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
  • B41M5/124—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
  • B41M5/30—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
  • B41M5/3336—Sulfur compounds, e.g. sulfones, sulfides, sulfonamides

Definitions

• X is advantageously halogen, methyl, methoxy, ethoxy, carboxyl and preferably especially hydrogen.
• the R-S0 2 group is advantageously in the o- or preferably in the p-position to the hydroxyl group.
• Lower alkyl and lower alkoxy are generally groups which have 1 to 5, in particular 1 to 3, carbon atoms, such as, for. B. methyl, ethyl, isopropyl, sec-butyl, tert-butyl or methoxy, ethoxy or isopropoxy.
• R represents an alkyl group, it can be straight-chain or branched.
• alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, isooctyl, nonyl or dodecyl.
• cycloalkyl R is, for example, cyclopentyl or preferably cyclohexyl.
• Preferred substituents in the phenyl group of the R radical are methyl or methoxy.
• Halogen means for example fluorine, bromine or preferably chlorine.
• the compounds of the formula (1) used according to the invention are known as substances, but they represent a new class of color developers or electron acceptors for color formers.
• they can be prepared by using a compound of the formula reacted with a compound RH or that a compound of the formula with a phenol compound of the formula X and R have the meaning given and Hal means halogen such as. B. chlorine, bromine or fluorine.
• the reaction takes place in an anhydrous medium in the presence of Lewis acids, such as. B. AlCl 3 . FeCls, ZnCl 2 , SnCl 4 , SbCl 5 or BF 3 and advantageously at a temperature of 50 to 200 ° C., preferably 80 to 130 ° C.
• Another method is that a compound of the formula where R and Hal have the meaning given, heated to 200 to 220 ° C. with aqueous potassium hydroxide solution.
• the compounds of formula (1) used according to the invention are practically colorless and odorless and very reactive with the usual color images, so that spontaneous, stable and non-fading records or copies are obtained.
• the compounds of formula (1) are suitable as color developers for pressure-sensitive or in particular for heat-sensitive recording material, which can be both copying and registration material.
• a pressure-sensitive material consists, for example, of at least one pair of sheets which contain at least one color former, dissolved in an organic solvent, and a developer of the formula (1).
• the developers are preferably applied in the form of a layer to the front of the receiver sheet.
• the developers of formula (1) can be used on their own, as mixtures or in mixtures with known developers.
• Typical examples of known developers are active clay substances, such as attapulgus clay, acid clay, bentonite, montmorillonite; activated sound, e.g. B. acid activated bentonite or montmorillonite; halloysite, zeolite, silicon dioxide, aluminum oxide, aluminum sulfate, aluminum phosphate, zinc chloride, zinc nitrate, kaolin or any clay or acid-reacting organic compounds, such as.
• B. optionally ring-substituted phenols, salicylic acid or salicylic acid esters and their metal salts; also an acidic polymeric material, such as. B.
• a phenolic polymer an alkylphenol acetylene resin, a maleic rosin resin or a partially or fully hydrolyzed polymer of maleic anhydride with styrene, ethylene or vinyl methyl ether, or carboxypolymethylene.
• the developers can also be mixed with per se unreactive or less reactive pigments or other auxiliaries such as silica gel.
• pigments are: talc, titanium dioxide, zinc oxide, chalk; Clays such as kaolin, as well as organic pigments, e.g. B. urea-formaldehyde or melamine-formaldehyde condensation products.
• the color former provides a colored marking at the points where it comes into contact with the developer.
• the color formers contained in the pressure-sensitive recording material are usually separated from the developer. This can expediently be achieved by placing the color formers in foam, sponge or incorporated honeycomb-like structures.
• the color formers are preferably enclosed in microcapsules which can usually be broken by pressure.
• the color formers are preferably encapsulated in the form of solutions in organic solvents.
• suitable solvents are preferably non-volatile solvents, e.g. B. polyhalogenated paraffin or diphenyl, such as chlorinated paraffin, monochlorodiphenyl or trichlorodiphenyl, also tricresyl phosphate, di-n-butyl phthalate; aromatic ethers such as benzylphenyl ether; Hydrocarbon oils, such as paraffin or kerosene, alkylated derivatives (e.g.
