high-boiling solvent which is a liquid at normal temperature as the core material in this invention.
  • organic solvents having a boiling point of higher than about 180°C such as phosphoric acid esters, phthalic acid esters, other carboxylic acid esters, fatty acid amides, alkylated biphenyls, alkylated terphenyls, chlorinated paraffins, alkylated naphthalenes, diarylethanes, etc., are preferred as suitable organic solvents.
  • Suitable organic solvents which can be used in this invention are tricresyl phosphate, trioctyl phosphate, octyldiphenyl phosphate, tricylohexyl phosphate, dibutyl phthalate, dioctyl phthalate, dilauryl phthalate,dicyclohexyl phthalate, butyl oleate, diethylene glycol dibenzoate, dioctyl sebacate, dibutyl sebacate, diocyl adipate, trioctyl trimellitate, acetyltriethyl citrate, octyl maleate, dibutyl maleate, isoprophlbiphenyl, iso- amylbiphenyl, chlorinated paraffin, diisopropylnaphthalene, l,l'-ditolylethane, 2,4-di-t-aminophenol, N,N-d
  • the microcapsules used in this invention are prepared by emulsifying a core material containing a reactive material and then forming a wall of a high molecular weight compound around the oil drops of the core material.
  • one or two of the foregoing diazo compound, the coupling component and the coloring activator are present in the microcapsules.
  • both components may be present in same microcapsules or may be present in different microcapsules.
  • the foregoing three components may be present in different microcapsules or two components are present in the same microcapsules and another component may be present in other microcapsule.
  • the term "encapsulating at least one of the three components" in this invention means the embodiments described above.
  • the reactant or reactants forming the high molecular weight material are added to the interior and/or the exterior of the oil droplets.
  • high molecular weight compounds thus formed are polyurethane,polyurea, polyamide, polyester, polycarbonate, a urea-formaldehyde resin, a melamine resin, polystyrene, a styrene-methacrylate copolymer, a styrene- acrylate copolymer, gelatin, polyvinyl pyrrolidone, polyvinyl alcohol, etc.
  • high molecular weight materials may be employed as the wall materials in this invention.
  • Preferred high molecular weight materials are polyurethane, polyurea, polyamide, polyester, polycarbonate, etc., and polyurethane and polyurea are more preferred.
  • the high molecular weight material used in this invention has preferably a melting point.higher than about 150°C so that the wall is not melted at the temperature of heat recording.
  • the diazo compound, the coupling component and the coloring activator which are the main components used in this invention is employed as the core material of the microcapsules. That is, the diazo compound, the coupling component or the coloring activator may be used as the core material; or the diazo compound and the coupling component, the diazo compound and the coloring activator, or the coupling component and the coloring activator may be used as the core material, and in the latter case, another component may be incorporated in the recording layer without being encapsulated.
  • both components may be present in the same microcapsules or different microcapsules. In this invention, each of the three components may be present in different microcapsule or two components may be present in the same microcapsules and another component is present in other microcapsules.
  • microcapsulation method involving polymerization of a reactant from the inside of the droplets of the core material can be effectively used. That is, in this case, microcapsules having a uniform particle size can be obtained in a short period of time and such microcapsules are preferred for a heat sensitive recording material having excellent shelf life.
  • a polyvalent isocyanate and a material e.g., a polyol
  • a material e.g., a polyol
  • the mixture is dispersed by emulsification in water, and the temperature is increased to cause a polymer-forming reaction at the interface of the oil droplets in the emulsion, whereby the wall of the microcapsules is formed.
  • a low-boiling auxiliary solvent having a high dissolving power can be used in the oily solution.
  • a tin salt, etc. may be used .for promoting the urethane forming reaction.
  • microcapsules used in this invention it is effective for obtaining a heat sensitive recording material-having a good shelf life and high coloring speed and high heat coloring property to use a polyhydric isocyanate as a first wall-forming material and a polyol as a second wall-forming material as described above.
  • polyhydric isocyanates used as the first wall-forming material are diisocyanates such as m-phenylene diisocyante, p-phenylene diisocyanate, 2,6-trichlene diisocyanate, 2,4-tolylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl-diisocyanate, 3,3'-dimethyldiphenyl- methane-4,4'-diisocyanate, xylylene-l,4-diisocyanate, 4,4'-diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-l,2-diisocyanate, butylene-1,2-diisocyanate, cyclohexylene-1,2-di
  • the polyol used as the second wall-forming material includes aliphatic and aromatic polyhydric alcohols, hydroxy polyesters, hydroxy polyalkylene ethers, etc.
