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-SO group is advantageously in the o- or preferably in the p-position to the hydroxyl group.
• Lower alkyl and lower alkoxy generally represent groups which have 1 to 5, in particular 1 to 3, carbon atoms, such as e.g. 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 formula (1) used according to the invention are known as substances, but represent a new class of color developers or electron acceptors for color formers.
• the preparation can be carried out by using a compound of the formula with a compound RH or that a compound of the formula with a phenol compound of the formula implements.
• X and R have the meaning given and Hal means halogen such as chlorine, bromine or fluorine.
• reaction takes place in an anhydrous medium in the presence of Lewis acids, such as A1C1 3 , FeCl 3 , ZnCl 2 , SnCl 4 , SbCl 5 or BF 3 and advantageously at a temperature of 50 to 200 ° C, preferably 80 to 130 ° C
• Lewis acids such as A1C1 3 , FeCl 3 , ZnCl 2 , SnCl 4 , SbCl 5 or BF 3
• A1C1 3 FeCl 3 , ZnCl 2 , SnCl 4 , SbCl 5 or BF 3
• Another method is to use a compound of formula wherein R and Hal have the meaning given, heated to 200 to 220 ° C. with aqueous potassium hydroxide solution.
• the compounds of the formula (1) used according to the invention are practically colorless and odorless and are very good with the customary color formers reactive, so that spontaneous, constant 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 of at least a pair of sheets, the at least one color former, dissolved in an organic solvent, and a developer of the formula
• 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 alone, as mixtures or in a mixture with known developers.
• Typical examples of known developers are active clay substances, such as attapulgus clay, acid clay, bentonite, montmorillonite; activated sound, e.g. acid activated bentonite or montmorillonite; halloysite, zeolite, silica, alumina, aluminum sulfate, aluminum phosphate, zinc chloride, zinc nitrate, kaolin or any clay or acidic organic compounds such as e.g. optionally ring-substituted phenols, salicylic acid or salicylic acid esters and their metal salts; an acidic polymeric material such as e.g.
• 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 used 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. 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 honeycomb-like structures incorporated.
• the color formers are preferably enclosed in microcapsules which can generally 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. polyhalogenated paraffin or diphenyl, such as chlorinated paraffin, monochlorodiphenyl or trichlorodiphenyl, furthermore 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 evenly around the droplets of the color former solution by coacervation forces, wherein the encapsulation material can consist, for example, of gelatin and gum arabic, as described, for example, in US Pat. No. 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 that are formed by interfacial polymerization, such as capsules made of polyester, polycarbonate, polysulfonamide, polysulfonate, but especially 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 in the arrangement of the capsules, the color reactants, i.e. 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.
• Another arrangement of the components is that the color capsule-containing microcapsules and the developer are present 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 primarily 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 used 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. heat sensitive recording and copying materials and papers. These systems are used, for example, to record information, e.g. used in electronic computers, remote printers, teletype machines or in recording devices and measuring instruments such as 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 these 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 4-tert-butylphenol, 4-phenylphenol, 4-hydroxydiphenyl ether, a-naphthol, ⁇ -naphthol, 4-hydroxybenzoic acid methyl ester , 4-hydroxyacetophenone, 2,2'-dihydroxydiphenyl, 4,4'-isopropylidene diphenol, 4,4'-isopropylidene-bis- (2-methylphenol), 4,4'-bis- (hydroxyphenyl) valeric acid, hydroquinone, pyrogallol, Phloroglucin, p-, m-, o-hydroxybenzoic acid, gallic acid, 1-hydroxy-2-naphthoic acid and boric acid and organic, preferably aliphatic dicarboxylic acids such as tartaric acid, oxalic acid, maleic acid, citric acid, citraconic acid and succinic acid.
• phenolic compounds such as 4-tert-butylphenol, 4-pheny
• 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. hydrophilic polymers, such as polyvinyl alcohol, polyacrylic acid, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, polyacrylamide, polyvinyl pyrrolidone, gelatin and starch.
• water-insoluble binders i.e. binders soluble in non-polar or only weakly polar solvents, e.g. Natural rubber, synthetic rubber, chlorinated rubber, alkyd resins, polystyrene, styrene / butadiene copolymers, polymethylacrylates, ethyl cellulose, nitrocellulose and polyvinyl carbazole
• binders soluble in non-polar or only weakly polar solvents
• 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 example talc, titanium dioxide, zinc oxide, calcium, can be used to improve the degree of whiteness, to facilitate printing on the papers and to prevent the heated spring from sticking carbonate (eg chalk), clays such as kaolin, and organic pigments such as urea formaldehyde or melamine formaldehyde polymers.
• talc titanium dioxide
• zinc oxide calcium
• carbonate eg chalk
• clays such as kaolin
• organic pigments such as urea formaldehyde or melamine formaldehyde polymers.
• substances such as urea, thiourea, diphenylthiourea, acetamide, acetanilide, stearic acid amide, phthalic anhydride, metal chlorides, metal stearates, for example zinc stearate, phthalic acid nitrile or other corresponding, meltable products which Induce melting of the color former and the developer, are added.
• Thermographic recording materials preferably contain waxes, for example 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, which saturates at about 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.
• Example 1 The procedure described in Example 1 is followed, except that 1 g of 2-phenylamino-3-methyl-6-diethylamino-fluorane is used for dispersion B instead of crystal violet lactone.
• 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.
• Example 5 Heat-sensitive recording paper using the following two dispersions G and H according to the process 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.
• Example 6 Heat-sensitive recording paper using only one dispersion K, which is produced according to the process 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.
• Example 7 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 suspension of the microcapsules obtained and dried.
• a second sheet of paper is coated with an aqueous dispersion P, which consists of a 35X solids content
• the first sheet and the paper coated with 4-hydroxydiphenyl sulfone are placed adjacent to one another with the coatings.
• pressure is exerted and an intense blue copy immediately develops on the sheet coated with the developer.
• an aqueous dispersion Q which consists of 25 parts of 4-hydroxydiphenyl sulfone, 110 parts of kaolin, 40 parts of urea-formaldehyde condensate (BET surface area 20 m 2 / g ), 20 parts of titanium dioxide, 20 parts of chalk, 35 parts of styrene / butadiene copolymer (50%) and 300 parts of water.
• Example 8 Heat-sensitive recording paper using the following two dispersions R and S according to the process 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.
• Example 10 Heat-sensitive recording paper using the following two dispersions T and U according to the method described in Example 1.
• 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.
• EXAMPLE 11 The procedure is as described in Example 10, but using 4-hydroxyphenyl methyl sulfone instead of 4-hydroxy-4'-chloro-diphenyl sulfone.
• the basic color of the recording paper thus obtained is colorless.
• a blue hue develops, the full color strength of which is reached at 150 ° C.
• Example 12 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)
• Heat Sensitive Colour Forming Recording (AREA)
• Color Printing (AREA)
• Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
• Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
• Investigating Or Analysing Biological Materials (AREA)
• Casting Or Compression Moulding Of Plastics Or The Like (AREA)

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Citations (7)

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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 EP EP82810246A patent/EP0067793B1/fr not_active Expired
  • 1982-06-09 DE DE8282810246T patent/DE3263106D1/de not_active Expired
  • 1982-06-09 AT AT82810246T patent/ATE12744T1/de not_active IP Right Cessation
  • 1982-06-14 ES ES513083A patent/ES8306343A1/es not_active Expired
  • 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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