Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
  • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
  • B41M5/337—Additives; Binders
  • B41M5/3375—Non-macromolecular compounds
• • 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
  • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
  • B41M5/132—Chemical colour-forming components; Additives or binders therefor
• • 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
  • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
  • B41M5/132—Chemical colour-forming components; Additives or binders therefor
  • B41M5/155—Colour-developing components, e.g. acidic compounds; Additives or binders therefor; Layers containing such colour-developing components, additives or binders
• • 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
  • B41M5/46—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 characterised by the light-to-heat converting means; characterised by the heat or radiation filtering or absorbing means or layers
• • 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
  • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
  • B41M5/132—Chemical colour-forming components; Additives or binders therefor
  • B41M5/136—Organic colour formers, e.g. leuco dyes
  • B41M5/145—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
  • B41M5/1455—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring characterised by fluoran compounds
• • 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
  • B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
  • B41M5/3275—Fluoran compounds

Definitions

• Heat-sensitive recording materials are generally produced by applying to the surface of a support such as paper a coating composition which consists of a mixture of a dispersion of a colorless chromogenic substance (color former) and a dispersion of a color developer as an electron acceptor.
• a coating composition which consists of a mixture of a dispersion of a colorless chromogenic substance (color former) and a dispersion of a color developer as an electron acceptor.
• Other tools such as Fillers and thermal sensitizers are usually also added.
• a chemical reaction of the chromogenic compound with the color developer takes place in the coating, with color formation.
• substituents X and Y independently of one another denote alkoxy each having 1 to 12 carbon atoms, for example methoxy, ethoxy, propoxy and butoxy, pentoxy, hexoxy, octoxy and dodecyloxy and corresponding branched isomers; also phenyl, which is optionally substituted by alkyl or alkoxy each having 1 to 12 carbon atoms or halogen.
• Suitable phenyl substituents are methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl and dodecyl as well as corresponding branched isomers, the alkoxy radicals mentioned and chlorine and bromine.
• X and Y independently of one another represent a radical of the formula -COR1, -CO2R1, -SO2R2, -P (O) (OR3) 2 or cyano.
• X and Y can also together form a radical of the formula -CO-OC n H 2n -O-CO-.
• the substituent R represents a group of the formula
• Index n is an integer from 1 to 5.
• R2 means alkyl having 1 to 12 carbon atoms. Suitable alkyl radicals are listed in the definition of R1. R2 can also mean phenyl.
• R3 is alkyl of 1 to 12 carbon atoms. Examples of suitable alkyl radicals are listed in the definitions of X and Y.
• Z In addition to -NH-, Z also means -O- or -S-.
• R4 and R5 are independently hydrogen or alkyl or alkoxy each having 1 to 12 carbon atoms. Suitable alkyl radicals are already enumerated in the definition of R1, and alkoxy radicals that can be used can be derived from these alkyl radicals. R4 and R5 can also mean alkoxycarbonyl, the alkoxy part then containing 1 to 18 carbon atoms, such as - In addition to the alkoxy radicals already mentioned R1 - tridecyloxy, pentadecyloxy, heptadecyloxy and octadecyloxy and corresponding branched isomers. Furthermore, R4 and R5 are independently hydroxyl or halogen, such as chlorine and bromine.
• R6 and R7 are independently hydrogen or alkyl each having 1 to 12 carbon atoms. Examples of such alkyl radicals are enumerated in the definition of R1. R6 and R7 can also form a morpholine, piperidine or piperazine radical together with the nitrogen atom to which they are attached.
• X and Y are preferably, independently of one another, alkoxy each having 1 to 4 carbon atoms, phenyl, phenyl substituted with alkyl or alkoxy each having 1 to 4 carbon atoms or halogen, -COR1, -CO2R1, -SO2R2 , -P (O) (OR3) 2, or cyano or X and Y form a group of the formula -CO-OC n H 2n -O-CO-, where R1, R2, R3 and n have the meaning given.
• the substituent R3 is preferably alkyl having 1 to 4 carbon atoms.
• Particularly suitable radicals R6 and R7 are hydrogen or alkyl each having 1 to 12 carbon atoms and the morpholine radical formed by these radicals together with the nitrogen atom to which they are attached.
• X and Y are particularly preferably independently of one another -CO2R1, -SO2R2 or cyano, or they form a group of the formula -CO-OC n H 2n -O-CO-, where R1, R2 and n have the meaning given.
• Components (a) and (b) come into contact with one another by pressure or heating, depending on the recording material, and leave records on the carrier material.
• the color is produced in accordance with the type of components (a) and (b), which represent the electron donor and form the chromogenic part.
• the color formation is caused by component (b).
• the desired colors e.g. yellow, orange, red, violet, blue, green, gray, black or mixed colors can be generated.
