US3884506A - Pressure-sensitive copying papers containing fluoran compounds - Google Patents

Pressure-sensitive copying papers containing fluoran compounds Download PDF

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Publication number
US3884506A
US3884506A US318048A US31804872A US3884506A US 3884506 A US3884506 A US 3884506A US 318048 A US318048 A US 318048A US 31804872 A US31804872 A US 31804872A US 3884506 A US3884506 A US 3884506A
Authority
US
United States
Prior art keywords
fluoran
benzo
color
diethylamino
pressure
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
US318048A
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English (en)
Inventor
Minoru Ozutsumi
Yoshihide Miyazawa
Katsuichi Motohashi
Masatake Kiritani
Akio Watanabe
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.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co 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
Priority to BE793349D priority Critical patent/BE793349A/xx
Priority to JP46104645A priority patent/JPS5224888B2/ja
Priority to GB5955972A priority patent/GB1368720A/en
Priority to DE2263292A priority patent/DE2263292C3/de
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Priority to US318048A priority patent/US3884506A/en
Priority to US05/539,887 priority patent/US3996212A/en
Application granted granted Critical
Publication of US3884506A publication Critical patent/US3884506A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C09B11/10—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

Definitions

  • ABSTRACT A pressure-sensitive copying paper comprising an adsorbent solid acid and a microencapsulated color former capable of forming a distinct color when reacted with the adsorbent acid coated on the same or a different surface of a support or supports, the microencapsulated color former being at least one fluoran compound represented by the formula;
  • R R Z, m and are as defined hereinafter, is disclosed.
  • the present invention relates to a pressure-sensitive copying paper, more particularly, to a pressuresensitive copying paper having a microcapsule layer containing a novel fluoran compound as a color former.
  • Pressure-sensitive copying papers generally comprise a transfer sheet having thereon a layer of fine capsules containing a solution of an electron donating colorless organic compound (hereinafter referred to as a color former) in an organic solvent, and a receiving sheet having thereon a layer of an electron accepting solid.
  • a transfer sheet having thereon a layer of fine capsules containing a solution of an electron donating colorless organic compound (hereinafter referred to as a color former) in an organic solvent
  • a receiving sheet having thereon a layer of an electron accepting solid.
  • a suitable binder is generally used for coating the electron accepting solid.
  • Pressure-sensitive copying paper systems comprising the aforesaid transfer sheet (hereinafter referred to as an upper sheet) and a receiving sheet (hereinafter referred to as a lower sheet) and an intermediate sheet (hereinafter referred to as a middle sheet) are also known.
  • the middle sheet is usually coated, on opposite surfaces, with a layer of microcapsules containing a color former solution and with a layer of a solid acid and a binder, respectively.
  • Another type of pressure-sensitive copying system is a recording sheet which can be prepared by applying the above described microcapsules and the adsorbent solid acid on the same surface of a support.
  • the solid acid used in conventional types of pressuresensitive copying papers includes active clay substrates such as acid clay, attapulgite, zeolite, bentonite and the like, solid organic acids such as succinic acid, tannic acid, benzoic acid and the like, and acidic organic polymers such as phenol-formaldehyde polycondensates, phenol-acetylene copolymers, styrene-maleic anhydride copolymers containing residual acidic radicals, salicylic acid-formaldehyde polycondensates and the like.
  • active clay substrates such as acid clay, attapulgite, zeolite, bentonite and the like
  • solid organic acids such as succinic acid, tannic acid, benzoic acid and the like
  • acidic organic polymers such as phenol-formaldehyde polycondensates, phenol-acetylene copolymers, styrene-maleic anhydride copolymers containing residual
  • the organic solvent for dissolving the color former which is conventionally used includes, for example, ethylene glycol, chlorobenzene, chlorodiphenyl, diethyl phthalate, trioctyl phosphate and alkylnaphthalene.
  • One object of the present invention is to provide pressure-sensitive copying papers containing as a color former a fluoran compound which forms a reddish violet, dark reddish-violet, violet, dark violet, dark green or dark bluish-black color having excellent lightfastness when it is brought into contact with a solid acid.
