US3669711A - Pressure-sensitive copying paper - Google Patents

Pressure-sensitive copying paper Download PDF

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Publication number
US3669711A
US3669711A US40481A US3669711DA US3669711A US 3669711 A US3669711 A US 3669711A US 40481 A US40481 A US 40481A US 3669711D A US3669711D A US 3669711DA US 3669711 A US3669711 A US 3669711A
Authority
US
United States
Prior art keywords
color
pressure
fluoran
copying paper
color former
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
US40481A
Other languages
English (en)
Inventor
Shiro Kimura
Sadao Ishige
Masataka Kiritani
Teruo Kobayashi
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
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Application granted granted Critical
Publication of US3669711A publication Critical patent/US3669711A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • B41M5/136—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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/914—Transfer or decalcomania
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31844—Of natural gum, rosin, natural oil or lac
    • Y10T428/31848—Next to cellulosic

Definitions

  • the present invention relates to a pressure-sensitive copyingpaper and more particnlarly'it is concerned with a pressureesensitive copying paper in which a fluoran de- M rivative is used as a color former 1 H I (2) Description of the priorart.
  • An object of the present invention is to provide a pressure-sensitive copying paper having a high light fastness and capable of forming a black, a dark green, or a dark grey color using only a single color former.
  • Another object of the present invention is to provide a pressure-sensitive copying paper capable of being colored a desired color such as blue black using the color former of this invention together with a conventional color former and which is neither discolored nor faded by light.
  • the present invention relates to a pressure-sensitive paper having a layer of microcapsules containing as a color former a fluoran derivative represented by the general formula,
  • R and R each represents an alkyl group having from 1 to 5 carbon'atoms; wherein R represents a hydrogen atom, an alkyl group having from'l to 5, carbon atoms, or a benzyl group; and wherein Rfrepresents an one surface thereof a layer of microcapsules containing the color former and on the. opposite surface the layer of the solid acid.
  • Rf represents an alkyl group having from 1 to 5 carbon'atoms
  • R represents a hydrogen atom, an alkyl group having from'l to 5, carbon atoms, or a benzyl group
  • the microcapsules containing the color former and the solid acid are applied to the same surface of a support, such as paper.
  • e can; can, H a d-diethylamino-F(ortho-toluidlno)-fluoran.
  • the color former used in the present invention can be prepared by the followingnianner.
  • I u v That is, general methods for preparing the color formers V wherein R1, R2, R3 and R4 are as above rdefined one a of the present invention are as follows. of Intermediate A, o-(4-dialky1amino-Z-hydroxybenzoyl) RI 'benzoic acid, and one mole of Intermediate 'B', p-N-arylaminophenoLare dissolved in 10-20 moles of sulfuric acid r I v and thersystem is reacted for 2-8 hours at 80-100 C.
  • reaction product is poured I into a large proportion of ice'wa'ter and the sulfuric acid in "thereaction product is neutralized with an aqueous v v alkali solution, such as an aqueous solution of sodium hy- (rnteymediate B) droxide; to convert the systein into a slightly alkaline state.
  • an aqueous v v alkali solution such as an aqueous solution of sodium hy- (rnteymediate B) droxide
  • the color, formers of theapresent invention can be prepared by the following "method generally; the method 5Bin h wver',' applicable to only the case of preparing a color former having the aforesaid general formula wherein R is a hydrogen atom;
  • R R and R are as above defined and R represents an alkyl group having 1 to 5 carbon atoms or an aryl group.
  • Intermediate A used as a starting material for preparing the color former of this invention can be prepared according to a known method as described in Fliedlendar, vol. 4, page 260, by refluxing under heating for a few hours 1 mole of meta-dialkylamino-phenol and 1 mole of phthalic anhydride in a solvent such as toluene.
  • Intermediate B having thewaforesaid general formula, wherein R is hydrogen atom can be prepared as product (11) below by a known method as described in Chemical Abstracts, 52, 718421, by heating an arylamine (I), hydroquinone, and cone. sulfuric acid to cause a dehydration and condensation reaction.
  • R represents an aryl group
  • Intermediate B having the above-described general formula wherein R is an alkyl group having from ltto 5 carbon atoms or a benzyl group can be prepared by. alkylating or benzylating compound (H) shown above in a conventional manner.
  • Intermediate B shown above can be prepared by acylating compound (II) in a conventional manner.
  • Color former No. 1 was prepared by causing the dehydration reaction of Intermediate A, wherein R is C H and R is C H o-(4-diethylamino-2-hydroxybenzoyl) benzoic acid, and Intermediate B, in which R is H and R is a phenyl group, p-anilinophenol, in concentrated sulfuric acid by the same procedure as in the general method described above.
  • the product was recrystallized from a benzene-ethanol mixture to provide white crystals of the color former having a melting point of 182-185 C.
  • the color formers Nos. 3, 4, 6, 7 and 8 were also prepared in the same manner using the corresponding startlng materials.
  • r For preparing the pressure-sensitive copymg paper of the present invention using the color formers described above, and/or conventional color formers such as crystal violet lactone, leuco methylene blue, malachite green lactone, rhodamine B lactram, and the like, the known method disclosed in, for example, the specification of US. Pat. Nos. 2,548,366, 2,800,457 and 2,800,458, that is, a method of preparing microcapsules utilizing a co-acervation technique can be employed.