• component (a) and component (c) are dissolved together in an organic solvent and the solutions obtained are encapsulated by processes such as those described, for example in the U.S. 2 712 507, 2 800 457, 3 016 308, 3 429 827 and 3 578 605 or in British patents 989 264, 1 156 725, 1 301 052 or 1 355124.
• microcapsules which are formed by interfacial polymerization are also suitable, e.g. Capsules made of polyester, polycarbonate, polysulfonamide, polysulfonate or polyamide or in particular made of polyurethane.
• the latter can also be achieved by incorporating components (a) and (c) together into foam, sponge or honeycomb structures.
• suitable solvents are preferably non-volatile solvents e.g. halogenated benzene, diphenyls or paraffin, e.g. Chlorinated paraffin, trichlorobenzene, monochlorodiphenyl, dichlorodiphenyl or trichlorodiphenyl; Esters, e.g.
• Mixtures of various solvents in particular mixtures of paraffin oils or kerosene and diisopropylnaphthalene or partially hydrogenated terphenyl, are often used in order to achieve optimum solubility for color formation, rapid and intensive coloring and a viscosity which is favorable for microencapsulation.
• Microcapsules containing components (a) and (c) can be used to produce pressure-sensitive copying materials of various known types.
• the different systems differ essentially in the arrangement of the capsules, the color reactants and the carrier material.
• components (a) and (c) are encapsulated in the form of a layer on the back of a transfer sheet and components (b) in the form of a layer on the front of a receiver sheet are advantageous.
• the arrangement can also be reversed.
• Another arrangement of the components is that the microcapsules containing components (a) and (c) and the developer (component (b)) are present in or on the same sheet in the form of one or more individual layers or in the paper pulp.
• the capsule mass which contains components (a) and (c) can be mixed with other capsules which contain conventional color formers. Similar results are obtained if components (a) and (c) are encapsulated together with one or more of the conventional color formers. Often, multiple color formers are used in the same capsule.
• the capsules are preferably attached to the carrier by means of a suitable binder.
• a suitable binder Since paper is the preferred substrate, this binder is used mainly around paper coating agents such as gum arabic, polyvinyl alcohol, hydroxymethyl cellulose, casein, methyl cellulose, dextrin, starch, starch derivatives or polymer latices. The latter are, for example, butadiene-styrene copolymers or acrylic homo- or copolymers.
• the paper used is not only normal paper made from cellulose fibers, but also papers in which the cellulose fibers are (partially or completely) replaced by fibers made from synthetic polymers.
• the substrate can also be a plastic film.
• Pressure-sensitive recording material can also be constructed in such a way that it contains a capsule-free layer containing components (a) and (c) and a color-developing layer which acts as color developer (component (b)) at least one inorganic metal salt, especially halides or nitrates, such as e.g. Contains zinc chloride, tin chloride, zinc nitrate or mixtures thereof.
• a capsule-free layer containing components (a) and (c) and a color-developing layer which acts as color developer (component (b)) at least one inorganic metal salt, especially halides or nitrates, such as e.g. Contains zinc chloride, tin chloride, zinc nitrate or mixtures thereof.
• the heat-sensitive recording material usually contains at least one layer support, components (a), (c) and (b) and optionally also a binder. If desired, activators or sensitizers can also be present in the recording material.
• Thermoreactive recording systems include, e.g. heat sensitive recording and copying materials and papers. These systems are used, for example, to record information, e.g. in electronic calculating machines, printers, facsimile or copying machines or in medical and technical recording devices and measuring instruments, e.g. Electrocardiograph used.
• the imaging (marking) can also be done manually with a heated spring.
• Another device for generating markings using heat is laser beams.
• thermoreactive recording material can be constructed such that components (a) and (c) are dissolved or dispersed in a binder layer and in a second layer the developer (component (b)) is dissolved or dispersed in the binder. Another possibility is that all three components are dispersed in the same layer.
• the layer or layers are softened or fused in specific areas by means of heat, components (a), (c) and (b) coming into contact with one another at the points at which heat is applied, and a dye immediately develops.
• thermoreactive recording material can also contain components (a) and (c) encapsulated.
• Water-soluble or at least water-swellable binders are, for example, hydrophilic polymers, such as polyvinyl alcohol, alkali metal polyacrylates, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, polyacrylamide, polyvinyl pyrrolidone, carboxylated butadiene-styrene copolymers, gelatin, starch or esterified corn starch.
• hydrophilic polymers such as polyvinyl alcohol, alkali metal polyacrylates, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, polyacrylamide, polyvinyl pyrrolidone, carboxylated butadiene-styrene copolymers, gelatin, starch or esterified corn starch.