  • Another object of the present invention is to provide pressure-sensitive copying papers which can be colored wherein R represents a hydrogen atom or a lower alkyl group containing 1 to 4 carbon atoms; R represents a lower alkyl group containing l to 4 carbon atoms; Z represents a hydrogen atom, chlorine atom or nitro group; m represents an integer of from 1 to 4; and
  • pressure-sensitive papers capable of being colored reddish-violet, dark reddish-violet, violet, dark violet, dark green, dark bluish-black or a like color can be obtained by using as a color former one or more novel fluoran compounds represented by general formula (I), and that a pressure-sensitive copying paper capable of being colored black can be obtained by the combined use of the novel fluoran compound and known color formers such as ohydroxybenzalacetophenone, Rhodamine B- anilinolactam, Malachite Green lactone, Crystal Violet lactone and benzoyl leucomethylene blue.
  • a pressure-sensitive copying paper wherein the novel fluoran compound represented by general formula (I) is used as a color former is colorless or extremely slightly colored before color formation, but when brought into contact with a color developer the paper immediately colors reddish-violet, dark reddish-violet, violet, dark violet, dark green, dark bluish-black, or a LII of the color formed is excellent.
  • a pressure-sensitive copying paper capable of being colored black, wherein a color former of the invention capable of forming a dark color is used in combination with one of the aforesaid known color formers, is colored black immediately when brought into contact with a color developer, the color exhibiting high density and an extremely small change in color tone after color formation.
  • the color former represented by general formula (I) can be obtained by reacting 1.0 mole of benzoylbenzene represented by the general formula;
  • the color former represented by the general formula (I) can be obtained by reacting 1.0 mole of benzoylnaphthalene represented by the general formula;
  • B-CI-IO wherein B is the same as defined in general formula (I), at a temperature of from 20 to 130C for -10 hours in a volatile organic solvent such as methanol, ethanol, chloroform, benzene, toluene, chlorobenzene, etc.', and, if necessary, in the presence of a basic material such as triethylamine, pyridine and quinoline, or glacial acetic acid, as a catalyst, pouring the reaction product into a cold water, rendering the resulting mixture alkaline with an aqueous sodiumhydroxide solution, filtrating out the precipitate formed or extracting the precipitate with chloroform, benzene, toluene or chloroform, and distilling off the solvent under reduced pressure. If necessary, the resulting color former can be recrystallized.
  • a volatile organic solvent such as methanol, ethanol, chloroform, benzene, toluene, chlorobenzene, etc.'
  • a basic material such as
  • Color former Solvent Catalyst M.P. (C) Appearance of crystals 0 No. 7 Ethanol Pyridine 271 273 Light brown No. 8 234 238 Light brown No. 9 253 254 Light brown No. 10 244 247 Light brown No. 12 Benzene Glacial 206 208 Light yellowish green acetic acid No. l3 205 208 Light yellowish green No. l4 21 I 215 Light yellowish green No. 15 Chloroform Triethyl- 203 208 Light brown amine No. 16 Benzene Glacial lll Continued Color former Solvent Catalyst M.P.
  • EXAMPLE 1 2.0 parts of each of color formers No. l to No. 3 3 was treated as follows. Each of the color formers was dissolved in 100 parts of trichlorodiphenyl and, at 50C, parts of gum arabic and 160 parts of water were added thereto and an emulsion formed. To the resulting emulsion were added 20 parts of acidprocessed gelatin and l60 parts of water and, with stirring, acetic acid was added thereto to adjust the pH to 5. Thereafte'r, 500 parts of water was added thereto to accelerate coacervation to form a dense liquid film of gelatin-gas arabic around the oil droplets of trichlorodiphenyl containing the color former.
  • the resulting upper sheet was closely placed in face to face alignment on a lower sheet coated with an active clay substance as a color developer and a localized pressure was applied to the combination of sheets by handwriting, the lower sheet including colored dark bluish-black at the pressed area, and almost no facing of the dark bluish-black color formed was encountered even when the colored area may directly exposed to sunlight for a long period of time.
  • the upper sheet was closely placed in face to face alignment on a lower sheet coated with an acidic organic polymer as a color developer and localized pressure was applied to the combination of sheets by handwriting, the lower sheet immediately colored dark green at the pressed area.
  • color formers corresponding to color formers No. 1 to No. 3 were prepared with the use of beta-naphthol, and were treated in the same manner as above to obtain the respective upper sheets.
  • the lower sheet was immediately colored dark reddish-violet at the pressed area, but, when exposed to sunlight directly for several hours, the dark reddishviolet color changed to a dark yellowish-brown color.
