Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B11/00—Diaryl- or thriarylmethane dyes
  • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
  • C09B11/10—Amino derivatives of triarylmethanes
  • C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/124—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

• X and X independently of the other, represent hydrogen, alkyl with one to 12 carbon atoms, alkenyl with at most 12 carbon atoms, alkoxyalkyl with two to eight carbon atoms, alkoxycarbonylalkyl with three to nine carbon atoms, cycloalkyl with five or six carbon atoms, acyl having one to 12 carbon atoms, or optionally substituted benzyl, phenyl or naphthyl, and
• the nitrogen ring A represents a heterocyclic radical which optionally includes a further hetero atom as aring member and the benzene ring B may be further substituted by nitro or one to four halogen atoms.
• These fluorans compounds are particularly useful as colour formers which give intense dark green, grey black or red colours when they are brought into contact with an electron-accepting co-reactant.
• the present invention provides novel fluoran compounds which are normally colourless or only weakly coloured but which by variation of the substituents in position 2 can give intense dark green, grey-black or red colours when contacted with an electron accepting co-reactant.
• the invention specifically relates to fluoran compounds, having in position 6 a nitrogen heterocyclic residue attached to the fluoran system through the nitrogen atom, and in position 2 a substituted amino group; a process for the manufacture of such compounds and their use as colour formers in pressuresensitive or thermo-reactive recording materials.
• the new fluoran compounds according to the invention correspond to the formula wherein R R and R independently of the other, represent hydrogen, alkyl with one to 12 carbon atoms, nitro or halogen, or
• R and R together complete a condensed carbocyclic ring, especially a condensed benzene or tetrahydro benzene ring,
• X and X independently of the other, represent hydrogen, alkyl with one to 12 carbon atoms, alkenyl with at most 12 carbon atoms, alkoxyalkyl with two to eight carbon atoms, alkoxycarbonylalkyl with three to nine carbon atoms, cycloalkyl with five or six carbon atoms, acyl having one to 12 carbon atoms, or optionally substituted phenyl, naphthyl or benzyl,
• the nitrogen ring A represents a heterocyclic radical which optionally includes a further hetero atom as ring member, especially oxygen, sulphur or nitrogen, and the benzene ring B may be substituted by nitro or one to four halogen atoms.
• Halogen in each occurrence in the definitions of the substituents, preferably stands for fluorine, bromine or especially chlorine.
• R R and R as well as X and X represent alkyl, they may be straight or branched chain alkyl groups. Examples of said alkyl groups are methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec.butyl or tert.butyl, octyl or dodecyl.
• R R and R are preferably hydrogen, halogen or alkyl having one to four carbon atoms such as methyl or ethyl.
• Alkenyl in X and X stands e.g. forallyl, 2-methallyl, 2-ethylallyl, 2-butenyl or octenyl.
• Alkoxyalkyl and Alkoxycarbonylalkyl in X and X may have one to four carbon atoms in each alkyl part and stand preferably for B-methoxyethyl or B-ethoxyethyl and B-methoxycarbonylethyl or B-ethoxycarbonylethyl, respectively.
• Cycloalkyl in the meaning of these X-radicals may be cyclopentyl or preferably cyclohexyl.
• the optional substituents in the benzyl, phenyl or naphthyl group may be alkyl with one to four carbon atoms, alkoxy with one to four carbon atoms, alkoxycarbonyl with two to five carbon atoms, acyl having one to four carbon atoms, nitro, halogen or an amino group optionally substituted by alkyl with one to four carbon atoms or by benzyl.
• aromatic or araliphatic radicals examples include p-methylbenzyl, p-chlorobenzyl, p-nitrobenzyl, p-tolyl, xylyl, p-chlorphenyl, p-nitrophenyl, l-methylnaphthyl-( 2) or 2-methylnaphthyl-( l Among the acyl groups the alkanoyl groups containing one to 12 carbon atoms, such as formyl, acetyl or propionyl are especially noteworthy.
• acyl substituents may be alkylsulphonyl having one to 12 carbon atoms, such as methylsulphonyl, as well as benzoyl or benzene-sulphonyl groups which may be substituted in benzene ring by halogen, methyl or methoxy groups.
• the nitrogen ring A denotes a heterocyclic radical which is attached to the fluoran ring through the nitrogen atom.
• the heterocyclic radical may have three to 12, preferably five or six ring members, wherein one or two hetero atoms may be included as ring members.