  • Preferred polyols are polyols having a molecular weight lower than 5,000 and having the following group (I), (II), (III) or (IV) between the two hydroxy groups in the molecular structure;
  • Ar' represents an unsubstituted or substituted aromatic moiety and the aliphatic hydrocarbon group of ( I ) has the moiety -CnH2n- wherein n is 2 to 8 as the fundamental skelton and the hydrogen atom may be replaced by another element.
  • polyols of group (I) are ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5 - pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, propylene glycol, 2,3-dihydroxybutane, 1,2-dihydroxybutane, 1,3-dihydroxybutane,'2,2-dimethyl-1,3-propanediol, 2,4-pentanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, dihydroxycyclohexane, diethylene glycol, 1,2,6-trihydroxyhexane, phenylethylene glycol, 1,1,1-trimethylolpropane, hexanetriol, pentaerythritol
  • polyols of group (II) are the condensation products of aromatic polyhydric alcohols such as 1,4-di(2-hydroxyethoxy)benzene, resorcinol dihydroxyethyl ether, etc., and alkylene oxides.
  • polyols of group (III) are p-xylylene glycol, m-xylylene glycol, ⁇ , ⁇ '-dihydroxy-p-diisopropylbenzene, etc.
  • polyols of group (IV) are 4,4'-dihydroxydiphenylmethane, 2-(p,p'-dihydroxydiphenylmethyl)benzyl alcohol, an addition product of bisphenol A and ethylene oxide,. an addition product of bisphenol A and propylene oxide, etc. It is preferred to use the polyol at 0.02 to 2 moles of the hydroxy group per mole of isocyanate group.
  • a water-soluble polymer in forming microcapsules in this invention, can be used and examples of water-soluble polymer used in this invention include a water-soluble anionic polymer, a water-soluble nonionic polymer and a water-soluble amphoteric polymer.
  • a natural anionic polymer and a synthetic anionic polymer can be used as the water-soluble anionic polymer.
  • anionic polymers having -COO group, -SO3 - group, etc. can be used.
  • Specific examples of anionic natural polymers are gum arabic, alginic acid, etc.
  • examples of the semisynthetic products are carboxy methyl cellulose, phthalated gelatin, sulfated starch, sulfated cellulose, ligninsulfonic acid, etc.
  • examples of the synthetic products are maleic anhydride (including hydrolyzed derivatives) copolymers, acrylic acid (including methacrylic acid) polymers and copolymers, vinylbenzenesulfonic acid-polymers and copolymers, carboxy-denatured polyvinyl alcohol, etc.
  • examples of nonionic polymers are polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, etc.
  • examples of the amphoteric anionic polymer are gelatin, etc.
  • Such a water-soluble polymer is used as an aqueous solution in an amount of 0.01 to 10% by weight of the polymer.
  • the particle size of the microcapsules is controlled to below about 20 ⁇ m. If the particle size of the microcapsules is over 20 ⁇ m, the quality of print images tends to be reduced. In particular, when the recording material is heated from the coated layer side by a thermal head, the particle size of the microcapsules is preferably less than 8 ⁇ m.
  • the microcapsules can be prepared from an emulsion containing the component or components to be encapsulated in an amount of higher than 0.2% by weight. It is also preferred for the component to permeate more smoothly through the wall of the microcapsules to encapsulate the component together with a high-boiling organic solvent as described hereinbefore.
  • the coupling component When one or two of the diazo compound, the coupling component and the coloring activator are present in microcapsules or present in the recording layer without being encapsulated, it is preferred for the coupling component to be used in an amount of about 0.1 to about 10 parts by weight to 1 part by weight of the diazo compound and the coloring activator is used in an amount of about 0.1 to about 20 parts by weight to 1 part by weight of the diazo compound. Also, it is preferred that the diazo compound be coated in an amount of about 0.05 to about 2.0 g/m 2 .
  • each component is in the form of a solid dispersion.
  • each component is each dispersed in a different water-soluble polymer solution.
  • the water-soluble polymer used in this case it is preferred to use the water-soluble polymer used for forming microcapsules.
  • the concentration of the water-soluble polymer is about 2 to about 30% by weight and each of the diazo compound, the coupling component and the coloring activator is added to each solution of the water-soluble polymer at a concentration of about 5 to about 40% by weight. It is preferred that the partcicle size of each component thus dispersed in the solution be less than about 10 ⁇ m.
  • a pigment such as silica, barium sulfate, titanium oxide, aluminum hydroxide, zinc oxide, calcium carbonate, etc., and a fine powder such as styrene beads,a urea-melamine resin powder, etc.
  • a fine powder such as styrene beads,a urea-melamine resin powder, etc.