• water-insoluble binders i.e. binders soluble in non-polar or only weakly polar solvents, e.g. Natural rubber, synthetic rubber, chlorinated rubber, polystyrene, styrene / butadiene copolymers, polymethylacrylates, ethyl cellulose, nitrocellulose and polyvinyl carbazole can be used.
• the preferred arrangement is one in which all three components are contained in one layer in a water-soluble binder.
• the material can be provided with an additional protective layer.
• Such protective layers usually consist of resins, conventional polymer materials or aqueous emulsions of these polymer materials.
• water-soluble polymer materials are polyvinyl alcohol, starch, starch derivatives, cellulose derivatives, such as methoxy cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose or ethyl cellulose, sodium polyacrylate, polyvinylpyrrolidone, polyacrylamide / acrylic acid ester copolymers, acrylamide / acrylic acid ester / methacrylic acid / copolymeric acid-alkali acid copolymer, styrene-copolymeric acid, styrene-copolymeric acid, styrene-copolymeric acid, styrene-copolymeric acid, styrene-copolymeric acid, styrene-copolymeric acid, styrene-copolymeric acid, styrene-copolymeric acid, styrene-acrylic acid copolymer / styrene-copoly
• the protective layer in combination with the water-soluble polymer resins mentioned, e.g. the following water-insoluble resins are used: polyvinyl acetate, polyurethanes, styrene / butadiene copolymers, polyacrylic acid, polyacrylic acid esters, vinyl chloride / vinyl acetate copolymers, polybutyl methacrylate, ethylene / vinyl acetate copolymers and styrene / butadiene / acrylic derivative copolymers.
• the protective layer can also contain UV absorbers.
• thermoreactive layers and the resin layers can contain further additives.
• these layers for example antioxidants, UV absorbers according to the invention and those of the benzophenone or hydroxybenzotriazole type and mixtures thereof, solution aids, talc, silica, titanium dioxide, zinc oxide , Aluminum oxide, aluminum hydroxide, calcium carbonate (eg chalk), clays or organic pigments such as urea-formaldehyde polymers, contain.
• substances such as urea, thiourea, diphenylthiourea, acetamide, acetanilide, benzenesulfanilide, bis-stearoylethylenediamide, stearic acid amide, phthalic anhydride, benzyloxybenzoic acid, benzate, methyl ester, benzate metal, eg, benzate, benzate, for example, benzate, benzylate, for example, benzate, zalatesilate, eg , Dibenzyl terephthalate, dibenzyl isophthalate, benzyldiphenyl or other corresponding meltable products which induce the simultaneous melting of the color former components and the developer can be added.
• heat sensitive recording materials contain waxes, e.g. Camama wax, montan wax, paraffin wax, polyethylene wax, condensates of higher fatty acid amides and formaldehyde or condensates of higher fatty acids and ethylenediamine.
• waxes e.g. Camama wax, montan wax, paraffin wax, polyethylene wax, condensates of higher fatty acid amides and formaldehyde or condensates of higher fatty acids and ethylenediamine.
• thermochromatic materials the three components (a), (c) and (b) can be enclosed in microcapsules.
• any of the above-known methods for enclosing color formers or other active substances in microcapsules can be used.
• the compounds of formula (1) can be used in combination with practically all color formers used in pressure- or heat-sensitive recording materials.
• color formers are 3,3- (bis-aminophenyl) phthalides such as CVL, 3-indolyl-3-aminophenylaza or -diazaphthalide, (3,3-bis-indolyl -) - phthalide, 3,3-bis- ( 1′-octyl-2′-methylindol-3′-yl) phthalide, 3,3-bis- (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3-aminofluorane, 6-dialkylamino-2-dibenzylaminofluroane, 6-dialkylamino- 3-methyl-2-arylaminofluroane, 3,6-bisalkoxyfluroane, 3,6-bis-diarylaminofluroane, 2-tert-butyl-6-diethylaminofluroane, leu
• Typical examples of inorganic developers are active clay substances, such as attapulgus clay, acid clay, bentonite, montmorillonite; activated sound e.g. acid-activated bentonite or montmorillonite as well as halloysite, kaolin, zeolite, silicon dioxide, zirconium dioxide, aluminum oxide, aluminum sulfate, aluminum phosphate or zinc nitrate.
• active clay substances such as attapulgus clay, acid clay, bentonite, montmorillonite
• activated sound e.g. acid-activated bentonite or montmorillonite as well as halloysite, kaolin, zeolite, silicon dioxide, zirconium dioxide, aluminum oxide, aluminum sulfate, aluminum phosphate or zinc nitrate.
• Solid organic acids advantageously aliphatic dicarboxylic acids, such as e.g. Tartaric acid, oxalic acid, maleic acid, citric acid, citraconic acid or succinic acid as well as alkylphenol acetylene resin, maleic acid rosin resin, carboxypolymethylene or a partially or fully hydrolyzed polymer of maleic anhydride with styrene, ethylene or vinyl methyl ether can be used.