  • EXAMPLE 2 2.0 parts of color formers No. 7 to No. 15 were treated in the same manner as in Example 1, applied to a paper and dried to obtain a colorless upper sheet.
  • the resulting upper sheet was closely placed in face to face alignment on a lower sheet coated with an active clay substance as a developer and a localized pressure was applied to the combination of sheets by handwriting, the lower sheet immediately colored dark bluish-black at the pressed area, and almost no fading of the dark bluish-dark color formed was recognized even when the sheet was directly exposed to sunlight for a long period of time.
  • the upper sheet was closely placed in face to face alignment on a lower sheet coated with an acidic organic polymer as a color developer and localized pressure was applied to the combination of the sheets by handwriting, the lower sheet immediately colored dark violet at the pressed areas.
  • EXAMPLE 3 2.0 parts of color formers No. 4 to No. 6 and No. 16 were treated in the same manner as in Example 1, applied to a paper, and dried to obtain a colorless upper sheet.
  • the resulting upper sheet was closely placed in face to face alignment on a lower sheet coated with an acidic organic polymer, active clay substance or a mixture thereof as a color developer and localized pressure was applied to the combination of the sheets by handwriting, the lower sheet immediately colored reddish-violet to dark reddish-violet at the pressed areas, and the reddish-violet to dark reddish-violet color showed sufficient stability with lapse of time to be practically useful.
  • color formers corresponding to color formers No. 4 to No. 6 were prepared with the use of beta-naphthol, and were subsequently treated in the same manner as in Example 1 to obtain respective upper sheets.
  • each of the resulting upper sheets was closely placed in face to face alignment on a lower sheet coated with an active clay substance and localized pressure was applied to the combination of the sheets by handwriting, the pressed areas of lower sheet immediately colored red to reddish-violet color.
  • the sheets were directly exposed to sunlight for several hours, the red to reddish-violet color changed to a yellowish-brown color.
  • EXAMPLE 4 2.0 parts of color formers No. 17 and No. 18 are treated in the same manner as in Example 1, applied to a paper and dried to obtain a colorless upper sheet.
  • an active clay substance or a mixture thereof as a color developer and localized pressure was applied to the combination of the sheets by handwriting, the lower sheet immediately colored violet to dark violet at the pressed areas, and the violet to dark violet color thus formed exhibited enough stability with the passage of time to be practically useful.
  • Example 2 Malachite Green lactone and 0.2 part of benzoyl leucomethylene blue were treated in the same manner as in Example 1 and applied to a paper to prepare an organic sheet.
  • the resulting upper sheet was closely placed in face to face alignment on a lower sheet coated with an active clay substance as a color developer and localized pressure was applied to the combination of the sheets by handwriting, the lower sheet immediately colored black at the pressed areas, and the color showed little change in tone with the passage of time.
  • EXAMPLE 6 A colorless upper sheet was obtained by treating 3.0 parts of color former No. 2, 0.25 parts of ohydroxybenzalacetophenone, 0.2 part of Rhodamine B-anilinolactam, 10 part of Crystal Violet lactone and 0.5 part of benzoyl leucomethylene blue in the same manner as in Example 1, applying the microcapsule system to a paper and drying the paper.
  • the resulting upper sheet was closely placed in face to face alignment on a lower sheet coated with an active clay substance as a color developer and localized pressure was applied to the combination of the sheets by handwriting, the lower sheet immediately colored black at the pressed areas. Almost no facing of the black color formed was seen even upon exposure to direct sunlight for a long period of time.
  • R represents a hydrogen atom or a lower alkyl group containing 1 to 4 carbon atoms
  • R represents a lower alkyl group containing 1 to 4 carbon atoms
  • Z represents one or more of a hydrogen atom, chlorine atom or nitro group
  • 111 represents an integer of from 1 to 4 and represents a naphthalene ring of the formula
  • said color former is a compound selected from the group consisting of 3'-diethylamino-9- ethyladeneamino-benzo(a)-fluoran, 3-diethylamino- 9-(2"-ethyl-hexylideneamino)-benzo(a)-fluoran, 3- diethylamino-9-(2"-butenylideneamion)-benzo(a)- fluoran, 3-diethylamino-9'-cinnamylideneaminobenzo(a)-fluoran, 3-diethylamino-9- benzylideneamino-benzo(a)-fluoran, 3-diethylamino- 9'-(p-methyl-benzylideneamino-benzo(a)-fluoran, 3- diethylamino-9'-(p-methoxy-benzylideneamino)- benzo