  • the feature of the present invention is in the use of the color former and the function of the pressure-sensitive copying paper of the present invention is not influenced by the method of preparing the pressure-sensitive copying paper employed, other methods than above described can also be employed in the present invention.
  • the proportion of the color former used usually ranges from 1 to 10% by Weight to the amount of the oily solvent employed.
  • suitable materials are clays, such as acid clay, active clay, attapulgite, zeolite or bentonite; organic acid maerials, such as succinic acid, tannic acid, gallic acid or pentachlorophenol resins, phenol compounds and phenolic resins.
  • organic solvent for dissolving the color former suitable solvents are chlorobenzene, chlorinated paraflins, and diphenyl chloride.
  • the pressure-sensitive copying paper of this invention is substantially colorless before color formation and when the copying paper is locally pressed together with the layer of the solid acid, the color forming reaction occurs instantaneously to form a black, drak green or dark grey color. That is, the color thus formed absorbs the entire visible region of from about 410 ru to about 650 m and also has absorption in the spectral region of from about 350 Inn to about 420 mp. This makes it possible to copy on a diazotype light-sensitive paper. Furthermore, the pressure-sensitive copying paper has excellent light fastness as compared with conventional ones.
  • Example l.-Three grams of each of the color formers No. 1 to No. 12 were processed as follows.
  • the color former was dissolved in 100 g. of diphenyl trichloride and the solution was added to a solution of 20 g. of gum arabic dissolved in 160 g. of water and then the mixture was emulsified.
  • a solution of 20 g. of acid-treated gelatin in 160 g. of water was added to the resultant emulsion, the pH of the system was reduced to 5 by adding acetic acid with stirring constantly, and then 500 g. of water was added to cause co-acervation, whereby a concentrated gelatin-gum arabic film was formed around an oil drop having dissolved therein the color former.
  • the pH of the system was further reduced to 4.4 and then 4 g. of 37% formalin was added as a hardening agent.
  • the above procedures were all conducted at a temperature of 50 C. Thereafter, the temperature of the system was lowered to C. for gelling the concentrated liquid film around the oil drop and further the pH thereof was increased to 9 for improving the hardening effect. Then, by allowing the system to stand for a few hours, the capsulation was finished.
  • the capsule-containing solution thus prepared was applied to a paper by roll coating or air-knife coating and dried to provide the pressure-sensitive copying paper (upper sheet).
  • the upper sheet was placed on a clay-coated sheet (under sheet prepared by applying the above-described active clay to a paper) and they Were locally pressurized by handwriting. Thereby, the following color was instantly formed on the clay-coated paper.
  • color formers No. 1, No. 6 and No. 7 were colored black; color formers No. 2, No. 3, No. 4, No. 5, N0. 9, and No. 10 were colored dark green, and color formers No. 8 and No. 11 were colored dark grey.
  • the dyes thus colored were not faded when they were exposed to sun light for a long period of time and wetted with water or glycerine.
  • the upper sheet having the layer of the microcapsules containing the color former was heated to 100 C. for 20 hours and exposed to sunlight for a long period of time, the color forming ability of the copying paper was not degraded.
  • the light fastness, water resistance, and heat resistance of the pressure-sensitive copying paper of this invention before color forming and after color forming were sufliciently high from a practical standpoint when the copying paper was stored for a long period of time.
  • Example 2 The same procedure as used in Example 1 was followed except that 1 g. of the color former No. 1, 1 g. of the color formed No. 3, 0.5 g. of Malachite Green Lactone, and 0.5 g. of benzoyl leucomethylene blue were used as a mixture thereof instead of the color former in the Example 1. The results were that the clay-coated paper was colored blue black.
  • a pressure-sensitive copying paper comprising a support having coated thereon a layer of microcapsules containing at least one fluoran derivative having the following general formula,
  • R and R each are an alkyl group having from 1 to 5 carbon atoms,.wherein R is selected from the group consisting of a hydrogen atom,*an alkyl group having from 1 to 5 carbon atoms, and a benzyl group, and wherein R is an aryl group.
  • said fluoran derivative is capable of forming a distinct color when contacted with a material selected from the group consisting of acid clay, active clay, attapulgite, zeolite, phenolic compounds and phenolic resins. 4. The pressure-sensitive copying paper as claimed in claim 1 wherein said fluoran derivative is used together with at least one color former selected from the group consisting of crystal violet lactone, leuco methylene blue, malachite green lactone and rhodamine B lactam.
  • a pressure-sensitive copying paper comprising an upper sheet having coated thereon a layer of microcapsules containing at least one fluoran derivative having the following general formula, 3 v
  • R and R each are an alkyl group having from 1 to 5 carbon atoms, wherein R is selected from the group port having coated on the same surface thereof two layers,-
  • one of said layers comprising microcapsules containing at least one fluoran derivative having the following general formula,
  • the pressure-sensitive copying-paper as claimed in the UNITED 7.
  • said eleetro accepting material is a member selected from the group consisting of acid clay, active clay, attapulgite, phenol compounds and phenolic resins.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Color Printing (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
US40481A 1969-05-23 1970-05-22 Pressure-sensitive copying paper Expired - Lifetime US3669711A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP4005669 1969-05-23