  • metal soaps, etc. can be used for the purposes of preventing adhesion of the recording paper to a thermal head and improving the writability.
  • the amount of the foregoing material is about 0.2 to about 7 g/m 2 .
  • a heat melting material can be used to increase the heat recording density.
  • the heat melting material is a material having a melting point of about 50 to about 150°C, which is in a solid state at normal temperature but is melted by heating due to the thermal heat at heat recording and thus dissolves the diazo compound, the coupling component or the coloring activator.
  • the heat melting material is dispersed as particle of a size of about 0.1 to about 10 ⁇ m and the amount used is about 0.2 to about 7 g/m 2 as .solid.
  • suitable heat melting material are fatty acid amides, N-substituted fatty acid amides, ketone compounds,N-substituted carbamate compounds, urea compounds, esters, etc.
  • the coating composition may be coated using an appropriate binder.
  • the amount of the binder used is about 0.5 to 5 g/m 2 .
  • the heat sensitive recording material of this invention may further.contain citric acid, tartaric acid, oxalic acid, boric acid, phosphoric acid, pyrophosphoric acid, etc., as an acid stabilizer in addition to the foregoing compounds.
  • a coating composition containing the diazo compound, the coupling component and the coloring activator together with, if desired, other additives as the core material of the microcapsules, a simple solid dispersion, or a solution thereof is prepared and coated on a support such as a paper, a synthetic resin film, etc., using coating method such as a bar coating method, a blade coating method, an air knife coating method, a gravure coating method, a roll coating method, a spray coating method,-a dip coating method, etc., followed by drying to form a heat sensitive recording layer having a solid content of about 2.5 to about 15 g/m2.
  • a coating composition containing the coupling component and the coloring activator as the main components together with, if desired, other components as the core Material of the microcapsules, a simple solid dispersion, or a solution thereof is prepared and coated on a support as above described followed by drying to form a pre-coated layer having a solid content of about 2 to about 10 g/m 2 , and further a coating composition containing the diazo compound as the main component together with other additives, if any, as the main core material of the microcapsules, a simple solid dispersion, or a solution thereof is prepared and coated on the pre-coated layer followed by drying to form a diazo compound layer having a solid content of about I to about 10 g/m 2 .
  • a double layer type heat sensitive recording material is prepared.
  • at least one of the diazo compound, the coupling component, and the color activator as the main components of the heat sensitive recording material is coated as a microencapsulated form.
  • the order of the layers may be opposite to the above described embodiment.
  • the double layers may be formed by successive coating or by simultaneous coating.
  • the double layer type heat sensitive recording material has particularly excellent long shelf life.
  • a neutral paper having a heat extraction pH of 6 to 9 sized with a neutral size such as an alkylketene dimer, etc., (e.g., as described in Japanese Patent Publication (Unexamined) No. 14,281/'80).
  • a paper having a Beck flatness of above 90 sec. and the following Stockigt sizing degree as described in Japanese Patent Publication (Unexamined) No. 116,687/'82 can be advantageously used.
  • the heat sensitive recording material of this invention can be used as printer papers for facsimile and computers requiring high-speed recording and can be fixed by exposing the recording material to light, after heat printing, to decompose the unreacted diazo compound. Furthermore, the heat sensitive recording material can be used as a heat developable copying paper.
  • each of the diazo compound in an amount shown in Table 1 below and 10 parts of the addition product of xylylene diisocyanate and trimethylolpropane (3 : 1 by weight) were dissolved in a mixture of 20 parts of dibutyl phthalate and 5 parts of ethyl acetate.
  • the solution of the diazo compound was mixed with an aqueous solution of 3.5 parts of polyvinyl alcohol, 1.7 parts of gelatin, and 3.6 parts of 1,5-di- hydroxypentane dissolved in 58 parts of water and the an mixture was emulsion dispersion at 20°C to provide an emulsion having a mean particle size of 3 ⁇ m.
  • To the emulsion was added 100 parts of water and the mixture was heated to 40 to 70°C with stirring.
  • three kinds of capsule-containing solutions containing the diazo compound as the core material of the microcapsules were obtained.
  • Each of the dispersions of coupling components (1) to (3) shown below having a mean particle size of about 3 ⁇ m was obtained by dispersing 20 parts of each coupling component and 5 parts of polyvinyl alcohol in 100 parts of water for about 24 hours using a sand mill.
  • Heat Sensitive Recording Materials (6) to (8) were prepared as comparison samples. That is, a dispersion of a diazo compound having a mean particle size of 3 ⁇ m was prepared by adding an appropriate amount of the diazo compound and 5.2 parts of polyvinyl alcohol to 93.8 parts of water and dispersing the diazo compound for about 24 hours using a sand mill.
