US3837889A - Colour formers - Google Patents

Colour formers Download PDF

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Publication number
US3837889A
US3837889A US00333347A US33334773A US3837889A US 3837889 A US3837889 A US 3837889A US 00333347 A US00333347 A US 00333347A US 33334773 A US33334773 A US 33334773A US 3837889 A US3837889 A US 3837889A
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US
United States
Prior art keywords
optionally substituted
parts
radical
colour
aryl
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.)
Expired - Lifetime
Application number
US00333347A
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English (en)
Inventor
N Hughes
A Renfrew
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.)
Arjo Wiggins Ltd
Original Assignee
Wiggins Teape 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
Application filed by Wiggins Teape Ltd filed Critical Wiggins Teape Ltd
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Publication of US3837889A publication Critical patent/US3837889A/en
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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
    • C09B11/26—Triarylmethane dyes in which at least one of the aromatic nuclei is heterocyclic
    • 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
    • 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

Definitions

  • R, R and R each independently represents hydrogen, an optionally substituted alkyl radical having from one to five carbon atoms or forms part of a heterocyclic ring containing the attached nitrogen atom;
  • R represents a halogen atom or an alkyl, aryl, aralkyl, alkoxy, nitro, optionally substituted amino, acyl, carboxy, cyano or sulphamyl radical;
  • n represents an integer of from 0 t0 4;
  • A represents an optionally substituted aromatic ring the points of attachment being at two pairs of ortho positions,
  • Y represents a direct link, optionally substituted methylene, oxygen, sulphur or a group of the formula NR wherein R denotes hydrogen or an optionally substituted alkyl, aryl or aralkyl radical; and Z represents an optionally substituted divalent organic radical such that a five-or six-membered ringis formed with Y,
  • a sheet of pressure-sensitive copying paper comprising a paper base carrying the colour former in encapsulated form is placed in contact with a copy sheet comprising a paper base having an active mineral surface coating, for example a surface coating of a so-called acid clay.
  • an active mineral surface coating for example a surface coating of a so-called acid clay.
  • colourless colour formers which. are compounds of the general formula:-
  • R" R each independently represents hydrogen, an optionally substituted alkyl radical having from one to five carbon atoms or forms part of a heterocyclic ring containing the attached nitrogen atom;
  • R represents a halogen atom or an alkyl, aryl, aralkyl, alkoxy, nitro, optionally substituted amino, acyl, carboxy, cyuno or sulphamyl radical;
  • n represents an integer of from to 4;
  • A represents an optionally substituted aromatic ring the points of attachment being at two pairs ofortho positions;
  • Y represents a direct link, optionally substituted methylene, o xygen, sulphur or a group of the formula NR wherein R denotes hydrogen or an o tionally substituted alkyl. aryl or aralkyl radical;
  • Z represents an optionally substituted divalent organic radical such that a fiveor six-membered ring is formed with Y, N R and A.
  • Alkyl radicals which may be represented by R and R include methyl and preferably ethyl.
  • R or R forms part of a heterocyclic ring containing the attached nitrogen atom this may be because R and R are joined together to form a divalent chain of atoms which together with the attached nitrogen atom constitutes a heterocyclic ring such as a pyrrolidine or morpholine ring.
  • A is preferably a benzene ring having points of attachment in the l, 2, and 4, 5 positions.
  • Z may be a 1,2- phenylene radical.
  • the colour formers of the invention may be prepared by reacting a compound of the formula:
  • the colour formers of the invention provide darker images than the colour formers which have generally been used to date, including black images in some cases, when reacted with a suitable electron-accepting substance.
  • suitable electron-accepting substance include silica and attapulgite, which is a so-called acid clay, and synthetic resins containing unreacted phenolic hydroxyl groups.