Publications (1)

Publication Number Publication Date
US3669711A true US3669711A (en) 1972-06-13

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US (1) US3669711A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
BE (1) BE750824A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DE (1) DE2025171C3 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
ES (1) ES379854A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
FR (1) FR2048614A5 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
GB (1) GB1277545A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
IE (1) IE34604B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3833400A (en) * 1970-11-13 1974-09-03 Fuji Photo Film Co Ltd Sheet with improved image durability
US3844817A (en) * 1970-12-15 1974-10-29 Yamamoto Kagaku Gosei Kk Pressure sensitive copying paper
US3947471A (en) * 1970-12-26 1976-03-30 Sumitomo Chemical Company, Ltd. Benz (c) fluoran compounds and recording sheet containing them
US3979141A (en) * 1974-11-21 1976-09-07 Moore Business Forms, Inc. Pressure-sensitive recording system comprising 3'-amino-6' or 7'-(pyrazol-1-yl)fluoran compounds as color precursors
US3996406A (en) * 1974-11-21 1976-12-07 Moore Business Forms, Inc. 2-Phenyl-1,2,3-triazolofluoran compounds
US4104437A (en) * 1974-09-24 1978-08-01 Champion International Corporation Pressure-sensitive copy system including ureido fluoran chromogenic compounds
US4187193A (en) * 1974-09-24 1980-02-05 Champion International Corporation Micro-capsules containing ureido fluoran chromogenic compounds
US4226912A (en) * 1978-02-15 1980-10-07 Kanzaki Paper Manufacturing Co., Ltd. Heat-sensitive recording material
US4274660A (en) * 1979-05-14 1981-06-23 Sterling Drug Inc. Carbonless duplicating and marking systems
US4302393A (en) * 1973-05-21 1981-11-24 Ciba-Geigy Corporation Fluoran compounds
US4330473A (en) * 1970-07-23 1982-05-18 Yamamoto Kagaku Gosei Kabushiki Kaisha Recording material
US4407886A (en) * 1980-11-24 1983-10-04 Basf Aktiengesellschaft Pressure-sensitive and heat-sensitive recording material
US4806657A (en) * 1983-09-26 1989-02-21 Ciba-Geigy Corporation Process for the preparation of fluoran compounds which are substituted by basic groups
US6680205B1 (en) 2000-04-26 2004-01-20 Battelle Memorial Instittue Solvent-activated color forming compositions
US6689619B2 (en) 2000-04-26 2004-02-10 Battelle Memorial Institute Solvent-activated color-forming compositions