• the benzene ring B may contain fluorine, bromine or especially chlorine. Preferably, it is not further substituted or contains four chlorine atoms.
• X represents alkyl with one to eight carbon atoms
• alkoxyalkyl with two to eight carbon atoms, cycloalkyl with five or six carbon atoms, acyl with one to seven carbon atoms, phenyl or benzyl optionally substituted in the ring by methyl or halogen,
• X represents hydrogen, alkyl with one to eight carbon atoms, cycloalkyl with five or six carbon atoms, acyl with one to seven carbon atoms or benzyl optionally substituted in the ring by methyl or halogen, and
• the nitrogen ring A and the benzene ring B have the given meanings.
• X represents alkyl with one to eight carbon atoms, acyl with one to seven carbon atoms, phenyl or benzyl,
• X represents hydrogen, alkyl with one to eight carbon atoms, acyl with one to seven carbon atoms or benzyl,
• the nitrogen ring A represents a morpholino, piperazino or especially a pyrrolidinyl or piperidino ring and the benzene ring B may be further substituted by one to four halogen atoms, especially chlorine atoms.
• fluoran compounds falling under formulae (1) to (3) which are listed under A, B and C, respectively.
• fluoran compounds are colour formers which give a grey or black colour when contacted with an electron accepting co-reactant.
• C. Compounds of the formula A N 7 I 5 X 9 O R X wherein COOH with a compound of the formula (8) Z20 R2 X 1 wherein A, B, R,, R R,,, X, and X have the given meanings and Z, and Z represent hydrogen or alkyl having one to four carbon atoms, such as methyl, ethyl or butyl.
• Z is hydrogen, methyl or ethyl and the other is hydrogen.
• Z is hydrogen and Z is hydrogen or methyl.
• the reaction is advantageously carried out at l0 to C by allowing the reactants of formulae (7) and (8) to react together in the presence of an acidic condensing agent.
• Suitable condensing agents are acetic anhydride, sulphuric acid, zinc chloride or phosphorous oxychloride. This reaction is preferably completed by the addition of a base.
• the bases may be organic or inorganic and can include, for example, alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide, as well as aliphatic amines, such as triethylamine or trihydroxyethylamine.
• the starting compounds of formula (7) are new and are generally prepared by reacting a phthalic anhydride of the formula with a compound of the formula oz 10) Q 1 wherein Z represents hydrogen or alkyl having one to four carbon atoms and A and B have the meaning described above.
• This reaction is suitably carried out in an organic solvent, such as acetone, benzene, toluene, xylene, or a chlorobenzene, preferably at temperatures at or below the boiling point of such solvents.
• the compounds of formula (10) may be produced by condensing the heterocyclic base A H, in which the cycle A has the meaning described above, with resorci nol or a monoalkyl ether derivative thereof at temperatures between 50 and 250C and optionally under pressure. This reaction may or may not be assisted by the use of a condensing agent, examples'of which are zinc chloride, aluminium chloride or sulphanilic acid.
• the compounds of formula (10) may be prepared from the reaction of meta hydroxyor alkoxyaniline with a a,w-dihalogenoalkanes in which the halogen is, for example, bromine or chlorine but more usually bromine.
• Compounds of formula (1), wherein X, or X or both represent acyl may be manufactured by reacting a compound of formula (1), wherein at least one of X and X represents hydrogen, with acylating agents having at most 12 carbon atoms, e.g. reactive functional derivatives of aliphatic carboxylic or sulphonic acids, particularly fatty acid halides and anhydrides such as acetyl chloride, acetyl bromide or acetic anhydride or of aromatic carboxylic or sulphonic acids such as benzoic acid halides or benzene sulphonic acid halides.
• acylating agents having at most 12 carbon atoms, e.g. reactive functional derivatives of aliphatic carboxylic or sulphonic acids, particularly fatty acid halides and anhydrides such as acetyl chloride, acetyl bromide or acetic anhydride or of aromatic carboxylic or sulphonic acids such as benzoic acid hal
• the acylation is generally carried out by known methods, e.g. in the presence of acid binding agents such as alkali metal carbonates or tertiary nitrogen bases such as pyridine and optionally in the presence of dride with styrene, ethylene, vinyl methylether or carboxy polymethylenes.