• the capsule walls can be formed uniformly around the droplets of the color former solution by coacervation forces, the encapsulation material, e.g. B. may consist of gelatin and gum arabic, as z. B. is described in U.S. Patent 2,800,457.
• the capsules can preferably also be formed from an aminoplast or from modified aminoplasts by polycondensation, as described in British Patents 989 264, 1 156 725, 1 301 052 and 1 355 127.
• microcapsules which are formed by interfacial polymerization, such as. B. capsules made of polyester, polycarbonate, polysulfonamide, polysulfonate, but especially made of polyamide or polyurethane.
• the microcapsules containing color formers can be used in combination with the color developers to produce pressure-sensitive copying materials of various known types.
• the different systems differ essentially from each other by the arrangement of the capsules, the color reactants, i. H. the developer and through the carrier material.
• An arrangement is preferred in which the encapsulated color former is present in the form of a layer on the back of a transfer sheet and the developer to be used according to the invention is in the form of a layer on the front of a receiver sheet.
• microcapsules containing color formers and the developer are in or on the same sheet in the form of one or more individual layers or in the paper pulp.
• the capsules are preferably attached to the carrier by means of a suitable binder.
• this binder is mainly 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 mono- 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 compounds of formula (1) are used in particular as developers in a thermoreactive recording material.
• This usually contains at least one carrier, a color former, a developer and optionally also a binder.
• Thermoreactive recording systems include e.g. B. heat sensitive recording and copying materials and papers. These systems are used, for example, to record information, e.g. B. used in electronic computers, remote printers, teleprinters or in recording devices and measuring instruments such. B. Electrocardiograph. The imaging (marking) can also be done manually with a heated spring. Another device for producing markings by means of heat is laser beams.
• thermoreactive recording material can be constructed such that the color former is dissolved or dispersed in a binder layer and the developer is dissolved or dispersed in the binder in a second layer. Another possibility is that both the color former and the developer are dispersed in one layer.
• the binder is softened by heat in specific areas and at those points where heat is applied, the color former comes into contact with the developer and the desired color develops immediately.
• the developers of the formula (1) can also be used alone in heat-sensitive recording materials, as mixtures or in a mixture with known developers.
• phenolic compounds such as. B. 4-tert-butylphenol, 4-phenylphenol, 4-hydroxydiphenyl ether, a-naphthol, d-naphthol, 4-hydroxybenzoic acid methyl ester, 4-hydroxyacetophenone, 2,2'-dihydroxydiphenyl, 4,4'-isopropylidenediphenol, 4,4 '-Isopropylidene-bis- (2-methylphenol), 4,4'-bis (hydroxyphenyl) valeric acid, hydroquinone, pyrogallol.
• Fusible, film-forming binders are preferably used to produce the thermoreactive recording material. These binders are usually water soluble, while the color former and developer are insoluble in water. The binder should be able to disperse and fix the color former and developer at room temperature.
• Water-soluble or at least water-swellable binders are e.g. B. hydrophilic polymers, such as polyvinyl alcohol, polyacrylic acid, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, polyacrylamide, polyvinyl pyrrolidone, gelatin and starch.
• hydrophilic polymers such as polyvinyl alcohol, polyacrylic acid, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, polyacrylamide, polyvinyl pyrrolidone, gelatin and starch.
• water-insoluble binders e.g. H. binders soluble in non-polar or only weakly polar solvents, such as e.g. B. natural rubber, synthetic rubber, chlorinated rubber, alkyd resins, polystyrene, styrene / butadiene copolymers, polymethylacrylates, ethyl cellulose, nitrocellulose and polyvinyl carbazole
• B. natural rubber, synthetic rubber, chlorinated rubber, alkyd resins, polystyrene, styrene / butadiene copolymers, polymethylacrylates, ethyl cellulose, nitrocellulose and polyvinyl carbazole can be used.
• the preferred arrangement is one in which the color former and the developer are contained in one layer in a water-soluble binder.
• thermoreactive layers can contain further additives.
• these layers for. B. talc, titanium dioxide, zinc oxide, calcium carbonate (e.g. chalk), clays such as kaolin, and organic pigments, such as. B. urea formaldehyde or melamine formaldehyde polymers.
