EP0076342A1 - Feuille de développement chromogène pour l'enregistrement sans carbone - Google Patents

Feuille de développement chromogène pour l'enregistrement sans carbone Download PDF

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Publication number
EP0076342A1
EP0076342A1 EP81304550A EP81304550A EP0076342A1 EP 0076342 A1 EP0076342 A1 EP 0076342A1 EP 81304550 A EP81304550 A EP 81304550A EP 81304550 A EP81304550 A EP 81304550A EP 0076342 A1 EP0076342 A1 EP 0076342A1
Authority
EP
European Patent Office
Prior art keywords
color
activated clay
developer sheet
parts
sodium silicate
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.)
Withdrawn
Application number
EP81304550A
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German (de)
English (en)
Inventor
Takahiro Torii
Hideo Ohye
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.)
Mitsubishi Paper Mills Ltd
Original Assignee
Mitsubishi Paper Mills 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 Mitsubishi Paper Mills Ltd filed Critical Mitsubishi Paper Mills Ltd
Priority to EP81304550A priority Critical patent/EP0076342A1/fr
Publication of EP0076342A1 publication Critical patent/EP0076342A1/fr
Withdrawn legal-status Critical Current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
    • B41M5/124—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
    • B41M5/1555—Inorganic mineral developers, e.g. clays