  • EXAMPLE 1 31.3 parts of 4-diethylamino-2-hydroxybenzoyl-obenzoic acid, 21.1 parts of 2-methoxyacidan and I00 parts of 98 percent sulphuric acid are heated at 100C with stirring for 2 hours than cooled. The reaction mixture is drowned into water and the solid which separates is filtered off and then slurred in an excess of 2N ammonium hydroxide solution to give an off-white solid. Filtration and drying gives the product, 39 parts.
  • a toluene soltuion of the product which has the structure gives a dark-coloured image on contact with a so-called acid clay.
  • EXAMPLE 2 6.23 Parts of o-(4-diethylamino-2-hydroxy)benzoyl benzoic acid, 4.87 parts of 2-methoxy-9-chloroacridine and 50 parts of polyphosphoric acid are heated at 100C with stirring for 6 hours then cooled. The reaction mixture is drowned into ice and the suspension made alkaline with ammonia. The solid which separates is collected, washed well with water and dried to give 4.7 parts of the product of structure:
  • a toluene solution of the above fluoran gives a dark blue image on contact with electron accepting surfaces.
  • EXAMPLE 4 3.1 1 Parts of o-(4-pyrrolidin-l-yl-2-hydroxy)benzoyl benzoic acid, 2.01 parts of 3-methoxy-5,6,7,8- tetrahydrocarbazole and 30 parts of sulphuric acid are heated at 80C for 6' hours then cooled. The reaction mixture is drowned into water and made alkaline with ammonia. The solid which is formed is collected,
  • EXAMPLE 5 4.51 Parts of o-(4-diethylamino-2-hydroxy)benzoyl-3 ',4',5.6-tetrachlorobenzoic acid, 1.97 parts of 3-methoxycarbazole and 30 parts of sulphuric acid are heated at 100C for 6 hours then cooled. The reaction mixture is drowned into water and made alkaline with ammonia. The solid which is formed is collected, Washed with water and dried to give 1.8 parts of the product of structure:
  • a toluene solution of the above colour former gives a dark bluish-red image on contact with electron accepting surfaces.
  • EXAMPLE 6 6.26 pagts ofol 4-diethy lamino-2-hydroxy benzoyl) benzoic acid, 494 parts of I-ethyI-Z-rnethyl-methyl- 3-carboethoxy-5-hydroxy indole and 22 parts of 98 percent sulphuric acid are heated at 75C for 12 hours. The reaction mixture is drowned into water and the precipitated tar is extracted into chloroform. After drying over magnesium sulphate, the chloroform solution is evaporated to dryness and the residue is recrystallised from petroleum ether.
  • Example 7 The preparation of Example 6 is repeated except that the reaction temperature is O5C. 9.3 parts of a white solid. melting point 253C and having the structure:
  • EXAMPLE 10 6.26 parts of o-(4-diethylamino-2-hydroxybenzoyl)- benzoic acid, 3.3 parts of l-methyl-6-hydroxy py-tetrahydroquenoline and 22 parts of 98 percent sulphuric acid are heated at 50-55C for 12 hours. The reaction mixture is drowned into water and neutralised by addi- 6 tion of concentrated ammonia hydroxide solution. The white precipitate is collected by filtration, washed with water and recrystallised from n-propanol. 7.3 parts of a white solid having the structure:
  • EXAMPLE 1 1 In place of the o-(4-diethylamino-2-hydroxybenzoyl) benzoic acid used in Example 10 there are used 6.54 parts of o-[ 4-( morpholinl -yl )-2-hydroxybenzoyl benzoic acid.
  • the product which has the structure:
  • a pressure sensitive copying paper comprising a paper base carrying in encapsulated form a colour former of the general formula matic ring the points of attachment being at two pairs of ortho positions;
  • Y represents a direct link, optionally substituted methylene, oxygen, sulphur or a group of the formula l lR wherein R denotes hydrogen or an optionally substituted alkyl, aryl or aralkyl radical; and
  • Z represents an optionally substituted divalent organic radical such that a fiveor six-membered ring is formed with Y, NR and A.
  • n is 0 and wherein Y represents a direct link, optionally substituted methylene, oxygen or sulphur.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Color Printing (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US00333347A 1972-02-21 1973-02-16 Colour formers Expired - Lifetime US3837889A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB784872A GB1412293A (en) 1972-02-21 1972-02-21 Fluoran compounds and their use in pressure-sensitive copying paper

Publications (1)

Publication Number Publication Date
US3837889A true US3837889A (en) 1974-09-24

Family

ID=9840949

Family Applications (1)

Application Number Title Priority Date Filing Date
US00333347A Expired - Lifetime US3837889A (en) 1972-02-21 1973-02-16 Colour formers

Country Status (13)

