US3816838A - Method of making recordings in a recording sheet material - Google Patents

Method of making recordings in a recording sheet material Download PDF

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Publication number
US3816838A
US3816838A US00210885A US21088571A US3816838A US 3816838 A US3816838 A US 3816838A US 00210885 A US00210885 A US 00210885A US 21088571 A US21088571 A US 21088571A US 3816838 A US3816838 A US 3816838A
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US
United States
Prior art keywords
color
recording sheet
suspension
phenolic
parts
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
US00210885A
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English (en)
Inventor
T Higaki
M Mikumo
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.)
Kanzaki Paper Manufacturing Co Ltd
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Kanzaki Paper Manufacturing Co Ltd
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Filing date
Publication date
Priority claimed from JP45127821A external-priority patent/JPS4913449B1/ja
Priority claimed from JP45126386A external-priority patent/JPS4913457B1/ja
Application filed by Kanzaki Paper Manufacturing Co Ltd filed Critical Kanzaki Paper Manufacturing Co Ltd
Application granted granted Critical
Publication of US3816838A publication Critical patent/US3816838A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • 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
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3331—Macromolecular 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
    • B41M5/124—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
    • 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
    • B41M5/155—Colour-developing components, e.g. acidic compounds; Additives or binders therefor; Layers containing such colour-developing components, additives or binders
    • 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
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds
    • B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof

Definitions

  • ABSTRACT A method of making recordings in a recording sheet material is disclosed, wherein the base sheet is applied with a suspension containing finely divided solid particles of color-forming components which essentially comprises (a) leuco dyes and (b) phenolic-aldehyde polymeric condensates and (c) particular types of monomeric substituted phenols the weight ratio of said components (b) and (c) in the range from 90 10 to 10 90.
  • the resultant product can produce an excellent color-formation when reactive contact among the color-forming components is caused by imparting heat or an ultrasonic vibrating energy.
  • Mark-forming system utilizing an electron donoracceptor color-forming reaction between basic dyes and monomeric phenols such as heat-sensitive or pressure-sensitive recording system is well known.
  • color-forming components comprising basic dyes and monomeric phenols react upon reactive contact to produce a visible color with the contact being achieved by the use of heat or pressure with or without the existence of any solvent.
  • the reactive contact herein described means that the molecular distance between electron donor and electron acceptor is close enough to each other to cause an electron donoracceptor colorforming reaction.
  • Australian Pat. No. 402,733 corresponding to US. Pat. No. 3,539,375, issued Nov.
  • a heat-sensitive record material comprising a support sheet having crystal violet lactone and a phenolic material solid at the room temperature but capable of liquefying and/or vaporizing at normal thermographic temperature.
  • Attemps have been made to use suchmonomeric phenols as 4-tertiary-buthylphenol, 4-phenylphenol, a-naphthol, 4,4'-isopropy1idene-diphenol and etc. as phenolic materials.
  • the above mentioned novel recording system has a number of advantages such as free from the effect of mechanical inertia, unnecessity of using transforming system such as photo-electronic transformation, and vice versa, less defacement of recording equipment, a simple in constraction and high sensitivity, all of which make it possible to apply it to highspeed printer, facsimile system and etc.
  • the recording sheet according to the invention comprises a base sheet having solid particles of colorforming components which essentially comprises (a) leuco dyes, (b) phenolic-aldehyde polymeric condensates and (c) monomeric substituted phenols.
  • R is alkyl group having four to 20 carbon atoms, aralkyl group, substituted aralkyl group, phenyl group substituted phenyl group or cycloalkyl group.
  • the weight ratio of phenolic-aldehyde polymeric condensates to monomeric substituted phenols should be within the range of from 10 to 10 90.
  • colorless dyes useful in this invention there are included the compounds having lactone ring, lactam ring or sultone ring, which are colorless or light color for themselves but react with acidic materials upon contact to produce a color.
  • Such compound is generally called as leuco dye, and the following compounds or combination thereof may be mentioned as typical leuco dyes:
  • monomeric substituted phenols are p-phenylphenol, p-ter-butylphenol, p-octylphenol, p-pentylphenol, 2,2-bis(4'-hydroxyphenyl)propane, p-benzyl-phenol, 2,2-bis (4'-hydroxyphenyl)-sec-isobutane p-(4'-chlorophenyl)phenol,cyclohexylphenol and so forth.
  • the most useful phenolic-aldehyde polymeric condensate in this invention is a material generally called as novolack which has a free hydroxyl group and fusability in the absence of cross-linking agent and is water insoluble.
  • phenolic material useful in this invention there are included the materials which are solid under the room temperature but liquefied under normal thermographic temperatures of 90-200 C.
  • the melting point of phenolic materials is not an indispensable factor in the recording system described.
  • the recording sheet of this invention may be produced by applying to a base sheet with an aqueous or non-aqueous suspension dispersing therein fine solid particles of color-forming components.
  • the base sheet is coated on one side with a suspension system containing solidparticles of colorforming components.
  • the solvent used in the non-squeous suspension must be selected from the materials which do not solve a color-forming components.
  • aliphatic hydrocarbons having 5 12 carbon atoms such as n-paraffinic hydrocarbon, isoparaffinic hydrocarbon and cycloparaffinic hydrocarbon.
  • aqueous systems are more preferable than non-aqueous systems from the view points of economy, handling, safety and others.
  • the suspension system may be added thereto with adhesives or bonding agents such as polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, casein, starch, syntheric latices and etc., in order that solid particles of color-forming components may be sticked to the base sheet.
  • adhesives or bonding agents such as polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, casein, starch, syntheric latices and etc.
  • One of the improvements of manufacturing method of this invention is control the pH of aqueous suspension containing color-forming components between 6.0 and l 1.0 by addition of basic materials or buffers such as sodium hydroxide, potassium hydroxide, ammonia, lower amines and basic salts thereof as well as urea and thiourea.
  • the control of pH helps to avoid smudge or background which often take place during storing or recording process.
  • Another improvement is to put coated and dried sheet to a calender treatment by means of, for example, supercalender. As the surface of the recording sheet is smoothened by this treatment,
  • this can accept an energy from a stylus uniformly. Also, this treatment makes the coated layer stronger since the coated layer can be mechanically densified/This may also save the quantity of adhesives in suspension and to simplify the mutual contact of color-forming components.
  • a further improvement is to prepare solid particles of phenolic materials by uniformly mixing phenolic-aldehyde polymeric condensates and monomeric substituted phenolsunder a melted condition,
  • Phenolic solid particles so obtained are more activated in color-forming reaction.
  • the particle size of phenolic materials under this invention is to be controlled between approximately I and 5 microns. However, this is not restricted within the above range since this may be voluntarily determined according to the required resolution.
  • FIGS. 1 and 2 show a typical equipment showing the improved recording-system.
  • electrodes 11 are attached on opposite sides of ceramic piezoelectric substance 12 on end of which a stylus 13 is connected:
  • This stylus 13 maybe a piano code of 700 microns wide by 15 microns thick by 3 milimeters long, and the edge comes in slight contact with the surface of the running record sheet 14, say, under a pressure of 1 5 grams.
  • AC alternating electric signal is applied to the ceramic piezoelectric substance 12 from an AC source 16
  • the substance 12 causes a continuous expansion and contraction making the stylus 13 vibrate according to the frequency of the-AC signal, and the vibrating energy is imparted on the surface of the recording sheet 14.
  • the frequency of vibration and preferably between from 10 KHz to KHz, this is not restricted within the above range since this may be determined according to the resonant frequency of the ceramic electric substance used.
  • Optimum frequency can be chosen at will according to the size and the shape of the stylus, the recordingspeed, the running speed and the sensitivity of the recording sheet, the line density of the stylus and so forth.
  • the vibration energy causes a virtual contact among color-forming components, and, as a result, a visible image is produced on the surface of recording sheet corresponding to the pattern of applied alternating electric signal.
  • the equipment has multi-styli' 15 consisting of a'number of stylus 15' each of which has a line density of three five linesper milimeter practically capable of producing any type of pattern.
  • Example 1 13.5 parts of p-phenylphenol (m.p. 169 C) was uniity controler) and 59.8 parts of water.
  • the particle size of the above premixed phenolic materials was approximately 3 5 microns after ball-milling.
  • Control-A and Control- B are similar to Example 1 except that each of p-phenylphenol (m.p. 169 C) and p-phenylphenol-formaldehyde polymeric condensate (5O 50 mp. 140 C) was'used singly. Namely, when the preparation of Component-A, each of above materials was used signly as fine particles and mixed with other components in the ball-mill.
  • Each recording sheet obtained through above exam ples and controls was put to a recording test by means of the equipment as shown in FIG. 1. Namely, ultrasonic energy caused according to alternating electric signal of 100 V (effective) with frequency of 30 KHZ was locally applied from the stylus to the surface of the recording sheet running at a speed of 50 millimeter per minute. On the other hand, a hot stylus with a temperature of 200 C. scanned over the surface of the recording sheet. The results of the experiment are as shown in the photograph of FIG. 3. In FIG. 3, the dotted line shows the colored image brought about by ultrasonic vibrating energy, and two lines of on the right side show the colored image brought about by the scanning hot stylus.
  • Example 8 This example is similar to Example 1 except that 7.5 parts of fine solid particles of p-phenylphenol and 7.5 parts of fine solid particles of p-phenylphenolformaldehyde polymeric condensate were without premixing them, mixed with 0.4 part of anionic surfactant, 0.5 part of hydroxipropyl cellulose and 59.8 parts of water in the ball-mill at preparation stage of Component-A.
  • Example 3 The resultant recording sheet was experimented in the same way as Example 1, and similar results as in Example 1 were obtained as shown in the attached photograph of FIG. 3.
  • Example 9 Component-A 8 parts of p-ter-butylphenol-formaldehyde polymeric condensate (50 50, mp. l28-l31 C) was uniformly mixed with 1.2 parts of p-phenylphenol (m. p. 169 C) under melt state. At that time, the weight ratio of both materials is 87: 13. This mixture was then solidified by cooling and repulverized. And further, this pulverized mixture was ground by ball-milling for 3 hours with 10 parts of 20 percent Nylgum A-85 (Starch phosphate ester, manufactured by W. A. Sholtens Chemishe F abrieken N-.V., I-Iolland) solution and parts of water.
  • Component-B 10 parts of crystal violet lactone and 10 parts of benzoyl leucomethylene blue were ground by ball-milling for 2 hours with 10 parts of 20 percent Nylgum A- (see above) solution and 70 parts of water.
  • Theparticle size of the above premixed phenolic materials was approximately 3 5 microns after ballmilling.
  • Component-B 7 10 parts of crystal violet lactone was ground by ballmilling for 3 hours with parts of mineral spirit and 0.5 part of cyclolized rubber.
  • the particle size of the above dye was approximately 3 microns after ballmilling.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Color Printing (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
US00210885A 1970-12-28 1971-12-22 Method of making recordings in a recording sheet material Expired - Lifetime US3816838A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP45127821A JPS4913449B1 (enrdf_load_stackoverflow) 1970-12-28 1970-12-28
JP45126386A JPS4913457B1 (enrdf_load_stackoverflow) 1970-12-29 1970-12-29

