US3669710A - Pressure sensitive copying sheet - Google Patents

Pressure sensitive copying sheet Download PDF

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Publication number
US3669710A
US3669710A US3669710DA US3669710A US 3669710 A US3669710 A US 3669710A US 3669710D A US3669710D A US 3669710DA US 3669710 A US3669710 A US 3669710A
Authority
US
United States
Prior art keywords
sheet
pressure sensitive
sensitive copying
color
coated
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
Other languages
English (en)
Inventor
Shiro Kimura
Sadao Ishige
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 US3669710A publication Critical patent/US3669710A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/025—Applications of microcapsules not provided for in other subclasses
    • 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
    • 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

  • R and R each is an alkyl group having 1 to 5 carbon atoms.
  • the present invention relates to a pressure sensitive copying sheet, and more particularly to a pressure sensitive copying sheet using as a color former a compound represented by the above general formula.
  • An ordinary pressure sensitive copying sheet consists of an upper sheet coated with an electron donating, colorless organic compound (hereinafter referred to as a color former) which is dissolved in an oil and enclosed in microcapsules, and a lower sheet coated with an electron accepting substance (hereinafter referred to as a solid acid) together with a suitable binder.
  • the sheets are superimposed in such a manner that the coating surfaces are contacted.
  • an intermediate sheet coated with the microcapsules on one side thereof and with the solid acid on the other side may be inserted between the upper sheet and the lower sheet.
  • the microcapsules and the solid acid may be coated simultaneously on one side of a support.
  • the above-identified solid acid includes acid clay, active clay, attapulgite, bentonite, organic acids and phenolic resins; and the color former includes rhodamine B lactone, rhodamine anilinolactarn, crystal violet lactone, malachite green lactone and benzoyl leucomethylene blue.
  • R and R each is an alkyl group having 1 to 5 carbon atoms.
  • the above compound maybe microcapsulated by a coacervation method such as that described in US. Pat. No.
  • the thus-prepared pressure sensitive copying sheet has excellent stability under atmospheric conditions prior to the rupturing of the microcapsules, that is, the compound contained in the microcapsules is not colored or decomposed by atmospheric conditions and therefore the color forming properties of the copying sheet are not destroyed or decreased before its use.
  • the copying sheet is able to form pure red images having a higher density when contacted with the electron accepting substance or solid acid.
  • the formed color dye is more excellent in light, heat and water resisting properties.
  • the color former of this invention may be used together with conventional yellow and blue color formers to give the various pressure-sensitive copying sheets capable of forming black or blue-black images without desensitizing the color formers.
  • the compound represented by the above general formula, used for the pressure sensitive copying sheet of this invention may be prepared by, for example, reacting o-(4- dialkyl amino-2-hydroxybenzoyl) benzoic acid with pphenyl phenol in 50-98% concentrated sulfuric acid at a temperature of from 30 to 60 C. for a period of time of from 1 to 24 hours and neutralizing the resulting reaction mixture.
  • any known process for the production of the microcapsules may be employed, including those processes described in US. Pat. Nos. 2,548,366, 2,800,457 and 2,800,458, i.e., whereby the phenomenon of the complex coacervation method is being utilized to make the microcapsules.
  • the sole characteristic feature of the present invention is to use the compound represented by the above formula as the color former.
  • the properties of the resulting pressure sensitive sheet of this invention are not dependent on the method by which the sheet is fabricated.
  • the color former may be used in an amount from 0.5 to by weight, based on the weight of the organic solvent in which the color former is dissolved.
  • active clay substances such as acid clay, active clay, attapulgite, zeolite or bentonite
  • organo-acidic substances such as succinic acid, tannic acid, gallic acid, pentachloro-phenol, or phenolic resin are generally used.
  • the organic solvent used for dissolving the color former may be benzene chloride, diphenyl chloride etc.
  • Each color former was dissolved in g. of trichlorodiphenyl, and the solution was emulsified with the addition of 20 g. of gum arabic and g. of water at 50 C.
  • 20 g. of gelatin and 160 g. of water were added and the pH of the resulting mixture was adjusted to 5 by adding acetic acid with stirring.
  • 500 g. of water was added to the mixture to initiate the coacervation to thereby form a thick liquid film of gelatin-gum arabic around the droplets of the color forming compound dissolved in the trichlorodiphenyl.
  • the pH of the mixture was adjusted to 4.4 and 3.8 g.
  • the thus-formed encapsulated solution was coated on paper by means of a roll-coating or an air-knife coating method, and the coated paper was dried.
  • the thus-prepared coated paper was used as an upper sheet and was faced to a lower sheet coated wtih acid clay, attapulgite, zeolite or bentonite clay, and pressure from a pencil or typewriter key was applied on the surface of the upper sheet. In this manner a color image was instantly formed on the surface of the lower sheet where the pressure or impact was applied. The color thus formed was pure red regardless of the kind of the clay used.
  • the formed color was exposed to direct sun light for a long period of time or soaked in water, and there was substantially no fading of color on the sheet.
  • the upper sheet coated with the color forming compound was heated at 100 C. for 20 hours, or exposed to direct sun light for a long period of time but no decrease of the color forming capacity of the sheet was observed.
  • Example 2 An upper sheet was prepared in the same manner as described in Example 1 but, instead, using 10.0 g. of color former (1) together with known color formers (0.5 g. of benzoyl-leucomethylene blue, 0.7 g. of malachite green lactone, 0.4 g. of crystal violet lactone and 1.5 g. of w-(2-hydroxybenzal) acetonephenone).
  • color formers 0.5 g. of benzoyl-leucomethylene blue, 0.7 g. of malachite green lactone, 0.4 g. of crystal violet lactone and 1.5 g. of w-(2-hydroxybenzal) acetonephenone.
  • Example 3 An upper sheet was prepared in the same manner as described in Example 1, but, instead, using 0.6 g. of color forming compound (1) together with known color formers (0.5 g. of benzoyl leucomethylene blue, 2.0 g. of crystal violet lactone and 0.4 g. of w(2-hydroxybenzal) acetophenone). The thus-prepared sheet was contacted with a lower sheet, and pressure was applied. In this manner, a blue-black color instantly appeared on the lower sheet.
  • known color formers 0.5 g. of benzoyl leucomethylene blue, 2.0 g. of crystal violet lactone and 0.4 g. of w(2-hydroxybenzal) acetophenone.
  • Example 4 Mircocapules containing liquid prepared in the same manner as described in Example 1 were coated on the underside of an intermediate sheet and an electron accepting substance was coated on one side of the sheet.
  • Several intermediate sheets so prepared were inserted between an upper sheet and a lower sheet prepared in the same manner as described in Example 1. Pressure was then applied on the upper sheet and a pure red color ap peared on every intermediate sheet and lower sheet.
  • Example 5 Microencapsulated color formers prepared in the same manner as in Example 1 were coated on paper on which an electron accepting substance had been previously coated. The thus-prepared pressure sensitive copying sheet was laid under ordinary paper, and pressure was applied onto the paper. A pure red color appeared on the pressure sensitive copying sheet.
  • a pressure sensitive copying sheet comprising a support having coated thereon a layer containing microcapsules, said microcapsules containing a colorless compound dissolved in oil and represented by the formula:
  • R and R each is an alkyl group having from 1 to 5 carbon atoms, said compound being capable of forming a color dye when contacted with an electron accepting solid acid.
  • a pressure sensitive copying sheet comprising an upper sheet having coated thereon a layer containing microcapsules containing a colorless compound dissolved in oil and represented by the formula:
  • R and R each is an alkyl group having from 1 to 5 carbon atoms, and a lower sheet having coated thereon a solid acid layer.
  • microcapsules contain from 0.5 to 10% by weight of said compound, based on the weight of said oil.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Color Printing (AREA)
US3669710D 1969-05-07 1970-05-07 Pressure sensitive copying sheet Expired - Lifetime US3669710A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP3496869 1969-05-07