• aliphatic dicarboxylic acids such as e.g. Tartaric acid, oxalic acid, maleic acid, citric acid, citraconic acid or succinic acid as well as alkylphenol acetylene resin, maleic acid rosin resin, carboxypolymethylene or a partially or fully hydrolyzed polymer of maleic anhydride with styrene, ethylene or vinyl methyl ether can be used.
• Compounds with a phenolic hydroxyl group are particularly suitable as organic color developers. These can be both monohydric and polyhydric phenols. These phenols can be substituted by halogen atoms, carboxyl groups, alkyl radicals, aralkyl radicals, such as ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, aryl radicals, acyl radicals, such as arylsulfonyl, or alkoxycarbonyl radicals or aralkoxycarbonyl radicals, such as benzyloxycarbonyl.
• phenols suitable as component (b) are 4-tert-butylphenol, 4-phenylphenol, methylene-bis- (p-phenylphenol), 4-hydroxydiphenyl ether, ⁇ -naphthol, ⁇ -naphthol, 4-hydroxybenzoic acid methyl ester or -benzyl ester, 2,4-dihydroxybenzoic acid methyl ester, 4-hydroxydiphenyl sulfone, 4'-hydroxy-4-methyldiphenyl sulfone, 4'-hydroxy-4-isopropoxydiphenyl sulfone, 4-hydroxy-acetophenone, 2,4-dihydroxybenzophenone, 2,2'-dihydroxydiphenyl 2,4-dihydroxydiphenyl sulfone, 4,4'-cyclohexylidene diphenol, 4,4'-isopropylidene diphenol, 4,4'-isopropylidene-bis- (2-methylphenol), 4,4-bis- (4- (4-
• the developers can also be mixed with per se unreactive or less reactive pigments or other auxiliaries such as silica gel or other UV absorbers, such as e.g. 2- (2'-hydroxyphenyl) benzotriazoles, benzophenones, cyanoacrylates, salicylic acid phenyl esters are used.
• pigments are: talc, titanium dioxide, aluminum oxide, aluminum hydroxide, zinc oxide, chalk, clays such as kaolin, and organic pigments, e.g. Urea-formaldehyde condensates (BET surface 2-75 m2 / g) or melamine-formaldehyde condensation products.
• the mixing ratio of component (b) to components (a) and (c) depends on the type of the three components, the type of color change, the color reaction temperature and of course also on the desired color concentration.
• This mixture results in a neutral black in pressure-sensitive recording materials with phenolic color developers.
• 5 g of the mixture are dissolved at 100 ° C in 75 g of diisopropylnaphthalene and 20 g of kerosene.
• a second solution is prepared from 50 g gelatin, 15 g sodium dioctylsulphosuccinate, 1.5 g octylphenyl poly (ethylene oxide 3EO) ether and water to a total weight of 1000 g.
• 0.1 g of the compound of formula (1) is dissolved in 4.9 g of color former solution. 1 g of this solution is mixed with 15 g of the gelatin solution and emulsified at 40 ° C with ultrasound.
• the emulsion is cast on a polyethylene-coated paper support to form a 100 nm thick layer and air-dried.
• Example 2 The example shows how UV absorbers according to the invention prevent the reddish discoloration of a microencapsulated mixture of colorants by light.
• the color former solution is microencapsulated in gelatin by coacervation.
• the microcapsules are then dispersed in a starch solution and applied to carbonless paper at a rate of 5 g / m2.
• microcapsules containing UV absorbers are also produced and applied to paper.
• an additional 2.0 g of UV absorber are dissolved in 93 g of the diisopropylnaphthalene / kerosene mixture specified above together with the color former.
• the paper on the side is irradiated with the microcapsules.
• 6 daylight fluorescent tubes (Osram L 40 W / 10S) serve as the light source at a distance of 10 cm from the tube center to the tube center. The distance between the sample and the light source is also 10 cm.
• the optical density of the sample is measured again. An increase in green density is noted. This increases in proportion to the reddish color.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Heat Sensitive Colour Forming Recording (AREA)
• Color Printing (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

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• 1991
  • 1991-09-11 DE DE59107068T patent/DE59107068D1/de not_active Expired - Fee Related
  • 1991-09-11 EP EP91810724A patent/EP0477140B1/fr not_active Expired - Lifetime
  • 1991-09-11 US US07/758,931 patent/US5318939A/en not_active Expired - Fee Related
  • 1991-09-13 CA CA002051320A patent/CA2051320A1/fr not_active Abandoned
  • 1991-09-17 JP JP3265220A patent/JPH04257486A/ja active Pending

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