Publications (1)

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US3816838A true US3816838A (en) 1974-06-11

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US00210885A Expired - Lifetime US3816838A (en) 1970-12-28 1971-12-22 Method of making recordings in a recording sheet material

Country Status (5)

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US (1) US3816838A (enrdf_load_stackoverflow)
BE (1) BE777296A (enrdf_load_stackoverflow)
CA (1) CA937050A (enrdf_load_stackoverflow)
DE (1) DE2164512C3 (enrdf_load_stackoverflow)
SE (1) SE377780B (enrdf_load_stackoverflow)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3962489A (en) * 1973-05-17 1976-06-08 Gerhard Ritzerfeld Copy sheet and method of printing the same
US4025399A (en) * 1974-04-08 1977-05-24 Canon Kabushiki Kaisha Image recording member
US4046073A (en) * 1976-01-28 1977-09-06 International Business Machines Corporation Ultrasonic transfer printing with multi-copy, color and low audible noise capability
US4046074A (en) * 1976-02-02 1977-09-06 International Business Machines Corporation Non-impact printing system
US4379721A (en) * 1980-03-14 1983-04-12 Spezial-Papiermaschinenfabrik August Alfred Krupp Gmbh & Co. Pressure sensitive recording materials
US6372329B1 (en) 1998-11-30 2002-04-16 Arkwright, Incorporated Ink-jet recording media having ink-receptive layers comprising modified poly(vinyl alcohols)
US20040212668A1 (en) * 2003-04-23 2004-10-28 Santiago Javier H. Apparatus, system, and method for frictionally reacting thermal paper
CN104656373A (zh) * 2015-01-08 2015-05-27 苏州瑞红电子化学品有限公司 一种用于gprc工艺中不含光敏剂的光刻胶组合物