Publications (1)

Publication Number Publication Date
US3669710A true US3669710A (en) 1972-06-13

Family

ID=12428928

Family Applications (1)

Application Number Title Priority Date Filing Date
US3669710D Expired - Lifetime US3669710A (en) 1969-05-07 1970-05-07 Pressure sensitive copying sheet

Country Status (6)

Country Link
US (1) US3669710A (fr)
BE (1) BE750030A (fr)
DE (1) DE2022339C3 (fr)
FR (1) FR2047363A5 (fr)
GB (1) GB1267629A (fr)
IE (1) IE34478B1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3930672A (en) * 1973-03-23 1976-01-06 Hodogaya Chemical Co., Ltd. Pressure-sensitive copying paper containing lactone compounds derived from pyridine-carboxylic acid
US3985930A (en) * 1976-03-04 1976-10-12 The Mead Corporation Cyclopolymethylenefluoran compounds
KR20190026499A (ko) * 2017-09-05 2019-03-13 충남대학교산학협력단 산 개시제를 사용하지 않는 감온변색 색소재료, 마이크로캡슐, 이의 제조방법 및 제품

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3930672A (en) * 1973-03-23 1976-01-06 Hodogaya Chemical Co., Ltd. Pressure-sensitive copying paper containing lactone compounds derived from pyridine-carboxylic acid
US3985930A (en) * 1976-03-04 1976-10-12 The Mead Corporation Cyclopolymethylenefluoran compounds
KR20190026499A (ko) * 2017-09-05 2019-03-13 충남대학교산학협력단 산 개시제를 사용하지 않는 감온변색 색소재료, 마이크로캡슐, 이의 제조방법 및 제품

Also Published As

Publication number Publication date
IE34478B1 (en) 1975-05-28
FR2047363A5 (fr) 1971-03-12
DE2022339B2 (de) 1972-03-30
IE34478L (en) 1970-11-07
DE2022339C3 (de) 1974-03-07
DE2022339A1 (de) 1970-11-19
BE750030A (fr) 1970-10-16
GB1267629A (en) 1972-03-22

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