• acid binding agents such as alkali metal carbonates or tertiary nitrogen bases such as pyridine
• dride with styrene, ethylene, vinyl methylether or carboxy polymethylenes e.g. in the presence of acid binding agents such as alkali metal carbonates or tertiary nitrogen bases such as pyridine
• the preferred co-reactants are attapulgus clay, silton clay or a phenol-formaldehyde resin, these electron acceptors, preferably, are coated on the front side of the receiving sheet.
• the fluoran compounds of formula (4) behave as dark green colour formers, while compounds of formula (5) behave as grey or black colour formers. On the other side, the fluoran compounds of the formula (6) behave as red or scarlet-red colour formers.
• Such a material e.g. includes at least one pair of sheets, which comprises at least a colour former of formula (1) dissolved in an organic solvent, preferably contained in pressure rupturable microcapsules and an electron accepting substance.
• the colourformer upon coming into contact with the electron accepting substance being able to produce a coloured marking at the points where the pressure is applied.
• colour formers which are comprised in the pressure-sensitive copying material are prevented from becoming active by being separated from the electron accepting substance. As a rule this is done by incorporating these colour formers into a foam-, spongeor honeycomb-like structure. Preferably however these colour formers are microencapsulated.
• these colourless colour formers of formula (1) When these colourless colour formers of formula (1) are dissolved in an organic solvent, they may be subjected to a microencapsulation process and subsequently used for making pressure-sensitive papers. When the capsules are ruptured by pressure from e.g. a pencil and the colour former solution is thus transferred into an adjacent sheet coated with a substrate capable of acting as an electron acceptor, a coloured image is produced. This new colour results from the thus produced dyestuff which absorbs in the visible region of the electromagnetic spectrum.
• the present colour formers are encapsulated dissolved in organic solvents.
• Suitable solvents are preferably non-volatile e.g. polyhalogenated diphenyl such as trichlorodiphenyl and its mixture with liquid paraffin, tricresyl phosphate, di-n-butyl phthalate, dioctyl phthalate, trichlorobenzene, nitrobenzene, trichloroethyl-phosphate, petroleumether, hydrocarbon oils, such as paraffin, condensated derivatives of 7 diphenyl or triphenyl, chlorinated or hydrogenated condensed aromatic hydrocarbons.
• the capsule walls preferably have been obtained by coacervation forces evenly around the droplets of the colour former solution, the encapsulating material consisting of gelatine, as e.g. described in US. Pat. No. 2,800,457.
• the capsules preferably may be made of aminoplast or modified aminoplasts by polycondensation as described in British Patent Specification Nos. 989,264 or 1,156,725.
• a preferred arrangement is wherein the encapsulated colour former is coated on the back side of a transfer sheet and the electron accepting substance is coated on the front side of a receiving sheet.
• one or more of the new fluorans are co-encapsulated with one or more other known colour formers, such as crystal violet lactone, benzoyl leuco methylene blue, or a bis-indolyl phthalide such as 3,3-bis(1 -noctyl-2'-methylindol-3-yl)- phthalide.
• one or more other known colour formers such as crystal violet lactone, benzoyl leuco methylene blue, or a bis-indolyl phthalide such as 3,3-bis(1 -noctyl-2'-methylindol-3-yl)- phthalide.
• microcapsules containing the colour formers of formula (1) are used for making pressure-sensitive copying material of the various types known in the art, such as so called Chemical Transfer and Chemical Self-contained papers.
• the various systems mainly are distinguished by the arrangement of the capsules, the colour reactants and the support material.
• the microcapsules may be in an undercoating of the upper sheet and the colour reactants, that is the electron acceptor and coupler, may be in the overcoating of the lower sheets.
• the components may also be used in the paper pulp. Such systems are called Chemical Transfer system.
• microcapsules containing the colour former and and the colour reactants are in or on the same sheet as one or more individual coatings or in the paper pulp.
• the capsules are preferably fixed to the carrier by means of a suitable adhesive.
• a suitable adhesive since paper is the preferred carried material, these adhesives are predominantly paper coating agents, such as e.g. gum arabic, polyvinyl alcohol, hydroxymethylcellulose, casein, methylcellulose or dextrin.
• the definition paper not only includes normal papers from cellulose fibres, but also papers in which the cellulose fibres are replaced (partially or completely) by synthetic fibres of polymers.
• the new fluoran compounds may also be used as colour former in thermoreactive recording material comprising at least a support, a binder, a colour former and an electron accepting substance.