Country Link
US (1) US3837889A (cs)
JP (1) JPS4894731A (cs)
AR (1) AR193580A1 (cs)
AU (1) AU472012B2 (cs)
BE (1) BE795746A (cs)
BR (1) BR7301278D0 (cs)
DE (1) DE2308624A1 (cs)
ES (1) ES411827A1 (cs)
FR (1) FR2173102B1 (cs)
GB (1) GB1412293A (cs)
IN (1) IN139665B (cs)
IT (1) IT980489B (cs)
NL (1) NL7302321A (cs)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3959571A (en) * 1973-05-22 1976-05-25 Shin Nisso Kako Co., Ltd. Chromogenic fluoran derivatives and the preparation and use thereof
US3988492A (en) * 1974-04-18 1976-10-26 The Mead Corporation Pressure sensitive copy paper employing pyrazoloxanthene compounds
US4122089A (en) * 1976-02-23 1978-10-24 Sankio Chemical Co., Ltd. Aminothiofluoran compounds, process for the production thereof, and recording elements containing the same
US4351768A (en) * 1977-03-01 1982-09-28 Sterling Drug Inc. 2-[(3-Indolyl)carbonyl]-4/5-carboxybenzoic acids
US4721702A (en) * 1985-03-20 1988-01-26 Fuji Photo Film Co., Ltd. Pressure-sensitive recording material
US4933448A (en) * 1988-04-27 1990-06-12 Ciba-Geigy Corporation Chromogenic lactone compounds of benzopyrano-2H-pyrazoles

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3501331A (en) * 1967-01-27 1970-03-17 Fuji Photo Film Co Ltd Pressure sensitive fluoran derivative containing copying paper
US3540912A (en) * 1967-01-30 1970-11-17 Ncr Co Pressure sensitive record sheets employing 3 - (phenyl) - 3 - (heterocyclic-substituted)-phthalides
US3649649A (en) * 1967-07-10 1972-03-14 Nisso Kako Co Ltd Fluoran derivatives and preparation thereof
US3725416A (en) * 1969-12-05 1973-04-03 Yamamoto Kagaku Gosei Kk 7-piperidinofluoran
US3746562A (en) * 1970-11-16 1973-07-17 Ncr Mark forming record materials

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2036817A1 (de) * 1970-07-24 1972-01-27 Farbwerke Hoechst AG vormals Meister Lucius & Brüning, 6000 Frankfurt Neue farbbildende Lactone, Verfahren zu ihrer Herstellung und ihre Anwendung bei druckempfindlichen Aufzeichnungs- und Vervielfältigungsmaterial

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3501331A (en) * 1967-01-27 1970-03-17 Fuji Photo Film Co Ltd Pressure sensitive fluoran derivative containing copying paper
US3540912A (en) * 1967-01-30 1970-11-17 Ncr Co Pressure sensitive record sheets employing 3 - (phenyl) - 3 - (heterocyclic-substituted)-phthalides
US3649649A (en) * 1967-07-10 1972-03-14 Nisso Kako Co Ltd Fluoran derivatives and preparation thereof
US3725416A (en) * 1969-12-05 1973-04-03 Yamamoto Kagaku Gosei Kk 7-piperidinofluoran
US3746562A (en) * 1970-11-16 1973-07-17 Ncr Mark forming record materials

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3959571A (en) * 1973-05-22 1976-05-25 Shin Nisso Kako Co., Ltd. Chromogenic fluoran derivatives and the preparation and use thereof
US3988492A (en) * 1974-04-18 1976-10-26 The Mead Corporation Pressure sensitive copy paper employing pyrazoloxanthene compounds
US4122089A (en) * 1976-02-23 1978-10-24 Sankio Chemical Co., Ltd. Aminothiofluoran compounds, process for the production thereof, and recording elements containing the same
US4351768A (en) * 1977-03-01 1982-09-28 Sterling Drug Inc. 2-[(3-Indolyl)carbonyl]-4/5-carboxybenzoic acids
US4721702A (en) * 1985-03-20 1988-01-26 Fuji Photo Film Co., Ltd. Pressure-sensitive recording material
US4933448A (en) * 1988-04-27 1990-06-12 Ciba-Geigy Corporation Chromogenic lactone compounds of benzopyrano-2H-pyrazoles

Also Published As

Publication number Publication date
FR2173102B1 (cs) 1977-04-29
AU472012B2 (en) 1976-05-13
GB1412293A (en) 1975-11-05
AR193580A1 (es) 1973-04-30
NL7302321A (cs) 1973-08-23
IT980489B (it) 1974-09-30
IN139665B (cs) 1976-07-17
FR2173102A1 (cs) 1973-10-05
BR7301278D0 (pt) 1974-05-16
JPS4894731A (cs) 1973-12-06
BE795746A (fr) 1973-08-21
ES411827A1 (es) 1976-09-01
AU5237773A (en) 1974-08-22
DE2308624A1 (de) 1973-09-06

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