  • Heat Sensitive Recording Materials (9) to (11) were prepared as comparison samples by following the same procedure as described above for preparing Heat Sensitive Recording Materials (1) to (5) except that each diazo compound was microencapsulated by the method shown in Example 1 of Japanese Patent Publication (Unexamined) No. 192,944/' 82.
  • Heat Sensitive Recording Materials (1) to (11) thus prepared were employed in heat recording using a recording machine, G II Mode (Panafax 7200) made by Matsushita Denso K .K. and then each sample was fixed by an overall light exposure to the sample using a copying machine, Ricopy High Start Type 4, made by Ricoh Company, Ltd. The blue density of the recorded images thus obtained was measured using a Macbeth reflection densitometer. The results obtained are shown in Table 1 below.
  • a capsule liquid of a coupling component was prepared by adding 5 parts of the coupling component in place of adding the diazo compound and also a dispersion of a diazo compound was prepared by adding an appropriate amount of a diazo compound in place of adding 20 parts of the coupling component.
  • Heat Sensitive Recording Materials (17) to (19) were prepared as comparison samples by employing the capsule wall-forming method described in Example 1 of Japanese Patent Publication (Unexamined) No. 192,244/'82, i.e., a method using a polymer for forming capsule walls in place of forming the wall by the polymerization of reactants as in this invention. That is, in 50 parts of cyclohexane were dissolved 10 parts of a copolymer of vinyl acetate, butyl methacrylate, and styrene and then 5 parts of a coupling component, and a solution composed of 5.2 parts of polyvinyl alcohol and 8.4 parts of water was added to the solution.
  • the samples of this invention wherein the coupling component was emulsified as the core material and then the capsule wall composed of a polymer was formed by polymerizing the reactants around the core material gave high image density as compared to the comparison samples wherein the microcapsules were prepared by dissolving a previously polymerized polymer and the increase of fog after the forced deterioration testing is less in the samples of this invention as compared to the comparison samples, which shows the excellent shelf life of the samples of this invention.
  • a capsule liquid was prepared. Then, a coating liquid was prepared by adding 50 parts of the capsule liquid thus obtained, 15 parts of the dispersion of coupling component (1) prepared in the same manner as in Examples (1) to (5), and 15 parts of the dispersion of diazo compound (1) prepared in the same manner as in Examples ( 1 ) to (5) to 20 parts of a 5% zinc stearate aqueous solution.
  • Heat Sensitive Recording Material (20) was prepared and tested as in the foregoing examples. The results obtained are shown in Table 3 below.
  • a capsule liquid was prepared.
  • a coating liquid was prepared by adding 65 parts of the capsule liquid thus obtained and 20 parts of the dispersion of triphenyl guanidine prepared by the same manner as in Examples (1) to (5) to 15 parts of a 5% zinc stearate aqueous solution and coated as in the foregoing examples to provide Heat Sensitive Recording Material (21).
  • the sample was also tested as in the for egoing examples. The results thus obtained are shown in Table 3 below.
  • Heat Sensitive Recording Materials (2D) and (21) of this invention each containing a part of the main components in the microcapsules show high image density and less increase of fog after the forced deterioration testing, which shows the excellent shelf life of the samples.
  • a coating liquid was prepared by adding 50 parts of the capsule liquid thus prepared, 15 parts of the dispersion of coupling component (1) prepared in the same manner as in Examples (1) to (5), and 15 parts of the dispersion of triphenyl guanidine prepared in the foregoing examples to 20 parts of a 5% zinc stearate aqueous solution and coated as in the foregoing examples to provide Heat Sensitive Recording Material (22).
  • the image density was 1.3 and the fog before and after the forced deterioration testing was 0.08 and 0.13, respectively. That is, the sample showed a high image density and excellent shelf life.
  • a coating liquid was prepared by adding 50 parts of the capsule liquid of diazo compound (1) thus prepared, 15 parts of the dispersion of coupling component (1), and 15 parts of the dispersion of triphenyl guanidine to 20 parts of a 5% zinc stearate aqueous solution and coated as in Examples 1 to 5 to provide Heat Sensitive Recording Material (22).
  • the image density was 1.1 and the fog before and after the forced deterioration testing was 0.08 and 0.13, respectively.
  • the sample showed a high image density and excellent shelf life.
  • Example 23 By following the same procedure as in Example 23 except that 0.2 part of terephthalic acid chloride was further added to the solution containing the diazo compound as the core material in the method of preparing the capsule liquid in Example 23, Heat Sensitive Recording Material (24) was prepared.