• Thermoreactive recording systems comprise heat-sensitive recording and copying materials and papers. These systems are used e.g. for the recording of information, for example, in electronic computers, in teleprinters or telewriters, in measuring instruments.
• the mark-forming also can be made manually with a heated pen.
• a further means for inducing heat-initiated marks are laser beams.
• thermoreactive recording material may be arranged in such a manner that the colour former is dissolved or dispersed in a layer of the binder, and in a second layer the developer and the electron-accepting substance are dissolved or dispersed in the binder.
• Another possibility consists in dispersing both the colour former and the developer in one layer.
• the developers are the same electron-accepting substances as are used in pressure sensitive papers. For practical reasons the developer should be solid at room temperature and melt or evaporate above 50 C. Examples of such products are the already mentioned clays, phenolic resins, phenolic compounds such as 4-tert.- butylphenol, 4-phenylphenol, 4-hydroxydiphenyloxide, a-naphthol, 4-hydroxybenzoic acid methyl ester, B- naphthol, 4-hydroxyacetophenone, 2,2'-dihydroxydiphenyl, 4,4'-isopropylidene-diphenol, 4,4'-isopropyliden-bis-(2-methylphenol), 4,4-bis-(hydroxyphenyl) valeric acid, hydroquinone, pyrogallol, phloroglucinol, p-, m-, o-hydroxybenzoic acid, gallic acid, 1- hydroxy-2-naphthoic acid, boric acid, and the aliphatic dicarboxylic acids
• binders Preferably fusible, film-forming binders are used. These binders should be water-soluble, since the nitrophthalides and the developer are water-insoluble. The binder should be able to disperse and fix the colour former and the developer at room temperature. In this way the two reactive components are present in the material in a non-associated form. After applying heat, the binder softens or melts, which enables the colour former to come into contact with the developer and to form a dyestuff.
• Water-soluble or at least water swellable binders are e.g. hydrophilic polymers such as polyvinyl alcohol, polyacrylic acid, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, polyacrylamide, polyvinylpyrrolidone gelatine or starch.
• hydrophilic polymers such as polyvinyl alcohol, polyacrylic acid, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, polyacrylamide, polyvinylpyrrolidone gelatine or starch.
• binders which are waterinsoluble may be used, i.e. binders soluble in non-polar or only weakly polar solvents, e.g. natural rubber, synthetic rubber, chlorinated rubber, alkyd resins, polystyrene, styrene-butadienecopolymers, polymethylmethacrylates, ethylcellulose, nitrocellulose or polyvinylcarbazole.
• non-polar or only weakly polar solvents e.g. natural rubber, synthetic rubber, chlorinated rubber, alkyd resins, polystyrene, styrene-butadienecopolymers, polymethylmethacrylates, ethylcellulose, nitrocellulose or polyvinylcarbazole.
• the preferred arrangement is colour former and developer in a water-soluble binder in one layer.
• thermoreactive material may contain further additives.
• these materials may contain e.g. talc, TiO ZnO or CaCO
• talc TiO ZnO
• CaCO e.g. talc, TiO ZnO or CaCO
• thermoreactive recording materials wherein the present colour formers may be used e.g. are described in German Pat. Application No. 2,228,581, French Pat. No. 1,524,826, Swiss Pat. No. 407,185,
• the benzophenone compound used in this example as starting material may be produced as follows: A mixture of 74 g phthalic anhydride, 81.5 g l-(3- hydroxyphenyl) pyrrolidine and 335 ml xylene is heated at 125 C for 6 hours, then cooled to 25 C. The precipitate is filtered off, washed with methanol and dried to yield 1 10.5 g yellow solid having m.p. 194 C after crystallisation from ethanol.
• EXAMPLE 2 2-Ethylamino-6-N-pyrrolidinylfluoran A mixture of 9.33- g 2-carboxy-2-hydroxy-4-N-pyrrolidinylbenzophenone, 4.54 g N-ethyl-p-anisidine and 30 ml 98% sulphuric acid is stirred at 60C for 5 hours and then quenched into 330 ml ice-water to precipitate a solid. The solid is filtered off, washed with water and added to 75 ml methanol and 16.5 ml triethylamine. The mixture is boiled with stirring for 12 hours, then cooled to 0 C.
• a solution of this compound in benzene is colourless and gives a black colour on contact with silica, greenish black on attapulgus or silton clay and green on phenolic resin.