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2911798C2 (de) * 1979-03-26 1983-08-18 Pelikan Ag, 3000 Hannover Anordnung zum Erzeugen hellfarbiger Markierungen auf einem dunkelfarbigen Untergrund für die Overhead-Projektion
US5091359A (en) * 1989-02-08 1992-02-25 Kanzaki Paper Manufacturing Co., Ltd. Heat-sensitive record material

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2661998A (en) * 1949-04-30 1953-12-08 Rca Corp Electric marking method, apparatus, and carrier for facsimile systems and the like
US3162763A (en) * 1962-04-05 1964-12-22 Dietzgen Co Eugene Thermographic reproduction paper, method of making and method of using
US3466184A (en) * 1967-02-14 1969-09-09 Ncr Co Record sheet sensitized with phenolic polymeric material
US3466185A (en) * 1967-03-21 1969-09-09 Ncr Co Process of a sensitizing paper with phenolic polymeric material
US3539375A (en) * 1966-06-01 1970-11-10 Ncr Co Thermo-responsive record sheet
US3576660A (en) * 1968-07-11 1971-04-27 Ncr Co Pressure-sensitive record sheet and coating composition
US3672935A (en) * 1964-08-27 1972-06-27 Ncr Co Pressure-sensitive record material

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2661998A (en) * 1949-04-30 1953-12-08 Rca Corp Electric marking method, apparatus, and carrier for facsimile systems and the like
US3162763A (en) * 1962-04-05 1964-12-22 Dietzgen Co Eugene Thermographic reproduction paper, method of making and method of using
US3672935A (en) * 1964-08-27 1972-06-27 Ncr Co Pressure-sensitive record material
US3539375A (en) * 1966-06-01 1970-11-10 Ncr Co Thermo-responsive record sheet
US3466184A (en) * 1967-02-14 1969-09-09 Ncr Co Record sheet sensitized with phenolic polymeric material
US3466185A (en) * 1967-03-21 1969-09-09 Ncr Co Process of a sensitizing paper with phenolic polymeric material
US3576660A (en) * 1968-07-11 1971-04-27 Ncr Co Pressure-sensitive record sheet and coating composition

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3962489A (en) * 1973-05-17 1976-06-08 Gerhard Ritzerfeld Copy sheet and method of printing the same
US4025399A (en) * 1974-04-08 1977-05-24 Canon Kabushiki Kaisha Image recording member
US4046073A (en) * 1976-01-28 1977-09-06 International Business Machines Corporation Ultrasonic transfer printing with multi-copy, color and low audible noise capability
US4046074A (en) * 1976-02-02 1977-09-06 International Business Machines Corporation Non-impact printing system
US4379721A (en) * 1980-03-14 1983-04-12 Spezial-Papiermaschinenfabrik August Alfred Krupp Gmbh & Co. Pressure sensitive recording materials
US6372329B1 (en) 1998-11-30 2002-04-16 Arkwright, Incorporated Ink-jet recording media having ink-receptive layers comprising modified poly(vinyl alcohols)
US20040212668A1 (en) * 2003-04-23 2004-10-28 Santiago Javier H. Apparatus, system, and method for frictionally reacting thermal paper
US6894708B2 (en) * 2003-04-23 2005-05-17 International Business Machines Corporation Apparatus, system, and method for frictionally reacting thermal paper
CN104656373A (zh) * 2015-01-08 2015-05-27 苏州瑞红电子化学品有限公司 一种用于gprc工艺中不含光敏剂的光刻胶组合物
CN104656373B (zh) * 2015-01-08 2018-10-12 苏州瑞红电子化学品有限公司 一种用于玻璃钝化整流芯片工艺中不含光敏剂的光刻胶组合物及其应用

Also Published As

Publication number Publication date
BE777296A (fr) 1972-04-17
DE2164512B2 (de) 1974-05-22
SE377780B (enrdf_load_stackoverflow) 1975-07-28
CA937050A (en) 1973-11-20
DE2164512C3 (de) 1975-01-23
DE2164512A1 (de) 1972-07-27

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