Definitions

  • This invention provides a color-developer sheet for carbonless copying, and more particularly such a color-developer sheet characterized in that a coating liquid is used which results from the use of activated clay in solid particulate form which has been in advance admixed with sodium silicate and optionally other dispersants.
  • Carbonless copying papers are known as disclosed for example in U.S. Patents No. 2,712,517, No. 2,800,457 and No. 2,730,457.
  • Such carbonless copying paper utilizes microcapsules containing a solution of an electron-donative, non-adsorptive, reactive colorless organic compound (hereinafter referred to as "color-former”) and an electror-acce p tive, reactive, adsorptive material (hereinafter referred to as "color-developer").
  • Microencapsulation is effected by means of coacerva- tion, interfacial polymerization, in situ polymerixation and other processes.
  • Color-formers include malachite green lactone, crystal violet lactone, benzoyl leuco methylene blue, rhodamine B lactam, 3-dialkylamino-7-dialkylamylfluoran, 3-methyl-2,2-spiropi(benzo[f]-chromene) and the like.
  • Color-developers include solid acids such as acid clay, activated clay, attapulgite, zeolite, bentonite and the like; an organic group of phenolic resins such as p-tert-butylphenol resin, p-phenylphenol resin, p-octylphencl resin and the like; organic compounds such as succinic acid, tannic acid, malonic acid, gallic acid and the like, or metal compounds thereof; and aromatic carboxylic acids such as benzoic acid, salicylic acid, substituted salicylic acids, naphthoic acid, diphenic acid and the like, or metal compounds thereof. Typical examples in the usual practice are activated clay phenolic resins and substituted salicylic acids.
  • Phenolic resins and substituted salicylic acids are adequate for high concentration sheet coating but give rise to poor ink absorptivity. These two color-davelopers have another drawback that due primarily to chemically synthesized substances, they are susceptible to degradation or decomposition of the printed marks under sunlight which would in turn fade away.
  • Inorganic activated clay is superior in ink absorptivity and inexpensive.
  • such activated clay color-developer is disadvantageous in that a coating liquid prepared therefrom is liable to become gelled in high concentrations, with ultimate difficulty in sheet coating, and that sheets of paper coated with low-concentration coating liquids involve blanket smear (piling) at the time of printing.
  • Activated clay used as the color-developer is, as disclosed in Japanese Patent Publications No. 41-2373, No. 41-7622 and No. 42-8811, about 200 m 2 /g or greater in surface area and prepared by treating acid clay or similar types of clay with a mineral acid to elute acid-soluble alumina, iron and other basic components.
  • Activated clay even if mixed with zinc, magnesium and other salts, may be used successfully.
  • An X-ray analysis shows that activated clay is amorphous, relatively large in surface area and characteristically different from ordinary paper coating pigments. When dispersed in water, activated clay requires a greater amount of water to complete the dispersion due to its shape, surface activity and other factors.
  • Kaolin clay typical of paper coating remains fluid in concentrations of 70% and above when dispersed in water, whereas activated clay becomes viscous and gelled in concentrations of about 45%.
  • Activated clay is difficult to process ior such high-concentration coating liquids for the reasons already stated.
  • An air-knife crater process is therefore currently employed using low-concentration coating liquids.
  • the color-developer sheet produced shows good . surface quality, smoothness and smudge resistance (against blurry spots caused by rubbing encapsulated surfaces) and free from blanket smear at the time of printing.
  • Activated clay used in the present invention may be prepared by treating acid clay with an acid to be then e.g. washed with water, dried and pulverized.
  • the sodium silicate and other dispersant if any may be mixed with the clay by various methods.
  • the dispersant may be added and mixed into and with it as aqueous solution.
  • the dispersant is added and mixed in a powder state.
  • the dispersant is added, mixed and crushed in powder state.
  • the dispersant in powdered state is added and mixed, but the invention is not restricted to these methods only.
  • sodium silicate inorganic dispersants such as sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate and so on and organic dispersants based on carboxylic acids (e.g. acrylates), and maleic acid particularly (e.g. styrene maleic anhydride salt and so on), and sulfonic acid compounds (such as naphthalene sulfonate and so on) can be used.
  • carboxylic acids e.g. acrylates
  • maleic acid particularly e.g. styrene maleic anhydride salt and so on
  • sulfonic acid compounds such as naphthalene sulfonate and so on
  • Sodium silicate as used in the invention is known as a water glass and includes kinds dissolved in water and othersin . particulate form. Typical examples commercially available are sodium silicate No. 1, No. 2 and No. 3, which are represented by the formula where n is about 2 for No. 1, about 2.5 for No. 2 and about 3 for No. 3.
  • Sodium meta-silicate is represented by the formula or
  • Sodium silicate according to the invention is preferably in amount of 0.5 - 20%, preferably 1 - 15%, based on the weight of activated clay. Smaller amounts may demonstrate no effect, while greater amounts may hinder color formation.
  • a dispersant co-used with sodium silicate is preferably in an amount of 0.1 - 15%, preferably 1 - 8%, based on the weight of activated clay. Smaller amounts may demonstrate no effect; while greater amounts do not adversely affect the viscosity but may reduce color-forming capabilities.
  • Particularly eligible dispersants used in combination with sodium silicate include sodium p yrophosphate, sodium tripolyphosphate and sodium hexametaphosphate.
  • Activated clay together with the above dispersants is-dispersed in water and with known pigments, adhesive compounds and additives forms a coating liquid to be applied onto a substrate such as paper.
  • a particularly suitable pigment is calcium carbonate.
  • an eligible adhesive there may be used polyvinyl alcohol and styrene-butadiene latexes.
  • activated clay particles are amorphous, and porous, they require more adhesives than do other paper making clays such as kaolin, calcium carbonate and the like in order to obtain a sufficient strength of the coated layer for printing.
  • attempts to use added amounts of synthetic rubber latexes, starch, casein, CMC and other water-soluble adhesive compounds as commonly used in art papers and coated papers would result in blocked activation of the activated clay and hence in reduced color-forming capabilities.
  • the sodium silicate according to the invention serves satisfactorily as a dispersant for the amorphous, porous activated clay and as a water-soluble inorganic adhesive as well, without hindering color formation unlike conventional synthetic rubber latexes and naturally occurring organic water-soluble adhesive compounds. Rather it acts to enhance color-developing ability of the activated can clay. Consequently, the use of the sodium silicate can lead, to saving of the adhesive compounds.
  • Oxides, hydroxides and carbonates of alkali or alkali earth metal are known to enhance the ability of activated clay as disclosed for example in Japanese Patent Publications No. 41-2373 and No. 42-8811.
  • addition of activated clay after sodium silicate has been first added to water, or addition of sodium silicate after activated clay has been first dispersed in water would result in a system which gelled as a whole.
  • a satisfactorily fluid, high-concentration coating liquid can be obtained according to the invention by using an activated clay in a particulate solid form which has been in advance admixed with sodium silicate and optionally other dispersants.
  • Such coating liquid may be conveniently applied by a blade coater to a substrate to produce a color-developer sheet which has a good surface quality fre p from smudge on contact with encapsulated surfaces and which is sufficiently strong and further free from blanket smear, picking and other troubles which would otherwise occur during printing.
  • No.l sodium silicate as shown in Example 1 is replaced by No.3 sodium silicate in equivalent amount (general formula Na 2 0.3 Si0 2 ).
  • 100 wt. parts of activated clay dry mixed with 3 wt. parts of sodium pyrophosphate in powder state is added with stirring to a solution obtained by mixing 50 wt. parts of aqueous solution of 10% polyvinyl alcohol (PVA-105) with 60 wt. parts of added water.
  • 10 wt. parts (solids content) of styrene-butadiene latex (Dow 670) is added and well stirred and the pH is adjusted to 9.5 with 20% caustic soda.
  • the coating liquid so prepared is coated on quality paper of 40 g/m 2 by means of a blade coater to give an 8 g/m 2 (solids content) coating.
  • 100 wt. parts of activated clay in powder state and 3 wt. parts of sodium pyrophosphate in powder state are mixed with a solution obtained by mixing 10 wt. parts of 50% No.l sodium silicate aqueous solution with 50 wt. parts of 10% polyvinyl alcohol (PVA-105) aqueous solution.
  • the suspension is gently mixed with 60 wt. parts of water with stirring and then with 10 wt. parts (solids content) of styrene-butadiene latex (Dow 607).
  • the pH is adjusted to 9.5 with 20% caustic soda and the coating liquid thus prepared.
  • This coating liquid is coated on quality paper of 40 g/m 2 by means of blade coater so that the coating amount may indicate 8 g/m 2 (solids content).
  • FIGS. 1 and 2 each are a rheological graph representing Examples 1 and 2; and FIGS. 3 - 6 each are a rheological graph representing Comparative Examples 1 - 4, respectively.