• This compound forms a red colour when brought in contact with electron accepting substances such as silica.
• the 2'-carboxy-2-ethoxy-4-N-pyrrolidinyl-benzophenone compound used in this example as starting material may be produced as follows:
• the emulsion is poured into 600 g ice-water and stirred for 3 hours to complete the coacervation.
• the resulting capsule slurry is coated onto paper and dried.
• a second sheet coated with silton clay, attapulgite clay or phenolic resin a dark green image is obtained after application of pressure by writing. Similar effect can be obtained by using any other colour former of the Examples 2 to 24.
• EXAMPLE 26 Preparation of Pressure-sensitive Copying Paper A solution containing 1.6 g of 2 -dibenzylamino-6-N- pyrrolidinylfluoran, 0.6 g of 3,3-bis(1-n-octyl-2- methylindol-3'-yl)phthalide, 0.1 g of Crystal violet lactone and 0.6 g of benzoyl leuco methylene blue in 100 g of hydrogenated terphenyl is emulsified at 50 C in 100 g of 12% pigskin gelatin solution. 100 g of 12% gum arabic solution is added followed by 200 ml of water at 50 C.
• the emulsion is poured into 600 g ice-water and stirred for 3 hours to complete the coacervation.
• the resulting capsule slurry is coated into paper and dried.
• a second sheet coated with silton clay or attapulgite clay a grey-black image is obtained after application of pressure by writing.
• EXAMPLE 28 Preparation of Thermoreactive Paper
• the colour formers in Example 27 are replaced by Z-dibenzylamino--N-pyrrolidinylfluoran and 3,3- bis(1'-n-octyl-2-methylindol-3-yl)phthalide in the ratio 6:4
• the resulting system gives an intense black wherein X represents hydrogen, alkyl with one to eight car- R,, R and R independently of the other, represent bon atoms, acyl with one to seven carbon atoms,
• the nitrogen ring A represents the pyrrolidinyl radical and the benzene ring B is unsubstituted or substituted by nitro or one to four halogen atoms.
• a fluoran compound according to claim 1 of the formula wherein X and X represent, independently of the other, R alkyl with one to eight carbon atoms, benzyl or 6 chlorobenzyl. 0 5 5.
• X represents hydrogen, alkyl with one to eight car- 6.
• R- 3. A fluoran compound according to claim 2, of the 6 formula 5 Q A R 6 N A N 4 x l I x co wherein X represents alkyl with one to eight carbon atoms, benzyl or phenyl and X represents acyl having one to seven carbon h atoms. w erem 7.
• the 2- hen lamino-3-meth l-6-N- rrolidin l- X represents alkyl with one to 12 carbon atoms, acyl fluoran.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Organic Chemistry (AREA)
• Color Printing (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
• Nitrogen Condensed Heterocyclic Rings (AREA)
• Heat Sensitive Colour Forming Recording (AREA)

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Citations (5)

• 1973
  • 1973-09-26 GB GB4504873A patent/GB1463815A/en not_active Expired
• 1974
  • 1974-09-12 SE SE7411504A patent/SE7411504L/xx unknown
  • 1974-09-17 DE DE19742444297 patent/DE2444297A1/de not_active Withdrawn
  • 1974-09-18 US US507158A patent/US3929831A/en not_active Expired - Lifetime
  • 1974-09-18 FI FI2727/74A patent/FI272774A/fi unknown
  • 1974-09-24 CA CA209,895A patent/CA1052381A/en not_active Expired
  • 1974-09-24 CH CH1292574A patent/CH596994A5/xx not_active IP Right Cessation
  • 1974-09-24 IT IT7453169A patent/IT1019368B/it active
  • 1974-09-24 ES ES430326A patent/ES430326A1/es not_active Expired
  • 1974-09-25 AT AT772174A patent/AT331824B/de not_active IP Right Cessation
  • 1974-09-25 BE BE148859A patent/BE820305A/xx not_active IP Right Cessation
  • 1974-09-25 NL NL7412673A patent/NL7412673A/xx not_active Application Discontinuation
  • 1974-09-25 YU YU2596/74A patent/YU37317B/xx unknown
  • 1974-09-25 FR FR7432349A patent/FR2257594B1/fr not_active Expired
  • 1974-09-26 JP JP49110056A patent/JPS5064319A/ja active Pending

Patent Citations (5)

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