• substances such as urea, thiourea, diphenylthiourea, acetamide, acetanilide, stearic acid amide, phthalic anhydride, metal chlorides, metal stearates z.
• Thermographic recording materials preferably contain waxes, e.g. B. carnauba wax, montana wax, paraffin wax; Polyethylene wax.
• the two dispersions are then mixed.
• the colorless mixture is applied to a paper with a basis weight of 50 g / m 2 using a doctor blade.
• the proportion of the mixture applied is 3 g / m 2 (dry weight).
• thermographic recording paper thus produced has a colorless surface and is stable at room temperature. At 90 ° C a blue hue quickly develops, the saturation of which is already at around 125 ° C.
• the basic color of the recording paper thus obtained is colorless. At 90 ° C a blue hue develops quickly, the full color strength of which is already reached at 125 ° C.
• the basic color of the recording paper thus obtained is white. At 90 ° C a blue hue develops quickly, the full color strength of which is already reached at 125 ° C.
• the basic color of the recording paper thus obtained is practically colorless. At 90 ° C, a black color quickly develops, the full color strength of which is already reached at 125 ° C.
• Heat-sensitive recording paper using the following two dispersions G and H according to the procedure described in Example 1.
• the basic color of the recording paper thus obtained is colorless. At 90 ° C, a black color quickly develops, the full color strength of which is already reached at 125 ° C.
• Heat-sensitive recording paper using only one dispersion K which is produced according to the method described in Example 1.
• the basic color of the recording paper thus obtained is practically colorless. At 90 ° C a blue hue develops quickly, the full color strength of which is already reached at 125 ° C.
• a solution of 3 g of crystal violet lactone in 97 g of partially hydrogenated terphenyl is emulsified in a solution of 12 g of pig skin gelatin in 88 g of water at 50 ° C.
• a solution of 12 g of gum arabic in 88 g of water at 50 ° C. is then added, and 200 ml of water at 50 ° C. are then added.
• the emulsion obtained is poured into 600 g of ice water and cooled, the coacervation being effected.
• a sheet of paper is coated with the resulting suspension of the microcapsules and dried.
• a second sheet of paper is coated with an aqueous dispersion P, which consists of a 350% solid content having.
• the first sheet and the paper coated with 4-hydroxydiphenyl sulfone are placed adjacent to one another with the coatings.
• pressure is applied and an intense blue copy immediately develops on the sheet coated with the developer.
• an aqueous dispersion Q which consists of consists.
• Heat-sensitive recording paper using the following two dispersions R and S according to the procedure described in Example 1.
• the basic color of the recording paper thus obtained is white. At 110 ° C, a blue hue quickly develops, the full color strength of which is reached at 150 ° C.
• the basic color of the recording paper thus obtained is colorless. At 110 ° C, a blue hue quickly develops, the full color strength of which is reached at 150 ° C.
• the basic color of the recording paper thus obtained is white. At 175 ° C a blue hue develops, the full color strength of which is reached at 225 ° C.
• Heat sensitive recording paper using 4-hydroxydiphenyl sulfone in combination with known color developers
• the basic color of the recording paper thus obtained is practically colorless. At 80 ° C a blue hue develops, the full color strength of which is reached at 160 ° C.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Color Printing (AREA)
• Heat Sensitive Colour Forming Recording (AREA)
• Investigating Or Analysing Biological Materials (AREA)
• Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
• Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
• Casting Or Compression Moulding Of Plastics Or The Like (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (3)

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• 1981
  • 1981-06-15 CH CH3930/81A patent/CH655906A5/de not_active IP Right Cessation
• 1982
  • 1982-06-07 US US06/385,595 patent/US4453744A/en not_active Expired - Lifetime
  • 1982-06-09 AT AT82810246T patent/ATE12744T1/de not_active IP Right Cessation
  • 1982-06-09 DE DE8282810246T patent/DE3263106D1/de not_active Expired
  • 1982-06-09 EP EP82810246A patent/EP0067793B1/de not_active Expired
  • 1982-06-14 ES ES513083A patent/ES513083A0/es active Granted
  • 1982-06-14 FI FI822124A patent/FI71694C/fi not_active IP Right Cessation
  • 1982-06-15 JP JP57101489A patent/JPS57210886A/ja active Granted

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