  • the capsule wall in this case was composed of polyurea and polyamide.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
EP19840104136 1983-04-13 1984-04-12 Wärmeempfindliche Aufzeichnungsmaterialien Expired EP0123224B1 (de)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP65043/83 1983-04-13
JP58065043A JPS59190886A (ja) 1983-04-13 1983-04-13 感熱記録材料
JP114752/83 1983-06-24
JP58114752A JPS606493A (ja) 1983-06-24 1983-06-24 感熱記録材料
JP158469/83 1983-08-30
JP58158469A JPS6049991A (ja) 1983-08-30 1983-08-30 感熱記録材料
JP169015/83 1983-09-13
JP58169015A JPS6061288A (ja) 1983-09-13 1983-09-13 感熱記録材料

Publications (3)

Publication Number Publication Date
EP0123224A2 true EP0123224A2 (de) 1984-10-31
EP0123224A3 EP0123224A3 (en) 1985-05-15
EP0123224B1 EP0123224B1 (de) 1988-06-29

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EP (1) EP0123224B1 (de)
DE (1) DE3472472D1 (de)
ES (1) ES8604048A1 (de)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2158958A (en) * 1984-05-17 1985-11-20 Fuji Photo Film Co Ltd Heat-sensitive recording material
US4598035A (en) * 1984-03-26 1986-07-01 Fuji Photo Film Co., Ltd. Heat-sensitive recording material containing microcapsules containing coloring component(s) and organic solvent
EP0118846A3 (en) * 1983-03-09 1987-05-27 Hoechst Aktiengesellschaft Two-component diazo type material
GB2206218A (en) * 1987-06-22 1988-12-29 Fuji Photo Film Co Ltd Photo- and heat-sensitive diazo recording material
EP0352122A3 (en) * 1988-07-21 1990-08-08 Fuji Photo Film Co., Ltd. Heat development type diazo copying material
EP0323887A3 (de) * 1988-01-06 1990-11-14 Fuji Photo Film Co., Ltd. Wärmeempfindliches Diazo-Bildaufzeichnungsmaterial
EP0337734A3 (en) * 1988-04-12 1990-12-19 Fuji Photo Film Co., Ltd. Heat-developable diazo copying material
EP0754564A3 (de) * 1995-07-18 1997-02-26 Mitsubishi Paper Mills Ltd

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3202510A (en) * 1961-07-11 1965-08-24 Frederick Post Co Production of encapsulated light-sensitive diazotype compositions and coatings
JPS553156B2 (de) * 1972-08-14 1980-01-23
JPS57204031A (en) * 1981-06-09 1982-12-14 Ricoh Co Ltd Heat development type diazo copying material

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0118846A3 (en) * 1983-03-09 1987-05-27 Hoechst Aktiengesellschaft Two-component diazo type material
US4598035A (en) * 1984-03-26 1986-07-01 Fuji Photo Film Co., Ltd. Heat-sensitive recording material containing microcapsules containing coloring component(s) and organic solvent
GB2158958A (en) * 1984-05-17 1985-11-20 Fuji Photo Film Co Ltd Heat-sensitive recording material
GB2206218A (en) * 1987-06-22 1988-12-29 Fuji Photo Film Co Ltd Photo- and heat-sensitive diazo recording material
EP0323887A3 (de) * 1988-01-06 1990-11-14 Fuji Photo Film Co., Ltd. Wärmeempfindliches Diazo-Bildaufzeichnungsmaterial
EP0337734A3 (en) * 1988-04-12 1990-12-19 Fuji Photo Film Co., Ltd. Heat-developable diazo copying material
US5236800A (en) * 1988-04-12 1993-08-17 Fuji Photo Film Co., Ltd. Heat-developable light-sensitive copying material comprising microcapsules having substantially no solvent
EP0352122A3 (en) * 1988-07-21 1990-08-08 Fuji Photo Film Co., Ltd. Heat development type diazo copying material
US5089371A (en) * 1988-07-21 1992-02-18 Fuji Photo Film Co., Ltd. Heat development type diazo copying material containing a light insensitive intermediate layer provided between the support and the photosensitive layer
EP0754564A3 (de) * 1995-07-18 1997-02-26 Mitsubishi Paper Mills Ltd
US5876898A (en) * 1995-07-18 1999-03-02 Mitsubishi Paper Mills Limited Heat sensitive recording material and recording method using the same

Also Published As

Publication number Publication date
ES531627A0 (es) 1986-01-16
EP0123224A3 (en) 1985-05-15
EP0123224B1 (de) 1988-06-29
DE3472472D1 (en) 1988-08-04
ES8604048A1 (es) 1986-01-16

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