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Color Printing (AREA)
EP81304550A 1981-10-01 1981-10-01 Feuille de développement chromogène pour l'enregistrement sans carbone Withdrawn EP0076342A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP81304550A EP0076342A1 (fr) 1981-10-01 1981-10-01 Feuille de développement chromogène pour l'enregistrement sans carbone

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP81304550A EP0076342A1 (fr) 1981-10-01 1981-10-01 Feuille de développement chromogène pour l'enregistrement sans carbone

Publications (1)

Publication Number Publication Date
EP0076342A1 true EP0076342A1 (fr) 1983-04-13

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EP81304550A Withdrawn EP0076342A1 (fr) 1981-10-01 1981-10-01 Feuille de développement chromogène pour l'enregistrement sans carbone

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0372927A2 (fr) * 1988-12-06 1990-06-13 The Mead Corporation Feuille de révélateur et méthode pour former des images, tous deux pour réaliser des images
DE4327158A1 (de) * 1993-08-12 1995-02-16 Sued Chemie Ag Verfahren zur Herstellung von neutralen bis alkalischen Farbentwicklerpigmenten
EP0678399A1 (fr) * 1994-04-20 1995-10-25 Süd-Chemie Ag Développeur de couleurs pour papier d'enregistrement sans carbone

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB760080A (en) * 1953-09-15 1956-10-31 Ncr Co Process for producing pigment-containing paper-coating compositions
DE1152429B (de) * 1951-05-26 1963-08-08 Ncr Co Beschichtungsmaterial fuer Farbreaktions-Durchschreibpapiere
US3223546A (en) * 1962-01-17 1965-12-14 Minerals & Chem Philipp Corp Color-reactable inorganic adsorbent pigment and coating composition containing the same
US3434864A (en) * 1965-06-17 1969-03-25 Engelhard Min & Chem Sensitized sheet material containing deammoniated,ammonium-exchanged molecular sieve
GB2050407A (en) * 1979-03-28 1981-01-07 Mitsubishi Paper Mills Ltd Colour developer coating colours for carbonless copying papers

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1152429B (de) * 1951-05-26 1963-08-08 Ncr Co Beschichtungsmaterial fuer Farbreaktions-Durchschreibpapiere
GB760080A (en) * 1953-09-15 1956-10-31 Ncr Co Process for producing pigment-containing paper-coating compositions
US3223546A (en) * 1962-01-17 1965-12-14 Minerals & Chem Philipp Corp Color-reactable inorganic adsorbent pigment and coating composition containing the same
US3434864A (en) * 1965-06-17 1969-03-25 Engelhard Min & Chem Sensitized sheet material containing deammoniated,ammonium-exchanged molecular sieve
GB2050407A (en) * 1979-03-28 1981-01-07 Mitsubishi Paper Mills Ltd Colour developer coating colours for carbonless copying papers

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0372927A2 (fr) * 1988-12-06 1990-06-13 The Mead Corporation Feuille de révélateur et méthode pour former des images, tous deux pour réaliser des images
EP0372927A3 (fr) * 1988-12-06 1990-07-11 The Mead Corporation Feuille de révélateur et méthode pour former des images, tous deux pour réaliser des images
DE4327158A1 (de) * 1993-08-12 1995-02-16 Sued Chemie Ag Verfahren zur Herstellung von neutralen bis alkalischen Farbentwicklerpigmenten
US5637552A (en) * 1993-08-12 1997-06-10 Sud-Chemie A.G. Process for producing neutral to alkali color developer pigments
EP0678399A1 (fr) * 1994-04-20 1995-10-25 Süd-Chemie Ag Développeur de couleurs pour papier d'enregistrement sans carbone

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Inventor name: TORII, TAKAHIRO

Inventor name: OHYE, HIDEO