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4444591A (en) * 1977-08-02 1984-04-24 Yamada Chemical Co., Ltd. Chromogenic compounds and the use thereof as color former in copying or recording materials
JPS5434909A (en) * 1977-08-08 1979-03-14 Yamada Chem Co Colored recording material
US4298215A (en) * 1979-05-14 1981-11-03 Sterling Drug Inc. Carbonless duplicating and marking systems
DE4010641C2 (de) * 1990-04-03 1997-05-22 Bayer Ag Farbbildner-Mischung für druck- und wärmeempfindliche Aufzeichnungssysteme

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4330473A (en) * 1970-07-23 1982-05-18 Yamamoto Kagaku Gosei Kabushiki Kaisha Recording material
US3833400A (en) * 1970-11-13 1974-09-03 Fuji Photo Film Co Ltd Sheet with improved image durability
US3844817A (en) * 1970-12-15 1974-10-29 Yamamoto Kagaku Gosei Kk Pressure sensitive copying paper
US3947471A (en) * 1970-12-26 1976-03-30 Sumitomo Chemical Company, Ltd. Benz (c) fluoran compounds and recording sheet containing them
US4349218A (en) * 1973-05-21 1982-09-14 Robert Garner Copying material employing fluoran color formers
US4302393A (en) * 1973-05-21 1981-11-24 Ciba-Geigy Corporation Fluoran compounds
US4104437A (en) * 1974-09-24 1978-08-01 Champion International Corporation Pressure-sensitive copy system including ureido fluoran chromogenic compounds
US4187193A (en) * 1974-09-24 1980-02-05 Champion International Corporation Micro-capsules containing ureido fluoran chromogenic compounds
US3979141A (en) * 1974-11-21 1976-09-07 Moore Business Forms, Inc. Pressure-sensitive recording system comprising 3'-amino-6' or 7'-(pyrazol-1-yl)fluoran compounds as color precursors
US3996406A (en) * 1974-11-21 1976-12-07 Moore Business Forms, Inc. 2-Phenyl-1,2,3-triazolofluoran compounds
US4226912A (en) * 1978-02-15 1980-10-07 Kanzaki Paper Manufacturing Co., Ltd. Heat-sensitive recording material
US4274660A (en) * 1979-05-14 1981-06-23 Sterling Drug Inc. Carbonless duplicating and marking systems
US4407886A (en) * 1980-11-24 1983-10-04 Basf Aktiengesellschaft Pressure-sensitive and heat-sensitive recording material
US4806657A (en) * 1983-09-26 1989-02-21 Ciba-Geigy Corporation Process for the preparation of fluoran compounds which are substituted by basic groups
US6680205B1 (en) 2000-04-26 2004-01-20 Battelle Memorial Instittue Solvent-activated color forming compositions
US6689619B2 (en) 2000-04-26 2004-02-10 Battelle Memorial Institute Solvent-activated color-forming compositions
US20040029289A1 (en) * 2000-04-26 2004-02-12 Elhard Joel D. Solvent-activated color forming compositions

Also Published As

Publication number Publication date
FR2048614A5 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1971-03-19
GB1277545A (en) 1972-06-14
ES379854A1 (es) 1972-09-01
IE34604L (en) 1970-11-23
BE750824A (fr) 1970-11-03
DE2025171A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1970-12-17
DE2025171B2 (de) 1976-11-04
DE2025171C3 (de) 1980-07-10
IE34604B1 (en) 1975-06-25

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