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Color Printing (AREA)
US318048A 1971-12-24 1972-12-26 Pressure-sensitive copying papers containing fluoran compounds Expired - Lifetime US3884506A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BE793349D BE793349A (fr) 1971-12-24 Composes de fluorane et papiers de copie sensibles a la pression en contenant
JP46104645A JPS5224888B2 (enrdf_load_stackoverflow) 1971-12-24 1971-12-24
GB5955972A GB1368720A (en) 1971-12-24 1972-12-22 Fluoran compounds and pressure-sensitive recording materials containing them
DE2263292A DE2263292C3 (de) 1971-12-24 1972-12-23 Fluoranverbindungen und druckempfindliches Kopierpapier
US318048A US3884506A (en) 1971-12-24 1972-12-26 Pressure-sensitive copying papers containing fluoran compounds
US05/539,887 US3996212A (en) 1971-12-24 1975-01-09 Fluoran compounds

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP46104645A JPS5224888B2 (enrdf_load_stackoverflow) 1971-12-24 1971-12-24
US318048A US3884506A (en) 1971-12-24 1972-12-26 Pressure-sensitive copying papers containing fluoran compounds
US05/539,887 US3996212A (en) 1971-12-24 1975-01-09 Fluoran compounds

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US05/539,887 Division US3996212A (en) 1971-12-24 1975-01-09 Fluoran compounds

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US3884506A true US3884506A (en) 1975-05-20

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US318048A Expired - Lifetime US3884506A (en) 1971-12-24 1972-12-26 Pressure-sensitive copying papers containing fluoran compounds
US05/539,887 Expired - Lifetime US3996212A (en) 1971-12-24 1975-01-09 Fluoran compounds

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US05/539,887 Expired - Lifetime US3996212A (en) 1971-12-24 1975-01-09 Fluoran compounds

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US (2) US3884506A (enrdf_load_stackoverflow)
JP (1) JPS5224888B2 (enrdf_load_stackoverflow)
BE (1) BE793349A (enrdf_load_stackoverflow)
DE (1) DE2263292C3 (enrdf_load_stackoverflow)
GB (1) GB1368720A (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4020056A (en) * 1975-04-10 1977-04-26 Ncr Corporation Di-vinyl phthalides color formers
US4263344A (en) * 1974-08-23 1981-04-21 Wiggins Teape Limited Paper coating methods

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55172416U (enrdf_load_stackoverflow) * 1979-05-26 1980-12-10
US4945171A (en) * 1987-08-10 1990-07-31 Molecular Probes, Inc. Xanthene dyes having a fused (C) benzo ring

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3654314A (en) * 1970-11-03 1972-04-04 Ncr Co Tetrachlorinated chromogenic compounds
US3730754A (en) * 1970-11-03 1973-05-01 Ncr Co Pressure sensitive recording sheet

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1309643A (en) * 1970-04-06 1973-03-14 Sumitomo Chemical Co Fluoran compounds for pressure-sensitive copy papers
US3825561A (en) * 1970-10-12 1974-07-23 Sumitomo Chemical Co Fluoran compounds
US3787325A (en) * 1970-11-16 1974-01-22 Ncr Alkylamino spiro {8 12-h{8 1{9 benzopyran {8 3,2f{9 {14 quinoline-12,1{40 phthalide
US3947471A (en) * 1970-12-26 1976-03-30 Sumitomo Chemical Company, Ltd. Benz (c) fluoran compounds and recording sheet containing them
US3694461A (en) * 1972-02-07 1972-09-26 Ncr Co Chromogenic compounds

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3654314A (en) * 1970-11-03 1972-04-04 Ncr Co Tetrachlorinated chromogenic compounds
US3730754A (en) * 1970-11-03 1973-05-01 Ncr Co Pressure sensitive recording sheet

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4263344A (en) * 1974-08-23 1981-04-21 Wiggins Teape Limited Paper coating methods
US4020056A (en) * 1975-04-10 1977-04-26 Ncr Corporation Di-vinyl phthalides color formers

Also Published As

Publication number Publication date
JPS4869613A (enrdf_load_stackoverflow) 1973-09-21
DE2263292B2 (de) 1980-04-30
DE2263292C3 (de) 1981-01-08
DE2263292A1 (de) 1973-06-28
JPS5224888B2 (enrdf_load_stackoverflow) 1977-07-04
BE793349A (fr) 1973-04-16
US3996212A (en) 1976-12-07
GB1368720A (en) 1974-10-02

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